WO2019187247A1

WO2019187247A1 - Warpage prevention laminate for cured sealing body and method for producing cured sealing body

Info

Publication number: WO2019187247A1
Application number: PCT/JP2018/036810
Authority: WO
Inventors: 明徳佐藤; 洋佑高麗; 高志阿久津; 康彦垣内; 岡本　直也; 忠知山田; 中山　武人
Original assignee: リンテック株式会社
Priority date: 2018-03-30
Filing date: 2018-10-02
Publication date: 2019-10-03
Also published as: JP7240376B2; KR20200138149A; JPWO2019187247A1; TWI788425B; KR102674354B1; KR102576309B1; TW201942286A; CN111902503A; CN111954703A; JPWO2019187248A1; WO2019187248A1; KR20200138150A; JP7240377B2; TWI796367B; TW201942283A

Abstract

Provided is a warpage prevention laminate for a cured sealing body, the warpage prevention laminate having a curable resin layer (I) including a thermosetting resin layer (X1), and a support layer (II) for supporting the curable resin layer (I), wherein: the thermosetting resin layer (X1) is directly laminated on the support layer (II); the adhesive force of a first surface of the curable resin layer (I) is 1.7N/25mm or more, which is a value measured when the first surface is adhered to the glass plate at 70°C, and then the curable resin layer (I) is peeled off at 23°C at a peeling angle of 180° and a peeling speed of 300 mm/min, the first surface being a surface opposite to the support layer (II); and on the first surface of the curable resin layer (I), an object to be sealed is sealed with a sealing material.

Description

Laminated body for preventing warpage of cured sealing body, and method for producing cured sealing body

The present invention relates to a laminate for warping prevention of a cured encapsulant and a method for producing the cured encapsulant.

In recent years, electronic devices have been reduced in size, weight, and functionality, and semiconductor chips are sometimes mounted in packages close to the size. Such a package may be referred to as a CSP (Chip Scale Package). Examples of the CSP include WLP (Wafer Level Package) that is processed up to the final package process with a wafer size, and PLP (Panel Level Package) that is processed and completed up to the final package process with a panel size larger than the wafer size. .

WLP and PLP are classified into fan-in type and fan-out type. In fan-out type WLP (hereinafter also referred to as “FOWLP”) and PLP (hereinafter also referred to as “FOPPL”), a semiconductor chip is covered with a sealing material so as to be an area larger than the chip size. Then, the re-wiring layer and the external electrode are formed not only on the circuit surface of the semiconductor chip but also on the surface region of the sealing material.

FOWLP and FOPLP are, for example, a placement step of placing a plurality of semiconductor chips on a temporary fixing sheet, a covering step of covering with a thermosetting sealing material, and curing the sealing material by thermosetting. A curing step for obtaining a sealing body, a separation step for separating the cured sealing body and the temporary fixing sheet, and a rewiring layer forming step for forming a rewiring layer on the surface of the exposed semiconductor chip. (Hereinafter, processing performed in the coating step and the curing step is also referred to as “sealing processing”).

Patent Document 1 discloses a heat-peelable pressure-sensitive adhesive sheet for temporarily fixing when cutting an electronic component, in which a heat-expandable pressure-sensitive adhesive layer containing heat-expandable microspheres is provided on at least one surface of a base material. In the production of FOWLP and FOPLP, it is also conceivable to use the heat-peelable pressure-sensitive adhesive sheet described in Patent Document 1.

JP 2001-131507 A

However, when a cured sealing body is produced using the pressure-sensitive adhesive sheet described in Patent Document 1 as a temporary fixing sheet, the cured sealing body tends to warp due to thermal contraction. This is because the semiconductor chip sealed in the cured sealing body is biased to the surface side in contact with the temporary fixing sheet, and therefore there is a semiconductor chip having a small thermal expansion coefficient in the cured sealing body. A region having a relatively high ratio and a region having a relatively high ratio of the cured resin having a large thermal expansion coefficient are generated, and stress is generated due to a difference in thermal contraction rate between the two regions. Conceivable. This problem tends to become more prominent as the package size increases, such as FOWLP and FOPLP.
For example, when the cured sealant is ground in the next process, cracks are likely to occur when the cured sealant is warped. Defects such as problems easily occur during delivery of the body can occur.

In view of the above problems, the present invention has a support layer and a curable resin layer, and can perform a sealing process by fixing an object to be sealed to the surface of the curable resin layer. A warp-preventing laminate capable of providing a cured resin layer as a warp-preventing layer to a cured sealing body formed by processing, and capable of preventing a deviation from occurring when fixing a sealing object. And it makes it a subject to provide the manufacturing method of the hardening sealing body using this laminated body for curvature prevention.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by setting the adhesive strength of the curable resin layer within a predetermined range, and the present invention has been completed. did.
That is, the present invention provides the following [1] to [11].

[1] A curable resin layer (I) including a thermosetting resin layer (X1);
A support layer (II) that supports the curable resin layer (I),
The thermosetting resin layer (X1) is directly laminated on the support layer (II),
The adhesive force of the first surface, which is the surface of the curable resin layer (I) opposite to the support layer (II), affixed the first surface to a glass plate at a temperature of 70 ° C., a temperature of 23 ° C., It is a value when measured by peeling the curable resin layer (I) at a peeling angle of 180 ° and a peeling speed of 300 mm / min, and is 1.7 N / 25 mm or more,
A laminate for preventing warpage of a cured sealing body produced by sealing a sealing object with a sealing material on the first surface of the curable resin layer (I).
[2] The warp-preventing laminate according to [1], wherein the curable resin layer (I) is a single-layer thermosetting resin layer (X1).
[3] The curable resin layer (I) includes a first layer located on the support layer (II) side and a second layer located on the first surface side,
The first layer is a first thermosetting resin layer (X1-1),
The said 2nd layer is said 2nd thermosetting resin layer (X1-2) whose surface adhesive force is higher than 1st thermosetting resin layer (X1-1). Laminated body for warping prevention.
[4] The curable resin layer (I) includes a first layer located on the support layer (II) side and a second layer located on the first surface side,
The first layer is a thermosetting resin layer (X1-1),
The layer for warpage prevention according to the above [1], wherein the second layer is an energy ray curable resin layer (X2).
[5] The warpage preventing laminate according to any one of [1] to [4] above, wherein the thickness of the curable resin layer (I) is 1 to 500 μm.
[6] The support layer (II) has a base material (Y) and an adhesive layer (V), and at least one of the base material (Y) and the adhesive layer (V) includes expandable particles,
[1] to [5], wherein the expandable particles are separated at the interface between the support layer (II) and the cured resin layer (I ′) obtained by curing the curable resin layer (I) by the treatment of expanding the expandable particles. The laminated body for warpage prevention as described in any one of these.
[7] The warp-preventing laminate according to [6], wherein the substrate (Y) has an expandable substrate layer (Y1) containing the expandable particles.
[8] The warp-preventing laminate according to [7], wherein the pressure-sensitive adhesive layer (V) is a non-intumescent pressure-sensitive adhesive layer (V1).
[9] The substrate (Y) has a non-expandable substrate layer (Y2) and an expandable substrate layer (Y1),
The support layer (II) has a non-expandable base layer (Y2), an expandable base layer (Y1), and an adhesive layer (V) in this order,
The laminate for warpage prevention according to the above [7] or [8], wherein the pressure-sensitive adhesive layer (V) and the thermosetting resin layer (X1) are directly laminated.
[10] A method for producing a cured encapsulant using the warp-preventing laminate according to any one of [1] to [9],
Place a sealing object on a part of the first surface of the curable resin layer (I) of the laminate for warpage prevention,
Covering the sealing object and the first surface of the curable resin layer (I) at least in the peripheral part of the sealing object with a thermosetting sealing material,
The sealing material is thermally cured to form a cured sealing body including the sealing object, and the curable resin layer (I) is also thermally cured to form a cured resin layer (I ′), The manufacturing method of the hardening sealing body which obtains the hardening sealing body with a cured resin layer.
[11] A method for producing a cured encapsulant using the warp-preventing laminate according to [4] above,
The energy ray curable resin layer (X2), which is the first surface of the curable resin layer (I) of the laminate for warpage prevention, is sealed on a part of the surface opposite to the first layer. Place the stop object,
Irradiate energy rays to cure the energy ray curable resin layer (X2),
Covering the sealing object and the surface of the curable resin layer (I) at least in the peripheral part of the sealing object with a thermosetting sealing material,
The sealing material is thermally cured to form a cured sealing body including the sealing object, and the curable resin layer (I) is also thermally cured to form a cured resin layer (I ′), The manufacturing method of the hardening sealing body which obtains the hardening sealing body with a cured resin layer.

According to the present invention, a sealing object can be fixed to the surface of the curable resin layer to perform a sealing process, and the cured sealing body formed by the sealing process can be used as a warp prevention layer. Curing prevention laminated body which can give hardening resin layer, and can prevent generating gap when fixing sealing object, and hardening sealing using this warping prevention laminated body A method of manufacturing a body can be provided.

It is a cross-sectional schematic diagram of the said laminated body which shows the structure of the laminated body for curvature prevention of the 1st aspect of this invention. It is a cross-sectional schematic diagram of the said laminated body which shows the structure of the laminated body for curvature prevention of the 2nd aspect of this invention. It is a cross-sectional schematic diagram of the said laminated body which shows the structure of the laminated body for curvature prevention of the 3rd aspect of this invention. It is a cross-sectional schematic diagram of the said laminated body which shows the structure of the laminated body for curvature prevention of the 4th aspect of this invention. It is a cross-sectional schematic diagram of the said laminated body which shows the structure of the laminated body for curvature prevention of the 5th aspect of this invention. It is a cross-sectional schematic diagram which shows the process of manufacturing the hardening sealing body with a hardening resin layer. It is a cross-sectional schematic diagram which shows the other manufacturing process of the hardening sealing body with a hardening resin layer.

First, terms used in this specification will be described.
In this specification, whether or not the target layer is a “non-expandable layer” is determined by performing a treatment for expansion for 3 minutes and then calculating a volume change rate calculated from the following formula before and after the treatment. Is less than 5%, it is determined that the layer is a “non-intumescent layer”. On the other hand, when the volume change rate is 5% or more, it is determined that the layer is an “expandable layer”.
Volume change rate (%) = {(volume of the layer after treatment−volume of the layer before treatment) / volume of the layer before treatment} × 100
As the “treatment for expanding”, for example, in the case of a layer containing thermally expandable particles, a heat treatment for 3 minutes may be performed at the expansion start temperature (t) of the thermally expandable particles.

In the present specification, the “active ingredient” refers to a component excluding a diluent solvent among components contained in a target composition.
In the present specification, the mass average molecular weight (Mw) is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method, specifically a value measured based on the method described in Examples. It is.
In the present specification, for example, “(meth) acrylic acid” indicates both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.
In the present specification, the lower limit value and the upper limit value described in a stepwise manner can be independently combined for a preferable numerical range (for example, a range such as content). For example, from the description “preferably 10 to 90, more preferably 30 to 60”, “preferable lower limit (10)” and “more preferable upper limit (60)” are combined to obtain “10 to 60”. You can also.

In the present specification, “energy beam” means an electromagnetic wave or charged particle beam having energy quanta, and examples thereof include ultraviolet rays, radiation, and electron beams. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, an LED lamp, or the like as an ultraviolet ray source. The electron beam can be emitted by an electron beam accelerator or the like.
In this specification, “energy ray curable” means a property that cures when irradiated with energy rays, and “non-energy ray curable” means a property that does not cure even when irradiated with energy rays. To do.

Hereinafter, embodiments of the present invention (hereinafter sometimes referred to as “present embodiments”) will be described.
[Laminated body for warpage prevention]
The warpage preventing laminate of one embodiment of the present invention includes a curable resin layer (I) including a thermosetting resin layer (X1) and a support layer (II) that supports the curable resin layer (I). . In the following description, the warp preventing laminate may be simply referred to as a “laminate”.
The thermosetting resin layer (X1) is directly laminated on the support layer (II).
The adhesive force of the first surface, which is the surface of the curable resin layer (I) opposite to the support layer (II), is affixed to the glass plate at the temperature of 70 ° C. A value obtained by peeling and measuring the curable resin layer (I) at a peeling angle of 180 ° and a peeling speed of 300 mm / min, which is 1.7 N / 25 mm or more.
This warp-preventing laminate is used to produce a cured encapsulant by encapsulating a sealing object with an encapsulant on the first surface of the curable resin layer (I). It plays a role in preventing the warpage of the cured sealing body.

<Configuration of warp preventing laminate>
The configuration of the warpage preventing laminate of the present embodiment will be described with reference to the drawings.
FIGS. 1 to 5 are schematic cross-sectional views of the laminates showing the configurations of the warp preventing laminates according to the first to fifth aspects of the present invention. In the laminates of the following first to fifth embodiments, the adhesive surface of the adhesive layer (V1) attached to a support (not shown) and the first surface (support layer) of the curable resin layer (I) From the standpoint of protecting the surface of the curable resin layer (I) and the support layer (II), a release material may be further laminated on the surface opposite to (II). The release material is peeled off and removed when the warp preventing laminate is used.

[Laminated body for warpage prevention of first aspect]
As the laminated body for warpage prevention according to the first aspect of the present invention,

laminated bodies

1a and 1b shown in FIG. 1 may be mentioned.

Laminate

1a, 1b is equipped with base material (Y) and support layer (II) which has an adhesive layer (V1), and curable resin layer (I), and base material (Y) and curable resin layer (I) and the direct lamination.
In the following description, the surface of the curable resin layer (I) opposite to the support layer (II) may be referred to as “first surface”, and the surface on the support layer (II) side may be referred to as “second surface”. .
The first surface of the curable resin layer (I) is an adhesive surface having a predetermined adhesive force. When the sealing object is placed, the sealing object can be fixed by the adhesive force.
In addition, in

laminated body

1a, 1b, the adhesive surface of an adhesive layer (V1) is affixed on the support body which is not shown in figure.

In the support layer (II), both the base material (Y) and the pressure-sensitive adhesive layer (V1) may be non-expandable, or at least one of the layers may be expandable. However, it is preferable that any one of the layers contains expandable particles and has expandability. In the laminated body 1a of Fig.1 (a), a base material (Y) has an expandable base material layer (Y1) containing an expandable particle.
The base material (Y) may be a single-layer base material composed of only the expandable base material layer (Y1) as in the laminate 1a shown in FIG. 1 (a), or FIG. 1 (b). Like the laminated body 1b shown to (2), the base material of the multilayer structure which has an expandable base material layer (Y1) and a non-expandable base material layer (Y2) may be sufficient.
In addition, when using the base material (Y) which has an expandable base material layer (Y1) and a non-expandable base material layer (Y2) in the curvature prevention laminated body of a 1st aspect, as shown in FIG.1 (b). The non-intumescent base material layer (Y2) is laminated on the surface of the pressure-sensitive adhesive layer (V1), and the inflatable base material layer (Y1) is laminated on the surface of the non-intumescent base material layer (Y2). It is preferable to have.

In the laminate 1a shown in FIG. 1 (a), the expandable particles contained in the expandable substrate layer (Y1) are expanded by expansion treatment by heating or the like, and irregularities are generated on the surface of the substrate (Y). The contact area with the cured resin layer formed by curing the curable resin layer (I) decreases. In the following description, a layer obtained by curing a curable resin layer is referred to as a cured resin layer (I ′).
At this time, the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (V1) is stuck to a support (not shown). The adhesive layer (V1) is affixed so as to be sufficiently adhered to the support, whereby the surface of the expandable substrate layer (Y1) on the pressure-sensitive adhesive layer (V1) side has a force to cause irregularities. Even if this occurs, a force repelling from the pressure-sensitive adhesive layer (V1) is likely to occur. Therefore, it is difficult for irregularities to be formed on the surface of the base material (Y) on the pressure-sensitive adhesive layer (V1) side.
As a result, the laminated body 1a can be easily separated at once by a slight force at the interface P between the base material (Y) of the support layer (II) and the cured resin layer (I ′).
In addition, it is also possible to make it more easily separable at the interface P by forming the pressure-sensitive adhesive layer (V1) of the laminate 1a with a pressure-sensitive adhesive composition that increases the adhesive strength to the support. is there. In the following description, the interface between the curable resin layer (I) and the support layer (II) may also be referred to as “interface P”.

From the viewpoint of suppressing the stress due to the expandable particles from being transmitted to the pressure-sensitive adhesive layer (V1) side, the base material (Y) is an expandable base material as in the laminate 1b shown in FIG. It is preferable to have a layer (Y1) and a non-expandable base material layer (Y2).
Since the stress due to the expansion of the expandable particles of the expandable base layer (Y1) is suppressed by the non-expandable base layer (Y2), it is difficult to be transmitted to the pressure-sensitive adhesive layer (V1).
Therefore, the surface of the pressure-sensitive adhesive layer (V1) on the support side is hardly uneven, and the adhesiveness between the pressure-sensitive adhesive layer (V1) and the support is almost unchanged before and after the expansion treatment by heating or the like, and has good adhesion. Can be held. Thereby, unevenness | corrugation is easy to be formed in the surface at the side of the curable resin layer (I) of an expandable base material layer (Y1), As a result, the expandable base material layer (Y1) and cured resin layer of a support layer (II) At the interface P with (I ′), the separation can be easily performed with a slight force.

In addition, like the laminated body 1b shown in FIG.1 (b), an expandable base material layer (Y1) and curable resin layer (I) directly laminate | stack, and hardening of a non-expandable base material layer (Y2) The pressure-sensitive adhesive layer (V1) is preferably laminated on the surface opposite to the adhesive resin layer (I).
Further, an adhesive layer or an anchor layer for adhering the two may be provided between the expandable base material layer (Y1) and the non-expandable base material layer (Y2), or may be directly laminated. .

[Laminated body for warpage prevention of second aspect]
Examples of the warp preventing laminate of the second aspect of the present invention include

warp preventing laminates

2a and 2b shown in FIG.
In the

laminates

2a and 2b, the pressure-sensitive adhesive layer included in the support layer (II) includes the first pressure-sensitive adhesive layer (V1-1) and the second pressure-sensitive adhesive layer (V1-2), and the first pressure-sensitive adhesive layer ( V1-1) and the second pressure-sensitive adhesive layer (V1-2) sandwich the substrate (Y), and the pressure-sensitive adhesive surface of the second pressure-sensitive adhesive layer (V1-2) is bonded to the curable resin layer (I). It has a directly stacked configuration. Hereinafter, the pressure-sensitive adhesive layers when the support layer (II) includes a plurality of pressure-sensitive adhesive layers, and the pressure-sensitive adhesive layers when the support layer (II) includes a single pressure-sensitive adhesive layer are collectively referred to. It may be called an adhesive layer (V).
In the warp preventing laminate of the second aspect, the pressure-sensitive adhesive surface of the first pressure-sensitive adhesive layer (V1-1) is attached to a support not shown.

Also in the warp preventing laminate of the second aspect, the substrate (Y) preferably has an expandable substrate layer (Y1) containing expandable particles.
The base material (Y) may be a single-layer base material composed of only the expandable base material layer (Y1) as in the laminate 2a shown in FIG. 2 (a). Like the laminated body 2b shown, the base material of a multilayer structure which has an expandable base material layer (Y1) and a non-expandable base material layer (Y2) may be sufficient.

However, as described above, from the viewpoint of forming a laminate that can maintain good adhesion between the first pressure-sensitive adhesive layer (V1-1) and the support before and after the expansion treatment by heating or the like, FIG. As shown, the substrate (Y) preferably has an expandable substrate layer (Y1) and a non-expandable substrate layer (Y2).
In addition, when using the base material (Y) which has an expandable base material layer (Y1) and a non-expandable base material layer (Y2) in the curvature prevention laminated body of a 2nd aspect, as shown in FIG.2 (b). The second pressure-sensitive adhesive layer (V1-2) is laminated on the surface of the expandable base material layer (Y1), and the first pressure-sensitive adhesive layer (V1-1) is formed on the surface of the non-expandable base material layer (Y2). It is preferable to have a laminated structure.

In the laminate of the second aspect, the expandable particles in the expandable substrate layer (Y1) constituting the substrate (Y) are expanded by the expansion treatment by heating or the like, and the surface of the expandable substrate layer (Y1) Concavities and convexities occur on the surface.
Then, the second pressure-sensitive adhesive layer (V1-2) is pushed up by the unevenness generated on the surface of the expandable base material layer (Y1), and unevenness is also formed on the pressure-sensitive adhesive surface of the second pressure-sensitive adhesive layer (V1-2). Therefore, the contact area between the second pressure-sensitive adhesive layer (V1-2) and the cured resin layer (I ′) is reduced. As a result, the separation can be easily and collectively performed with a slight force at the interface P between the second pressure-sensitive adhesive layer (V1-2) and the cured resin layer (I ′) of the support layer (II).
In addition, in the laminated body of the second embodiment, from the viewpoint of making the laminated body easily separable at a slight force at the interface P, the expandable group of the base material (Y) of the support layer (II) The material layer (Y1) and the second pressure-sensitive adhesive layer (V1-2) are preferably laminated directly.

