TW202014302A - Laminate and manufacturing method of cured sealing body that includes a resin layer and a supporting layer of which one includes thermally expandable particles that are expandable to separate the resin layer and the supporting layer from each other - Google Patents

Abstract

The present invention relates to a laminate, which comprises: an energy ray curable resin layer (I) and a supporting layer (II) that supports the energy ray curable resin layer (I), wherein the energy ray curable resin layer (I) has a surface having adhesiveness, and the supporting layer (II)_has a substrate (Y) and an adhesive layer. At least one of the substrate (Y) and the adhesive layer comprises thermally expandable particles. A cured resin layer (I') that is formed through curing of the energy ray curable resin layer and the supporting layer (II) are separated from each other at an interface therebetween by subjecting to a process for expanding the thermally expandable particles.

Description

Manufacturing method of laminated body and hardened sealing body

The invention relates to a method for manufacturing a laminated body and a hardened sealing body.

In recent years, with the miniaturization, weight reduction, and high performance of electronic devices, semiconductor chips have been practically packaged in a manner approaching their size. These packages are also called CSP (Die Scale Package; Chip Scale Package). Examples of CSPs include WLP (Wafer Level Package) completed at the wafer size and the last step of packaging, and PLP (Panel) completed at the final step of the package at a larger panel size than the wafer size. Level Package) etc.

WLP and PLP can be divided into fan-in (Fan-In) type and fan-out (Fan-Out) type. In the fan-out WLP (hereinafter, also referred to as "FOWLP") and PLP (hereinafter, also referred to as "FOPLP") processes, the semiconductor wafer is encapsulated with a larger area than the wafer size The coating forms a hardened sealing body of the semiconductor wafer, and the wire redistribution layer (RDL) and external electrodes are formed not only on the circuit surface of the semiconductor wafer but also on the surface area of the sealing material.

FOWLP and FOPLP, for example, can be obtained by placing a plurality of semiconductor wafers on a temporary fixing sheet, a coating step covered with a thermosetting sealing material, and thermally curing the sealing material to produce a hardened seal The hardening step, the separation step of separating the hardened sealing body from the temporary fixing sheet, and the method of forming a wire redistribution layer (RDL) on the surface of the exposed semiconductor wafer side to form a wire redistribution layer (RDL) Manufactured (hereinafter, the processing of coating step and hardening step is also called "sealing process").

Patent Document 1 discloses a heat-peelable adhesive sheet for provisional fixing for cutting electronic components provided with a thermally expandable adhesive layer containing thermally expandable microspheres on at least one side of a substrate. In the production of FOWLP and FOPLP, it is presumed that the heat-peelable adhesive sheet described in Patent Document 1 can also be used. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Patent No. 3594853

[Problems to be solved by the invention]

However, when manufacturing a cured sealing body using the adhesive sheet as a temporary fixing sheet described in Patent Document 1, the cured sealing body tends to warp when subjected to heat shrinkage. At this point, it is presumed that since the semiconductor wafer sealed in the hardened sealing body exists near the surface side adjacent to the temporary fixing sheet, the hardened sealing body has a small thermal expansion coefficient but exists in the semiconductor wafer The region on the side with a relatively higher ratio is the region on the side with a larger coefficient of thermal expansion and a relatively higher ratio of the presence of hardened resin, which is caused by the difference in the thermal shrinkage rates of the two regions. This problem tends to be more pronounced when the package size of FOWLP and FOPLP is larger. Warpage of the hardened seal body, for example, when the hardened seal body is ground in the next step, it will easily break, and when the hardened seal body is transported using the device, when the arm is used to receive the transfer hardened seal body, it will be easy to get out of order problem.

As a method for suppressing the deformation of the hardened sealing body, for example, a method of using a laminate including a temporary fixing layer provided with a thermally expandable adhesive layer containing thermally expandable particles and a thermosetting resin layer has been studied. That is, the placing step and the coating step of placing the semiconductor wafer on the thermosetting resin layer included in the laminate are performed, and thereafter, the thermosetting resin layer and the sealing material are thermally cured to produce a cured resin layer After the sealing body is cured, the thermally expandable particles are expanded to separate the cured sealing body with the cured resin layer from the temporary fixing layer. According to this method, since the hardened resin layer functions as a deformation-resistant layer of the hardened sealing body, a hardened sealing body that can suppress the occurrence of deformation can be produced.

On the other hand, according to the above method, since the treatment of expanding the thermally expandable particles and the treatment of curing the thermosetting resin layer are both heat treatments, the heat treatment of curing the thermosetting resin layer In the case, the thermally expandable particles in the temporary fixing layer may foam. According to the research results of the present inventors and others, it is known that if the thermally expandable particles in the temporary fixing layer are foamed before the thermosetting resin layer is fully cured, the separation property of the temporary fixing layer will be reduced in the subsequent separation step There is a deterioration. Therefore, it is highly expected that a cured resin layer suitable for supplying a cured resin layer with a deformation-resistant layer to a cured seal body can be easily separated from the temporary fixing layer to form a cured seal after forming the cured resin body with the cured resin layer Laminated body.

In view of the above problems, the present invention proposes a support layer and a curable resin layer, which can fix a sealing object on the surface of the curable resin layer and perform a sealing process, and can also provide the sealing process The hardened resin layer of the warpage-resistant layer of the formed hardened sealing body, and a laminate in which the hardened resin layer and the support layer can be easily separated, and a method of manufacturing the hardened sealing body using the laminated body. [Method for solving the problem]

The present inventors have made intensive studies on solving the above-mentioned problems and found that the above-mentioned problems can be solved by the following invention, and thus the present invention has been completed. That is, the present invention relates to the following [1] to [11]. [1] A laminate characterized by having an energy ray-curable resin layer (I), and a support layer (II) supporting the energy ray-curable resin layer (I); an energy ray-curable resin layer (I), To have an adhesive surface, the support layer (II) has a substrate (Y) and an adhesive layer (X), at least one of the substrate (Y) and the adhesive layer (X) contains thermally expandable particles The cured resin layer (I') and the support layer (II) formed by curing the energy ray-curable resin layer (I) are separated at the interface by the treatment of expanding the thermally expandable particles. [2] The laminate as described in [1] above, wherein the cured resin layer (I′) formed by curing the energy ray-curable resin layer (I) has a storage elastic modulus E′ at 23° C. of 1.0×10 ⁷ ~1.0×10 ¹³ Pa. [3] The laminate according to [1] or [2] above, wherein the thickness of the energy ray-curable resin layer (I) is 1 to 500 μm. [4] The laminate according to any one of [1] to [3] above, wherein the visible light transmittance of the energy ray-curable resin layer (I) is 5% or more. [5] The laminate according to any one of the above [1] to [4], wherein the base material (Y) is an expandable base material layer (Y1) containing the thermally expandable particles. [6] The laminate as described in [5] above, wherein the adhesive layer (X) is a non-expandable adhesive layer. [7] The laminate as described in [5] or [6] above, wherein the adhesive layer (X) and the energy ray-curable resin layer (I) are directly laminated. [8] The laminate according to any one of [5] to [7] above, wherein the base material (Y) has a non-expandable base material layer (Y2) and an expandable base material layer (Y1) and is supported The layer (II) has a non-expandable substrate layer (Y2), an expansible substrate layer (Y1), and an adhesive layer (X) in sequence, the adhesive layer (X) and the energy ray-curable resin layer (I) For the direct laminate. [9] The laminate according to any one of the above [1] to [8], which is used to form a cured sealing body including the object to be sealed, which is attached to the energy ray-curable resin layer (I) A part of the surface is placed with an object to be sealed, and the energy ray-curable resin layer (I) is irradiated with energy rays to form a cured resin layer (I′) formed by curing the energy ray-curable resin layer (I). The object to be sealed, and the surface of the hardened resin layer (I') at least in the peripheral part of the object to be sealed are covered with a thermosetting sealing material, and after the sealing material is thermally cured, the thermally expandable particles are expanded, The hardened resin layer (I') and the support layer (II) are separated at this interface. [10] The laminate as described in [9] above, which is used to prevent warpage of the hardened sealing body. [11] A method for manufacturing a hardened seal, which is a method for manufacturing a hardened seal using the laminate according to any one of the above [1] to [10], characterized by having the following steps (i) to ( iv): Step (i): Step of placing the sealing object on a part of the surface of the energy ray-curable resin layer (I) of the laminate. Step (ii): Irradiation of energy ray for curing Resin layer (I), a step of forming a cured resin layer (I′) formed by curing an energy ray-curable resin layer (I) Step (iii): the aforementioned sealing object, and at least the peripheral portion of the sealing object The surface of the hardened resin layer (I') is covered with a thermosetting sealing material, and the sealing material is thermally cured to form a cured sealing body including the sealing object. Step (iv): After the thermal expansion The process of expanding the particles to separate the hardened resin layer (I') and the support layer (II) at the interface, thereby producing a hardened sealing body with a hardened resin layer. [Effect of invention]

The content of the present invention is to provide a support layer and a curable resin layer, which can be used to fix the object to be sealed on the surface of the curable resin layer and perform the sealing process. A cured resin layer that cures the warpage-resistant layer of the sealing body, and a laminate that can easily separate the cured resin layer and the support layer, and a method of manufacturing the cured sealing body using the laminated body.