[Laminated body for warping prevention of third aspect]
As the laminated body for warpage prevention of the third aspect of the present invention, there is a laminated body for warpage prevention 3 shown in FIG.
The laminated body 3 shown in FIG. 3 has the 1st adhesive layer (V1) which is a non-expandable adhesive layer in the one surface side of a base material (Y), and the other side of a base material (Y). Provided on the surface side is a support layer (II) having a second pressure-sensitive adhesive layer (V2) which is an expandable pressure-sensitive adhesive layer containing expandable particles, and the second pressure-sensitive adhesive layer (V2) and the curable resin layer (I) and the direct lamination.
In the laminate 3, the pressure-sensitive adhesive surface of the first pressure-sensitive adhesive layer (V1) is attached to a support not shown.
In addition, it is preferable that the base material (Y) which the laminated body 3 of this 3rd aspect has is comprised from the non-expandable base material layer (Y2).

In the laminate 3 of the third aspect, the expandable particles in the second pressure-sensitive adhesive layer (V2), which is an expandable pressure-sensitive adhesive layer, are expanded by the expansion treatment such as heating, and the second pressure-sensitive adhesive layer (V2). Asperities are formed on the surface, and the contact area between the second pressure-sensitive adhesive layer (V2) and the curable resin layer (I) decreases.
On the other hand, since the surface on the base material (Y) side of the first pressure-sensitive adhesive layer (V1) is laminated on the base material (Y), it is difficult to produce irregularities.
Therefore, unevenness is easily formed on the surface of the second pressure-sensitive adhesive layer (V2) on the side of the curable resin layer (I) by an expansion treatment such as heating, and as a result, the second pressure-sensitive adhesive layer (II) of the support layer (II) ( At the interface P between V2) and the cured resin layer (I ′), separation can be easily performed at a time with a slight force.

[Laminated body for warpage prevention of fourth aspect]
The warp preventing laminate 4 of the fourth aspect of the present invention includes the warp preventing laminate 4 shown in FIG.
The laminate 4 shown in FIG. 4 has a configuration in which a non-expandable pressure-sensitive adhesive layer (V1), an expandable base material layer (Y1), and a curable resin layer (I) are stacked in this order.
In the laminate 4, the curable resin layer (I) is positioned on the side opposite to the first thermosetting resin layer (X1-1) positioned on the base (Y) side and the base (Y). It consists of a curable resin layer (I) provided with a second thermosetting resin layer (X1-2). Both the first thermosetting resin layer (X1-1) and the second thermosetting resin layer (X1-2) are non-expandable.
Here, the second thermosetting resin layer (X1-2) has higher surface adhesive strength than the first thermosetting resin layer (X1-1). In the laminated body 4, those having different characteristics can be used by constituting the curable resin layer (I) with two thermosetting resin layers. For example, a thermosetting resin layer containing a more adhesive composition is selected for the curable resin layer on the side opposite to the support layer (II), and the curable resin layer on the support layer (II) side, Those having better separability from the support layer (II) can be selected.

[Laminated body for warpage prevention of fifth aspect]
An example of the laminate for warpage prevention according to the fifth aspect of the present invention is the laminate 5 for warpage prevention shown in FIG.
The laminate 5 shown in FIG. 5 has a configuration in which a non-expandable pressure-sensitive adhesive layer (V1), an expandable base material layer (Y1), and a curable resin layer (I) are stacked in this order.
In the laminate 5, the curable resin layer (I) includes a thermosetting resin layer (X1-1) located on the base (Y) side and an energy ray curing located on the side opposite to the base (Y). It consists of curable resin layer (I) provided with curable resin layer (X2). Both the first thermosetting resin layer (X1-1) and the energy beam curable resin layer (X2) are non-expandable.
In the laminate 5, the curable resin layer (I) is divided into an energy ray curable resin layer (X2) and a thermosetting resin layer (X1-1), and those having different characteristics are used. Can do. For example, on the side opposite to the support layer (II), an energy curable resin layer made of an energy ray curable composition that is easy to adjust so as to have a relatively high adhesive force is disposed, and on the support layer (II) side, A thermosetting resin layer having better separability from a sealing material described later can be disposed.

[Use of laminated body for warpage prevention]
The laminate for warpage prevention of the present embodiment has a sealing object placed on the surface of the curable resin layer, and the sealing object and the thermosetting resin layer at least in the peripheral part of the sealing object. The surface is covered with a sealing material, the sealing material is cured, and the cured sealing body including a sealing object is used for manufacturing a cured sealing body.
In addition, the specific aspect regarding manufacture of the hardening sealing body using the laminated body for curvature prevention is mentioned later.

For example, after placing a sealing object on the adhesive surface of an adhesive laminate such as a general wafer mount tape as used in the manufacturing method described in Patent Document 1, the sealing object and its surroundings Consider the case where the adhesive surface of the part is covered with a sealing material, the sealing material is thermally cured, and a cured sealing body is manufactured.
When the sealing material is thermally cured, the sealing material is subjected to a stress that tends to shrink. However, since the adhesive laminate is fixed to the support, the stress of the sealing material is suppressed.
However, the cured sealing body obtained by separating from the support and the adhesive laminate is difficult to suppress the stress to be contracted. In the cured sealing body after separation, the amount of the sealing material is different between the surface side on the side where the object to be sealed is present and the opposite surface side, and therefore a difference in shrinkage stress is likely to occur. The difference of the shrinkage stress causes the warp generated in the cured sealing body.
In addition, from the viewpoint of productivity, the cured sealed body after heating is generally separated from the support and the adhesive laminate in a state of being heated to some extent. Therefore, even after the separation, curing of the sealing material proceeds and shrinkage due to natural cooling occurs, so that the cured sealing body is more likely to warp.

On the other hand, when the laminate for warpage prevention of one embodiment of the present invention is used, a cured sealed body in which warpage is effectively suppressed can be obtained for the following reason.
That is, when a sealing object is placed on the surface of the thermosetting resin layer of the warpage preventing laminate of one embodiment of the present invention, covered with a sealing material, and the sealing material is thermally cured, The thermosetting resin layer is also thermoset. At this time, the thermosetting resin layer is provided on the surface side on the side where the sealing object which is considered to have a small amount of the sealing material and the shrinkage stress due to the curing of the sealing material is small. The shrinkage stress due to thermosetting of the thermosetting resin layer works.
As a result, it is considered that a difference in shrinkage stress between the two surfaces of the cured sealing body can be reduced, and a cured sealing body in which warpage is effectively suppressed can be obtained.

Moreover, the thermosetting resin layer which has contributed to suppression of the curvature of a hardening sealing body can be made into a hardening resin layer by thermosetting.
That is, by using the laminate for warpage prevention of one embodiment of the present invention, the cured resin layer can be simultaneously formed on one surface of the cured encapsulant by passing through the above-described sealing step. A process for forming the cured resin layer can be omitted, which contributes to an improvement in productivity.

Furthermore, the curable resin layer (I) in the warp-preventing laminate of one embodiment of the present invention includes a curable resin composition, but the surface has a high adhesive strength of 1.7 N / 25 mm or more. Therefore, when the sealing object is fixed to the surface of the curable resin layer (I), the sealing object can be prevented from being displaced.

<Various physical properties of the laminate>
(Adhesive strength of first surface of curable resin layer (I))
In the laminate of one embodiment of the present invention, the curable resin layer (I) is a surface on which the sealing object is placed (first surface) from the viewpoint of improving the adhesion with the sealing object. Has tackiness.
The adhesive strength of the first surface of the curable resin layer (I) is determined by sticking the first surface to a glass plate at a temperature of 70 ° C., the curable property at a temperature of 23 ° C., a peeling angle of 180 °, and a peeling speed of 300 mm / min. The value measured by peeling off the resin layer is 1.7 N / 25 mm or more, preferably 2.3 N / 25 mm or more, more preferably 3.0 N / 25 mm or more, and even more preferably 4.0 N / 25 mm or more. Moreover, it is preferably 20 N / 25 mm or less, more preferably 15 N / 25 mm or less, and further preferably 10 N / 25 mm or less.
When the adhesion of the first surface of the curable resin layer (I) is less than 1.7 N / 25 mm, the object to be sealed is fixed when the object to be sealed is fixed to the surface of the curable resin layer (I). There is a risk that the object will be displaced. If the adhesive force of the 1st surface of curable resin layer (I) is 20 N / 25mm or less, material selection of curable resin layer (I) will become easy.

(Shearing force of curable resin layer (I))
In the laminate of one embodiment of the present invention, the curable resin layer (I) has an appropriate shearing force from the viewpoint of favorably holding the sealing object when sealing the sealing object. Is preferred. Specifically, a silicon chip (mirror surface) having a thickness of 350 μm and a size of 3 mm × 3 mm is used as the above-mentioned measurement adherend and the shear strength for the measurement adherend of the curable resin layer (I) is 70 ° C. , 130 gf for 1 second, the mirror surface of the measurement adherend is pressed and pasted on the curable resin layer and measured at a speed of 200 μm / s, preferably 20 N / (3 mm × 3 mm) or more. More preferably, it is 25 N / (3 mm × 3 mm), more preferably 30 N / (3 mm × 3 mm) or more, preferably 100 N / (3 mm × 3 mm) or less, more preferably 90 N / (3 mm). × 3 mm) or less.
When the shear strength of the curable resin layer (I) with respect to the measurement adherend is 20 N / (3 mm × 3 mm) or more, the sealing object is fixed to the surface of the curable resin layer (I) and sealed. When covering the object to be sealed with the material, it is possible to prevent the object to be sealed from being displaced or inclined due to the flow of the sealing material. Moreover, material selection of curable resin layer (I) becomes easy that the said shear strength is 100 N / (3 mm x 3 mm) or less.

(Adhesive strength of thermosetting resin layer (X1))
In the laminate of one embodiment of the present invention, the adhesive strength of the thermosetting resin layer (I) alone at room temperature (23 ° C.) is preferably 0.1 to 10.0 N / 25 mm, more preferably 0.2. It is ˜8.0 N / 25 mm, more preferably 0.4 to 6.0 N / 25 mm, and still more preferably 0.5 to 4.0 N / 25 mm.
When the laminate 4 shown in FIG. 4 has the first thermosetting resin layer (X1-1) and the second thermosetting resin layer (X1-2), each has the above-mentioned adhesive strength. In particular, the adhesive force of the second thermosetting resin layer (X1-2) is preferably higher than the adhesive force of the first thermosetting resin layer (X1-1). By making the adhesive force of the second thermosetting resin layer (X1-2) higher than the adhesive force of the first thermosetting resin layer (X1-1), the object to be sealed is cured more reliably. It can fix to the 1st surface of a conductive resin layer (I).

(Adhesive strength of energy ray curable resin layer (X2))
In the laminate of one embodiment of the present invention, the adhesive strength of the energy ray curable resin layer (X2) alone at room temperature (23 ° C.) is preferably 0.1 to 10.0 N / 25 mm, more preferably 0.8. It is 2 to 8.0 N / 25 mm, more preferably 0.4 to 6.0 N / 25 mm, and still more preferably 0.5 to 4.0 N / 25 mm.

(Adhesive strength of adhesive layer (V))
In the laminate of one embodiment of the present invention, the pressure-sensitive adhesive layer (V) (first pressure-sensitive adhesive layer (V1) and second pressure-sensitive adhesive layer (V2)) of the support layer (II) at room temperature (23 ° C.). The adhesive strength is preferably 0.1 to 10.0 N / 25 mm, more preferably 0.2 to 8.0 N / 25 mm, still more preferably 0.4 to 6.0 N / 25 mm, and still more preferably 0.5. -4.0 N / 25 mm. In the following description, regardless of whether the pressure-sensitive adhesive layer is single or plural, the pressure-sensitive adhesive layer located on the curable resin layer (I) side is opposite to the first pressure-sensitive adhesive layer and the curable resin layer. The pressure-sensitive adhesive layer located in the region may be referred to as a second pressure-sensitive adhesive layer.
When the support layer (II) has the first pressure-sensitive adhesive layer (V1-1) or (V1) and the second pressure-sensitive adhesive layer (V1-2) or (V2), the first pressure-sensitive adhesive layer (V1-1) ) Or (V1) and the adhesive strength of the second pressure-sensitive adhesive layer (V1-2) or (V2) are preferably in the above ranges, respectively, but the adhesion with the support is improved and the adhesive strength at the interface P is increased. Thus, from the viewpoint of making separation more easily, the adhesive force of the first adhesive layer (V1-1) or (V1) to be attached to the support is the second adhesive layer (V1-2) or (V2). It is more preferable that it is higher than the adhesive force of

(Measurement of adhesive strength of first surface of curable resin layer (I))
In this specification, the adhesive force of the 1st surface of curable resin layer (I) is measured in the following procedures.
First, the laminated body for warpage prevention provided with the curable resin layer (I) and the support layer (II) is cut into 25 mm width × 250 mm length (MD direction is 250 mm) to produce a primary sample. Moreover, a glass plate (3 mm float plate glass (JIS R3202 product) manufactured by Yuko Trading Company) is prepared as an adherend. Using a laminator apparatus (VA-400, manufactured by Taisei Laminator Co., Ltd.), a glass plate is attached so as to be in direct contact with the first surface of the curable resin layer (I) to obtain a test piece. At this time, the roller temperature is 70 ° C., and the sticking speed is 0.2 m / min. The test piece thus obtained was allowed to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity), and then, under the same environment, a tensile load measuring machine (A & A) based on JIS Z 0237: 2000. (Denshi, Tensilon), the test piece was peeled from the glass plate under the conditions of a peeling angle of 180 °, a peeling speed of 300 mm / min, and a peeling temperature of 23 ° C., and the adhesive strength was measured. Let it be the adhesive force of the first surface of the resin layer (I).

(Measurement of shear force of curable resin layer (I))
In the present specification, the shearing force of the curable resin layer (I) is measured by the following procedure.
First, a 350 μm-thick silicon chip having a 3 mm × 3 mm mirror surface is used as an adherend for measurement. Then, on the first surface of the curable resin layer (I) of each laminate obtained in each Example and Comparative Example described later, the mirror surface of the adherend for measurement is applied at a temperature of 70 ° C. for 1 second at 130 gf. Press and paste. Then, the shear force is measured at a speed of 200 μm / s using a universal bond tester (DAGE 4000, manufactured by Nordson Advanced Technology).

(Measurement of adhesive strength of adhesive layer (V), thermosetting resin layer (X1), energy ray curable resin layer (X2))
On the surface of the pressure-sensitive adhesive layer (V), thermosetting resin layer (X1) or energy ray-curable resin layer (X2) formed on the release film, a pressure-sensitive adhesive tape (product name “PL Shin” manufactured by Lintec Corporation) is used. ]).
Then, the surface of the pressure-sensitive adhesive layer (V), the thermosetting resin layer (X1), or the energy ray curable resin layer (X2) exposed by peeling off the release film is coated with a glass plate (Yuko) as an adherend. It was attached to a float plate glass 3 mm (JIS R3202 product) manufactured by a trading company. At this time, the sticking temperature of the pressure-sensitive adhesive layer (V) was 23 ° C., and the sticking temperatures of the thermosetting resin layer (X1) and the energy ray curable resin layer (X2) were 70 ° C. And after leaving the said glass plate with which each layer was affixed for 24 hours in the environment of 23 degreeC and 50% RH (relative humidity), 180 degree pulling was performed under the same environment based on JISZ0237: 2000. By the peeling method, the pressure-sensitive adhesive layer (V), the thermosetting resin layer (X1), or the energy beam curable resin layer (X2) is peeled off from the glass plate together with the pressure-sensitive adhesive tape at a pulling speed of 300 mm / min. Thus, the adhesive strength at 23 ° C. is measured.

(Peeling force before performing expansion treatment (F ₀ ))
The support layer (II) and the curable resin are used from the viewpoint of sufficiently fixing the object to be sealed before the curable resin layer (I) is cured and before the expansion treatment so as not to adversely affect the sealing operation. The adhesiveness with the layer (I) is preferably high.
From the above viewpoint, in the laminate of one embodiment of the present invention, the interface P between the support layer (II) and the curable resin layer (I) before the curable resin layer (I) is cured and before the thermal expansion treatment is performed. The separation force (F ₀ ) at the time of separation is preferably 100 mN / 25 mm or more, more preferably 130 mN / 25 mm or more, still more preferably 160 mN / 25 mm or more, and preferably 50,000 mN / 25 mm or less. is there.
The release force (F ₀₎ is a value measured by the following measuring methods.
(Measurement of peel force (F ₀ ))
After the laminate was allowed to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity), the support layer (II) side of the laminate was placed on a glass plate (float made by Yuko Trading Company) via the adhesive layer Affix to plate glass 3 mm (JIS R3202 product)). In addition, an adhesive tape (product name “PL Thin” manufactured by Lintec Corporation) is attached to the first surface side of the laminate. Next, the end of the glass plate to which the laminate has been attached is fixed to the lower chuck of a universal tensile testing machine (product name “Tensilon UTM-4-100” manufactured by Orientec Co., Ltd.).
Subsequently, the laminate was stuck to the curable resin layer (I) of the laminate with an upper chuck of a universal tensile tester so as to be peeled off at the interface P between the support layer (II) of the laminate and the curable resin layer (I). Fix the end of the adhesive tape. Then, under the same environment as described above, the curable resin layer (I) and the adhesive tape are bonded to the support layer (II at the interface P at a tensile speed of 300 mm / min by a 180 ° peeling method based on JIS Z 0237: 2000. The peeling force measured when peeling from ( ₁ ) is defined as “peeling force (F ₀ )”.

(Peeling force after expansion treatment (F ₁ ))
The laminate of one embodiment of the present invention includes a support layer (II), a curable resin layer (I), or a cured resin layer (I ′) obtained by curing the curable resin layer (I) by an expansion treatment. At the interface P, separation can be easily performed at a time with a slight force.
Here, in the laminated body of one embodiment of the present invention, the curable resin layer (I) is cured to form the cured resin layer (I ′), and then the support layer (II) and the cured resin layer (I) are subjected to an expansion treatment. The peeling force (F ₁ ) when separating at the interface P with ') is usually 2,000 mN / 25 mm or less, preferably 1,000 mN / 25 mm or less, more preferably 500 mN / 25 mm or less, more preferably 150 mN / It is 25 mm or less, more preferably 100 mN / 25 mm or less, still more preferably 50 mN / 25 mm or less, and most preferably 0 mN / 25 mm.
In the case where the peeling force (F ₁ ) is 0 mN / 25 mm, even if an attempt is made to measure the peeling force, the case where the measurement is impossible because the peeling force is too small is included.
The release force (F ₁₎ is a value measured by the following measuring methods.

(Measurement of peel force (F ₁ ))
The support layer (II) side of the laminate is attached to a glass plate (float plate glass 3 mm (JIS R3202 product) manufactured by Yuko Trading Company) via an adhesive layer. Next, the glass plate and the laminate are heated at 130 ° C. for 2 hours to cure the curable resin layer (I) to form the cured resin layer (I ′). When the curable resin layer (I) includes the energy ray curable resin layer (X2) as in the laminate 4 in FIG. 4, the energy ray is applied after the thermosetting resin layer (X1-1) is thermally cured. Irradiate energy rays that can cure the curable resin layer (X2) (in the case of ultraviolet rays, irradiate with an illuminance of 215 mW / cm ² and a light amount of 187 mJ / cm ² three times) to irradiate the energy ray curable resin layer (X2). Harden.
Next, the expandable particles contained in the support layer (II) are expanded. Specifically, when the thermally expandable particles are used, the glass plate to which the laminate is attached is heated at 240 ° C. for 3 minutes, and the expandable base material layer (Y1) of the laminate or the expandable pressure-sensitive adhesive. The thermally expandable particles in the layer (V2) are expanded. Thereafter, an adhesive tape (product name “PL Thin”, manufactured by Lintec Corporation) is applied to the first surface side of the laminate, and the measurement is performed in the same manner as in the measurement of the peeling force (F ₀ ) described above. The peeling force measured when peeling at the interface P between the layer (II) and the cured resin layer (I ′) is defined as “peeling force (F ₁ )”.
When measuring the peel force (F ₁ ), when trying to fix the end of the adhesive tape affixed to the cured resin layer (I ′) of the laminate with the upper chuck of the universal tensile tester, the interface P When the cured resin layer (I ′) is completely separated and cannot be fixed for measurement, the measurement is terminated and the peeling force (F ₁ ) at that time is set to “0 mN / 25 mm”. .

(Probe tack value of substrate (Y))
The base material (Y) which support layer (II) has is a non-adhesive base material.
In one embodiment of the present invention, the determination as to whether or not the substrate is a non-adhesive substrate has a probe tack value measured in accordance with JIS Z 0237: 1991 of less than 50 mN / 5 mmφ with respect to the surface of the target substrate. Then, the said base material is judged as a "non-adhesive base material". On the other hand, if the probe tack value is 50 mN / 5 mmφ or more, the substrate is determined to be an “adhesive substrate”.
The probe tack value on the surface of the substrate (Y) of the support layer (II) used in one embodiment of the present invention is usually less than 50 mN / 5 mmφ, preferably less than 30 mN / 5 mmφ, more preferably less than 10 mN / 5 mmφ. More preferably, it is less than 5 mN / 5 mmφ.
The probe tack value on the surface of the substrate (Y) is a value measured by the following measuring method.
(Measurement of probe tack value)
A substrate to be measured is cut into a square having a side of 10 mm and then left to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity) as a test sample. Using a tacking tester (manufactured by Nippon Special Instrument Co., Ltd., product name “NTS-4800”) in an environment of 23 ° C. and 50% RH (relative humidity), the probe tack value on the surface of the test sample was measured according to JIS. Measured according to Z0237: 1991. Specifically, a stainless steel probe having a diameter of 5 mm is brought into contact with the surface of the test sample at a contact load of 0.98 N / cm ² for 1 second, and then the probe is moved at a speed of 10 mm / sec. The force required to move away from the surface is measured and the value obtained is taken as the probe tack value for the test sample.

Next, each layer constituting the warp preventing laminate of one embodiment of the present invention will be described.

<Curable resin layer (I)>
The warpage preventing laminate of one embodiment of the present invention has a curable resin layer (I) including a thermosetting resin layer (X1).
The curable resin layer (I) is cured to reduce the difference in shrinkage stress between the two surfaces of the cured encapsulant due to the curing of the encapsulant, and the warp that can occur in the resulting cured encapsulant Contributes to the suppression of
The curable resin layer (I) becomes a cured resin layer (I ′) by being cured. The cured resin layer (I ′) is formed on one surface of the obtained cured sealing body.

The storage elastic modulus E ′ at 23 ° C. of the cured resin layer (I ′) is preferably 1. from the viewpoint of obtaining a warp-preventing laminate capable of producing a cured sealing body having a flat surface while suppressing warpage. 0 × 10 ⁷ Pa or more, more preferably 1.0 × 10 ⁸ Pa or more, further preferably 1.0 × 10 ⁹ Pa or more, still more preferably 5.0 × 10 ⁹ Pa or more, and preferably It is 1.0 × 10 ¹³ Pa or less, more preferably 1.0 × 10 ¹² Pa or less, further preferably 5.0 × 10 ¹¹ Pa or less, and still more preferably 1.0 × 10 ¹¹ Pa or less.

The storage elastic modulus E ′ of the cured resin layer (I ′) is measured by the following procedure.
First, after laminating the curable resin layer (I) so as to have a thickness of 200 μm, in a measurement using a state in which curing is substantially completed (differential scanning calorimeter (DSCQ2000, manufactured by TA Instruments), Curing is performed until the exothermic peak disappears at 130 ° C. In the case of the thermosetting resin layers (X1), (X1-1), and (X1-2), the resin is placed in an oven in an air atmosphere, and the resin is heated at 130 ° C. for 2 hours to give a heat of 200 μm in thickness. The curable resin layer is thermally cured. When the energy ray curable resin layer (X2) and the thermosetting resin layer (X1-1) are included, the energy ray is irradiated (in the case of ultraviolet rays, the illuminance is 215 mW / cm ² and the light amount is 187 mJ / cm ² three times. Irradiation) to cure the energy ray curable resin layer (X2), and then thermoset the thermosetting resin layer (X1-1) under the above conditions.
Next, using a dynamic viscoelasticity measuring apparatus (TA Instruments, product name “DMAQ800”), the test start temperature is 0 ° C., the test end temperature is 300 ° C., the heating rate is 3 ° C./min, and the frequency is 11 Hz. The storage elastic modulus E ′ of the formed cured resin layer at 23 ° C. is measured under the condition of an amplitude of 20 μm.

The 1st surface which is the surface on the opposite side to a support layer of curable resin layer (I) has adhesiveness. As described above, the adhesive force is applied to the glass plate by attaching the first surface at a temperature of 70 ° C., and peeling off the curable resin layer at a temperature of 23 ° C., a peeling angle of 180 °, and a peeling speed of 300 mm / min. It is a value when measured by measuring 1.7 N / 25 mm or more.
In this specification, in the measurement of the adhesive strength of the curable resin layer (I), “applying at a temperature of 70 ° C.” means that the laminated body is a pressing body such as a pressure roller having a heat generation temperature of 70 ° C. By pressing on a glass plate, it means sticking a laminated body on a glass plate.
Although the sealing target is placed on the first surface of the curable resin layer (I), the surface of the curable resin layer (I) has the above-described adhesiveness, so that it is in close contact with the sealing target. When the sealing object such as a semiconductor chip is disposed on the first surface, the sealing object is tilted or the sealing object is disposed and then sealed against the curable resin layer (I). It is possible to prevent the position of the object to be stopped from deviating from the intended position.

The shear strength of the curable resin layer (I) to the measurement adherend is 130 gf at a temperature of 70 ° C. with a silicon chip (mirror surface) having a thickness of 350 μm and a size of 3 mm × 3 mm as the measurement adherend. It is a value when the mirror surface of the adherend for measurement is pressed and pasted on the curable resin layer for 1 second and measured at a speed of 200 μm / s, and is preferably 20 N / (3 mm × 3 mm) or more.

The adhesive force of the first surface of the curable resin layer (I) and the shearing force of the curable resin layer (I) on the measurement adherend are the thermosetting resin composition constituting the curable resin layer (I). Or by adjusting the types and blending ratios of the components of the energy beam curable resin composition. Adhesive force and shear force vary depending on the composition and blending ratio of the resin composition, and shear force also varies depending on the configuration of the entire curable resin layer (I). It becomes easy to make it a high value by using the acrylic polymer mentioned later as a polymer component, using an epoxy resin as a thermosetting component, or using a coupling agent. Moreover, about a shear force, it becomes easy to make it a high value by increasing content of an inorganic filler and a crosslinking agent, for example.

The thickness of the curable resin layer (I) is preferably 1 to 500 μm, more preferably 5 to 300 μm, still more preferably 10 to 200 μm, and still more preferably 15 to 100 μm.

(Thermosetting resin layer (X1))
The thermosetting resin layers (X1), (X1-1), and (X1-2) may be formed from a thermosetting resin composition containing the polymer component (A) and the thermosetting component (B). preferable. The thermosetting resin layers (X1), (X1-1), and (X1-2) are sometimes collectively referred to as a thermosetting resin layer (X1).
The curable resin composition may further contain one or more selected from a colorant (C), a coupling agent (D), and an inorganic filler (E). It is preferable to contain at least an inorganic filler (E) from the viewpoint of suppressing the warpage and obtaining a warp-preventing laminate capable of producing a cured sealing body having a flat surface.

The curing start temperature of the thermosetting resin layer (X1) is preferably 80 to 200 ° C, more preferably 90 to 160 ° C, and further preferably 100 to 150 ° C.
When the support layer (II) contains thermally expandable particles, a thermosetting resin layer (X1) having a curing start temperature lower than the expansion start temperature of the thermally expandable particles is used. The curing start temperature of the thermosetting resin layer (X1) is preferably 5 ° C. or less, more preferably 10 ° C. or less, and further preferably 20 ° C. or less than the expansion start temperature of the thermally expandable particles.

The thickness of the thermosetting resin layer (X1) may be in the same numerical range as the thickness of the curable resin layer (I).
When the thermosetting resin layer (X1) includes two layers like the thermosetting resin layers (X1-1) and (X1-2), the total thickness is curable. What is necessary is just to make it become the numerical value range similar to the thickness of resin layer (I). The thickness of the thin layer among these layers is preferably 10% or more, more preferably 20% or more, and further preferably 30% or more of the thickness of the thick layer.

(Polymer component (A))
The polymer component (A) contained in the thermosetting resin composition means a compound having a mass average molecular weight of 20,000 or more and having at least one repeating unit.
When the thermosetting resin composition contains the polymer component (A), the thermosetting resin layer to be formed has flexibility and film-forming properties, and the property maintaining property of the laminate is improved. be able to.
The mass average molecular weight (Mw) of the polymer component (A) is preferably 20,000 or more, more preferably 20,000 to 3,000,000, more preferably 50,000 to 2,000,000, and even more preferably 100,000 to 1,500,000. More preferably, it is 200,000 to 1,000,000.

The content of the component (A) is preferably 5 to 50% by mass, more preferably 8 to 40% by mass, and still more preferably 10% with respect to the total amount (100% by mass) of the active ingredients of the thermosetting resin composition. ~ 30% by mass.

Examples of the polymer component (A) include acrylic polymers, polyesters, phenoxy resins, polycarbonates, polyethers, polyurethanes, polysiloxanes, rubber polymers, and the like.
These polymer components (A) may be used alone or in combination of two or more.
In the present specification, the acrylic polymer having an epoxy group and the phenoxy resin having an epoxy group have thermosetting properties, but these have a mass average molecular weight of 20,000 or more and at least 1 Any compound having a repeating unit of a seed is included in the concept of the polymer component (A).

Among these, it is preferable that a polymer component (A) contains an acrylic polymer (A1).
The content of the acrylic polymer (A1) in the polymer component (A) is preferably from 60 to the total amount (100% by mass) of the polymer component (A) contained in the thermosetting resin composition. The amount is 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass.

(Acrylic polymer (A1))
The weight average molecular weight (Mw) of the acrylic polymer (A1) is preferably 20,000 to 3,000,000, more preferably 10 from the viewpoint of imparting flexibility and film forming property to the thermosetting resin layer to be formed. It is 10,000 to 1,500,000, more preferably 150,000 to 1,200,000, still more preferably 250,000 to 1,000,000.

The glass transition temperature (Tg) of the acrylic polymer (A1) is produced using a viewpoint of imparting good adhesiveness to the surface of the thermosetting resin layer to be formed, and a warp preventing laminate. From the viewpoint of improving the reliability of the cured encapsulant with a cured resin layer, it is preferably −60 to 50 ° C., more preferably −50 to 30 ° C., further preferably −40 to 10 ° C., and still more preferably −35 to 5 ° C.

Examples of the acrylic polymer (A1) include polymers having an alkyl (meth) acrylate as a main component. Specifically, the alkyl (meth) acrylate (a1 ′) having an alkyl group having 1 to 18 carbon atoms. An acrylic polymer containing the structural unit (a1) derived from (hereinafter also referred to as “monomer (a1 ′)”) is preferred, and the functional group-containing monomer (a2 ′) (hereinafter referred to as “monomer ( An acrylic copolymer containing the structural unit (a2) derived from “a2 ′)” is more preferable.
Acrylic polymer (A1) may be used independently and may use 2 or more types together.
In addition, when the acrylic polymer (A1) is a copolymer, the form of the copolymer may be any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer. Good.

The number of carbon atoms of the alkyl group contained in the monomer (a1 ′) is preferably 1 to 18, more preferably 1 to 12, more preferably 1 to 12, from the viewpoint of imparting flexibility and film forming property to the thermosetting resin layer to be formed. Preferably, it is 1-8. The alkyl group may be a straight chain alkyl group or a branched chain alkyl group.
These monomers (a1 ′) may be used alone or in combination of two or more.

From the viewpoint of improving the reliability of a cured encapsulant with a cured resin layer produced using a warp-preventing laminate, the monomer (a1 ′) is an alkyl (meth) having an alkyl group having 1 to 3 carbon atoms. An acrylate is preferably contained, and a methyl (meth) acrylate is more preferably contained.
From the above viewpoint, the content of the structural unit (a11) derived from the alkyl (meth) acrylate having an alkyl group having 1 to 3 carbon atoms is based on the total structural unit (100% by mass) of the acrylic polymer (A1). The content is preferably 1 to 80% by mass, more preferably 5 to 80% by mass, and still more preferably 10 to 80% by mass.

The monomer (a1 ′) preferably contains an alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms, and more preferably contains an alkyl (meth) acrylate having an alkyl group having 4 to 6 carbon atoms. More preferably, butyl (meth) acrylate is included.
From the above viewpoint, the content of the structural unit (a12) derived from the alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms (preferably 4 to 6, more preferably 4) is the acrylic polymer (A1). Is preferably 1 to 70% by mass, more preferably 5 to 65% by mass, and still more preferably 10 to 60% by mass with respect to all the structural units (100% by mass).

The content of the structural unit (a1) is preferably 50% by mass or more, more preferably 50 to 99% by mass, and still more preferably 55% with respect to the total structural unit (100% by mass) of the acrylic polymer (A1). It is -90 mass%, More preferably, it is 60-90 mass%.

The monomer (a2 ′) is preferably at least one selected from hydroxy group-containing monomers and epoxy group-containing monomers.
In addition, a monomer (a2 ') may be used independently and may use 2 or more types together.

Examples of the hydroxy group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl ( Examples thereof include hydroxyalkyl (meth) acrylates such as meth) acrylate and 4-hydroxybutyl (meth) acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol.
Among these, as the hydroxy group-containing monomer, hydroxyalkyl (meth) acrylate is preferable, and 2-hydroxyethyl (meth) acrylate is more preferable.

Examples of the epoxy-containing monomer include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 3-epoxycyclo-2-hydroxypropyl (meth) acrylate. Epoxy group-containing (meth) acrylates such as glycidyl crotonate and allyl glycidyl ether.
Among these, as an epoxy-containing monomer, an epoxy group-containing (meth) acrylate is preferable, and glycidyl (meth) acrylate is more preferable.

The content of the structural unit (a2) is preferably 1 to 50% by weight, more preferably 5 to 45% by weight, and still more preferably based on the total structural unit (100% by weight) of the acrylic polymer (A1). It is 10 to 40% by mass, more preferably 10 to 30% by mass.

In addition, the acrylic polymer (A1) may have a structural unit derived from another monomer other than the structural units (a1) and (a2) as long as the effects of the present invention are not impaired.
Examples of other monomers include vinyl acetate, styrene, ethylene, α-olefin and the like.

(Thermosetting component (B))
The thermosetting component (B) plays a role of thermosetting the formed thermosetting resin layer to form a hard cured resin layer, and is a compound having a mass average molecular weight of less than 20,000.
The mass average molecular weight (Mw) of the thermosetting component (B) is preferably 10,000 or less, more preferably 100 to 10,000.

As the thermosetting component (B), an epoxy compound (B1), which is a compound having an epoxy group, from the viewpoint of making a cured sealing body having a flat surface while suppressing warpage, which can be produced. ) And a thermosetting agent (B2), and it is more preferable that a curing accelerator (B3) is further included together with the epoxy compound (B1) and the thermosetting agent (B2).

Examples of the epoxy compound (B1) include polyfunctional epoxy resins, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, and bisphenol A type epoxy resins. And epoxy compounds having a bifunctional or higher functionality in the molecule such as a bisphenol F type epoxy resin and a phenylene skeleton type epoxy resin and having a mass average molecular weight of less than 20,000.
An epoxy compound (B1) may be used independently and may use 2 or more types together.

The content of the epoxy compound (B1) is a polymer contained in the thermosetting resin composition from the viewpoint of making a laminate for warpage prevention capable of producing a cured sealing body having a flat surface while suppressing warpage. The amount is preferably 1 to 500 parts by mass, more preferably 3 to 300 parts by mass, still more preferably 10 to 150 parts by mass, and still more preferably 20 to 120 parts by mass with respect to 100 parts by mass of the component (A).

The thermosetting agent (B2) functions as a curing agent for the epoxy compound (B1).
As a thermosetting agent, the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule is preferable.
Examples of the functional group include phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups, and acid anhydrides. Among these, a phenolic hydroxyl group, an amino group, or an acid anhydride is preferable from the viewpoint of producing a pressure-sensitive adhesive laminate with a cured resin layer having a flat surface while suppressing warpage, and phenol. An amino group is more preferable, and an amino group is more preferable.

Examples of the phenolic thermosetting agent having a phenol group include polyfunctional phenolic resins, biphenols, novolac type phenolic resins, dicyclopentadiene type phenolic resins, zylock type phenolic resins, and aralkylphenolic resins.
Examples of the amine-based thermosetting agent having an amino group include dicyandiamide.
These thermosetting agents (B2) may be used independently and may use 2 or more types together.

The content of the thermosetting agent (B2) is 100 masses of the epoxy compound (B1) from the viewpoint of producing a pressure-sensitive adhesive laminate with a cured resin layer having a flat surface while suppressing warpage. The amount is preferably 0.1 to 500 parts by mass, more preferably 1 to 200 parts by mass with respect to parts.

The curing accelerator (B3) is a compound having a function of increasing the rate of thermosetting when the thermosetting resin layer to be formed is thermoset.
Examples of the curing accelerator (B3) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, Imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; tributylphosphine, diphenylphosphine, triphenylphosphine, etc. Organic phosphines; tetraphenyl boron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate.
These curing accelerators (B3) may be used alone or in combination of two or more.

The content of the curing accelerator (B3) is such that the epoxy compound (B1) and the thermosetting agent (from the viewpoint of making a cured sealing body having a flat surface while suppressing warpage can be produced. The total amount of B2) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 6 parts by mass, and still more preferably 0.3 to 4 parts by mass with respect to 100 parts by mass.

(Colorant (C))
The thermosetting resin composition used in one embodiment of the present invention may further contain a colorant (C).
When a thermosetting resin layer formed from a thermosetting resin composition containing a colorant (C) is thermoset to form a cured resin layer, it is easy to determine whether the cured resin layer is stuck or not in appearance. In addition to providing an effect, it is possible to provide an effect such as blocking infrared rays generated from surrounding devices and preventing malfunction of a sealing object (such as a semiconductor chip).

As the colorant (C), organic or inorganic pigments and dyes can be used.
As the dye, for example, any dye such as an acid dye, a reactive dye, a direct dye, a disperse dye, and a cationic dye can be used.
Moreover, it does not restrict | limit especially as a pigment, It can select from a well-known pigment suitably and can be used.
Among these, black pigments are preferable from the viewpoint of good shielding properties against electromagnetic waves and infrared rays.
Examples of the black pigment include carbon black, iron oxide, manganese dioxide, aniline black, activated carbon, and the like. From the viewpoint of improving the reliability of the semiconductor chip, carbon black is preferable.
In addition, these coloring agents (C) may be used independently and may use 2 or more types together.

However, in the thermosetting resin composition used in one embodiment of the present invention, the content of the colorant (C) is 8% by mass with respect to the total amount (100% by mass) of the active ingredients of the thermosetting resin composition. It is preferable that it is less than.
If content of a coloring agent (C) is less than 8 mass%, it can be set as the laminated body for the curvature prevention which can confirm the presence or absence of the crack of the surface of a chip | tip, and chipping | visual_checking visually.
From the above viewpoint, in the thermosetting resin composition used in one embodiment of the present invention, the content of the colorant (C) is preferably based on the total amount (100% by mass) of the active ingredients of the thermosetting resin composition. Is less than 5% by weight, more preferably less than 2% by weight, even more preferably less than 1% by weight, and even more preferably less than 0.5% by weight.

Further, from the viewpoint of expressing the effect of shielding infrared rays or the like on the cured resin layer formed by thermosetting the thermosetting resin layer to be formed, the content of the colorant (C) is effective for the thermosetting resin composition. Preferably it is 0.01 mass% or more with respect to the whole quantity (100 mass%) of a component, More preferably, it is 0.05 mass% or more, More preferably, it is 0.10 mass% or more, More preferably, it is 0.15 mass% That's it.

(Coupling agent (D))
The thermosetting resin composition used in one embodiment of the present invention may further contain a coupling agent (D).
The thermosetting resin layer formed from the thermosetting resin composition containing the coupling agent (D) can improve the adhesion with the sealing object when the sealing object is placed. Moreover, the cured resin layer obtained by thermosetting the thermosetting resin layer can also improve water resistance without impairing heat resistance.

As a coupling agent (D), the compound which reacts with the functional group which a component (A) or a component (B) has is preferable, and a silane coupling agent is specifically preferable.
Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (methacryloxy) Propyl) trimethoxysilane, 3-aminopropyltrimethoxysilane, N-6- (aminoethyl) -3-aminopropyltrimethoxysilane, N-6- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N -Phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltri Metoki Silane, methyl triethoxy silane, vinyl trimethoxy silane, vinyl triacetoxy silane, imidazole silane, and the like.
These coupling agents (D) may be used independently and may use 2 or more types together.

The molecular weight of the coupling agent (D) is preferably 100 to 15,000, more preferably 125 to 10,000, more preferably 150 to 5,000, still more preferably 175 to 3,000, still more preferably. 200 to 2,000.

The content of the component (D) is preferably 0.01 to 10% by mass, more preferably 0.05 to 7% by mass, based on the total amount (100% by mass) of the active ingredients of the thermosetting resin composition. More preferably, it is 0.10 to 4% by mass, and still more preferably 0.15 to 2% by mass.

(Inorganic filler (E))
The thermosetting resin composition used in one embodiment of the present invention is an inorganic filler (E) from the viewpoint of a warp-preventing laminate capable of producing a cured sealing body having a flat surface while suppressing warpage. ) Is preferably contained.
By using a thermosetting resin layer formed from a thermosetting resin composition containing an inorganic filler (E), when the sealing material is thermoset, the shrinkage stress between the two surfaces of the cured encapsulant is reduced. The degree of thermosetting of the thermosetting resin layer can be adjusted so as to reduce the difference. As a result, it is possible to manufacture a cured sealing body having a flat surface while suppressing warpage.
Moreover, the thermal expansion coefficient of the cured resin layer formed by thermosetting the thermosetting resin layer to be formed can be adjusted to an appropriate range, and the reliability of the object to be sealed can be improved. Moreover, the moisture absorption rate of the said cured resin layer can also be reduced.

Examples of the inorganic filler (E) include powders of silica, alumina, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide, boron nitride, beads formed by spheroidizing them, single crystal fibers, glass fibers, and the like. Non-thermally expandable particles are mentioned.
These inorganic fillers (E) may be used alone or in combination of two or more.
Among these, silica or alumina is preferable from the viewpoint of suppressing the warpage to obtain a warp-preventing laminate capable of producing a cured sealing body having a flat surface.