In this specification, the method of judging whether the target layer is a "non-expandable layer" is that, after performing a 3-minute swelling process, and calculating the volume change rate before and after the process of less than 5% according to the following formula, the The layer is judged as "non-expandable layer". In addition, when the above-mentioned volume change rate is 5% or more, the layer is judged as an "expandable layer".・Volume change rate (%)={(Volume of the aforementioned layer after treatment-Volume of the aforementioned layer before treatment)/Volume of the aforementioned layer before the treatment ｝100 100, and ‘expanding treatment’, for example, to include thermal expansion In the case of a layer of inert particles, the heat-expandable particles may be subjected to a heat treatment for 3 minutes at the initial expansion temperature (t).

In this specification, "effective ingredient" refers to the ingredient contained in the target composition after removing the diluted solvent.

In this specification, the mass average molecular weight (Mw) is the value converted to standard polystyrene measured using the gel permeation chromatography (GPC) method, specifically, the value measured based on the method described in the examples.

In this specification, for example, "(meth)acrylic acid" means both "acrylic acid" and "methacrylic acid", and other similar terms are also the same.

In the present specification, in the preferable numerical range (for example, the range of content and the like), the lower limit value and the upper limit value described in stages are independent and can be combined. For example, the description of "preferably 10 to 90, more preferably 30 to 60" can be combined with "better lower limit (10)" and "better upper limit (60)", respectively, and For "10 ~ 60".

Each component and material exemplified in this specification can be used alone or in combination of two or more types, and in combination of two or more types, the combination and ratio of these types can be used without particular limitation. Make any choice.

In this specification, "energy ray" refers to an electromagnetic wave or a charged particle ray that has energy ions, such as ultraviolet rays, radiation, and electron rays. Ultraviolet rays can be irradiated using, for example, a high-pressure mercury lamp, a fusion lamp (Fusion Light), a xenon lamp, a fluorescent lamp, or an LED lamp as an ultraviolet light source. The electron beam is used to irradiate electrons generated by using an electron beam accelerator. In this manual, "energy ray curability" means having the property of being hardened by irradiation with energy rays, and "non-energy ray hardening" means having the property of being hardened by irradiation of energy rays.

[Laminate] The laminate of one aspect of the present invention is an energy ray-curable resin layer (I) and a support layer (II) that supports the energy ray-curable resin layer (I).　　The energy ray-curable resin layer (I) has an adhesive surface. The support layer (II) has a base material (Y) and an adhesive layer (X). At least one of the base material (Y) and the adhesive layer (X) contains thermally expandable particles.

In the laminated body of one aspect of the present invention, the heat-expandable particles in the support layer (II) are subjected to an expansion treatment, so that the cured resin layer (I′) formed by curing the energy ray-curable resin layer (I) and The support layer (II) is separated at its interface. That is, the laminate of one aspect of the present invention expands the heat-expandable particles through the heat-expansion treatment, and irregularities are generated on the surface of the layer containing the heat-expandable particles, thereby reducing the support layer (II) and the energy ray hardenability The contact area of the hardened resin layer (I') formed by hardening the resin layer (I). As a result, at the interface between the support layer (II) and the hardened resin layer (I'), the entirety can be easily separated when only a little force is used. In addition, in the laminate of one aspect of the present invention, when the energy ray-curable resin layer (I) is cured, there is no need for heat treatment, so when the energy ray-curable resin layer (I) is cured, it is supported The heat-expandable particles in the layer (II) do not swell, but can make the cured resin layer (I') formed by curing the support layer (II) and the energy ray-curable resin layer (I) having excellent separability .

The laminated body according to one aspect of the present invention is a method suitable for forming a hardened sealing body including the aforementioned sealing object. The method is: a part of the surface of the energy ray-curable resin layer (I) is placed and sealed The object, the energy ray-curable resin layer (I) is irradiated with energy rays to form a cured resin layer (I') formed by curing the energy ray-curable resin layer (I), and the object to be sealed and the object to be sealed The surface of the hardened resin layer (I') of at least the peripheral part of the object is covered with a thermosetting sealing material. After the thermosetting material is cured, the hardening resin layer (I') is treated by expanding the thermally expandable particles. Separated from the support layer (II) at this interface. The hardened sealing body formed by the above method is the one with a hardened resin layer (I’) on the side where the semiconductor wafer has a relatively high proportion. As a result, it is presumed that the difference in shrinkage stress between the two surfaces of the hardened seal body can be reduced, and a hardened seal body that can effectively suppress deformation can be obtained. That is, the laminated body according to one aspect of the present invention is suitable as an anti-warpage laminate for a hardened seal body. In this case, the laminated body of one aspect of the present invention has the energy ray-curable resin layer (I) which can adjust the adhesive force more easily than the thermosetting resin layer, so that the object to be sealed can be more surely A part fixed on the surface. In addition, when the thermosetting resin layer is heated at a high temperature, it is softened mainly in the initial stage of curing, and it is likely to cause wafer shift. For the energy ray-curable adhesive composition, It will be hardened by the irradiation of energy rays without softening, so it can avoid the wafer shift phenomenon that occurs during the hardening process.

<Construction Content of Laminated Body> Subsequently, the structure of the laminated body of one aspect of the present invention will be described with reference to the drawings. FIGS. 1 to 3 are schematic cross-sectional views of a laminate showing the structure of the laminate of the first aspect to the third aspect of the present invention. In addition, in the following laminates of the first aspect to the third aspect of the present invention, the adhesive surface (ie, the adhesive layer (X) (or the second adhesive layer (X2)) attached to the support body (ie, The surface opposite to the support) and the surface opposite to the support layer (II) side of the energy ray-curable resin layer (I) may further have a laminated release material.

[Layer of the First Aspect] The laminate of the first aspect of the present invention is, for example, the laminates 1a and 1b shown in FIG. 1. The laminate 1a, 1b is provided with an energy ray-curable resin layer (I), and a support layer (II) having a base material (Y) and an adhesive layer (X), which has a base material (Y) and energy The linear curable resin layer (I) is directly laminated. Also, in the laminate of the first aspect of the present invention, the adhesive surface of the adhesive layer (X) is attached to the support (not shown in the drawings).

The support layer (II) contains at least one layer containing heat-expandable particles. In the laminate 1a, the base material (Y) is composed of only a single layer of the expandable base material layer (Y1) containing heat-expandable particles. Substrate. The base material (Y), like the laminate 1a shown in FIG. 1(a), may be a base material composed of only a single layer formed of an expandable base material layer (Y1), or as shown in FIG. 1(b) Like the laminate 1b, it is a base material having a multilayer structure including an expandable base material layer (Y1) and a non-expandable base material layer (Y2). When the base material (Y) has an expandable base material layer (Y1) and a non-expandable base material layer (Y2), the base material (Y) may be composed of only the expandable base material layer (Y1) and the non-expandable base material layer (Y2) constituted by.　　Furthermore, it is better to have an intumescent base material layer (Y1) and a non-intumescent base material layer (Y2) directly laminated.

The laminate 1a shown in FIG. 1(a) expands the heat-expandable particles contained in the expandable base material layer (Y1) through heat expansion treatment, and forms unevenness on the surface of the base material (Y), which can be reduced The contact area of the energy ray-curable resin layer (I) and the cured resin layer (I′) previously cured. At this time, the adhesive surface of the adhesive layer (X) is attached to the support body not marked in the pattern. The adhesive layer (X) and the support are attached in an extremely close manner, so even if the surface of the expandable base material layer (Y1) on the adhesive layer (X) side generates an uneven force, the adhesive Layer (X) is also susceptible to counterweight. Therefore, it is difficult to form irregularities on the surface of the base material (Y) on the side of the adhesive layer (X). As a result, in the laminate 1a, the interface P between the base material (Y) of the support layer (II) and the hardened resin layer (I') can be easily separated as a whole with a little force. In addition, the adhesive layer (X) included in the laminate 1a is formed of an adhesive composition having high adhesive force to the support, so that it can be easily separated at the interface P.

In addition, from the viewpoint of suppressing the stress generated by the thermally expandable particles from being transmitted to the adhesive layer (X) side, the base material (Y) has an expandable base material layer like the laminate 1b shown in FIG. 1(b) ( Y1) and the non-expandable base material layer (Y2) are preferred. The stress caused by the expansion of the thermally expandable particles of the expandable substrate layer (Y1) is suppressed by the non-expandable substrate layer (Y2), so it is difficult to communicate to the adhesive layer (X). Therefore, the surface of the adhesive layer (X) on the support side is less likely to be uneven, and the adhesiveness of the adhesive layer (X) and the support is almost unchanged before and after the heat expansion treatment, and can maintain a good Adhesion. In this way, irregularities are more easily formed on the surface of the energy base curable resin layer (I) side of the expandable base material layer (Y1), and as a result, the expandable base material layer (Y1) of the support layer (II) and the hardened resin The interface P of the layer (I') can be easily separated as long as it uses a little force. Moreover, like the laminate 1b shown in FIG. 1(b), the expandable base material layer (Y1) and the energy ray-curable resin layer (I) are directly laminated, and are included in the non-expandable base material layer (Y2 ) Is preferably formed by laminating an adhesive layer (X) on the surface opposite to the expandable base material layer (Y1).

[Laminate of the second aspect] The laminate of the second aspect of the present invention may include the laminates 2a and 2b shown in FIG. 2. In the laminates 2a and 2b, the adhesive layer (X) included in the support layer (II) has a first adhesive layer (X1) and a second adhesive layer (X2), and has a first adhesive layer (X1) and the second adhesive layer (X2) sandwich the substrate (Y), and the adhesive surface of the first adhesive layer (X1) is directly laminated with the energy ray-curable resin layer (I). In the laminate of the second aspect of the present invention, the adhesive surface of the second adhesive layer (X2) is attached to the support (not shown in the drawings).