The average particle diameter of the inorganic filler (E) is preferably 0.01 to 50 μm, more preferably from the viewpoint of improving the gloss value of the cured resin layer formed by thermosetting the thermosetting resin layer to be formed. The thickness is 0.1 to 30 μm, more preferably 0.3 to 30 μm, and particularly preferably 0.5 to 10 μm.

The content of the component (E) is the total amount of effective components of the thermosetting resin composition from the viewpoint of a warp-preventing laminate capable of producing a cured sealing body having a flat surface while suppressing warpage ( 100% by mass), preferably 25 to 80% by mass, more preferably 30 to 70% by mass, still more preferably 40 to 65% by mass, and still more preferably 45 to 60% by mass.

(Other additives)
The thermosetting resin composition used in one embodiment of the present invention may further contain other additives other than the above components (A) to (E) as long as the effects of the present invention are not impaired.
Examples of other additives include a crosslinking agent, a leveling agent, a plasticizer, an antistatic agent, an antioxidant, an ion scavenger, a gettering agent, and a chain transfer agent.
However, the total content of additives other than the components (A) to (E) is preferably 0 to 20% by mass with respect to the total amount (100% by mass) of the active ingredients of the thermosetting resin composition. More preferably, it is 0 to 10% by mass, and still more preferably 0 to 5% by mass.

When the curable resin layer (I) is composed of a single layer of the thermosetting resin layer (X1) as shown in FIGS. 1, 2, and 3, this single thermosetting resin layer (X1) Has the above configuration. As shown in FIG. 4, the curable resin layer (I) has a first thermosetting resin layer (X1-1) located on the support layer (II) side and the side opposite to the support layer (II) ( In the case where the second thermosetting resin layer (X1-2) located on the first surface side) is included, it is preferable that at least these adhesive forces are different, particularly the second heat located on the first surface side. The curable resin layer (X1-2) may be a second thermosetting resin layer (X1-2) having a higher surface adhesion than the first thermosetting resin layer (X1-1). preferable. In addition, as a method for making the adhesive force of the second thermosetting resin layer higher than the adhesive force of the first thermosetting resin layer, for example, by changing the type of the coupling agent, higher adhesive force is generated. For example, it is possible to select what is to be reduced, and to reduce the addition ratio of the inorganic filler.
Further, the former may be increased by making the shear force of the first thermosetting resin layer (X1-1) different from the shear force of the second thermosetting resin layer (X1-2). In this case, for example, by increasing the amount of the inorganic filler added to the first thermosetting resin layer (X1-1), the shear force is made larger than that of the second thermosetting resin layer (X1-2). can do.

(Energy ray curable resin layer)
As shown in FIG. 5, the curable resin layer (I) may include a thermosetting resin layer (X1-1) and an energy beam curable resin layer (X2).
In this case, the curable resin layer (I) includes a first layer located on the support layer side and a second layer located on the first surface side, and the first layer is a thermosetting resin layer (X1- 1), and the second layer is preferably an energy ray curable resin layer (X2). The thermosetting resin layer (X1-1) has the above-described configuration.
The energy ray curable resin layer (X2) is preferably formed from an energy ray curable pressure sensitive adhesive composition containing an energy ray curable pressure sensitive resin and a photopolymerization initiator.
Since the energy ray curable resin layer (X2) is easier to adjust to increase the adhesive force than the thermosetting resin layer, it is easy to reliably fix the object to be sealed to the first surface.
By curing the energy ray curable resin layer using such an energy ray curable pressure-sensitive adhesive layer by irradiating it with energy rays, it is possible to cure the encapsulating material as will be described later. Curing shrinkage of the resin layer can be made difficult to occur, which is advantageous in preventing warpage of the cured sealing body. In addition, when the thermosetting pressure-sensitive adhesive composition is heated at a high temperature, it softens mainly in the initial stage of curing, which may cause chip misalignment, whereas the energy ray-curable pressure-sensitive adhesive composition is In addition, since it is not softened by curing with energy beam irradiation, it is possible to avoid the occurrence of chip misalignment associated with curing.
Examples of energy rays include ultraviolet rays, electron beams, and radiation, but ultraviolet rays are preferable from the viewpoint of availability of the curable resin composition and ease of handling of the energy ray irradiation apparatus.

The energy ray-curable pressure-sensitive adhesive composition includes an energy ray-curable pressure-sensitive adhesive resin in which a polymerizable functional group such as a (meth) acryloyl group or a vinyl group is introduced into the side chain of the above-mentioned pressure-sensitive adhesive resin. It may be a product, and may be a composition containing a monomer or oligomer having a polymerizable functional group.
In addition, it is preferable that these compositions contain a photoinitiator further.

Examples of the photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzyl phenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyrol. Nitrile, dibenzyl, diacetyl, 8-chloroanthraquinone and the like can be mentioned.
These photoinitiators may be used independently and may use 2 or more types together.
The content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0 to 100 parts by mass of the energy ray-curable adhesive resin or 100 parts by mass of the monomer or oligomer having a polymerizable functional group. 0.03 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and particularly preferably 0.1 to 3 parts by mass.

By increasing the shear force of the thermosetting resin layer (X1-1) to be greater than the shear force of the energy ray curable resin layer (X2), the shear force of the entire curable resin layer (I) is increased. May be.

<Support layer (II)>
The support layer (II) included in the laminate of one embodiment of the present invention includes a base material (Y) and an adhesive layer (V), and at least one of the base material (Y) and the adhesive layer (V) is expanded. It is preferable that it contains a conductive particle. As above-mentioned, support layer (II) is a layer isolate | separated from curable resin layer (I) by an expansion process etc., and is a layer which plays the role as a temporary fixing layer.
The support layer (II) used in one embodiment of the present invention includes a case where the layer containing expandable particles is included in the configuration of the base material (Y) and a case where the layer is included in the configuration of the pressure-sensitive adhesive layer (V). Are divided into the following modes.
-1st aspect of support layer (II): Support layer (II) provided with the base material (Y) which has the expandable base material layer (Y1) containing an expandable particle.
-2nd aspect of support layer (II): The 2nd adhesive layer (V2) which is an expandable adhesive layer containing an expandable particle is provided in one side of a base material (Y), and the other The support layer (II) having the first pressure-sensitive adhesive layer (V1) which is a non-intumescent pressure-sensitive adhesive layer on the surface.

(First embodiment of support layer (II))
As a first aspect of the support layer (II), as shown in FIGS. 1 to 2, 4, and 5, the substrate (Y) has an expandable substrate layer (Y1) containing expandable particles. Is mentioned.
From the viewpoint of enabling easy separation at a slight force at the interface P, the pressure-sensitive adhesive layer (V) is preferably a non-expandable pressure-sensitive adhesive layer.
Specifically, in the

laminates

1a and 1b shown in FIG. 1, the laminate 4 shown in FIG. 4, and the support layer (II) included in the laminate 5 shown in FIG. 5, the pressure-sensitive adhesive layer (V1) is A non-intumescent adhesive layer is preferred.
Further, in the support layer (II) of the

laminates

2a and 2b shown in FIG. 2, both the first pressure-sensitive adhesive layer (V1-1) and the second pressure-sensitive adhesive layer (V1-2) are non-intumescent. It is preferable that it is an adhesive layer.
Since the base material (Y) has the expandable base material layer (Y1) as in the first embodiment of the support layer (II), the pressure-sensitive adhesive layer (V1) does not need to be expandable, and is expandable. It is not constrained by the composition, composition and process for imparting. Thereby, in designing the pressure-sensitive adhesive layer (V1), for example, it is possible to design with priority given to performances other than expansibility, such as performance such as adhesiveness, productivity, economy, etc. V) The degree of freedom in design can be improved.

In the first aspect of the support layer (II), the thickness of the base material (Y) before the expansion treatment is preferably 10 to 1,000 μm, more preferably 20 to 700 μm, still more preferably 25 to 500 μm, and still more. The thickness is preferably 30 to 300 μm.

The thickness of the pressure-sensitive adhesive layer (V) before the expansion treatment in the first aspect of the support layer (II) is preferably 1 to 60 μm, more preferably 2 to 50 μm, still more preferably 3 to 40 μm, and even more preferably. Is 5 to 30 μm.

In the present specification, for example, as shown in FIG. 2, when the support layer (II) has a plurality of pressure-sensitive adhesive layers, the above-mentioned “thickness of the pressure-sensitive adhesive layer (V)” indicates the respective pressure-sensitive adhesive layers. It means the thickness of the adhesive layer (in FIG. 2, the thickness of each of the first adhesive layer (V1-1) and the second adhesive layer (V1-2)).
Moreover, in this specification, the thickness of each layer which comprises a laminated body means the value measured by the method as described in an Example.

In the first aspect of the support layer (II), the thickness ratio [(Y1) / (V)] between the expandable substrate layer (Y1) and the pressure-sensitive adhesive layer (V) before the expansion treatment is as follows: Preferably it is 1,000 or less, More preferably, it is 200 or less, More preferably, it is 60 or less, More preferably, it is 30 or less.
If the thickness ratio is 1,000 or less, a laminate that can be easily and collectively separated by a slight force at the interface P between the support layer (II) and the cured resin layer (I ′) by expansion treatment. It can be.
The thickness ratio is preferably 0.2 or more, more preferably 0.5 or more, still more preferably 1.0 or more, and still more preferably 5.0 or more.

In the first aspect of the support layer (II), the base material (Y) may be composed only of the expandable base material layer (Y1) as shown in FIG. As shown in FIG. 1B, the curable resin layer (I) has an expandable base layer (Y1) and the pressure-sensitive adhesive layer (V) has a non-expandable base layer (Y2). You may have.

In the first aspect of the support layer (II), the thickness ratio [(Y1) / (Y2)] of the expandable substrate layer (Y1) and the non-expandable substrate layer (Y2) before the expansion treatment Is preferably 0.02 to 200, more preferably 0.03 to 150, and still more preferably 0.05 to 100.
In the first embodiment of the support layer (II), the thickness of the support layer (II) is preferably 0.02 to 200 μm, more preferably 0.03 to 150 μm, still more preferably 0.05 to 100 μm.

(Second embodiment of support layer (II))
As a 2nd aspect of support layer (II), as shown in FIG. 3, the 1st adhesive layer (V1) which is a non-expandable adhesive layer is arrange | positioned on one surface of a base material (Y). In the other surface, a second pressure-sensitive adhesive layer (V2) that is an expandable pressure-sensitive adhesive layer containing expandable particles is disposed.
In the second aspect of the support layer (II), the second pressure-sensitive adhesive layer (V2), which is an expandable pressure-sensitive adhesive layer, and the curable resin layer (I) are in direct contact.
In the second embodiment of the support layer (II), the substrate (Y) is preferably a non-intumescent substrate. The non-expandable base material is preferably composed only of the non-expandable base material layer (Y2).

In the second embodiment of the support layer (II), the second pressure-sensitive adhesive layer (V2) which is an expandable pressure-sensitive adhesive layer and the first pressure-sensitive adhesive layer (non-expandable pressure-sensitive adhesive layer) before the expansion treatment ( The thickness ratio [(V2) / (V1)] to V1) is preferably 0.1 to 80, more preferably 0.3 to 50, and still more preferably 0.5 to 15.

Further, in the second embodiment of the support layer (II), the thickness ratio [(V2 ) / (Y)] is preferably 0.05 to 20, more preferably 0.1 to 10, and still more preferably 0.2 to 3.
In the second embodiment of the support layer (II), the thickness of the support layer (II) is preferably 0.05 to 20 μm, more preferably 0.1 to 10 μm, still more preferably 0.2 to 3 μm.

Hereinafter, after explaining the expandable particles that can be contained in any of the layers constituting the support layer (II), the expandable substrate layer (Y1) and the non-expandable substrate layer constituting the substrate (Y) (Y2) and the pressure-sensitive adhesive layer (V) will be described in detail.

(Expandable particles)
The expandable particles used in one embodiment of the present invention may expand themselves by an external stimulus, thereby forming irregularities on the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (V2) and reducing the adhesive force with the adherend. There is no particular limitation as long as it is possible.
Examples of the expandable fine particles include thermally expandable particles that expand by heating, energy ray expandable fine particles that expand by irradiation with energy rays, and the like, from the viewpoint of versatility and handleability, by a predetermined heat expansion treatment. Preferably, the thermally expandable particles are expanded.
The average particle diameter before expansion at 23 ° C. of the expandable particles used in one embodiment of the present invention is preferably 3 to 100 μm, more preferably 4 to 70 μm, still more preferably 6 to 60 μm, and still more preferably 10 to 50 μm. It is.
The average particle diameter of the expandable particles before expansion is the volume-median particle diameter (D ₅₀ ), and a laser diffraction particle size distribution measuring device (for example, product name “Mastersizer 3000” manufactured by Malvern) is used. In the particle distribution of the expandable particles before expansion measured by use, it means the particle diameter corresponding to 50% of the cumulative volume frequency calculated from the smaller particle diameter of the expandable particles before expansion.

The 90% particle diameter (D ₉₀ ) before expansion at 23 ° C. of the expandable particles used in one embodiment of the present invention is preferably 10 to 150 μm, more preferably 20 to 100 μm, still more preferably 25 to 90 μm, and more. More preferably, it is 30 to 80 μm.
The 90% particle diameter (D ₉₀ ) before expansion of the expandable particles is measured using a laser diffraction particle size distribution measuring device (for example, product name “Mastersizer 3000” manufactured by Malvern), before expansion. Mean particle diameter corresponding to 90% of the cumulative volume frequency calculated from the smaller particle diameter of the expandable particles before expansion.

The heat-expandable particles used in one embodiment of the present invention may be particles that do not expand when the sealing material is cured, and have an expansion start temperature (t) higher than the curing temperature of the sealing material. Specifically, it is preferably a thermally expandable particle having an expansion start temperature (t) adjusted to 60 to 270 ° C.
The expansion start temperature (t) is appropriately selected according to the curing temperature of the sealing material to be used.
Moreover, in this specification, the expansion start temperature (t) of a thermally expansible particle means the value measured based on the method as described in an Example.

The thermally expandable particles include a microencapsulated foaming agent composed of an outer shell made of a thermoplastic resin and an encapsulated component encapsulated in the outer shell and vaporized when heated to a predetermined temperature. Preferably there is.
Examples of the thermoplastic resin constituting the outer shell of the microencapsulated foaming agent include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, and polysulfone.

Examples of the inclusion component contained in the outer shell include propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentane, isohexane, isoheptane, isooctane, isononane, isodecane, cyclopropane, cyclobutane, cyclopentane. , Cyclohexane, cycloheptane, cyclooctane, neopentane, dodecane, isododecane, cyclotridecane, hexylcyclohexane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nanodecane, isotridecane, 4-methyldodecane, isotetradecane, isopentadecane, iso Hexadecane, 2,2,4,4,6,8,8-heptamethylnonane, isoheptadecane, isooctadecane, isonanodecane, , 6,10,14-tetramethylpentadecane, cyclotridecane, heptylcyclohexane, n-octylcyclohexane, cyclopentadecane, nonylcyclohexane, decylcyclohexane, pentadecylcyclohexane, hexadecylcyclohexane, heptadecylcyclohexane, octadecylcyclohexane, etc. .
These encapsulated components may be used alone or in combination of two or more.
The expansion start temperature (t) of the thermally expandable particles can be adjusted by appropriately selecting the type of inclusion component.

The maximum volume expansion coefficient when heated to a temperature equal to or higher than the expansion start temperature (t) of the thermally expandable particles used in one embodiment of the present invention is preferably 1.5 to 100 times, more preferably 2 to 80 times, Preferably it is 2.5 to 60 times, and more preferably 3 to 40 times.

<Expandable base material layer (Y1)>
The expandable base material layer (Y1) included in the support layer (II) used in one embodiment of the present invention is a layer that contains expandable particles and can be expanded by an expansion treatment such as a predetermined heat treatment.

In addition, from the viewpoint of improving interlayer adhesion between the expandable base material layer (Y1) and other layers to be laminated, the surface of the expandable base material layer (Y1) is a surface by an oxidation method, an unevenness forming method, or the like. Treatment, easy adhesion treatment, or primer treatment may be performed.
Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), hot air treatment, ozone, and ultraviolet irradiation treatment. Examples of the unevenness method include sand blast method and solvent treatment method. Etc.

In one embodiment of the present invention, when the expandable substrate layer (Y1) includes thermally expandable particles, the expandable substrate layer (Y1) preferably satisfies the following requirement (1).
Requirement (1): The storage elastic modulus E ′ (t) of the expandable base material layer (Y1) at the expansion start temperature (t) of the thermally expandable particles is 1.0 × 10 ⁷ Pa or less.
In the present specification, the storage elastic modulus E ′ of the expandable base material layer (Y1) at a predetermined temperature means a value measured by the method described in the examples.

The requirement (1) can be said to be an index indicating the rigidity of the expandable base material layer (Y1) immediately before the thermally expandable particles expand.
In order to enable easy separation with a slight force at the interface P between the support layer (II) and the cured resin layer (I ′), when the support layer is heated to a temperature higher than the expansion start temperature (t), It is necessary to make it easy to form irregularities on the surface of the layer II and the curable resin layer (I).
That is, the expandable base material layer (Y1) satisfying the above requirement (1) becomes sufficiently large by expansion of the thermally expandable particles at the expansion start temperature (t), and the curable resin layer (I) is laminated. Unevenness is likely to be formed on the surface of the support layer (II) on the side where it is present.
As a result, a laminate that can be easily separated with a slight force at the interface P between the support layer (II) and the cured resin layer (I ′) can be obtained.

From the above viewpoint, the storage elastic modulus E ′ (t) of the expandable base material layer (Y1) defined by requirement (1) is preferably 9.0 × 10 ⁶ Pa or less, more preferably 8.0 × 10. ⁶ Pa or less, more preferably 6.0 × 10 ⁶ Pa or less, and even more preferably 4.0 × 10 ⁶ Pa or less.
Moreover, the flow of the expanded expansible particles is suppressed, and the shape maintaining property of the unevenness formed on the surface of the support layer (II) on the side where the curable resin layer (I) is laminated is improved. The storage elastic modulus E ′ (t) of the expandable base material layer (Y1) defined by the requirement (1) is preferably 1.0 × 10 ³ Pa from the viewpoint of enabling easy separation with a slight force. As mentioned above, More preferably, it is 1.0 * 10 < ⁴ > Pa or more, More preferably, it is 1.0 * 10 < ⁵ > Pa or more.

The expandable base layer (Y1) is preferably formed from a resin composition (y) containing a resin and expandable particles.
In addition, you may contain the additive for base materials in the resin composition (y) in the range which does not impair the effect of this invention as needed.
Examples of the substrate additive include an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, and a colorant.
These base material additives may be used alone or in combination of two or more.
When these base material additives are contained, the content of each base material additive is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to about 100 parts by mass of the resin. 10 parts by mass.

The content of the expandable particles is preferably 1 to 40 with respect to the total mass (100% by mass) of the expandable base material layer (Y1) or the total amount (100% by mass) of the active ingredients of the resin composition (y). The amount is 5% by mass, more preferably 5 to 35% by mass, still more preferably 10 to 30% by mass, and still more preferably 15 to 25% by mass.

The resin contained in the resin composition (y) that is a material for forming the expandable base material layer (Y1) may be a non-adhesive resin or an adhesive resin.
That is, even if the resin contained in the resin composition (y) is an adhesive resin, the adhesive resin is polymerizable in the process of forming the expandable substrate layer (Y1) from the resin composition (y). The resin obtained by polymerization reaction with the compound may be a non-adhesive resin, and the expandable base material layer (Y1) containing the resin may be non-adhesive.

The mass average molecular weight (Mw) of the resin contained in the resin composition (y) is preferably 1,000 to 1,000,000, more preferably 1,000 to 700,000, and still more preferably 1,000 to 500,000. It is.

Further, when the resin is a copolymer having two or more kinds of structural units, the form of the copolymer is not particularly limited, and any of a block copolymer, a random copolymer, and a graft copolymer It may be.

The content of the resin is preferably 50 to 99 mass with respect to the total mass (100 mass%) of the expandable base material layer (Y1) or the total amount of active ingredients (100 mass%) of the resin composition (y). %, More preferably 60 to 95% by mass, still more preferably 65 to 90% by mass, and still more preferably 70 to 85% by mass.

In addition, from the viewpoint of forming an expandable base material layer (Y1) that satisfies the above requirement (1), the resin contained in the resin composition (y) is selected from acrylic urethane resins and olefin resins. It is preferable to contain seeds or more.
Moreover, as said acrylic urethane type resin, acrylic urethane type resin (U1) formed by superposing | polymerizing urethane prepolymer (UP) and the vinyl compound containing (meth) acrylic acid ester is preferable.

(Acrylic urethane resin (U1))
Examples of the urethane prepolymer (UP) serving as the main chain of the acrylic urethane resin (U1) include a reaction product of a polyol and a polyvalent isocyanate.
The urethane prepolymer (UP) is preferably obtained by further subjecting it to a chain extension reaction using a chain extender.

Examples of the polyol used as a raw material for the urethane prepolymer (UP) include alkylene type polyols, ether type polyols, ester type polyols, ester amide type polyols, ester / ether type polyols, and carbonate type polyols.
These polyols may be used independently and may use 2 or more types together.
The polyol used in one embodiment of the present invention is preferably a diol, more preferably an ester diol, an alkylene diol, and a carbonate diol, and even more preferably an ester diol and a carbonate diol.

Examples of ester type diols include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol; ethylene glycol, propylene glycol, One or more selected from diols such as alkylene glycols such as diethylene glycol and dipropylene glycol; phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, diphenylmethane-4 , 4'-dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, het acid, maleic acid, fumaric acid, itaconic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, hexa Hydrophthalic acid, Examples thereof include condensation polymers of one or more selected from dicarboxylic acids such as hexahydroisophthalic acid, hexahydroterephthalic acid, and methylhexahydrophthalic acid, and anhydrides thereof.
Specifically, polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexamethylene adipate diol, Polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, poly (3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate diol and polyneo Examples thereof include pentyl terephthalate diol.

Examples of the alkylene type diol include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol; ethylene glycol, propylene glycol, And alkylene glycols such as diethylene glycol and dipropylene glycol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; polyoxyalkylene glycols such as polytetramethylene glycol; and the like.

Examples of the carbonate type diol include 1,4-tetramethylene carbonate diol, 1,5-pentamethylene carbonate diol, 1,6-hexamethylene carbonate diol, 1,2-propylene carbonate diol, and 1,3-propylene carbonate diol. 2,2-dimethylpropylene carbonate diol, 1,7-heptamethylene carbonate diol, 1,8-octamethylene carbonate diol, 1,4-cyclohexane carbonate diol, and the like.

Examples of the polyvalent isocyanate used as a raw material for the urethane prepolymer (UP) include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.
These polyvalent isocyanates may be used alone or in combination of two or more.
These polyisocyanates may be a trimethylolpropane adduct type modified product, a burette type modified product reacted with water, or an isocyanurate type modified product containing an isocyanurate ring.

Among these, the polyisocyanate used in one embodiment of the present invention is preferably diisocyanate, and 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2,6 More preferred is at least one selected from tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and alicyclic diisocyanate.

Examples of the alicyclic diisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane. Examples include diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, and isophorone diisocyanate (IPDI) is preferred.

In one embodiment of the present invention, the urethane prepolymer (UP) serving as the main chain of the acrylic urethane resin (U1) is a reaction product of a diol and a diisocyanate, and is a straight chain having ethylenically unsaturated groups at both ends. A urethane prepolymer is preferred.
As a method for introducing an ethylenically unsaturated group into both ends of the linear urethane prepolymer, an NCO group at the end of the linear urethane prepolymer obtained by reacting a diol and a diisocyanate compound, and a hydroxyalkyl (meth) acrylate And a method of reacting with.

Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxy Examples thereof include butyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.

As a vinyl compound used as the side chain of acrylic urethane type resin (U1), at least (meth) acrylic ester is contained.
The (meth) acrylic acid ester is preferably one or more selected from alkyl (meth) acrylates and hydroxyalkyl (meth) acrylates, and more preferably used in combination with alkyl (meth) acrylates and hydroxyalkyl (meth) acrylates.

When alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate are used in combination, the proportion of hydroxyalkyl (meth) acrylate to 100 parts by mass of alkyl (meth) acrylate is preferably 0.1 to 100 parts by mass, The amount is preferably 0.5 to 30 parts by mass, more preferably 1.0 to 20 parts by mass, and still more preferably 1.5 to 10 parts by mass.

The carbon number of the alkyl group of the alkyl (meth) acrylate is preferably 1 to 24, more preferably 1 to 12, still more preferably 1 to 8, and still more preferably 1 to 3.

Moreover, as hydroxyalkyl (meth) acrylate, the same thing as the hydroxyalkyl (meth) acrylate used in order to introduce | transduce an ethylenically unsaturated group into the both ends of the above-mentioned linear urethane prepolymer is mentioned.

Examples of vinyl compounds other than (meth) acrylic acid esters include aromatic hydrocarbon vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl acetate and vinyl propionate. Polar group-containing monomers such as (meth) acrylonitrile, N-vinylpyrrolidone, (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, and meta (acrylamide).
These may be used alone or in combination of two or more.

The content of the (meth) acrylic acid ester in the vinyl compound is preferably 40 to 100% by mass, more preferably 65 to 100% by mass, and still more preferably based on the total amount (100% by mass) of the vinyl compound. It is 80 to 100% by mass, more preferably 90 to 100% by mass.

The total content of alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate in the vinyl compound is preferably 40 to 100% by mass, more preferably 65 to 100% by mass with respect to the total amount (100% by mass) of the vinyl compound. It is 100% by mass, more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass.

In the acrylic urethane resin (U1) used in one embodiment of the present invention, the content ratio of the structural unit (u11) derived from the urethane prepolymer (UP) and the structural unit (u12) derived from the vinyl compound [(u11 ) / (U12)] is preferably 10/90 to 80/20, more preferably 20/80 to 70/30, still more preferably 30/70 to 60/40, and still more preferably 35 by mass ratio. / 65 to 55/45.

(Olefin resin)
The olefin resin suitable as the resin contained in the resin composition (y) is a polymer having at least a structural unit derived from an olefin monomer.
The olefin monomer is preferably an α-olefin having 2 to 8 carbon atoms, and specifically includes ethylene, propylene, butylene, isobutylene, 1-hexene and the like.
Among these, ethylene and propylene are preferable.

Specific olefinic resins, for example, ultra low density polyethylene (VLDPE, density: 880 kg / ^{m 3} or more 910 kg / ^m less than ^3), low density polyethylene (LDPE, density: 910 kg / ^{m 3} or more 915 kg / ^m less than ³ ), Medium density polyethylene (MDPE, density: 915 kg / m ³ or more and less than 942 kg / m ³ ), high density polyethylene (HDPE, density: 942 kg / m ³ or more), linear low density polyethylene, etc .; polypropylene resin (PP); polybutene resin (PB); ethylene-propylene copolymer; olefin elastomer (TPO); poly (4-methyl-1-pentene) (PMP); ethylene-vinyl acetate copolymer (EVA); Vinyl alcohol copolymer (EVOH); ethylene-propylene Olefinic terpolymers such as-(5-ethylidene-2-norbornene); and the like.

In one embodiment of the present invention, the olefin resin may be a modified olefin resin further modified by one or more selected from acid modification, hydroxyl group modification, and acrylic modification.

For example, as an acid-modified olefin resin obtained by subjecting an olefin resin to acid modification, a modified polymer obtained by graft polymerization of the above-mentioned unmodified olefin resin with an unsaturated carboxylic acid or its anhydride. Is mentioned.
Examples of the unsaturated carboxylic acid or anhydride thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth) acrylic acid, maleic anhydride, itaconic anhydride. , Glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, and the like.
In addition, unsaturated carboxylic acid or its anhydride may be used independently and may use 2 or more types together.

An acrylic modified olefin resin obtained by subjecting an olefin resin to acrylic modification is a modification obtained by graft polymerization of an alkyl (meth) acrylate as a side chain to the above-mentioned unmodified olefin resin that is a main chain. A polymer is mentioned.
The number of carbon atoms of the alkyl group contained in the alkyl (meth) acrylate is preferably 1 to 20, more preferably 1 to 16, and still more preferably 1 to 12.
As said alkyl (meth) acrylate, the same thing as the compound which can be selected as a below-mentioned monomer (a1 ') is mentioned, for example.

Examples of the hydroxyl group-modified olefin resin obtained by subjecting an olefin resin to hydroxyl group modification include a modified polymer obtained by graft polymerization of a hydroxyl group-containing compound to the above-mentioned unmodified olefin resin, which is the main chain.
Examples of the hydroxyl group-containing compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate and 4-hydroxybutyl (meth) acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol.

(Resin other than acrylic urethane resin and olefin resin)
In one embodiment of the present invention, the resin composition (y) may contain a resin other than the acrylic urethane-based resin and the olefin-based resin as long as the effects of the present invention are not impaired.
Examples of such resins include vinyl resins such as polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer Polycarbonate; Polyurethane not applicable to acrylic urethane resin; Polysulfone; Polyetheretherketone; Polyethersulfone; Polyphenylene sulfide; Polyimide resin such as polyetherimide and polyimide; Polyamide resin; Acrylic resin; Fluorine resin etc. are mentioned.

However, from the viewpoint of forming the expandable base material layer (Y1) that satisfies the above requirement (1), the content ratio of the resin other than the acrylic urethane resin and the olefin resin in the resin composition (y) is smaller. preferable.
The content ratio of the resin other than the acrylic urethane-based resin and the olefin-based resin is preferably less than 30 parts by weight, more preferably 20 parts by weight with respect to 100 parts by weight of the total amount of the resin contained in the resin composition (y). Less than 10 parts by weight, more preferably less than 10 parts by weight, even more preferably less than 5 parts by weight, and even more preferably less than 1 part by weight.

(Solvent-free resin composition (y1))
As the resin composition (y) used in one embodiment of the present invention, an oligomer having an ethylenically unsaturated group having a mass average molecular weight (Mw) of 50,000 or less, an energy ray polymerizable monomer, and the above-mentioned expandable particles A solventless resin composition (y1) that is blended and does not contain a solvent is mentioned.
In the solventless resin composition (y1), no solvent is added, but the energy beam polymerizable monomer contributes to the improvement of the plasticity of the oligomer.
By irradiating the coating film formed from the solventless resin composition (y1) with energy rays, it is easy to form an expandable base material layer (Y1) that satisfies the above requirement (1).

In addition, the type, shape, and blending amount (content) of the expandable particles blended in the solventless resin composition (y1) are as described above.

The mass average molecular weight (Mw) of the oligomer contained in the solventless resin composition (y1) is 50,000 or less, preferably 1,000 to 50,000, more preferably 20,000 to 40. 3,000, more preferably 3,000 to 35,000, and still more preferably 4,000 to 30,000.

Moreover, as said oligomer, what is necessary is just to have an ethylenically unsaturated group whose mass mean molecular weight is 50,000 or less among resin contained in the above-mentioned resin composition (y). Polymer (UP) is preferred.
As the oligomer, a modified olefin resin having an ethylenically unsaturated group can also be used.

The total content of the oligomer and the energy beam polymerizable monomer in the solventless resin composition (y1) is preferably 50 to 100% based on the total amount (100% by mass) of the solventless resin composition (y1). It is 99% by mass, more preferably 60 to 95% by mass, still more preferably 65 to 90% by mass, and still more preferably 70 to 85% by mass.

Examples of the energy ray polymerizable monomer include isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, cyclohexyl (meth) acrylate, adamantane ( Cycloaliphatic polymerizable compounds such as (meth) acrylate and tricyclodecane acrylate; Aromatic polymerizable compounds such as phenylhydroxypropyl acrylate, benzyl acrylate and phenol ethylene oxide modified acrylate; Tetrahydrofurfuryl (meth) acrylate, morpholine acrylate, N- And heterocyclic polymerizable compounds such as vinylpyrrolidone and N-vinylcaprolactam.
These energy beam polymerizable monomers may be used independently and may use 2 or more types together.

The mixing ratio of the oligomer to the energy beam polymerizable monomer (the oligomer / energy beam polymerizable monomer) is preferably 20/80 to 90/10, more preferably 30/70 to 85/15, and still more preferably 35/65. ~ 80/20.

In one embodiment of the present invention, it is preferable that the solventless resin composition (y1) is further blended with a photopolymerization initiator.
By containing the photopolymerization initiator, the curing reaction can be sufficiently advanced even by irradiation with a relatively low energy beam.

Examples of the photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzyl phenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyrol. Nitrile, dibenzyl, diacetyl, 8-chloroanthraquinone and the like can be mentioned.
These photoinitiators may be used independently and may use 2 or more types together.

The blending amount of the photopolymerization initiator is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 4 parts by mass with respect to the total amount (100 parts by mass) of the oligomer and energy beam polymerizable monomer. The amount is preferably 0.02 to 3 parts by mass.

<Non-expandable base material layer (Y2)>
Examples of the material for forming the non-intumescent base material layer (Y2) constituting the base material (Y) include paper materials, resins, metals, and the like. You can choose.
Here, in one embodiment of the present invention, when the expandable particles contained in the expandable substrate layer (Y1) expand, the expandable substrate layer (Y1) on the non-expandable substrate layer (Y2) side is provided. From the viewpoint of suppressing the formation of irregularities on the surface and forming irregularities predominantly on the surface of the expandable substrate layer (Y1) on the pressure-sensitive adhesive layer (V1) side, Y2) preferably has such a rigidity that it does not deform due to expansion of the expandable particles. Specifically, the storage elastic modulus E ′ (t) of the non-expandable base material layer (Y2) at the temperature (t) at the start of expansion of the expandable particles is 1.1 × 10 ⁷ Pa or more. Is preferred.

Examples of the paper material include thin paper, medium quality paper, high quality paper, impregnated paper, coated paper, art paper, sulfate paper, glassine paper, and the like.
Examples of the resin include polyolefin resins such as polyethylene and polypropylene; vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer; polyethylene terephthalate, poly Polyester resins such as butylene terephthalate and polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; urethane resin such as polyurethane and acrylic modified polyurethane; polymethylpentene; polysulfone; polyether ether ketone; Polyethersulfone; Polyphenylene sulfide; Polyimide resin such as polyetherimide and polyimide; Polyamide resin; Acrylic resin; Tsu Motokei resin, and the like.
Examples of the metal include aluminum, tin, chromium, and titanium.

These forming materials may be composed of one kind or in combination of two or more kinds.
As a non-intumescent substrate layer (Y2) using two or more kinds of forming materials in combination, a paper film is laminated with a thermoplastic resin such as polyethylene, and a metal film is formed on the surface of a resin film or sheet containing the resin. And the like.
As a method for forming the metal layer, for example, the above metal is deposited by a PVD method such as vacuum deposition, sputtering, or ion plating, or a metal foil made of the above metal is attached using a general adhesive. And the like.

From the viewpoint of improving interlayer adhesion between the non-expandable base layer (Y2) and other layers to be laminated, when the non-expandable base layer (Y2) contains a resin, the non-expandable base layer Also on the surface of (Y2), similarly to the above-mentioned expandable base material layer (Y1), a surface treatment by an oxidation method, a concavo-convex method, an easy adhesion treatment, or a primer treatment may be performed.

Moreover, when the non-intumescent base material layer (Y2) contains a resin, it may contain the above-mentioned base material additive that can be contained in the resin composition (y) together with the resin.

A non-expandable base material layer (Y2) is a non-expandable layer judged based on the above-mentioned method.
Therefore, the volume change rate (%) of the non-expandable base material layer (Y2) calculated from the above formula is less than 5% by volume, preferably less than 2% by volume, more preferably less than 1% by volume. More preferably, it is less than 0.1 volume%, More preferably, it is less than 0.01 volume%.

Moreover, as long as a volume change rate is the said range, a non-expandable base material layer (Y2) may contain an expandable particle. For example, by selecting the resin contained in the non-expandable base material layer (Y2), the volume change rate can be adjusted to the above range even if the expandable particles are contained.
However, it is preferable that the non-expandable base material layer (Y2) does not contain expandable particles. When the non-expandable base material layer (Y2) contains inflatable particles, the content is preferably as small as possible, and the specific content of the inflatable particles is the total of the non-expandable base material layer (Y2). Usually less than 3% by mass, preferably less than 1% by mass, more preferably less than 0.1% by mass, still more preferably less than 0.01% by mass, and still more preferably 0.001% with respect to mass (100% by mass) It is less than mass%.

<Adhesive layer (V)>
The pressure-sensitive adhesive layer (V) of the support layer (II) used in one embodiment of the present invention can be formed from a pressure-sensitive adhesive composition (v) containing a pressure-sensitive resin.
The pressure-sensitive adhesive composition (v) may contain pressure-sensitive adhesive additives such as a crosslinking agent, a tackifier, a polymerizable compound, and a polymerization initiator, if necessary.
Hereinafter, each component contained in the pressure-sensitive adhesive composition (v) will be described.
Even when the support layer (II) has the first pressure-sensitive adhesive layer (V1-1) or (V1) and the second pressure-sensitive adhesive layer (V1-2) or (V2), the first pressure-sensitive adhesive layer (V1-1) or (V1) and the second pressure-sensitive adhesive layer (V1-2) or (V2) can also be formed from the pressure-sensitive adhesive composition (v) containing the following components.

(Adhesive resin)
As the adhesive resin used in one embodiment of the present invention, the resin alone is preferably a polymer having adhesiveness and a mass average molecular weight (Mw) of 10,000 or more.
The mass average molecular weight (Mw) of the adhesive resin used in one embodiment of the present invention is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000, and even more preferably 30,000, from the viewpoint of improving adhesive force. ~ 1 million.

Specific examples of the adhesive resin include rubber resins such as acrylic resins, urethane resins, and polyisobutylene resins, polyester resins, olefin resins, silicone resins, and polyvinyl ether resins.
These adhesive resins may be used alone or in combination of two or more.
In addition, when these adhesive resins are copolymers having two or more kinds of structural units, the form of the copolymer is not particularly limited, and a block copolymer, a random copolymer, and a graft copolymer are not limited. Any of polymers may be used.

In one embodiment of the present invention, the adhesive resin preferably contains an acrylic resin from the viewpoint of exhibiting excellent adhesive strength.
When the support layer (II) having the first pressure-sensitive adhesive layer (V1-1) or (V1) and the second pressure-sensitive adhesive layer (V1-2) or (V2) is used, the curable resin layer (I As the first pressure-sensitive adhesive layer (V1-1) or (V1) in contact with) contains an acrylic resin, irregularities are formed on the surface of the first pressure-sensitive adhesive layer (V1-1) or (V1). It can be made easy.

The content of the acrylic resin in the adhesive resin is preferably from 30 to the total amount (100% by mass) of the adhesive resin contained in the adhesive composition (v) or the adhesive layer (V). It is 100% by mass, more preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, and still more preferably 85 to 100% by mass.

The content of the adhesive resin is preferably 35 to 100 with respect to the total amount (100% by mass) of the active ingredients of the adhesive composition (v) or the total mass (100% by mass) of the adhesive layer (V). The mass is more preferably 50 to 100% by mass, still more preferably 60 to 98% by mass, and still more preferably 70 to 95% by mass.

(Crosslinking agent)
In one aspect of the present invention, the pressure-sensitive adhesive composition (v) preferably further contains a cross-linking agent when it contains a pressure-sensitive adhesive resin having a functional group.
The said crosslinking agent reacts with the adhesive resin which has a functional group, and bridge | crosslinks adhesive resins by using the said functional group as a crosslinking origin.

Examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent.
These crosslinking agents may be used independently and may use 2 or more types together.
Among these crosslinking agents, an isocyanate-based crosslinking agent is preferable from the viewpoints of increasing cohesive force and improving adhesive force, and availability.

The content of the crosslinking agent is appropriately adjusted depending on the number of functional groups that the adhesive resin has, but is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the adhesive resin having a functional group, The amount is more preferably 0.03 to 7 parts by mass, still more preferably 0.05 to 5 parts by mass.

(Tackifier)
In one embodiment of the present invention, the pressure-sensitive adhesive composition (v) may further contain a tackifier from the viewpoint of further improving the adhesive strength.
In the present specification, the “tackifier” is a component that assists in improving the adhesive strength of the above-mentioned adhesive resin, and refers to an oligomer having a mass average molecular weight (Mw) of less than 10,000. It is distinguished from a functional resin.
The weight average molecular weight (Mw) of the tackifier is preferably 400 to 10,000, more preferably 500 to 8,000, and still more preferably 800 to 5,000.

Examples of the tackifier are obtained by copolymerizing C5 fractions such as rosin resin, terpene resin, styrene resin, pentene, isoprene, piperine, 1,3-pentadiene generated by thermal decomposition of petroleum naphtha. And C9 petroleum resin obtained by copolymerizing C9 fractions such as indene generated by thermal decomposition of petroleum naphtha and vinyltoluene, and hydrogenated resins obtained by hydrogenating these.

The softening point of the tackifier is preferably 60 to 170 ° C, more preferably 65 to 160 ° C, and further preferably 70 to 150 ° C.
In the present specification, the “softening point” of the tackifier means a value measured according to JIS K2531.
A tackifier may be used independently and may use 2 or more types from which a softening point, a structure, etc. differ.
And when using 2 or more types of several tackifier, it is preferable that the weighted average of the softening point of these several tackifier belongs to the said range.

The content of the tackifier is preferably 0.01 to the total amount (100% by mass) of the active ingredient in the adhesive composition (v) or the total mass (100% by mass) of the adhesive layer (V). It is 65% by mass, more preferably 0.1 to 50% by mass, still more preferably 1 to 40% by mass, and still more preferably 2 to 30% by mass.

(Adhesive additive)
In one aspect of the present invention, the pressure-sensitive adhesive composition (v) contains an additive for pressure-sensitive adhesives used for general pressure-sensitive adhesives in addition to the above-mentioned additives, as long as the effects of the present invention are not impaired. You may do it.
Examples of such adhesive additives include antioxidants, softeners (plasticizers), rust inhibitors, pigments, dyes, retarders, reaction accelerators (catalysts), ultraviolet absorbers, antistatic agents, and the like. Is mentioned.
These pressure-sensitive adhesive additives may be used alone or in combination of two or more.
When these pressure-sensitive adhesive additives are contained, the content of each pressure-sensitive adhesive additive is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 100 parts by mass of the adhesive resin. ~ 10 parts by mass.