In the laminate of the second aspect of the present invention, the base material (Y) preferably has an expandable base material layer (Y1) containing thermally expandable particles. The base material (Y), like the laminate 2a shown in FIG. 2(a), may be a base material composed of only a single layer formed of an expandable base material layer (Y1), or as shown in FIG. 2(b) Like the laminate 2b, it may also be a base material having a multilayer structure formed of an expandable base material layer (Y1) and a non-expandable base material layer (Y2).

In addition, as described above, from the viewpoint of maintaining a good adhesion between the second adhesive layer (X2) and the support before and after the heat expansion treatment, as shown in FIG. 2(b), the substrate ( Y) Preferably, it has an intumescent base material layer (Y1) and a non-intumescent base material layer (Y2). In addition, in the laminate of the second aspect, when the base material (Y) having the expandable base material layer (Y1) and the non-expandable base material layer (Y2) is used, as shown in FIG. 2(b), The first adhesive layer (X1) is laminated on the surface of the energy ray-curable resin layer (I) side of the intumescent base material layer (Y1) to the intumescent base of the non-intumescent base material layer (Y2) The material layer (Y1) is preferably formed by laminating a second adhesive layer (X2) on the surface on the opposite side.

In the laminate of the second aspect, the heat-expandable particles in the expandable base material layer (Y1) constituting the base material (Y) can be expanded by heat-expansion treatment on the surface of the expandable base material layer (Y1) Form bumps. Subsequently, due to the unevenness generated on the surface of the expandable substrate layer (Y1), it is pressed against the first adhesive layer (X1), so that the adhesive surface of the first adhesive layer (X1) also forms unevenness As a result of this process, the contact area between the first adhesive layer (X1) and the energy ray-curable resin layer (I), which is previously cured, can be reduced. As a result, the interface P between the first adhesive layer (X1) and the cured resin layer (I') of the support layer (II) can be easily separated as a whole with a little force. In addition, the laminate of the second aspect of the present invention is a laminate that can be easily separated as a whole by using a little force on the interface P. The substrate (Y) of the support layer (II) It is preferable that the expandable base material layer (Y1) and the first adhesive layer (X1) have a structure directly laminated.

[Layer of Third Aspect] The laminate of the third aspect of the present invention may include the laminate 3 shown in FIG. 3. The laminate 3 shown in FIG. 3 has a first adhesive layer (X1) having an expandable adhesive layer containing heat-expandable particles on the surface side of the substrate (Y) side, and on the substrate ( Y) The surface side of the other side is provided with a support layer (II) of a second adhesive layer (X2) with a non-expandable adhesive layer, and the first adhesive layer (X1) and energy ray-curable resin The layer (I) is formed by direct lamination. In 　　 laminate 3, the adhesive surface of the second adhesive layer (X2) is attached to the support (not shown in the drawing). The base material (Y) of the laminate of the third aspect of the present invention is preferably composed of a non-expandable base material layer.

The laminate of the third aspect of the present invention, through heat expansion treatment, can cause the thermally expandable particles in the first adhesive layer (X1) of the expandable adhesive layer to expand, and the first adhesive layer (X1) Concavo-convex is formed on the surface of the surface, and the contact area between the first adhesive layer (X1) and the energy ray-curable resin layer (I) is cured in advance by the cured resin layer (I′). On the other hand, the surface of the first adhesive layer (X1) on the substrate (Y) side is difficult to generate irregularities because the substrate (Y) is laminated. Therefore, when heat-expanded, the surface of the first adhesive layer (X1) can be easily formed with irregularities on the surface of the energy ray-curable resin layer (I). As a result, the first adhesive layer on the support layer (II) (X1) The interface P with the cured resin layer (I') can be easily separated as a whole with a little force.

The laminated body according to one aspect of the present invention may be composed of only the support layer (II) and the energy ray-curable resin layer (I), and has a support layer (II) and the energy ray-curable resin layer (I) Other layers are also acceptable. Examples of other layers are, for example, an adhesive layer provided on the opposite side of the support layer (II) provided on the energy ray-curable resin layer (I). In addition, the laminated body according to one aspect of the present invention has the viewpoint that it is not necessary to perform extreme heating in steps other than heat expansion treatment, and it is preferable that it does not have a thermosetting resin layer. However, the thermosetting resin layer here means a layer that has thermosetting properties and is not energy-ray curable.

<Various physical properties of the laminate> (Peeling force (F ₀ )) Before the energy ray-curable resin layer (I) is cured and before the heat expansion treatment, the object to be sealed can be sufficiently fixed without causing damage to the sealing operation From the viewpoint of adverse effects, the higher the adhesion between the support layer (II) and the energy ray-curable resin layer (I), the better. Based on the above viewpoints, in the laminate of one aspect of the present invention, the energy ray-curable resin layer (I) is before the curing and before the heat expansion treatment, on the support layer (II) and the energy ray-curable resin layer (I ) The peeling force (F ₀ ) at the time of separation on the interface P is preferably 100 mN/25 mm or more, more preferably 130 mN/25 mm or more, particularly preferably 160 mN/25 mm or more, and preferably 50,000 mN/25 mm or less . In addition, the peeling force (F ₀ ) is a value measured according to the following measuring method. <Measurement of peel force (F ₀ )> After placing the laminate in an environment of 23° C. and 50% RH (relative humidity) for 24 hours, the adhesive tape (manufactured by Linde Co., Ltd., product name “PL- SHIN") is attached to the surface of the energy ray-curable resin layer (I). Subsequently, the support layer (II) side of the laminate was attached to a glass plate (made by U-KOU Chamber of Commerce Co., Ltd., float glass, 3 mm (JIS R 3202 product)) via an adhesive. Next, the end of the above-mentioned glass plate to which the laminate is attached is fixed to the lower jig of a universal tensile testing machine (manufactured by Dongfang Technology Co., Ltd., product name "TENSILON UTM-4-100"). Subsequently, the adhesive tape and the support layer (II) were fixed with an upper jig of a universal tensile testing machine in such a manner that the interface P of the support layer (II) of the laminate and the energy ray-curable resin layer (I) were peeled off. Subsequently, in the same environment as above, based on JIS Z 0237:2000, using the 180˚ tensile peeling method at a stretching speed of 300 mm/min, the peeling force measured when peeling is formed at the interface P is set to " Peeling force (F ₀ )".

(Peeling force (F ₁ )) In the laminate of one aspect of the present invention, after the energy ray-curable resin layer (I) is cured to form a cured resin layer (I′), it is subjected to heat expansion treatment to the support layer (II) The peeling force (F ₁ ) at the time of separation from the interface P of the cured resin layer (I′) can be easily separated from the entirety of the interface P using only a small amount of force, but it is usually 2000 mN/25 mm or less, It is preferably 1000 mN/25 mm or less, more preferably 500 mN/25 mm or less, more preferably 150 mN/25 mm or less, particularly preferably 100 mN/25 mm or less, most preferably 50 mN/25 mm or less, and most preferably 0 mN/25 mm. When the peeling force (F ₁ ) is 0 mN/25 mm, the measurement includes the case where the peeling force is measured, but the peeling force is too low to be measured. In addition, the peel force (F ₁ ) is a value measured according to the following measuring method. <Measurement of peel force (F ₁ )> After placing the laminate in an environment of 23° C. and 50% RH (relative humidity) for 24 hours, the adhesive tape (manufactured by Linde Co., Ltd., product name “PL- SHIN") attached to the surface of the energy ray-curable resin layer (I) of the laminate. Subsequently, the support layer (II) side of the laminate was attached to a glass plate (made by U-KOU Chamber of Commerce Co., Ltd., float glass, 3 mm (JIS R 3202 product)) via an adhesive. Next, ultraviolet rays were irradiated three times under the conditions of illuminance 215 mW/cm ² and light quantity 187 mJ/cm ^{2 to} cure the energy ray-curable resin layer (I) to form a cured resin layer (I′). Subsequently, the glass plate and the laminate were heated at the maximum expansion temperature for 3 minutes to expand the thermally expandable particles in the expandable base material layer (Y1) of the laminate. Thereafter, the peeling force measured when peeling the interface P between the support layer (II) and the hardened resin layer (I′) under the same conditions is the same as the measurement of the peeling force (F ₀ ) described above. "Peeling force (F ₁ )". In addition, in the measurement of the peeling force (F ₁ ), when the upper jig of the universal tensile tester is used to fix the support layer (II) of the laminate, the hardened resin layer (I′) can be completely separated on the interface P , But there is no fixed situation, the measurement is ended, and the peeling force (F ₁ ) at this time is "0mN/25mm".

(Adhesive force of adhesive layer (X)) In the laminate of one aspect of the present invention, at room temperature (23°C), the adhesive layer (X) of the support layer (II) (first adhesive) The adhesive force of the layer (X1) and the second adhesive layer (X2)) is preferably 0.1 to 10.0 N/25 mm, more preferably 0.2 to 8.0 N/25 mm, and particularly preferably 0.4 to 6.0 N/25 mm, the best It is 0.5～4.0N/25mm. When the support layer (II) has the first adhesive layer (X1) and the second adhesive layer (X2), the adhesive force of the first adhesive layer (X1) and the second adhesive layer (X2) is within the above range It is better, but from the viewpoint of improving the adhesion to the support and making it possible to form an integral separation at the interface P, the adhesion of the second adhesive layer (X2) attached to the support is higher than that of the first adhesive The higher the adhesion of the layer (X1), the better.