In addition, when using the support layer (II) of the above-mentioned 3rd aspect which has the 2nd adhesive layer (V2) which is an expandable adhesive layer, the 2nd adhesive layer (V2) which is an expandable adhesive layer ) Is formed from the above-mentioned pressure-sensitive adhesive composition (v) and the expandable pressure-sensitive adhesive composition (v22) further containing expandable particles.
The expandable particles are as described above.
The content of the expandable particles is preferably 1 with respect to the total amount (100% by mass) of the active ingredient in the expandable pressure-sensitive adhesive composition (v22) or the total mass (100% by mass) of the expandable pressure-sensitive adhesive layer. It is ˜70% by mass, more preferably 2 to 60% by mass, further preferably 3 to 50% by mass, and still more preferably 5 to 40% by mass.

On the other hand, when the pressure-sensitive adhesive layer (V) is a non-expandable pressure-sensitive adhesive layer, the pressure-sensitive adhesive composition (v) which is a material for forming the non-expandable pressure-sensitive adhesive layer preferably does not contain expandable particles. .
When the expandable particles are contained, the content is preferably as small as possible, and the total amount (100% by mass) of the active ingredient in the pressure-sensitive adhesive composition (v) or the total mass (100% by mass) of the pressure-sensitive adhesive layer (V). On the other hand, it is preferably less than 1% by mass, more preferably less than 0.1% by mass, further preferably less than 0.01% by mass, and still more preferably less than 0.001% by mass.

Note that, like the

laminates

2a and 2b shown in FIG. 2, a support layer having a first pressure-sensitive adhesive layer (V1-1) and a second pressure-sensitive adhesive layer (V1-2), which are non-intumescent pressure-sensitive adhesive layers. When (II) is used, the storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (V1-1), which is a non-expandable pressure-sensitive adhesive layer at 23 ° C., is preferably 1.0 × 10 ^8. Pa or less, more preferably 5.0 × 10 ⁷ Pa or less, and even more preferably 1.0 × 10 ⁷ Pa or less.
If the storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (V1-1), which is a non-expandable pressure-sensitive adhesive layer, is 1.0 × 10 ⁸ Pa or less, for example, the laminate shown in FIG. The first pressure-sensitive adhesive layer that is in contact with the cured resin layer (I ′) due to the expansion of the expandable particles in the expandable base material layer (Y1) by the heat expansion treatment when the configuration is as in 2a and 2b Unevenness is easily formed on the surface of (V1-1).
As a result, it is possible to obtain a laminate that can be easily separated in a lump with a slight force at the interface P between the support layer (II) and the cured resin layer (I ′).
The storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (V1-1), which is a non-expandable pressure-sensitive adhesive layer, at 23 ° C. is preferably 1.0 × 10 ⁴ Pa or more, and more preferably Is 5.0 × 10 ⁴ Pa or more, more preferably 1.0 × 10 ⁵ Pa or more.

The light transmittance at a wavelength of 365 nm of the support layer (II) included in the laminate of one embodiment of the present invention is preferably 30% or more, more preferably 50% or more, and further preferably 70% or more. When the light transmittance is within the above range, the curing degree of the curable resin layer (I) is further improved when the curable resin layer (I) is irradiated with energy rays (ultraviolet rays) via the support layer (II). To do. The upper limit of the light transmittance at a wavelength of 365 nm is not particularly limited, but can be, for example, 95% or less.
From the viewpoint of achieving the above light transmittance, the substrate (Y) and the pressure-sensitive adhesive layer (V) included in the support layer (II) preferably do not contain a colorant.
When the colorant is contained, the content is preferably as small as possible, and is based on the total amount (100% by mass) of the active ingredients of the pressure-sensitive adhesive composition (v) or the total mass (100% by mass) of the pressure-sensitive adhesive layer (V). Preferably less than 1% by mass, more preferably less than 0.1% by mass, still more preferably less than 0.01% by mass, still more preferably less than 0.001% by mass, and in the substrate (Y) The content of the colorant is preferably less than 1% by mass with respect to the total amount (100% by mass) of the active ingredients of the resin composition (y) or the total mass (100% by mass) of the substrate (Y). Preferably it is less than 0.1 mass%, More preferably, it is less than 0.01 mass%, More preferably, it is less than 0.001 mass%.

(Sealing object)
Examples of the sealing object placed on a part of the surface of the curable resin layer (I) include a semiconductor chip, a semiconductor wafer, a compound semiconductor, a semiconductor package, an electronic component, a sapphire substrate, a display, a panel substrate, and the like. Is mentioned.

For example, when the object to be sealed is a semiconductor chip, a semiconductor chip with a cured resin layer can be manufactured by using the warp preventing laminate of one embodiment of the present invention.
A conventionally known semiconductor chip can be used as the semiconductor chip, and an integrated circuit composed of circuit elements such as transistors, resistors, and capacitors is formed on the circuit surface.
And it is preferable that a semiconductor chip is mounted so that the back surface on the opposite side to a circuit surface may be covered with the surface of a thermosetting resin layer. In this case, the circuit surface of the semiconductor chip is exposed after placement.
For mounting the semiconductor chip, a known device such as a flip chip bonder or a die bonder can be used.
The layout and number of semiconductor chips may be determined as appropriate according to the target package form, number of production, and the like.

[Manufacturing method of laminate for warpage prevention]
The laminate for warpage prevention can be produced by the following method.
First, a curable resin layer (I) is formed on a release film by applying and drying a curable resin composition.
When the curable resin layer (I) is composed of two layers, each curable resin composition is formed on a separate release film and laminated so that both layers are in direct contact with each other. A resin layer is produced. The first curable resin composition is coated on the release film and dried to form the first curable resin layer (X1-1). Next, the first curable resin layer (X1-1) is formed on the release film. A laminated curable resin layer can also be produced by applying and drying the second curable resin layer (X1-2) or (X2).
By sticking the pressure-sensitive adhesive layer (V) of the support layer (II) to the curable resin layer (I) or via a pressure-sensitive adhesive layer different from the support layer (II). By sticking the resin layer (I) and the support layer (II), a warp preventing laminate can be obtained.
The support layer (II) is formed by applying and drying the pressure-sensitive adhesive composition on the release film to form the pressure-sensitive adhesive layer (V), and then applying the resin material constituting the base material layer to the pressure-sensitive adhesive layer. It can be produced by coating and drying on top or attaching a sheet-like base material to the pressure-sensitive adhesive layer to form the base material layer. When the base material layer is composed of a plurality of layers, after the first base material layer is formed, the resin material constituting the second base material layer is applied and dried on the first base material layer, and then the second base material layer is formed. The base material layer is formed. In the case of the support layer having the second pressure-sensitive adhesive layer on the second base material layer, the pressure-sensitive adhesive composition is applied and dried on the second base material layer to form the second pressure-sensitive adhesive layer. .

[First production method of cured encapsulant]
The first aspect of the method for producing a cured encapsulant of the present invention is a method for producing a cured encapsulant using the laminate of one aspect of the present invention, comprising the following steps (i) to (iv): Have.
Step (i): A sealing object is placed on a part of the first surface of the curable resin layer (I) of the laminate for warpage prevention.
Step (ii): The sealing object and at least the first surface of the curable resin layer (I) at the periphery of the sealing object are covered with a thermosetting sealing material.
Step (iii): The above-mentioned sealing material is thermally cured to form a cured sealing body including the sealing object, and the curable resin layer (I) is also thermally cured to cure the cured resin layer (I ′). To obtain a cured encapsulant.
Step (iv): The cured resin layer (I ′) and the support layer (II) are separated at the interface by a treatment for expanding the expandable particles to obtain a cured sealed body with a cured resin layer.

FIG. 6 is a schematic cross-sectional view showing a process for producing a cured encapsulant with a cured resin layer, and more specifically, a cured encapsulant using a warp-preventing laminate 1a shown in FIG. 1 (b). It is the cross-sectional schematic diagram which showed the process of manufacturing. Hereinafter, each process described above will be described with reference to FIG. 6 as appropriate.

<Process (i)>
In the step (i), the sealing object is placed on a part of the surface of the curable resin layer (I) included in the warpage preventing laminate of one embodiment of the present invention.
FIG. 6A shows a state where the adhesive surface of the pressure-sensitive adhesive layer (V1) of the support layer (II) is attached to the support 50 using the warp-preventing laminate 1b, and FIG. These show a mode that the sealing target object 60 is mounted in a part of surface of curable resin layer (I).
6 shows an example in which the laminate 1b shown in FIG. 1B is used. Similarly, when the laminate for warpage prevention according to another aspect of the present invention is used, the support is similarly used. Then, the warp preventing laminate and the sealing object are laminated or placed in this order.

As the temperature condition in the step (i), when thermally expandable particles are used as the expandable particles, it is preferably performed at a temperature at which the thermally expandable particles do not expand, for example, in an environment of 0 to 80 ° C. (however, When the expansion start temperature (t) is 60 to 80 ° C., it is preferably performed in an environment less than the expansion start temperature (t). In the case of using energy ray-expandable particles, the irradiation device is stopped or at a position away from the irradiation device, as necessary, so that the energy rays that contribute to particle expansion are not irradiated. Step (i) is performed under a filter or mask for cutting energy rays.

The support is preferably attached to the entire pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (V1) of the laminate.
Therefore, the support is preferably plate-shaped. Moreover, as shown in FIG. 6, it is preferable that the area of the adhesive surface of the adhesive layer (V1) and the surface of the support on the side to be attached is equal to or larger than the area of the adhesive surface of the adhesive layer (V1).

As the material constituting the support, depending on the type of sealing object, the type of sealing material used in step (ii), etc., considering the required properties such as mechanical strength and heat resistance, it is appropriate Selected.
Specific materials constituting the support include, for example, metal materials such as SUS; non-metallic inorganic materials such as glass and silicon wafers; epoxy resins, ABS resins, acrylic resins, engineering plastics, super engineering plastics, polyimide resins, Examples thereof include resin materials such as polyamideimide resin; composite materials such as glass epoxy resin, and among these, SUS, glass, silicon wafer and the like are preferable.
Examples of engineering plastics include nylon, polycarbonate (PC), and polyethylene terephthalate (PET).
Examples of super engineering plastics include polyphenylene sulfide (PPS), polyether sulfone (PES), and polyether ether ketone (PEEK).

Although the thickness of a support body is suitably selected according to the kind of sealing target object, the kind of sealing material used at process (ii), etc., Preferably it is 20 micrometers or more and 50 mm or less, More preferably, it is 60 micrometers or more. 20 mm or less.

On the other hand, examples of the sealing object placed on a part of the surface of the curable resin layer (I) include, for example, semiconductor chips, semiconductor wafers, compound semiconductors, semiconductor packages, electronic components, sapphire substrates, displays, and panels. Examples include substrates. In the following description, a case where a semiconductor chip is used as the sealing object 60 will be described as an example.

When the object to be sealed is a semiconductor chip, a semiconductor chip with a cured resin layer can be manufactured by using the stacked body of one embodiment of the present invention.
A conventionally known semiconductor chip can be used as the semiconductor chip, and an integrated circuit composed of circuit elements such as transistors, resistors, and capacitors is formed on the circuit surface.
And it is preferable that a semiconductor chip is mounted so that the back surface on the opposite side to a circuit surface may be covered with the surface of curable resin layer (I). In this case, the circuit surface of the semiconductor chip is exposed after placement.
For mounting the semiconductor chip, a known device such as a flip chip bonder or a die bonder can be used.
The layout and number of semiconductor chips may be determined as appropriate according to the target package form, number of production, and the like.

The surface of the curable resin layer (I) of this embodiment (in the example of FIG. 6, the surface of the non-expandable thermosetting resin layer (X1) opposite to the support layer (II)) is curable. As described above, the adhesive strength is such that the first surface is affixed to a glass plate at a temperature of 70 ° C., and is curable at a temperature of 23 ° C., a peeling angle of 180 °, and a peeling speed of 300 mm / min. Since the value measured by peeling off the resin layer (I) is 1.7 N / 25 mm or more, the bonding of the semiconductor chip 60 as an object to be sealed to the surface of the curable resin layer (I) is performed. At this time, the semiconductor chip 60 is securely fixed, and displacement can be prevented. In particular, it is possible to reliably prevent misalignment (hereinafter referred to as tilt misalignment) that rotates around an axis in a direction perpendicular to the warp preventing laminate 1b, which is difficult to discriminate as compared to a simple misalignment in the plane direction. can do.

Here, in the stacked body of one embodiment of the present invention, a region larger than the chip size is covered with a sealing material, such as FOWLP and FOPLP, so that not only the circuit surface of the semiconductor chip but also the sealing material is used. It is preferable to apply to a package for forming a redistribution layer also in the surface region.
Therefore, the semiconductor chip is placed on a part of the surface of the curable resin layer (I), and the plurality of semiconductor chips are placed on the surface in a state where they are aligned at a predetermined interval. It is preferable that the plurality of semiconductor chips be mounted on the surface in a state where they are arranged in a matrix of a plurality of rows and a plurality of columns with a certain interval.
The interval between the semiconductor chips may be determined as appropriate according to the form of the target package.

<Process (ii)>
In the step (ii), the sealing object placed on the curable resin layer (I) and the first surface of the curable resin layer (I) at least around the sealing object are heated. Cover with a curable sealing material (hereinafter also referred to as “coating treatment”).
In the coating process, first, the sealing object and at least the peripheral part of the sealing object on the surface of the curable resin layer (I) are covered with a sealing material. Specifically, as shown in FIG. 6C, a laminated body 1b that is affixed on a support 50 and on which a semiconductor chip 60 that is an object to be sealed is placed on the curable resin layer (I) is provided. The molding die 70 is disposed so as to be positioned in the molding die 70. Then, the sealing material is injected through the injection hole 71 into the forming space 72 formed between the forming die 70, the laminate 1 b and the sealing object 60.
The sealing material fills the gaps between the plurality of semiconductor chips while covering the entire exposed surface of the semiconductor chip 60 that is the object to be sealed.
When the molding die 70 is removed after the injection of the sealing resin and the resin molding are completed, the surfaces of the semiconductor chip 60 and the curable resin layer (I) are all sealed with the sealing material 80 as shown in FIG. Covered.

In addition, when the sealing material 80 is injected into the molding space 72 using a resin molding method in which a resin material is injected into a mold, represented by the transfer molding method, the curable resin (I) The flow of the sealing material 80 is generated in the direction along the surface (see the arrow in FIG. 6C). In the manufacturing method of this aspect, the sealing object 60 is fixed by the curable resin layer (I), and the shear strength of the curable resin layer (I) with respect to the measurement adherend is as described above. A silicon chip (mirror surface) having a thickness of 350 μm and a size of 3 mm × 3 mm is used as the above-mentioned measurement adherend, and at a temperature of 70 ° C., the mirror surface of the measurement adherend is pressed against the curable resin layer (I) at 130 gf for 1 second. When the value is 20 N / (3 mm × 3 mm) or more when measured at a speed of 200 μm / s, it is easy to prevent the sealing object 60 from being displaced or inclined.

The sealing material has a function of protecting the object to be sealed and its accompanying elements from the external environment.
The sealing material 80 used in the manufacturing method of one embodiment of the present invention is a thermosetting sealing material containing a thermosetting resin.

The sealing material may be a solid such as a granule, a pellet, or a film at room temperature, or a liquid in the form of a composition. From the viewpoint of workability, a sealing resin film that is a film-like sealing material is preferable.

As a coating method, besides the transfer molding method, it can be appropriately selected and applied according to the type of the sealing material from methods applied in the conventional sealing process, for example, a roll laminating method. A vacuum pressing method, a vacuum laminating method, a spin coating method, a die coating method, a compression molding mold method, or the like can be applied.

<Process (iii)>
In the step (iii), the encapsulant after the coating treatment is thermally cured to form a cured encapsulant including an object to be encapsulated. Further, the curable resin layer (I) is also cured to form the cured resin layer (I ′).
Specifically, as illustrated in FIG. 6E, a cured sealing body 85 in which the semiconductor chip 60 that is an object to be sealed is covered with the cured sealing material 81 by curing the sealing material 80. Get. As a result, the semiconductor chip 60 is protected by the hard material while maintaining the layout. At this time, in the manufacturing method of this aspect, since the thermosetting resin layer (X1) is used as the curable resin layer (I), the curing start temperature of the thermosetting sealing material 80 starts to be cured. By setting the temperature to the same level as the temperature, or when the curing start temperatures of the two are different, by heating above the higher curing start temperature, the sealing material is cured and the thermosetting resin layer is heated once. (The production | generation of the hardened thermosetting resin layer (X1 ')) can be advanced simultaneously. Therefore, in these cases, the number of heating steps for curing can be reduced, and the manufacturing process can be simplified.

Moreover, in the manufacturing method of this aspect, by providing curable resin layer (I), the difference of the shrinkage stress between the two surfaces of the obtained cured sealing body 85 can be made small, and hardening is carried out. Warpage generated in the sealing body 85 can be effectively suppressed. In particular, by thermosetting the thermosetting resin layer (X1) simultaneously with the thermosetting of the encapsulant, the difference in shrinkage stress between the two surfaces of the cured encapsulant 85 is reduced even in the curing process. And warpage is more effectively suppressed.
As described above, the heating temperature for curing in step (iii) is lower than the heating temperature for expansion in step (iv).

<Process (iv)>
In the step (iv), the cured resin layer (I ′) and the support layer (II) are separated at the interface by performing a treatment for expanding the expandable particles contained in the expandable base material layer (Y1). Thus, a cured sealing body with a cured resin layer is obtained.
FIG. 6 (f) shows that the expandable base material layer (Y1) becomes an expandable base material layer (Y1 ′) by the treatment for expanding the expandable particles, and the cured resin layer (I ′) and the support layer expanded. The state which isolate | separated in the interface with (II ') is shown.
As shown in FIG. 6 (f), the cured resin layer-cure having the cured sealing body 85 and the cured resin layer (I ′) in which the sealing object 60 is sealed by being separated at the interface. The sealing body 200 can be obtained.
In addition, the presence of the cured resin layer (I ′) has a function capable of effectively suppressing the warpage generated in the cured sealed body, and contributes to the improvement of the reliability of the sealed object.

The “expanding process” in the step (iv) is a process of expanding the thermally expandable particles by heating at an expansion start temperature (t) or higher when thermally expandable particles are used as the expandable particles. As a result of the treatment, irregularities are generated on the surface of the support layer (II) on the cured resin layer (I ′) side. As a result, the separation can be easily performed at the interface P with a slight force.
In the case where thermally expandable particles are used as the expandable particles, the “temperature above the expansion start temperature (t)” for expanding the heat expandable particles is “expansion start temperature (t) + 10 ° C.” or more and “expansion start temperature” It is preferably (t) + 60 ° C. or less, more preferably “expansion start temperature (t) + 15 ° C.” or more and “expansion start temperature (t) + 40 ° C.” or less.
In addition, it does not specifically limit as a heating method for expanding a thermally expansible particle, For example, although the heating method by a hotplate, oven, a baking furnace, an infrared lamp, a hot air blower etc. is mentioned, support layer (II) and From the viewpoint of facilitating separation at the interface P with the cured resin layer (I ′), a method in which a heat source during heating can be provided on the support 50 side is preferable.

The cured encapsulant 200 with a cured resin layer thus obtained is further subjected to necessary processing. The cured resin layer as the warp correction layer is removed by grinding or the like while the semiconductor device is finally manufactured, and does not remain in the final semiconductor device.

[Second Method for Producing Cured Sealed Body]
The second aspect of the method for producing a cured encapsulant of the present invention is a method for producing a cured encapsulant using the laminate of one aspect of the present invention, which comprises the following steps (i ′) to (iv): Have
Step (i ′): A part of the surface opposite to the first layer of the energy ray curable resin layer (X2), which is the first surface of the curable resin layer of the laminate for warpage prevention, Place the object to be sealed.
Step (ii ′)-1: The energy beam curable resin layer (X2) is cured by irradiating energy beams.
Step (ii ′)-2: The object to be sealed and the first surface of the curable resin layer at least in the periphery of the object to be sealed are covered with a thermosetting sealing material.
Step (iii ′): The sealing material is thermally cured to form a cured sealing body including the sealing object, and the curable resin layer (I) is also thermally cured to cure the cured resin layer (I ′). To obtain a cured encapsulant.
Step (iv): The cured resin layer (I ′) and the support layer (II) are separated at the interface by a treatment for expanding the expandable particles to obtain a cured sealed body with a cured resin layer.

In the following, each step will be described in detail, but in order to avoid redundancy, the same steps and operations as those in the first aspect of the manufacturing method described above apply to those described in the first aspect of the manufacturing method as they are. Detailed explanation is omitted.

<Process (i ')>
In the step (i ′), the sealing object is placed on a part of the surface of the curable resin layer (I) included in the warpage preventing laminate of one embodiment of the present invention.
FIG. 7 (a) shows that the curable resin layer (I) has a thermosetting resin layer (X1-1) on the support layer (II) side and an energy ray curable property on the side opposite to the support layer (II). The state where the adhesive surface of the pressure-sensitive adhesive layer (V1) of the support layer (II) is stuck to the support 50 using the warp-preventing laminate 5 (see FIG. 5) consisting of the resin layer (X2) is shown in FIG. 7 (b) shows a state in which the sealing object 60 is placed on a part of the surface of the curable resin layer (I).

The surface of the curable resin layer (I) of the present embodiment (in the example of FIG. 7, the surface opposite to the support layer (II) of the energy ray curable resin layer (X2)) is curable. However, the adhesive strength is that the first surface is attached to a glass plate at a temperature of 70 ° C., and the curable resin layer (I) is peeled off at a temperature of 23 ° C., a peeling angle of 180 °, and a peeling speed of 300 mm / min. Since the measured value is 1.7 N / 25 mm or more, the sealing object 60 is securely fixed when the sealing object 60 is bonded to the surface of the curable resin layer (I). In addition, it is possible to prevent positional deviation including tilt deviation.

<Step (ii ')-1>
Step (ii ′)-1 irradiates the energy ray curable resin layer (X2) with energy rays to form a cured resin layer (I ^* ) formed by curing the energy ray curable resin layer (X2). It is a process to do.

FIG. 7C is partially cured by forming a cured energy beam curable resin layer (X2 ′) by curing the energy beam curable resin layer (X2) in this step ( That is, it shows a state in which a cured resin layer (I ^* ) in which the first surface side layer is cured) is formed.
The type of energy beam and the irradiation conditions are not particularly limited as long as the energy beam curable resin layer (X2) is cured to such an extent that it sufficiently exhibits its function. What is necessary is just to select suitably according to the process to perform.
When an ultraviolet curable resin composition is used as a material constituting the energy ray curable resin layer (X2), a wide range of materials can be selected, and it is easily available as an energy ray source for curing the composition. It is possible to use an ultraviolet irradiation device that is excellent in handleability.
The illuminance of the energy rays at the time of curing of the energy ray curable resin layer (X2) is preferably 4 to 280 mW / cm ² , and the light amount of the energy rays at the time of curing is 3 to 1,000 mJ / cm 2. ² is preferable.

Prior to the step (iii ′) including thermosetting, irradiation of energy rays in the step (ii ′)-1 prevents the energy ray curable resin from being cleaved by heating and causing a curing reaction to proceed. The curing reaction by the line can be efficiently advanced. Moreover, it can also prevent that the low molecular component (photopolymerization initiator etc.) contained in energy-beam curable resin volatilizes by heating, and contaminates a sealing target object. Further, by curing the energy ray curable resin layer with energy rays prior to thermosetting, the energy ray curable resin (X2) is prevented from being cured and contracted by heating for thermosetting, and the sealing resin. And the adhesiveness between the energy ray curable resin (X2) can be prevented from being lowered.

<Process (ii ')-2>
After the sealing object 60 is arranged and the energy beam curable resin layer (X2 ′) cured by irradiating the energy beam is formed, in step (ii ′)-2, FIG. In the same manner as described above, the sealing material 80 is injected using a molding die (not shown). At this time, although the flow of the sealing material is generated in the surface direction, the sealing object 60 is fixed by the cured energy ray curable resin layer (X2 ′) and is used for measuring the curable resin layer (I). The silicon chip having a thickness of 350 μm with a mirror surface of 3 mm × 3 mm is used as the measurement adherend, and the mirror surface of the measurement adherend is cured at 130 gf for 1 second at a temperature of 70 ° C. By pressing and pasting the resin layer (I) and measuring at a speed of 200 μm / s, the sealing object 60 may be displaced or inclined by setting it to 20 N / (3 mm × 3 mm) or more. It becomes easy to prevent.
When the injection of the sealing resin is completed, as shown in FIG. 7D, the surface of the cured object 60 and the surrounding energy ray curable resin layer (X2 ′) is covered with the sealing material 80 as shown in FIG. Is called.

<Process (iii ')>
In the step (iii ′), the encapsulant after the coating treatment is thermally cured to form a cured encapsulant including an object to be encapsulated. Further, the thermosetting resin layer (X1-1) is also cured to form a cured thermosetting resin layer (X1-1 ′), and both the first layer and the second layer are cured resin layers ( I ′).
By curing the sealing material 80, as shown in FIG. 7E, a cured sealing body 85 in which the sealing object 60 is covered with the cured sealing material 81 is obtained. At this time, in the present production example, since the thermosetting resin layer (X1-1) is used as the curable resin layer (I), the thermosetting sealing material 80 and the curing start temperature are set to the same level. If the curing start temperature is different, or by heating to a higher curing start temperature or higher, the sealing material and the thermosetting resin layer can be cured simultaneously by one heating. be able to.

<Process (iv)>
In the step (iv), the cured resin layer (I ′) and the support layer (II) are separated at the interface by performing a treatment for expanding the expandable particles contained in the expandable base material layer (Y1). Thus, a cured sealing body with a cured resin layer is obtained.
FIG. 7 (f) shows that the expandable base material layer (Y1) becomes the expandable base material layer (Y1 ′) by the treatment for expanding the expandable particles, and the cured resin layer (I ′) and the expanded support layer (II ′). It shows a state of separation at the interface with).
As shown in FIG.7 (f), it hardens | cures with a cured resin layer which has the cured sealing body 85 and cured resin layer (I ') by which the sealing target object 60 is sealed by making it isolate | separate at an interface. The sealing body 201 can be obtained.

After the cured sealing body 85 is produced by the above procedure, the necessary processing is performed on the cured sealing body 201 with the cured resin layer.

Next, although the specific Example of this invention is described, this invention is not limited at all by these examples.
In the following description, the curable resin layer (I) refers to both the “energy ray curable resin layer (X2)” and the “thermosetting resin layers (X1-1), (X1-2)”. Shall mean.
In addition, the physical-property value in the following manufacture examples and Examples is a value measured by the following method.

<Mass average molecular weight (Mw)>
Using a gel permeation chromatograph (product name “HLC-8020” manufactured by Tosoh Corporation), measurement was performed under the following conditions, and values measured in terms of standard polystyrene were used.
(Measurement condition)
Column: “TSK guard column HXL-L”, “TSK gel G2500HXL”, “TSK gel G2000HXL”, and “TSK gel G1000HXL” (both manufactured by Tosoh Corporation) Column temperature: 40 ° C.
・ Developing solvent: Tetrahydrofuran ・ Flow rate: 1.0 mL / min

<Measurement of thickness of each layer>
It was measured using a constant pressure thickness measuring instrument (model number: “PG-02J”, standard: conforming to JIS K6783, Z1702, Z1709) manufactured by Teclock Co., Ltd.

<Measurement of expansion start temperature (t) and maximum expansion temperature of thermally expandable particles>
The expansion start temperature (t) of the thermally expandable particles used in each example was measured by the following method.
To an aluminum cup having a diameter of 6.0 mm (inner diameter 5.65 mm) and a depth of 4.8 mm, 0.5 mg of thermally expandable particles to be measured is added, and an aluminum lid (diameter 5.6 mm, thickness 0. 1 mm) is prepared.
Using a dynamic viscoelasticity measuring device, the height of the sample is measured from the upper part of the aluminum lid while a force of 0.01 N is applied to the sample by a pressurizer. Then, in a state where a force of 0.01 N is applied by the pressurizer, heating is performed from 20 ° C. to 300 ° C. at a rate of temperature increase of 10 ° C./min, and the amount of displacement of the pressurizer in the vertical direction is measured. Let the displacement start temperature be the expansion start temperature (t).
Further, the maximum expansion temperature refers to a temperature at which the displacement amount becomes maximum.

<Measurement of adhesive strength of thermosetting resin layer>
On the surface of the thermosetting resin layer formed on the release film, an adhesive tape (manufactured by Lintec Corporation, product name “PL Shin”) was laminated.
Then, the release film was removed, and the surface of the exposed thermosetting resin layer was attached to the smooth surface of a glass plate (float plate glass 3 mm (JIS R3202 product) manufactured by Yuko Trading Co., Ltd.) as an adherend. The application temperature of the thermosetting resin layer (X1) was 70 ° C. And after leaving the said glass plate with which each layer was affixed for 24 hours in an environment of 23 degreeC and 50% RH (relative humidity), it peeled 180 degree | times based on JISZ0237: 2000 in the same environment. By the method, the adhesive strength at 23 ° C. was measured at a pulling speed of 300 mm / min.

The release materials used in the following production examples are as follows.
Heavy release film: manufactured by Lintec Corporation, product name “SP-PET382150”, polyethylene terephthalate (PET) film provided with a release agent layer formed from a silicone release agent on one side, thickness: 38 μm
Light release film: manufactured by Lintec Corporation, product name “SP-PET381031”, a PET film provided with a release agent layer formed from a silicone release agent on one side, thickness: 38 μm

<Measurement of adhesive strength of first surface of curable resin layer (I)>
The laminate obtained in each Example and Comparative Example described later was cut into 25 mm width × 250 mm length so that the MD direction was 250 mm, and a primary sample for measurement was produced.
Moreover, the glass plate (The float plate glass 3mm (JIS R3202 product) made from a Yuko trading company) was prepared as a to-be-adhered body.
A laminator device (VA-400 type, manufactured by Taisei Laminator Co., Ltd.) was applied so that the curable resin layer (I) of each primary sample from which the release film was removed was in direct contact with the smooth surface of this glass plate. A test piece was obtained. At this time, the roller temperature was set to 70 ° C., and the sticking speed was set to 0.2 m / min. In Example 3, the curable resin layer 2 located on the first surface side is in direct contact with the glass plate, and in Example 4, the curable resin layer 3 located on the first surface side is in direct contact with the glass plate. Affixed to. Moreover, about the comparative example 2, it stuck so that an adhesive layer might contact | connect a glass plate directly.
The test piece thus obtained was allowed to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity), and then, under the same environment, a tensile load measuring machine (A & A) based on JIS Z 0237: 2000. The laminate for measurement was peeled from the glass plate at a peeling angle of 180 °, a peeling speed of 300 mm / min, and a peeling temperature of 23 ° C., and the adhesive strength was measured.

<Measurement of shear force of curable resin layer (I)>
A silicon chip with a thickness of 350 μm having a mirror surface of 3 mm × 3 mm was used as an adherend for measurement. Then, on the first surface of the curable resin layer (I) of each laminate obtained in each Example and Comparative Example described later, the mirror surface of the adherend for measurement is applied at a temperature of 70 ° C. for 1 second at 130 gf. Pressed and pasted. Then, the shear force was measured at a speed of 200 μm / s using an all-purpose bond tester (manufactured by Nordson Advanced Technology, DAGE4000).

<Chip displacement evaluation 1>
The curable resin layer (I) used for each Example and Comparative Example to be described later was attached to a glass plate (float plate glass 3 mm (JIS R3202 product) manufactured by Yuko Trading Co., Ltd.) to prepare a bonded surface. At this time, the first thermosetting resin layer was applied to Example 3 and the thermosetting resin layer was applied to Example 4 so as to be in direct contact with the glass plate.
On the other hand, a bonding chip was prepared by dicing a Si wafer (6 inches, 350 μm thickness, mirror surface) into a size of 2 mm × 2 mm.
Next, the bonding chip was bonded to the bonding surface using a manual bonding apparatus (manufactured by Daisy Japan Co., Ltd., EDB-65) with the mirror surface facing the bonding surface. At this time, the bonding temperature was 70 ° C., the pressing force during bonding was 130 gf, and the bonding time was 1 s.
After bonding five chips, a glass plate workpiece having the chip adhered and fixed to the bonding surface was placed on a metal experimental table for 5 seconds to cool the workpiece including the chip.
For Examples 1 to 3, 5 and Comparative Examples 1 and 2 to be described later, immediately after cooling, the workpiece is inverted so that the chip surface for bonding is down, and what is the bonding surface of the glass plate? By hitting with a finger from the opposite surface, vibration was applied in the vertical direction, and it was investigated whether the chip was displaced from the surface to be bonded or whether the chip was detached from the surface to be bonded and dropped. For Example 4 to be described later, after cooling, after irradiating ultraviolet rays having an illuminance of 215 mW / cm ² and a light amount of 187 mJ / cm ² three times to cure the energy ray curable resin layer, the same procedure as described above was performed. The presence or absence of chip displacement or detachment was examined. For each of the examples and comparative examples, for the 10 workpieces, the above-described operation of giving vibrations and confirming the presence or absence of deviation or dropping is performed twice, and by determining the ratio of occurrence of deviation or dropping, Chip evaluation was set to 1.

<Evaluation of chip displacement 2>
The curable resin layer (I) used for each Example and Comparative Example to be described later was attached to a glass plate (float plate glass 3 mm (JIS R3202 product) manufactured by Yuko Trading Co., Ltd.) to prepare a bonded surface. At this time, the first thermosetting resin layer was applied to Example 3 and the thermosetting resin layer was applied to Example 4 so as to be in direct contact with the glass plate.
On the other hand, a bonding chip was prepared by dicing a Si wafer (6 inches, 350 μm thickness, mirror surface) into a size of 3 mm × 3 mm.
Next, the bonding chip was bonded using a manual bonding apparatus (manufactured by Daisy Japan Co., Ltd., EDB-65) so that the mirror surface was directed to the surface to be bonded. At this time, the bonding temperature was 70 ° C., the pressing force during bonding was 130 gf, and the bonding time was 1 s.
After the five chips were bonded, they were taken out, and the glass plate workpiece with the chips adhered and fixed to the bonding surface was left on a metal experimental table for 5 seconds to cool the workpiece including the chips.
In Examples 1 to 3, 5 and Comparative Examples 1 and 2 described later, an arbitrary chip was selected immediately after cooling, and the side surface was lightly pressed with tweezers to confirm whether the chip was displaced. For Example 4 to be described later, after cooling, after irradiating ultraviolet rays having an illuminance of 215 mW / cm ² and a light amount of 187 mJ / cm ² three times to cure the energy ray curable resin layer, the same procedure as described above was performed. It was confirmed whether the chip was displaced. For each of the examples and comparative examples, the above-described operation was performed twice on 10 workpieces, and the rate of occurrence of misalignment was determined to obtain a chip misalignment evaluation of 2.

<Evaluation of warpage>
The thermosetting resin layers of the warp-preventing laminates of Examples 1 to 5 and Comparative Example 2 were respectively attached to a 12-inch 100-μm-thick silicon wafer, opposite to the case where the thermosetting resin layer was attached. The epoxy resin composition was applied to a thickness of 30 μm on this surface. And the layer of the said epoxy resin composition and the thermosetting resin layer of each laminated body were heated and hardened. After completion of curing, a silicon wafer with a cured resin layer was placed on a horizontal table, and then visually observed, and the presence or absence of warpage was evaluated based on the following criteria.
A: The amount of warpage is 3 mm or less.
B: The amount of warpage is greater than 3 mm and less than 15 mm.
C: The amount of warpage is 15 mm or more.
As the epoxy resin composition, a mixture of “Epofix Resin” manufactured by Struers and a curing agent “Epofix Hardener” manufactured by the same company was used. In this evaluation, a silicon wafer with a large diameter is used as an adherend to simplify the experimental procedure, while an epoxy resin layer is provided on the back side of the adherend so that warpage is likely to occur. By doing so, the evaluation of warpage was made appropriate.

Production Example 1
(1) Preparation of curable resin composition Each component of the following types and blending amounts (both "effective ingredient ratio") are blended, further diluted with methyl ethyl ketone, and stirred uniformly to obtain a solid content concentration (effective Component concentration: A thermosetting resin composition solution of 61% by mass was prepared.
Acrylic polymer: blending amount = 21 parts by mass n-butyl acrylate 55 parts by mass, methyl acrylate 10 parts by mass, glycidyl methacrylate 20 parts by mass, and 2-hydroxyethyl acrylate 15 parts by mass Combined (mass average molecular weight: 800,000, glass transition temperature: −28 ° C.), corresponding to component (A1) above.
Epoxy compound (1): blending amount = 10 parts by mass Liquid bisphenol A type epoxy resin (manufactured by Nippon Shokubai Co., Ltd., product name “BPA328”, epoxy equivalent = 220 to 240 g / eq), corresponding to the above component (B1).
Epoxy compound (2): Blending amount = 2.0 parts by mass Solid bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name “Epicoat 1055”, epoxy equivalent = 800 to 900 g / eq), component (B1) above Equivalent.
Epoxy compound (3): Blending amount = 5.6 parts by mass Dicyclopentadiene type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product name “XD-1000L”, epoxy equivalent = 274 to 286 g / eq), component (B1) Equivalent to
Thermosetting agent: blending amount = 0.5 parts by mass Dicyandiamide (manufactured by ADEKA, product name “Adeka Hardener EH-3636AS”, active hydrogen amount = 21 g / eq), corresponding to the above component (B2).
Curing accelerator: blending amount = 0.5 part by mass 2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., product name “Curazole 2PHZ”), corresponding to the above component (B3).
Silane coupling agent: Blending amount = 0.4 parts by mass Epoxy group-containing oligomer type silane coupling agent (manufactured by Mitsubishi Chemical Corporation, product name “MSEP2”), which corresponds to the component (D).
Inorganic filler (1): blending amount = 6 parts by mass Spherical silica filler (manufactured by Admatechs, product name “SC2050MA”, average particle size = 0.5 μm), corresponding to the above component (E).
Inorganic filler (2): blending amount = 54 parts by mass Spherical silica filler (manufactured by Tatsumori, product name “SV-10”, average particle size = 8 μm), corresponding to the above component (E).

(2) Formation of thermosetting resin layer On the release-treated surface of the light release film, the solution of the thermosetting resin composition prepared in Production Example 1 (1) was applied to form a coating film, and the coating The film was dried at 120 ° C. for 2 minutes to form a thermosetting resin layer having a thickness of 25 μm. This is designated as a curable resin layer 1.
The adhesive force of the formed thermosetting resin layer 1 was 0.5 N / 25 mm.
The thermosetting resin layer 1 can be cured within 2 hours by heating to 130 ° C. or higher, which is the curing start temperature.

Production Example 2
(1) Preparation of curable resin composition Each component of the following types and blending amounts (both "effective ingredient ratio") are blended, further diluted with methyl ethyl ketone, and stirred uniformly to obtain a solid content concentration (effective Component concentration: A thermosetting resin composition solution of 61% by mass was prepared.
Acrylic polymer: blending amount = 27 parts by mass n-butyl acrylate 10 parts by mass, methyl acrylate 70 parts by mass, glycidyl methacrylate 5 parts by mass, and 2-hydroxyethyl acrylate 15 parts by mass acrylic copolymer Combined (mass average molecular weight: 800,000, glass transition temperature: −28 ° C.), corresponding to component (A1) above.
Epoxy compound (1): blending amount = 10 parts by mass Liquid bisphenol A type epoxy resin (manufactured by Nippon Shokubai Co., Ltd., product name “BPA328”, epoxy equivalent = 220 to 240 g / eq), corresponding to the above component (B1).
Epoxy compound (2): Blending amount = 2.0 parts by mass Solid bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name “Epicoat 1055”, epoxy equivalent = 800 to 900 g / eq), component (B1) above Equivalent.
Epoxy compound (3): Blending amount = 5.0 parts by mass Dicyclopentadiene type epoxy resin (manufactured by DIC, product name “HP-7200HH”, epoxy equivalent = 275 to 280 g / eq), the above component (B1) Equivalent.
Thermosetting agent: blending amount = 0.4 parts by mass Dicyandiamide (manufactured by ADEKA, product name “Adeka Hardener EH-3636AS”, active hydrogen amount = 21 g / eq), corresponding to the above component (B2).
Curing accelerator: blending amount = 0.4 parts by mass 2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., product name “Curesol 2PHZ”), corresponding to the above component (B3).
Silane coupling agent (1): blending amount = 0.10 part by mass 3-glycidoxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM403”), molecular weight = 236.64, the above components ( Equivalent to D).
Silane coupling agent (2): blending amount = 0.15 parts by mass γ-glycidoxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBE403”), molecular weight = 278.4, the above components ( Equivalent to D).
Inorganic filler (1): blending amount = 5.8 parts by mass Spherical silica filler (manufactured by Admatechs, product name “SC2050MA”, average particle size = 0.5 μm), corresponding to the above component (E).
Inorganic filler (2): blending amount = 50 parts by mass Spherical silica filler (manufactured by Tatsumori, product name “SV-10”, average particle size = 8 μm), corresponding to the above component (E).

(2) Formation of thermosetting resin layer On the release-treated surface of the light release film, the solution of the thermosetting resin composition prepared in Production Example 2 (1) was applied to form a coating film, and the coating The film was dried at 120 ° C. for 2 minutes to form a thermosetting resin layer having a thickness of 25 μm. This is designated as a curable resin layer 2.
The thermosetting resin layer 2 can be cured within 2 hours by heating to 130 ° C. or higher, which is the curing start temperature.