(Adhesion of the energy ray-curable resin layer (I)) The laminate of one aspect of the present invention has a good adhesion to the object to be sealed, and the energy ray-curable resin layer (I) is placed and sealed The surface on the object side (that is, the surface opposite to the supporting layer (II)) is adhesive. Specifically, at room temperature (23°C), the adhesive force of the energy ray-curable resin layer (I) on the surface on which the object to be sealed is placed is preferably 0.05 from the viewpoint of sufficiently fixing the object to be sealed N/25mm or more, more preferably 0.10N/25mm or more, particularly preferably 0.50N/25mm or more. The upper limit of the adhesive force of the above-mentioned surface is not particularly limited, but it is usually 50 N/25 mm or less, or 40 N/25 mm or less and 30 N/25 mm or less.

In addition, in this specification, these adhesive forces are the values measured by the following measuring methods. <Measurement of Adhesive Force> On the surface of the adhesive layer (X) or the energy ray-curable resin layer (I) formed on the peeling film, a 50 μm thick PET film (manufactured by Toyobo Co., Ltd., product name “COSMO”) is laminated -SHUNE A4100"). Subsequently, the surface of the adhesive layer (X) or the energy ray-curable resin layer (I) was attached to the stainless steel plate of the adherend (SUS304 360 polishing) at 23°C, 50% RH (relative humidity) Under the environment, after standing for 24 hours, under the same environment, in accordance with JIS Z 0237: 2000, using 180˚ tensile peeling method, the tensile speed of 300mm/min under the condition of its adhesion at 23 ℃ .

(Tensile strength value of base material (Y)) The base material (Y) included in the support layer (II) is a non-adhesive base material. In one aspect of the present invention, the judgment as to whether it is a non-adhesive base material refers to the surface of the target base material when the tensile strength value measured according to JIS Z 0237: 1991 is 50mN/5mmφ , The substrate is judged to be a "non-adhesive substrate". In addition, when the above-mentioned tensile strength value is 50 mN/5 mmφ or more, the base material is judged to be an “adhesive base material”. The tensile strength value of the surface of the base material (Y) possessed by the support layer (II) used in one aspect of the present invention is usually less than 50 mN/5 mmφ, preferably less than 30 mN/5 mmφ, and more preferably It is less than 10mN/5mmφ, especially good is less than 5mN/5mmφ. The tensile strength value on the surface of the base material (Y) is a value measured according to the following measuring method. <Measurement of Tensile Strength Value> After the substrate to be measured was cut into a square with a side of 10 mm, it was allowed to stand for 24 hours in an environment of 23° C. and 50% RH (relative humidity) as a test sample. The surface of the test sample was measured in accordance with JIS Z0237:1991 using a viscosity testing machine (manufactured by Japan Special Instruments Co., Ltd., product name "NTS-4800") at 23°C and 50%RH (relative humidity). The tensile strength value. Specifically, after contacting the surface of the test sample with a stainless steel detector with a diameter of 5 mm for 1 second and a contact load of 0.98 N/cm ² , the detector was measured at a speed of 10 mm/sec. The necessary force when the surface is away, the obtained value is taken as the tensile strength value of the test sample.

Subsequently, the contents of each layer constituting the laminate of one aspect of the present invention will be explained.

<Support layer (II)> The support layer (II) of the laminate according to one aspect of the present invention includes a base material (Y) and an adhesive layer (X), and the base material (Y) and the adhesive At least one of the layers (X) contains thermally expandable particles. As described above, the support layer (II) is a layer separated by the energy ray-curable resin layer (I) supporting the object through heating and expansion treatment, that is, a layer having a function as a temporary fixing layer. The layer containing the heat-expandable particles is included in the constituent content of the base material (Y), and in the case of included in the adhesive layer (X), the support layer (II) used in one aspect of the present invention ) Can be divided into the following forms. Supporting layer (II) in the first aspect: a supporting layer (II) provided with a base material (Y) having an expandable base material layer (Y1) containing thermally expandable particles.・Support layer (II) of the second aspect: On both sides of the base material (Y), there is a first adhesive layer (X1) containing an expandable adhesive layer as thermally expandable particles as a non-expandable adhesive The support layer (II) of the second adhesive layer (X2) of the layer.

[Support layer (II) of the first aspect] As shown in FIGS. 1 to 2, the support layer (II) of the first aspect, the base material (Y) is an expandable base material layer containing thermally expandable particles ( Y1). In the first aspect of the support layer (II), the interface P can be easily separated by using a small amount of force. The adhesive layer (X) is preferably a non-expandable adhesive layer. Specifically, in the support layer (II) of the laminates 1a and 1b shown in FIG. 1, the adhesive layer (X) is preferably a non-expandable adhesive layer. In addition, in the support layer (II) included in the laminates 2a and 2b shown in FIG. 2, any of the first adhesive layer (X1) and the second adhesive layer (X2) is non-expandable adhesive The agent layer is preferred. As shown in the support layer (II) of the first aspect, since the base material (Y) has an expandable base material layer (Y1), the adhesive layer (X) does not need to have expandability, and does not need to be provided with expandability Constraints on composition, composition and process. In this way, when designing the adhesive layer (X), for example, performance such as adhesiveness, productivity, economy, etc., and the expected performance other than expansibility can be prioritized to improve the adhesive layer (X ) Design freedom.

The thickness of the substrate (Y) before the heat expansion treatment of the support layer (II) in the first aspect is preferably 10 to 1000 μm, more preferably 20 to 700 μm, particularly preferably 25 to 500 μm, and most preferably 30 to 300μm.

The thickness of the adhesive layer (X) before the heat expansion treatment of the support layer (II) of the first aspect is preferably 1 to 60 μm, more preferably 2 to 50 μm, particularly preferably 3 to 40 μm, and most preferably 5 ~30μm.

In addition, in this specification, for example, as shown in FIG. 2, when the support layer (II) has a plurality of adhesive layers (X), the “thickness of the adhesive layer (X)” refers to each adhesive layer The thickness (in FIG. 2 is the thickness of the first adhesive layer (X1) and the second adhesive layer (X2)). In this specification, the thickness of each layer constituting the laminate means the value measured according to the method described in the embodiment.

In the support layer (II) of the first aspect, the thickness ratio of the expandable substrate layer (Y1) before the heat expansion treatment to the adhesive layer (X) [(Y1)/(X)] is preferably 1000 or less, more preferably 200 or less, particularly preferably 60 or less, and most preferably 30 or less. When the thickness ratio is 1000 or less, after heating and expansion treatment, an interface P between the support layer (II) and the hardened resin layer (I') can be formed, and the laminate can be easily separated as a whole by using a little force. In addition, the thickness ratio is preferably 0.2 or more, more preferably 0.5 or more, particularly preferably 1.0 or more, and most preferably 5.0 or more.

Furthermore, in the support layer (II) of the first aspect, the base material (Y), as shown in FIG. 1(a), may be composed of only the expandable base material layer (Y1), as shown in FIG. 1( As shown in b), the energy ray-curable resin layer (I) side may have an expandable base material layer (Y1), and the adhesive layer (X) side may have a non-expandable base material layer (Y2).

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

[Support layer (II) of the second aspect] The support layer (II) of the second aspect, as shown in FIG. 3, is on both sides of the base material (Y), and has expansions containing thermally expandable particles, respectively. The first adhesive layer (X1) of the adhesive layer and the second adhesive layer (X2) as the non-expandable adhesive layer. In the second aspect of the support layer (II), the first adhesive layer (X1) as the expandable adhesive layer is in direct contact with the energy ray-curable resin layer (I). In the second aspect of the support layer (II), the base material (Y) is preferably a non-expandable base material. The non-expandable substrate is preferably composed of only the non-expandable substrate layer (Y2).

In the support layer (II) of the second aspect, the first adhesive layer (X1) which is the expandable adhesive layer before the heat expansion treatment, and the second adhesive layer (X2) which is the non-expandable adhesive layer The thickness ratio [(X1)/(X2)] is preferably 0.1 to 80, more preferably 0.3 to 50, and particularly preferably 0.5 to 15.

In addition, the thickness ratio of the first adhesive layer (X1) which is the expandable adhesive layer before the heat expansion treatment of the support layer (II) of the second aspect to the base material (Y) [(X1)/(Y )], preferably 0.05 to 20, more preferably 0.1 to 10, and particularly preferably 0.2 to 3.

Hereinafter, the thermally expandable particles contained in any layer constituting the support layer (II) will be described, and the expandable substrate layer (Y1) and the non-expandable substrate layer (Y2) constituting the substrate (Y) will be described in detail. , And the adhesive layer (X).

[Thermally Expandable Particles] The heat-expandable particles used in one aspect of the present invention may be any particles that can undergo expansion by specific heat-expansion treatment. The average particle diameter of the thermally expandable particles used in one aspect of the present invention before expansion at 23° C. is preferably 3 to 100 μm, more preferably 4 to 70 μm, particularly preferably 6 to 60 μm, and most preferably 10 to 50μm. The average particle diameter before expansion of the thermally expandable particles refers to the volume median particle diameter (D ₅₀ ), which was measured using a laser diffraction type particle size distribution measuring device (for example, product name “MASTERSIZER 3000” manufactured by Malvern Corporation). In the particle distribution of the heat-expandable particles before expansion obtained, the cumulative volume frequency calculated from the side where the particle diameter of the heat-expandable particles before expansion is smaller is equivalent to 50% of the particle diameter.

The 90% particle diameter (D ₉₀ ) of the thermally expandable particles used in one aspect of the present invention before expansion at 23° C. is preferably 10 to 150 μm, more preferably 20 to 100 μm, and particularly preferably 25 to 90 μm. The best is 30 ~ 80μm. The 90% particle diameter (D ₉₀ ) before expansion of the thermally expandable particles refers to the thermal expansion before expansion measured using a laser diffraction particle size distribution measuring device (for example, manufactured by Malvern Corporation, product name "MASTERSIZER 3000") In the particle distribution of the sexual particles, the cumulative volume frequency calculated from the side where the particle diameter of the thermally expandable particles before expansion is smaller is equivalent to 90% of the particle diameter.

The heat-expandable particles used in one aspect of the present invention need only be particles that do not expand when the sealing material is hardened and have a higher expansion start temperature (t) than the hardening temperature of the sealing material, specifically In particular, it is preferable to adjust the thermally expandable particles whose expansion starting temperature (t) is 60 to 270°C. In addition, the expansion initiation temperature (t) can be appropriately selected in accordance with the hardening temperature of the sealing material used. In addition, in this specification, the expansion starting temperature (t) of thermally expandable particles means the value measured according to the method described in the embodiment.

The heat-expandable particles preferably have a shell composed of a thermoplastic resin, and a microencapsulated foaming agent composed of an encapsulated component contained in the shell and vaporized when heated to a specific temperature. Thermoplastic resin constituting the outer shell of the microencapsulated foaming agent, for example, chlorinated vinylene-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polychloride Vinylidene, polystyrene, etc.

Contained components contained in the shell, for example, propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentane, isohexane, isoheptane , Isooctane, isononane, isodecane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, neopentane, dodecane, isododecane, cyclo Tridecane, hexylcyclohexane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, isotridecane, 4-methyldodecane, Isotetradecane, isopentadecane, isohexadecane, 2,2,4,4,6,8,8-heptamethylnonane, isoheptadecane, isooctadecane, isodecadecane, 2,6,10,14-tetramethylpentadecane, cyclotridecane, heptylcyclohexane, n-octylcyclohexane, cyclopentadecane, nonylcyclohexane, decylcyclohexane , Pentadecylcyclohexane, hexadecylcyclohexane, heptadecylcyclohexane, octadecylcyclohexane, etc.　　These in-house ingredients can be used alone or in combination of two or more.　　The initial temperature (t) of the expansion of the thermally expandable particles can be adjusted by appropriately selecting the type of the contained components.

The heat-expandable particles used in one aspect of the present invention have a maximum volume expansion rate when heated to a temperature above the expansion start temperature (t), preferably 1.5 to 100 times, more preferably 2 to 80 times. The best is 2.5 to 60 times, and the best is 3 to 40 times.

<Expandable base material layer (Y1)> The expandable base material layer (Y1) included in the support layer (II) used in one aspect of the present invention contains thermally expandable particles and undergoes specific heat expansion treatment , Can produce an expanded layer.

In addition, from the viewpoint of improving the interlayer adhesion with the expandable base material layer (Y1) and the other layers laminated, the surface of the expandable base material layer (Y1) may be subjected to an oxidation method, a bumping method, etc. Surface treatment, easy subsequent treatment, or primer treatment. Oxidation methods, such as corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet type), hot air treatment, ozone, and ultraviolet irradiation treatment, etc., bumping method, for example, sandblasting method, solvent treatment method, etc.

In one aspect of the present invention, the expandable base material layer (Y1) preferably satisfies the following requirements (1).・Requirement (1): At the expansion start temperature (t) of the thermally expandable particles, the storage elastic modulus E′(t) of the expandable base material layer (Y1) is 1.0×10 ⁷ Pa or less. In addition, in this specification, the storage elastic modulus E'of the expandable base material layer (Y1) at a specific temperature means the value measured by the method described in the examples.

The above requirement (1) is also referred to as an index indicating the rigidity of the expandable substrate layer (Y1) of the thermally expandable particles before expansion. From the viewpoint that the interface P between the support layer (II) and the hardened resin layer (I') can be easily separated with only a little force, when heated to a temperature above the expansion start temperature (t), it is used as a support layer (II) The surface on the side where the energy ray-curable resin layer (I) is laminated must be easily formed into an uneven state. That is, the expandable base material layer (Y1) that satisfies the above requirement (1) can expand the thermally expandable particles to a larger size at the expansion starting temperature (t), and the energy ray can be combined with the curable resin layer (I ) The surface of the supporting layer (II) on the lamination side is more likely to form irregularities. As a result, a laminate can be produced at the interface P between the support layer (II) and the hardened resin layer (I’), which can be easily separated with only a little force.

The storage elastic modulus E'(t) of the expandable base material layer (Y1) specified in the requirement (1) is preferably 9.0×10 ⁶ Pa or less, more preferably 8.0×10 ⁶ Pa or less, based on the above viewpoint. It is preferably 6.0×10 ⁶ Pa or less, and most preferably 4.0×10 ⁶ Pa or less. In addition, the flow of thermally expandable particles after expansion can be suppressed, and the maintenance of the uneven shape on the surface of the support layer (II) laminated on the side of the energy ray-curable resin layer (I) can be improved. It is easy to separate with a little force. The storage elastic modulus E'(t) of the expandable substrate layer (Y1) specified in the requirement (1) is preferably 1.0×10 ³ Pa or more, and more preferably 1.0× 10 ⁴ Pa or more, particularly preferably 1.0×10 ⁵ Pa or more.

The expandable base material layer (Y1) is preferably formed of a resin composition (y) containing resin and thermally expandable particles. In addition, the resin composition (y) may contain additives for the base material, if necessary, within a range that does not impair the effects of the present invention. Additives for substrates, such as light stabilizers, antioxidants, antistatic agents, sliding agents, anti-adhesive agents, colorants, etc.　　Furthermore, the additives for these substrates can be used alone or in combination of two or more. When the additives for base materials are contained, the content of the respective additives for base materials is preferably 0.0001 to 20 parts by mass, and more preferably 0.001 to 10 parts by mass relative to 100 parts by mass of the resin.

The content of the heat-expandable particles is preferably 1 to 40% by mass relative to the total amount (100% by mass) of the expandable substrate layer (Y1) or the total amount (100% by mass) of the active ingredients of the resin composition (y). It is more preferably 5 to 35% by mass, particularly preferably 10 to 30% by mass, and most preferably 15 to 25% by mass.

The resin containing the resin composition (y) as the forming material of the expandable base layer (Y1) may be a non-adhesive resin or an adhesive resin. That is, when the resin contained in the resin composition (y) is an adhesive resin, in the process of forming the expandable substrate layer (Y1) from the resin composition (y), the adhesive resin will react with the polymerizable compound The polymerization reaction proceeds to make the obtained resin a non-adhesive resin, so long as the expandable base layer (Y1) containing the resin is non-adhesive.

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

In addition, when the resin is a copolymer having two or more structural units, the form of the copolymer is not particularly limited, but may be a block copolymer, a random copolymer, and a graft copolymer. Any one.

The content of the above resin is preferably 50 to 99% by mass relative to the total amount (100% by mass) of the expandable base material layer (Y1) or the total amount (100% by mass) of the effective ingredients of the resin composition (y). It is preferably 60 to 95% by mass, particularly preferably 65 to 90% by mass, and most preferably 70 to 85% by mass.

From the viewpoint of forming the expandable base material layer (Y1) that satisfies the above requirement (1), the resin contained in the resin composition (y) is composed of a urethane acrylate resin and an olefin resin. The selected one or more is better. In addition, the above-mentioned urethane acrylate resin is preferably the following resin (U1). Carbamate prepolymer (UP) is a urethane acrylate resin (U1) obtained by polymerizing a vinyl compound containing (meth)acrylate.

(Urethane acrylate resin (U1)) urethane prepolymer (UP) as the main chain of urethane acrylate resin (U1), for example, a reactant of polyalcohol and polyvalent isocyanate Wait.　　Furthermore, the urethane prepolymer (UP) is preferably obtained by using a chain extension agent to apply a chain extension reaction.

Polyols as raw materials for urethane prepolymers (UP), for example, alkylene type polyols, ether type polyols, ester type polyols, amide ester type polyols, ester/ether type polyols , Carbonate type polyalcohol, etc.　　These polyols can be used alone or in combination of two or more. The polyalcohol used in one aspect of the present invention is preferably a diol, preferably an ester-type diol, an alkylene-type diol, and a carbonate-type diol, and preferably uses an ester-type diol, a carbonate-type two Alcohol is better.

Ester-type diol, for example, a chain consisting of 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, etc. Alkanediol; Alkanediols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, etc.; one or more of the selected diols, etc. Phthalic acid, naphthalene dicarboxylic acid, 4,4-diphenyl dicarboxylic acid, diphenyl methane-4,4'-dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, chlorine Mycolic acid, maleic acid, fumaric acid, itaconic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, hexahydrophthalic acid, hexahydroisophthalic acid Condensation polymers formed from one or more selected dicarboxylic acids such as formic acid, hexahydroterephthalic acid, methylhexahydrophthalic acid, and these anhydrous substances. Specifically, for example, polyethylene adipate diol, polybutene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol 、Polypivalyl adipate diol, Polypropylene adipate diol, Polyethylene butyl adipate diol, Polybutylene hexamethyl adipate diol, Polydiethylidene adipate diol, poly(polytetramethylene ether) adipate diol, poly(3-methylpentene adipate) diol, polyethylene acetate diol , Polyethylene sebacate diol, polybutene azelate diol, polybutene sebacate diol and poly neopentyl terephthalate diol.

Alkylene glycols, for example, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, etc. Alkanediol; alkanediols such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; polybutene glycol, etc. Of polyoxyalkylene glycol; etc.