Production Example 3
(1) Preparation of curable resin composition Each component of the following types and blending amounts (both "effective ingredient ratio") are blended, further diluted with methyl ethyl ketone, and stirred uniformly to obtain a solid content concentration (effective Component concentration: A solution of 61% by mass of an ultraviolet curable resin composition was prepared.
Acrylic polymer: blending amount = 17 parts by mass n-butyl acrylate 55 parts by mass, methyl acrylate 10 parts by mass, glycidyl methacrylate 20 parts by mass, and 2-hydroxyethyl acrylate 15 parts by mass Combined (mass average molecular weight: 800,000, glass transition temperature: −28 ° C.), corresponding to component (A1) above.
Epoxy compound (1): blending amount = 16 parts by mass Liquid bisphenol A type epoxy resin (manufactured by Nippon Shokubai Co., Ltd., product name “BPA328”, epoxy equivalent = 220 to 240 g / eq), corresponding to the above component (B1).
Epoxy compound (2): Compounding amount = 18 parts by mass Dicyclopentadiene type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product name “XD-1000L”, epoxy equivalent = 274 to 286 g / eq), the above component (B1) Equivalent.
Epoxy compound (3): Blending amount = 27 parts by mass Dicyclopentadiene type epoxy resin (manufactured by DIC, product name “HP-7200HH”, epoxy equivalent = 275 to 280 g / eq), corresponding to the above component (B11).
Thermosetting agent: blending amount = 1.5 parts by mass Dicyandiamide (manufactured by ADEKA, product name “Adeka Hardener EH-3636AS”, active hydrogen amount = 21 g / eq), corresponding to the above component (B2).
Curing accelerator: Blending amount = 1.5 parts by mass 2-Phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., product name “Curesol 2PHZ”), corresponding to the above component (B3).
-UV curable resin: blending amount = 17.6 parts by mass polyfunctional UV curable resin (product name "KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd.)
Photopolymerization initiator: blending amount = 0.5 part by mass Photopolymerization initiator (BASF, product name “IRGACURE-184”)
・ Crosslinking agent: Blending amount = 0.5 part by mass TDI-based crosslinking agent (manufactured by Toyochem, product name “BHS-8515”)

(2) Formation of ultraviolet ray curable resin layer On the release-treated surface of the light release film, a solution of the ultraviolet ray curable resin composition prepared in Production Example 3 (1) was applied to form a coating film, The coating film was dried at 120 ° C. for 2 minutes to form an ultraviolet ray curable resin layer having a thickness of 25 μm. This is designated as a curable resin layer 3.
The curable resin layer 3 can be cured by irradiating ultraviolet rays having an illuminance of 215 mW / cm ² and a light amount of 187 mJ / cm ² three times.

Production Example 4
(1) Preparation of curable resin composition Each component of the following types and blending amounts (both "effective ingredient ratio") are blended, further diluted with methyl ethyl ketone, and stirred uniformly to obtain a solid content concentration (effective Component concentration: A thermosetting resin composition solution of 61% by mass was prepared.
Acrylic polymer: blending amount = 18 parts by mass n-butyl acrylate 1 part by mass, methyl acrylate 74 parts by mass, glycidyl methacrylate 15 parts by mass, and 2-hydroxyethyl acrylate 10 parts by mass Combined (mass average molecular weight: 440,000, glass transition temperature: 8 ° C.), corresponding to the component (A1).
Epoxy compound (1): blending amount = 3 parts by mass Liquid bisphenol A type epoxy resin (manufactured by Nippon Shokubai Co., Ltd., product name “BPA328”, epoxy equivalent = 220 to 240 g / eq), corresponding to the above component (B1).
Epoxy compound (2): blending amount = 20 parts by mass Solid bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name “Epicoat 1055”, epoxy equivalent = 800 to 900 g / eq), corresponding to the above component (B1).
Epoxy compound (3): Blending amount = 1.5 parts by mass Dicyclopentadiene type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product name “XD-1000L”, epoxy equivalent = 274 to 286 g / eq), component (B1) Equivalent to
Thermosetting agent: blending amount = 0.5 parts by mass Dicyandiamide (manufactured by ADEKA, product name “Adeka Hardener EH-3636AS”, active hydrogen amount = 21 g / eq), corresponding to the above component (B2).
Curing accelerator: blending amount = 0.5 part by mass 2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., product name “Curazole 2PHZ”), corresponding to the above component (B3).
Silane coupling agent: blending amount = 0.5 part by mass Epoxy group-containing oligomer type silane coupling agent (product name “MSEP2” manufactured by Mitsubishi Chemical Corporation), which corresponds to the component (D).
Inorganic filler (1): blending amount = 6 parts by mass Spherical silica filler (manufactured by Admatechs, product name “SC2050MA”, average particle size = 0.5 μm), corresponding to the above component (E).
Inorganic filler (2): blending amount = 50 parts by mass Spherical silica filler (manufactured by Tatsumori, product name “SV-10”, average particle size = 8 μm), corresponding to the above component (E).

(2) Formation of thermosetting resin layer On the release-treated surface of the light release film, a solution of the thermosetting resin composition prepared in Production Example 4 (1) was applied to form a coating film, and the coating The film was dried at 120 ° C. for 2 minutes to form a thermosetting resin layer having a thickness of 25 μm. This is designated as a curable resin layer 4.
The thermosetting resin layer 4 can be cured within 2 hours by heating to 130 ° C. or higher, which is the curing start temperature.

Production Example 5
(1) Production of Support Layer Supporting a heat-peeling laminate (product name “NITTO 3195” manufactured by Nitto Denko Corporation) having a structure in which a heat-peeling adhesive layer is provided on a polyester film substrate. Used as a layer. This is designated as support layer 1. In addition, when producing the laminated body for curvature prevention mentioned later, the release liner provided in the surface of the heat-peeling adhesive layer was peeled off and used. The support layer 1 has a pressure-sensitive adhesive layer containing a base material and thermally expandable particles, and the heat-expandable particles expand by being heated to an expansion start temperature of 170 ° C. or more, whereby the surface of the pressure-sensitive adhesive layer This produces a fine uneven shape.

Production Example 6
(1) Synthesis of urethane prepolymer In a reaction vessel under a nitrogen atmosphere, isophorone diisocyanate is mixed with hydroxyl group of carbonate-type diol and isophorone with respect to 100 parts by mass (solid content ratio) of carbonate-type diol having a mass average molecular weight of 1,000. It mix | blends so that the equivalent ratio with the isocyanate group of diisocyanate may be set to 1/1, Furthermore, 160 mass parts of toluene is added, and it is 80 degreeC until an isocyanate group density | concentration reaches | attains theoretical amount, stirring under nitrogen atmosphere. For 6 hours or more.
Next, a solution obtained by diluting 1.44 parts by mass (solid content ratio) of 2-hydroxyethyl methacrylate (2-HEMA) in 30 parts by mass of toluene was added, and further at 80 ° C. until the isocyanate groups at both ends disappeared. The reaction was performed for 6 hours to obtain a urethane prepolymer having a mass average molecular weight of 29,000.

(2) Synthesis of acrylic urethane-based resin In a reaction vessel under a nitrogen atmosphere, 100 parts by mass of urethane prepolymer obtained in Production Example 1 (solid content ratio), 117 parts by mass of methyl methacrylate (MMA) (solid content ratio), 2-hydroxyethyl methacrylate (2-HEMA) 5.1 parts by mass (solid content ratio), 1-thioglycerol 1.1 parts by mass (solid content ratio) and toluene 50 parts by mass were added and stirred at 105 ° C. The temperature was raised to.
Further, a solution obtained by further diluting 2.2 parts by mass (solid content ratio) of radical initiator (manufactured by Nippon Finechem Co., Ltd., product name “ABN-E”) with 210 parts by mass of toluene in a reaction vessel was heated to 105 ° C. It was dripped over 4 hours, maintaining.
After completion of the dropping, the reaction was carried out at 105 ° C. for 6 hours to obtain a solution of an acrylic urethane resin having a mass average molecular weight of 105,000.

(3) Preparation of pressure-sensitive adhesive composition (1) To 100 parts by mass of the following acrylic copolymer (i), which is an adhesive resin, 5.0 parts by mass of the following isocyanate-based crosslinking agent (i) (solid The pressure-sensitive adhesive composition (1) having a solid content concentration (active ingredient concentration) of 25% by mass was prepared by mixing with water, diluting with toluene, and stirring uniformly.
Acrylic copolymer (i): having a structural unit derived from a raw material monomer consisting of 2-ethylhexyl acrylate (2EHA) / 2-hydroxyethyl acrylate (HEA) = 80.0 / 20.0 (mass ratio), An acrylic copolymer having a mass average molecular weight of 600,000.
Isocyanate crosslinking agent (i): manufactured by Tosoh Corporation, product name “Coronate L”, solid content concentration: 75 mass%.

(4) Preparation of pressure-sensitive adhesive composition (2) The following isocyanate-based crosslinking agent (i) 5.0 parts by mass (solid) The pressure-sensitive adhesive composition (2) having a solid content concentration (active ingredient concentration) of 25% by mass was prepared by mixing with water, diluting with toluene, and stirring uniformly.
Acrylic copolymer (i): having a structural unit derived from a raw material monomer consisting of 2-ethylhexyl acrylate (2EHA) / 2-hydroxyethyl acrylate (HEA) = 80.0 / 20.0 (mass ratio), An acrylic copolymer having a mass average molecular weight of 600,000.
Isocyanate crosslinking agent (i): manufactured by Tosoh Corporation, product name “Coronate L”, solid content concentration: 75 mass%.

(5) Formation of pressure-sensitive adhesive layer (1) The pressure-sensitive adhesive composition (1) is applied to the surface of the release layer of the light release film to form a coating film, and the coating film is formed at 100 ° C for 60 seconds. It dried and formed the adhesive layer (1) of thickness 5 micrometers.
(6) Formation of pressure-sensitive adhesive layer (2) The pressure-sensitive adhesive composition (2) is applied to the surface of the release layer of the heavy release film to form a coating film, and the coating film is formed at 100 ° C for 60 seconds. It dried and formed the 10-micrometer-thick adhesive layer (2).

(7) Preparation of support layer The above-mentioned pressure-sensitive adhesive layer (2) was pasted on one side of a 50 μm-thick polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., product name “Cosmo Shine A4100”) as a base material. .
On the other side of the PET film, 100 parts by mass of a polyester-based pressure-sensitive adhesive (glass transition temperature: −50 ° C., mass average molecular weight: 21,000, OH value: 4 mg KOH / g) and 4 parts by mass of an HDI nurate cross-linking agent The composition to which was added was applied and dried at 100 ° C. for 1 minute to form an anchor layer having a thickness of 40 μm.
To 100 parts by mass of the solid content of the acrylic urethane resin obtained in Production Example 5 (2), 6.3 is added an isocyanate-based crosslinking agent (product name “Coronate L”, solid content concentration: 75% by mass, manufactured by Tosoh Corporation). Parts by mass (solid content ratio), dioctyltin bis (2-ethylhexanoate) 1.4 parts by mass (solid content ratio) as a catalyst, and the thermally expandable particles (product name “S2640” manufactured by Kureha Corporation) , Expansion start temperature (t) = 208 ° C., average particle size (D ₅₀ ) = 24 μm, 90% particle size (D ₉₀ ) = 49 μm), diluted with toluene, stirred uniformly, and solid content concentration (Active ingredient concentration) A resin composition of 30% by mass was prepared. The content of thermally expandable particles was 20% by mass relative to the total amount (100% by mass) of the active ingredients in the obtained resin composition.
The resin composition containing the thermally expandable particles is applied onto the anchor layer to form a coating film, and the coating film is dried by heating at 100 ° C. for 2 minutes to a thickness of 35 μm. Formed.
The pressure-sensitive adhesive layer (1) was pasted on the thermally expandable layer. Thus, a support layer having a release film laminated on the front and back was prepared. This is designated as support layer 2.
The support layer 2 has a base material including a pressure-sensitive adhesive layer and thermally expandable particles. When heated to 208 ° C. or higher, the thermally expandable particles expand, and the surface of the support layer has a fine uneven shape. Cause it to occur.

Example 1
The peeling film laminated | stacked on the adhesive layer of the support layer 1 of the manufacture example 5 is removed, and the adhesion surface of the exposed adhesive layer and the surface of the curable resin layer 1 formed in the manufacture example 1 are stuck. The substrate / pressure-sensitive adhesive layer / thermosetting resin layer / release film was laminated in this order to obtain a laminate for preventing warpage with a release film.

(Example 2)
The peeling film laminated | stacked on the adhesive layer of the support layer 1 of the manufacture example 5 is removed, and the adhesive surface of the exposed adhesive layer and the surface of the curable resin layer 2 formed in the manufacture example 2 are stuck. The substrate / pressure-sensitive adhesive layer / thermosetting resin layer / release film was laminated in this order to obtain a laminate for preventing warpage with a release film.

Example 3
The peeling film laminated | stacked on the adhesive layer of the support layer 1 of the manufacture example 5 is removed, and the adhesion surface of the exposed adhesive layer and the surface of the curable resin layer 1 formed in the manufacture example 1 are stuck. Combined (first thermosetting resin layer). The release film laminated on the curable resin layer 1 of this laminate was removed, and the exposed curable resin layer 1 and the surface of the curable resin layer 2 formed in Production Example 2 were bonded together. (Second thermosetting resin layer). Thus, a laminate for warpage prevention with a release film was obtained in which the base material / adhesive layer / first thermosetting resin layer / second thermosetting resin layer / release film were laminated in this order.

Example 4
The peeling film laminated | stacked on the adhesive layer of the support layer 1 of the manufacture example 5 is removed, and the adhesion surface of the exposed adhesive layer and the surface of the curable resin layer 1 formed in the manufacture example 1 are stuck. Combined. The release film laminated on the curable resin layer 1 of this laminate was removed, and the exposed curable resin layer 1 was bonded to the surface of the curable resin layer 3 formed in Production Example 3. . Thus, a laminate for warpage prevention with a release film was obtained in which the base material / adhesive layer / thermosetting resin layer / ultraviolet curable resin layer / release film were laminated in this order.

(Example 5)
The peeling film laminated | stacked on the 2nd adhesive layer of the support layer 2 obtained by manufacture example 6 was removed, the adhesive surface of the 2nd adhesive layer exposed, and the curable resin formed in manufacture example 1 The surface of layer 1 was laminated, and a heavy release film / first pressure-sensitive adhesive layer / base material / anchor layer / thermal expansion layer / second pressure-sensitive adhesive layer / thermosetting resin layer / release film were laminated in this order. A laminate for preventing warpage with a release film was obtained.

(Comparative Example 1)
The peeling film laminated | stacked on the adhesive layer of the support layer 1 of manufacture example 5 is removed, and the adhesion surface of the exposed adhesive layer and the surface of the thermosetting resin layer formed in manufacture example 4 are stuck. The substrate / pressure-sensitive adhesive layer / curable resin layer / release film was laminated in this order to obtain a laminate for preventing warpage with a release film.

(Comparative Example 2)
The support layer 1 of Production Example 5 was used as it was.

The warp prevention laminates obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were measured and evaluated according to the measurement method and evaluation procedure described above. The results are shown in Table 1.

As is apparent from the results in Table 1, warpage prevention as a laminate for warpage prevention, in which the adhesive force of the first surface of the curable resin layer on the side opposite to the support layer is 1.7 N / 25 mm or more. In Examples 1 to 5 using the laminates for manufacturing, it was confirmed that the chip shift 1 was evaluated well, there was no chip shift, and the occurrence of warpage could be suppressed. In Example 4, when the adhesive strength was measured, the backing layer was destroyed due to the strong adhesive strength of the first surface of the curable resin layer (I). Although it was confirmed that the distance was 25 mm or more, an accurate numerical value could not be measured.
On the other hand, chip displacement occurred in Comparative Example 1 using the warp preventing laminate having an adhesive strength of less than 1.7 N / 25 mm. For this reason, since Comparative Example 1 has a problem in chip retainability, it was determined that the assembly for warpage prevention was rejected before the determination of the presence or absence of warpage, and the warpage was not evaluated. In Comparative Example 2, which did not have a curable resin layer but had a pressure-sensitive adhesive laminate having an adhesive strength of 1.7 N / 25 mm or more, the evaluation of chip displacement 1 was above the standard. A large warp 5 times more than 1 to 5 occurred.

Further, as is apparent from the results in Table 1, a warp-preventing laminate in which the shear force of the first surface of the curable resin layer on the side opposite to the support layer is 20 N / (3 mm × 3 mm) or more. In Examples 1 to 5 using the warp-preventing laminate, the evaluation of the chip deviation 2 was good, and it was confirmed that there was no chip deviation and the occurrence of warpage could be suppressed. On the other hand, chip displacement occurred in Comparative Example 1 using the laminate for warpage prevention having a shearing force of less than 20 N / (3 mm × 3 mm). In Comparative Example 2 using an adhesive laminate having a shearing force of 20 N / (3 mm × 3 mm) or more, which does not have a curable resin layer, the evaluation of chip displacement 2 was above the standard. As described above, a large warp occurred.

(I): Curable resin layer (I ′): Curable resin layer (I ^* ): Partially cured curable resin layer (II): Support layer (II ′): Expanded support layer (V): Adhesive Layer (V1): (First) pressure-sensitive adhesive layer (V1-1): First pressure-sensitive adhesive layer (V2), (V1-2): Second pressure-sensitive adhesive layer (X1), (X1-1), (X1) -2): thermosetting resin layer (X1 '): cured thermosetting resin layer (X1-1'): cured thermosetting resin layer (X2): energy beam curable resin layer (X2 '): Cured energy ray curable resin layer (Y): substrate (Y1): expandable substrate layer (Y1 ′): expanded expandable substrate layer (Y2):

non-expandable substrate layers

1a, 1b,

2a

2b, 3, 4, 5: Laminated body 50 for preventing warpage: Support body 60: Object to be sealed (semiconductor chip)
70: Mold 71: Injection hole 72: Molding space 80: Sealant 81: Cured sealant 85: Cured sealant 200: Cured sealant with cured resin layer P: Interface

Claims

A curable resin layer (I) including a thermosetting resin layer (X1);
A support layer (II) that supports the curable resin layer (I),
The thermosetting resin layer (X1) is directly laminated on the support layer (II),
The adhesive force of the first surface, which is the surface of the curable resin layer (I) opposite to the support layer (II), affixed the first surface to a glass plate at a temperature of 70 ° C., a temperature of 23 ° C., It is a value when measured by peeling the curable resin layer (I) at a peeling angle of 180 ° and a peeling speed of 300 mm / min, and is 1.7 N / 25 mm or more,
A laminate for preventing warpage of a cured sealing body produced by sealing a sealing object with a sealing material on the first surface of the curable resin layer (I).
The laminate for warpage prevention according to claim 1, wherein the curable resin layer (I) is a single thermosetting resin layer (X1).
The curable resin layer (I) includes a first layer located on the support layer (II) side, and a second layer located on the first surface side,
The first layer is a first thermosetting resin layer (X1-1),
The said 2nd layer is a 2nd thermosetting resin layer (X1-2) whose surface adhesive force is higher than the 1st thermosetting resin layer (X1-1). Laminated body for warpage prevention.
The curable resin layer (I) includes a first layer located on the support layer (II) side, and a second layer located on the first surface side,
The first layer is a thermosetting resin layer (X1-1),
The laminate for warpage prevention according to claim 1, wherein the second layer is an energy ray-curable resin layer (X2).
The laminate for warpage prevention according to any one of claims 1 to 4, wherein the thickness of the curable resin layer (I) is 1 to 500 µm.
The support layer (II) has a base material (Y) and a pressure-sensitive adhesive layer (V), and at least one of the base material (Y) and the pressure-sensitive adhesive layer (V) includes expandable particles,
The process according to any one of claims 1 to 5, wherein the expandable particles are separated at the interface between the support layer (II) and the cured resin layer (I ') obtained by curing the curable resin layer (I). The laminate for warpage prevention according to item 1.
The substrate for warpage prevention according to claim 6, wherein the substrate (Y) has an expandable substrate layer (Y1) containing the expandable particles.
The laminate for warpage prevention according to claim 7, wherein the pressure-sensitive adhesive layer (V) is a non-expandable pressure-sensitive adhesive layer (V1).
The substrate (Y) has a non-expandable substrate layer (Y2) and an expandable substrate layer (Y1),
The support layer (II) has a non-expandable base layer (Y2), an expandable base layer (Y1), and an adhesive layer (V) in this order,
The laminate for warpage prevention according to claim 7 or 8, wherein the pressure-sensitive adhesive layer (V) and the thermosetting resin layer (X1) are directly laminated.
A method for producing a cured sealing body using the warp-preventing laminate according to any one of claims 1 to 9,
Place a sealing object on a part of the first surface of the curable resin layer (I) of the laminate for warpage prevention,
Covering the sealing object and the first surface of the curable resin layer (I) at least in the peripheral part of the sealing object with a thermosetting sealing material,
The sealing material is thermally cured to form a cured sealing body including the sealing object, and the curable resin layer (I) is also thermally cured to form a cured resin layer (I ′), The manufacturing method of the hardening sealing body which obtains the hardening sealing body with a cured resin layer.
A method for producing a cured encapsulant using the warp-preventing laminate according to claim 4,
The energy ray curable resin layer (X2), which is the first surface of the curable resin layer (I) of the laminate for warpage prevention, is sealed on a part of the surface opposite to the first layer. Place the stop object,
Irradiate energy rays to cure the energy ray curable resin layer (X2),
Covering the sealing object and the surface of the curable resin layer (I) at least in the peripheral part of the sealing object with a thermosetting sealing material,
The sealing material is thermally cured to form a cured sealing body including the sealing object, and the curable resin layer (I) is also thermally cured to form a cured resin layer (I ′), The manufacturing method of the hardening sealing body which obtains the hardening sealing body with a cured resin layer.