Carbonate type diols, for example, 1,4-tetramethylene carbonate diol, 1,5-pentamethyl carbonate diol, 1,6-hexamethylene carbonate diol, 1,2 -Propylene carbonate diol, 1,3-propylene carbonate diol, 2,2-dimethylpropylene carbonate diol, 1,7-heptyl methyl carbonate diol, 1 , 8-octyl methyl carbonate diol, 1,4-cyclohexane carbonate diol, etc.

The polyvalent isocyanate as the raw material of the urethane prepolymer (UP) includes, for example, aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate, and the like.　　These polyvalent isocyanates can be used alone or in combination of two or more. In addition, these polyvalent isocyanates may also be modified trimethylolpropane adducts, biuret modified after reacting with water, and isocyanurate containing isocyanurate ring Type degeneration.

Among these, the polyvalent isocyanate used in one aspect of the present invention is preferably diisocyanate, and is composed of 4,4′-diphenylmethane diisocyanate (MDI) and 2,4-tolyl diisocyanate The selected one or more of isocyanate (2,4-TDI), 2,6-tolyl diisocyanate (2,6-TDI), hexamethyl diisocyanate (HMDI), and alicyclic diisocyanate are Better.

Alicyclic diisocyanate, for example, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3 -Cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, etc., and isophorone Diisocyanate (IPDI) is preferred.

In one aspect of the present invention, the urethane prepolymer (UP) which is the main chain of the urethane acrylate resin (U1) is a reactant of diol and diisocyanate, and has both ends A linear urethane prepolymer with an ethylenic unsaturated group is preferred. A method of introducing an ethylenic unsaturated group to both ends of the linear urethane prepolymer, for example, a linear urethane prepolymer obtained by reacting a diol and a diisocyanate compound The NCO group at the end of the compound is reacted with hydroxyalkyl (meth)acrylate.

Hydroxyalkyl (meth)acrylate, for example, 2-hydroxy(meth)acrylate, 2-hydroxy(meth)acrylate, 3-hydroxy(meth)acrylate, 2-hydroxy(methyl ) Butyl acrylate, 3-hydroxy (meth) acrylate, 4-hydroxy (meth) acrylate, etc.

The vinyl compound as a side chain of the urethane acrylate resin (U1) contains at least (meth)acrylate. (Meth) acrylate, preferably one or more selected from alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate, and a combination of alkyl (meth) acrylate and hydroxy (meth) acrylate Alkyl esters are preferred.

When the alkyl (meth)acrylate and the hydroxyalkyl (meth)acrylate are used together, the addition ratio of the hydroxyalkyl (meth)acrylate to 100 parts by mass of the (meth)acrylate is preferably 0.1 to 100 parts by mass, more preferably 0.5 to 30 parts by mass, particularly preferably 1.0 to 20 parts by mass, and most preferably 1.5 to 10 parts by mass.

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

In addition, the hydroxyalkyl (meth)acrylate is, for example, the same as the hydroxyalkyl (meth)acrylate used when the ethylenic unsaturated group is introduced at both ends of the linear urethane prepolymer. Of content.

Vinyl compounds other than (meth)acrylates, for example, aromatic hydrocarbon-based vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether Class; vinyl acetate, vinyl propionate, (meth)acrylonitrile, N-vinylpyrrolidone, (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, methacrylic acid Monomers containing polar groups; etc.　　These can be used alone or in combination of two or more.

The content of the (meth)acrylate in the vinyl compound is preferably 40 to 100% by mass, more preferably 65 to 100% by mass, and particularly preferably 80 to 100% by mass of the vinyl compound. 100% by mass, preferably 90 to 100% by mass.

In the vinyl compound, the total content of alkyl (meth)acrylate and hydroxyalkyl (meth)acrylate is preferably 40 to 100% by mass relative to the total amount of the vinyl compound (100% by mass), more preferably It is 65 to 100% by mass, particularly preferably 80 to 100% by mass, and most preferably 90 to 100% by mass.

In the urethane acrylate resin (U1) used in one aspect of the present invention, the structural unit (u11) produced by the urethane prepolymer (UP) and the structural unit produced by the vinyl compound The content ratio of (u12) [(u11)/(u12)], based on the mass ratio, is preferably 10/90 to 80/20, more preferably 20/80 to 70/30, and particularly preferably 30/70 to 60/40, the best is 35/65～55/45.

(Olefin-based resin) Among the resins contained in the resin composition (y), a preferred olefin-based resin is, for example, a polymer having at least a structural unit produced by an olefin monomer. The olefin monomer is preferably an alpha-olefin having 2 to 8 carbon atoms, specifically, for example, vinyl, propenyl, butenyl, isobutenyl, 1-hexenyl, and the like. Among these, vinyl and acrylic groups are preferred.

Specifically, olefin-based resins, for example, ultra-low density polyethylene (VLDPE, density: 880 kg/m ³ or more, less than 910 kg/m ³ ), low-density polyethylene (LDPE, density: 910 kg/m ³ or more, not Up to 915kg/m ³ ), medium density polyethylene (MDPE, density: 915kg/m ³ or more, less than 942kg/m ³ ), high density polyethylene (HDPE, density: 942kg/m ³ or more), linear low Polyethylene resin such as density polyethylene; polypropylene resin (PP); polybutene resin (PB); ethylene-propylene copolymer; olefin-based elastomer (TPO); poly(4-methyl-1-pentene) (PMP); ethylene-vinyl acetate copolymer (EVA); ethylene-vinyl alcohol copolymer (EVOH); olefin terpolymers such as ethylene-propylene-(5-ethylene-2-norcamene); Wait.

In one aspect of the present invention, the olefin-based resin may be a modified olefin-based resin obtained by further applying one or more types of denaturation selected from acid denaturation, hydroxyl denaturation, and acrylic-based denaturation.

For example, an acid-modified olefin-based resin obtained by subjecting an olefin-based resin to acid modification, for example, a denatured polymer obtained by graft-polymerizing the above-mentioned unmodified olefin-based resin with an unsaturated carboxylic acid or its anhydride, etc. . The above unsaturated carboxylic acid or its anhydride, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaric acid, tetrahydrophthalic acid, aconitic acid, (meth)acrylic acid, maleic acid Maleic anhydride, itaconic anhydride, glutaric anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, etc.　　Furthermore, unsaturated carboxylic acid or its anhydride can be used alone or in combination of two or more.

Acrylic-modified olefin-based resin obtained by subjecting an olefin-based resin to acrylic-based denaturation, for example, on the above-mentioned undenatured olefin-based resin as the main chain, it is carried out with alkyl (meth)acrylate as a side chain Denatured polymers obtained by graft polymerization. The carbon number of the alkyl group in the alkyl (meth)acrylate mentioned above is preferably 1-20, more preferably 1-16, and particularly preferably 1-12. The aforementioned (meth)acrylic acid alkyl esters, for example, have the same contents as the compounds that can be selected as monomers (a1') described later.

The hydroxy-modified olefin-based resin obtained by subjecting an olefin-based resin to hydroxy-modification is, for example, a denatured polymer obtained by graft-polymerizing the above-mentioned unmodified olefin-based resin with a hydroxyl group-containing compound. The above-mentioned hydroxyl-containing compound, for example, ethyl 2-hydroxy(meth)acrylate, propyl 2-hydroxy(meth)acrylate, propyl 3-hydroxy(meth)acrylate, butyl 2-hydroxy(meth)acrylate Hydroxyalkyl (meth)acrylates such as esters, 3-hydroxy(meth)acrylate, 4-hydroxy(meth)acrylate, etc.; unsaturated alcohols such as vinyl alcohol, allyl alcohol, etc.

(Resin other than urethane acrylate resin and olefin resin) In one aspect of the present invention, the resin composition (y) may contain urethane acrylate resin and Resins other than olefin resins. These resins, for example, vinyl resins such as polyvinyl chloride, polyvinyl chloride, polyvinyl alcohol, etc.; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc. Polyester resin; Polystyrene; Acrylonitrile-butadiene-styrene copolymer; Cellulose triacetate; Polycarbonate; Polyurethane not equivalent to urethane acrylate resin; Polyphenol ; Polyether-ether ketone; Polyether sulfone; Polyphenylene sulfide; Polyetherimide-based resins such as polyetherimide, polyimide; Polyamide-based resin; Acrylic resin; Fluorine-based resin and so on.

Among them, from the viewpoint of forming the expandable substrate layer (Y1) that satisfies the above requirement (1), the content ratio of the resin other than the urethane acrylate resin and the olefin resin in the resin composition (y) is: The lesser is better. The content ratio of the resin other than the urethane acrylate resin and the olefin resin is 100 parts by mass relative to the total amount of the resin contained in the resin composition (y), preferably less than 30 parts by mass, and more preferably Up to 20 parts by mass, more preferably less than 10 parts by mass, particularly preferably less than 5 parts by mass, and most preferably less than 1 part by mass.

(Solvent-free resin composition (y1)) The resin composition (y) used in one aspect of the present invention is, for example, an oligomer having an ethylenically unsaturated group with a mass average molecular weight (Mw) of 50,000 or less It is a solvent-free resin composition (y1) obtained by blending the energy ray polymerizable monomer and the above-mentioned heat-expandable particles without adding a solvent. In the solventless resin composition (y1), since no solvent is added, the energy ray polymerizable monomer is one that can improve the plasticity of the oligomer. When a coating film formed of a solvent-free resin composition (y1) is irradiated with energy rays, an expandable substrate layer (Y1) satisfying the above requirement (1) will be easily formed.

The type, shape, and amount (content) of the heat-expandable particles added to the solvent-free 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 2,000 to 40,000, particularly preferably 3,000 to 35,000, most preferably It is 4000～30,000.

In addition, the oligomer may be any resin having an ethylenically unsaturated group having a mass average molecular weight of 50,000 or less in the resin contained in the resin composition (y), and the above-mentioned carbamate Prepolymer (UP) is preferred. In addition, the oligomer can also use a modified olefin resin having an ethylenically unsaturated group.

In the solventless resin composition (y1), the total content of the oligomer and the energy ray polymerizable monomer is preferably 50 to 100% relative to the total amount (100% by mass) of the solventless resin composition (y1). 99% by mass, more preferably 60 to 95% by mass, particularly preferably 65 to 90% by mass, and most preferably 70 to 85% by mass.

Energy ray polymerizable monomers, for example, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentane (meth)acrylate, dicyclopentenyloxy (meth)acrylate Alicyclic polymerizable compounds such as esters, cyclohexyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecyl acrylate, etc.; phenyl hydroxypropyl acrylate, benzyl acrylate, phenol ethylene oxide Aromatic polymerizable compounds such as denatured acrylate; heterocyclic polymerizable compounds such as tetrahydrofurfuryl (meth)acrylate, morpholine acrylate, N-vinylpyrrolidone, N-vinylcaprolactam Wait.　　These energy-ray polymerizable monomers can be used alone or in combination of two or more.

The addition ratio of the oligomer to the energy ray polymerizable monomer (the oligomer/energy ray polymerizable monomer) is preferably 20/80 to 90/10, more preferably 30/70 to 85/15, Especially good is 35/65～80/20.

In one aspect of the present invention, the solvent-free resin composition (y1) is preferably added with a photopolymerization initiator. When the photopolymerization initiator is contained, even when a lower energy beam is irradiated, the curing reaction can be sufficiently performed.

Photopolymerization initiators, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, benzoin, benzoin methyl ether, benzoin ether, benzoin propyl ether, benzyl phenyl sulfide, tetramethyl Gyurum monosulfide, azobisisobutyronitrile, dibenzyl ester, diethyl acetyl ester, 8-chloroanthraquinone, etc.　　These photopolymerization initiators can be used alone or in combination of two or more.

The amount of the photopolymerization initiator added is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 4 parts by mass, particularly preferably the total amount of the oligomer and the energy ray polymerizable monomer (100 parts by mass). It is 0.02 to 3 parts by mass.

<Non-expandable base material layer (Y2)> The forming material of the non-expandable base material layer (Y2) constituting the base material (Y), for example, paper, resin, metal, etc., can be combined with one aspect of the present invention The use of the laminate is appropriately selected.

Paper materials, for example, thin-leaf paper, medium-quality paper, high-quality paper, impregnated paper, coated paper, drawing paper, sulfuric acid paper, cellophane, etc. Resins, for example, polyolefin resins such as polyethylene and polypropylene; vinyl resins such as polyvinyl chloride, polyvinyl chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymers, and ethylene-vinyl alcohol copolymers; Polyester resins such as ethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; Polycarbonate; urethane resins such as polyurethane, acrylic-modified polyurethane, etc.; polymethylpentene; polyphenol; polyether-ether ketone; polyether resin; polyphenylene Thioether; polyimide-based resins such as polyetherimide and polyimide; polyamide-based resin; acrylic resin; fluorine-based resin, etc.　　Metals, such as aluminum, tin, chromium, titanium, etc.

These forming materials may be composed of one kind, or two or more kinds may be used in combination. A non-expandable base material layer (Y2) in which two or more forming materials are used in combination, for example, a paper material is laminated with a thermoplastic resin such as polyethylene, or a metal film is formed on a resin-containing resin film or sheet surface. In addition, a method of forming a metal layer, for example, a method of vapor-depositing the above-mentioned metal using a PVD method such as vacuum deposition, sputtering, ion plating, or using a general adhesive to attach a metal foil formed of the above-mentioned metal Methods, etc.

Among them, in one aspect of the present invention, when the expandable particles contained in the expandable base material layer (Y1) expand, the non-expandable base material layer (Y2) that can suppress the expandable base material layer (Y1) The non-expandable base material layer (Y2) is provided with an uneven surface, a non-expandable base material layer (Y2), which is not subject to swelling due to the viewpoint that it can form excellent unevenness on the surface of the adhesive layer (X1) side of the expandable base material layer (Y1) The degree of rigidity at which the sex particles expand and deform is better. Specifically, at the temperature (t) when the expandable particles start to expand, the storage elastic modulus E′(t) of the non-expandable base material layer (Y2) is preferably 1.1×10 ⁷ Pa or more.

In addition, from the viewpoint of improving the interlayer adhesion between the other layers laminated with the non-expandable substrate layer (Y2), when the non-expandable substrate layer (Y2) contains a resin, the non-expandable substrate layer The surface of (Y2) is subjected to surface treatment, easy adhesion treatment, or primer treatment in the same manner as the above-mentioned swellable base material layer (Y1) using an oxidation method, a bumping method, or the like.

In addition, when the non-expandable base material layer (Y2) contains a resin, it may contain the resin composition (y) at the same time as the resin, or may contain the above-mentioned base material additives.

The non-expandable base material layer (Y2) is a non-expandable layer determined based on the above method. Therefore, the volume change rate (%) of the non-expandable substrate layer (Y2) calculated from the above formula is less than 5%, preferably less than 2%, more preferably less than 1%, and particularly preferably less than Up to 0.1%, the best is less than 0.01%.

In addition, in the non-expandable base material layer (Y2), when the volume change rate is within the above range, the thermally expandable particles may be contained. 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 when heat-expandable particles are contained. Among them, the non-expandable substrate layer (Y2) is preferably one that does not contain heat-expandable particles. When the non-expandable substrate layer (Y2) contains heat-expandable particles, the content is as small as possible. The specific content of the heat-expandable particles is the total amount (100% by mass) relative to the non-expandable substrate layer (Y2). It is usually less than 3% by mass, preferably less than 1% by mass, more preferably less than 0.1% by mass, particularly preferably less than 0.01% by mass, and most preferably less than 0.001% by mass.

<Adhesive layer (X)> The adhesive layer (X) included in the support layer (II) used in one aspect of the present invention may be formed of an adhesive composition (x) containing an adhesive resin. In addition, the adhesive composition (x) may contain additives for adhesives such as crosslinking agents, tackifiers, polymerizable compounds, and polymerization initiators, if necessary. In the following, each component contained in the adhesive composition (x) will be explained. In addition, in the case where the first adhesive layer (X1) and the second adhesive layer (X2) are included in the supporting layer (II), the first adhesive layer (X1) and the second adhesive layer (X2) may also be composed of It is formed by the adhesive composition (x) containing each component shown below.

(Adhesive resin) The adhesive resin used in one aspect of the present invention is preferably a polymer having adhesiveness alone and having a mass average molecular weight (Mw) of 10,000 or more. The mass average molecular weight (Mw) of the adhesive resin used in one aspect of the present invention can improve the adhesive strength, preferably 10,000 to 2 million, more preferably 20,000 to 1.5 million, and particularly preferably 3 Ten thousand to one million.

Specific adhesive resins include, for example, rubber-based resins such as acrylic resins, urethane-based resins, and polyisobutylene-based resins, polyester-based resins, olefin-based resins, polysiloxane-based resins, and polyvinyl ether-based resins Wait.　　These adhesive resins can be used alone or in combination of two or more. In addition, when these adhesive resins are copolymers having two or more structural units, the form of the copolymer is not particularly limited, but may be block copolymers, random copolymers, and grafts Any of the copolymers.

In one aspect of the present invention, from the viewpoint of producing excellent adhesion, the adhesive resin preferably contains acrylic resin. In addition, when the support layer (II) having the first adhesive layer (X1) and the second adhesive layer (X2) is used, the first adhesive layer (X1) due to contact with the energy ray-curable resin layer (I) Since the acrylic resin is contained, the surface of the first adhesive layer (X1) can be easily formed with irregularities.

The content ratio of the acrylic resin in the adhesive resin is, relative to the total amount (100% by mass) of the adhesive resin contained in the adhesive composition (x) or the adhesive layer (X), preferably 30 to 100 mass %, more preferably 50-100% by mass, particularly preferably 70-100% by mass, and most preferably 85-100% by mass.

The content of the adhesive resin is preferably 35 to 100% by mass relative to the total amount (100% by mass) of the effective ingredients of the adhesive composition (x) or the total amount (100% by mass) of the adhesive layer (X). It is preferably 50 to 100% by mass, particularly preferably 60 to 98% by mass, and most preferably 70 to 95% by mass.

(Crosslinking agent) In one aspect of the present invention, the adhesive composition (x) is a case of an adhesive resin containing a functional group, and it is better to further contain a crosslinking agent. The cross-linking agent is capable of reacting with an adhesive resin having a functional group, and using the functional group as a starting point for cross-linking, a cross-linker is formed between the adhesive resins.

The crosslinking agent is, for example, an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, an aziridine-based crosslinking agent, a metal chelate-based crosslinking agent, and the like.　　These cross-linking agents can be used alone or in combination of two or more. Among these cross-linking agents, the viewpoint of improving cohesive force, improving adhesion, and easy availability are preferred. Isocyanate-based cross-linking agents are preferred.

The content of the crosslinking agent can be appropriately adjusted by the number of functional groups possessed by the adhesive resin, and is generally 0.01 to 10 parts by mass, and more preferably 0.03 to 100 parts by mass of the adhesive resin having functional groups. 7 parts by mass, particularly preferably 0.05 to 5 parts by mass.

(Tackifier) In one aspect of the present invention, the adhesive composition (x) can further enhance the adhesion, and may contain a tackifier. In this specification, "tackifier" refers to a component that can assist in improving the adhesion of the above-mentioned adhesive resin, and the mass average molecular weight (Mw) is less than 10,000 oligomers. The above-mentioned adhesive resins are distinguished. The mass average molecular weight (Mw) of the tackifier is preferably 400-9000, more preferably 500-8000, and particularly preferably 800-5000.

Tackifiers, for example, C5 distillation of rosin-based resins, terpene-based resins, styrene-based resins, pentene, isoprene, piperine, 1,3-pentadiene, etc. produced by thermal decomposition of naphtha Copolymerized C5 petroleum resin, indene produced by thermal decomposition of petroleum naphtha, vinyl toluene and other C9 fractions are copolymerized C9 petroleum resin, and these hydrogenated hydrogenated resins.

The softening point of the tackifier is preferably 60 to 170°C, more preferably 65 to 160°C, and particularly preferably 70 to 150°C. In this manual, the "softening point" of the tackifier means the value measured according to JIS K 2531.　　Tackifier can be used alone, or two or more different softening points and structures can be used in combination. When using more than two kinds of plural tackifiers, the weighted average of the softening points of these plural tackifiers is preferably within the above range.

The content of the tackifier is preferably 0.01 to 65% by mass relative to the total amount (100% by mass) of the active ingredients of the adhesive composition (x) or the total amount (100% by mass) of the adhesive layer (X). It is preferably 0.1 to 50% by mass, particularly preferably 1 to 40% by mass, and most preferably 2 to 30% by mass.

(Additives for Adhesive) In one aspect of the present invention, the adhesive composition (x), as long as the effect of the present invention is not impaired, in addition to the above-mentioned additives, it may also contain additives for adhesives used in general adhesives . These additives for adhesives, such as antioxidants, softeners (plasticizers), rust inhibitors, pigments, dyes, extenders, reaction accelerators (catalysts), ultraviolet absorbers, antistatic agents, etc.　　Furthermore, these adhesive additives can be used alone or in combination of two or more. When these adhesive additives are contained, the content of each adhesive additive is preferably 0.0001 to 20 parts by mass, and more preferably 0.001 to 10 parts by mass relative to 100 parts by mass of the adhesive resin.

Also, when the support layer (II) having the second aspect described above having the first adhesive layer (X1) as the swellable adhesive layer is used, the formation of the first adhesive layer (X1) as the swellable adhesive layer The material is formed of the above-mentioned adhesive composition (x) and an expandable adhesive composition (x11) containing thermally expandable particles.　　The thermally expandable particles are as described above. The content of the heat-expandable particles is preferably 1 to 70% by mass relative to the total amount (100% by mass) of the active ingredient of the expandable adhesive composition (x11) or the total amount (100% by mass) of the expandable adhesive layer. It is more preferably 2 to 60% by mass, particularly preferably 3 to 50% by mass, and most preferably 5 to 40% by mass.

On the other hand, when the adhesive layer (X) is a non-expandable adhesive layer, it is preferable that the adhesive composition (x) as a material for forming the non-expandable adhesive layer does not contain heat-expandable particles. In the case of containing heat-expandable particles, the content is as small as possible, generally relative to the total amount (100% by mass) of the active ingredients of the adhesive composition (x) or the total amount (100% by mass) of the adhesive layer (X), It is preferably less than 1% by mass, more preferably less than 0.1% by mass, particularly preferably less than 0.01% by mass, and most preferably less than 0.001% by mass.

In addition, as shown in the laminates 2a and 2b shown in FIG. 2, a support layer (II) having a first adhesive layer (X1) and a second adhesive layer (X2) as a non-expandable adhesive layer is used At 23°C, the storage shear elastic modulus G′(23) of the first adhesive layer (X1) as the non-expandable adhesive layer is preferably 1.0×10 ⁸ Pa or less, and more preferably 5.0× 10 ⁷ Pa or less, particularly preferably 1.0×10 ⁷ Pa or less. When the storage shear elastic modulus G'(23) of the first adhesive layer (X1) as the non-expandable adhesive layer is 1.0×10 ⁸ Pa or less, for example, it is a laminate 2a, 2b shown in FIG. 2, etc. In the structure, it can expand the thermally expandable particles in the expandable base material layer (Y1) through heat expansion treatment, and the surface of the first adhesive layer (X1) in contact with the cured resin layer (I') It is easier to form irregularities. As a result, a laminate can be formed at the interface P between the support layer (II) and the hardened resin layer (I′), which can be easily separated as a whole with a little force. Further, at 23° C., the storage shear elastic modulus G′(23) of the first adhesive layer (X1) as the non-expandable adhesive layer is preferably 1.0×10 ⁴ Pa or more, and more preferably 5.0× 10 ⁴ Pa or more, particularly preferably 1.0×10 ⁵ Pa or more.

The light transmittance of the supporting layer (II) having a wavelength of 375 nm of the laminate of one aspect of the present invention is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the light transmittance is in the above range, when the energy ray (ultraviolet rays) is irradiated through the support layer (II) and the energy ray-curable resin layer (I) is irradiated, the energy ray can make the curing degree of the curable resin layer (I) more upward Promote. In addition, the upper limit of the light transmittance at a wavelength of 375 nm is not particularly limited, and may be, for example, 95% or less. The above-mentioned transmittance can be measured using a known method of a spectrophotometer. From the viewpoint of achieving the above-mentioned light transmittance, when the base material (Y) and the adhesive layer (X) included in the support layer (II) contain a colorant, the content is adjusted so as not to hinder the effect of the present invention. Better is better. When the coloring agent is contained, the content is as small as possible. Generally, it is preferably relative to the total amount (100% by mass) of the active ingredients of the adhesive composition (x) or the total amount (100% by mass) of the adhesive layer (X). It is less than 1% by mass, more preferably less than 0.1% by mass, particularly preferably less than 0.01% by mass, most preferably less than 0.001% by mass, and the content of the coloring agent in the substrate (Y), relative to The total amount (100% by mass) of the active ingredient of the resin composition (y) or the total amount (100% by mass) of the base material (Y) is preferably less than 1% by mass, more preferably less than 0.1% by mass, particularly preferably It is less than 0.01 mass%, and the best is less than 0.001 mass%.

<Energy ray-curable resin layer (I)> The energy-ray-curable resin layer (I) is not particularly limited as long as it can be cured by irradiating energy rays. For example, it contains energy ray-curable components. (a) The energy ray curable resin composition is formed.

[Energy ray hardening component (a)] The energy ray hardening component (a) is a component hardened by irradiation of energy ray. The energy ray-curable component (a), for example, a polymer (a1) having an energy ray-curable double bond with a mass average molecular weight (Mw) of 80,000 to 2,000,000 (hereinafter, also referred to simply as "polymer (a1)"), has A compound (a2) having a molecular weight of 100 to 80,000 with an energy ray-curable double bond (hereinafter, also referred to simply as "compound (a2)"), etc.　　Energy ray hardening component (a) can be used alone or in combination of two or more.

(Polymer (a1)) The 　　 polymer (a1) is a polymer having an energy ray-curable double bond with a mass average molecular weight (Mw) of 80,000 to 2,000,000. The polymer (a1), for example, an acrylic polymer (a11) having a functional group X capable of reacting with a group possessed by other compounds, a group Y having an energy group capable of reacting with the above functional group X, and having an energy ray The energy ray-curable compound (a12) of a curable double bond, an acrylic resin (a1-1) formed by polymerization, and the like.　　Polymer (a1) can be used alone or in combination of two or more.

・Acrylic polymer (a11) The functional group X of the acrylic polymer (a11), for example, hydroxyl group, carboxyl group, amine group, substituted amine group (one or two hydrogen atoms in the amine group, can be A group obtained by substituting a group other than a hydrogen atom) and an epoxy group to select one or more.

The acrylic polymer (a11), for example, is formed by copolymerizing an acrylic monomer having the above functional group X with an acrylic monomer not having the above functional group X, or other than these monomers, and then acrylic acid It is formed by copolymerizing monomers other than the system monomer (non-acrylic monomer). The acrylic polymer (a11) may be a random copolymer or a block copolymer. The acrylic polymer (a11) can be used alone or in combination of two or more.

The acrylic monomer having the above functional group X includes, for example, a monomer containing a hydroxyl group, a monomer containing a carboxyl group, a monomer containing an amine group, a monomer containing a substituted amine group, a monomer containing an epoxy group, and the like. Monomers containing hydroxyl groups, for example, hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (Meth)acrylic acid hydroxyalkyl such as (meth)acrylic acid 2-hydroxybutyl, (meth)acrylic acid 3-hydroxybutyl, (meth)acrylic acid 4-hydroxybutyl; vinyl alcohol, allyl alcohol, etc. Non-(meth)acrylic unsaturated alcohols (unsaturated alcohols that do not have a (meth)acryloyl skeleton)), etc. Monomers containing carboxyl groups, such as (meth)acrylic acid, crotonic acid and other ethylenically unsaturated monocarboxylic acids (monocarboxylic acids with ethylenically unsaturated bonds); fumaric acid, itaconic acid, maleic acid Ethylene unsaturated dicarboxylic acid (dicarboxylic acid with ethylenic unsaturated bond) such as acid and citraconic acid; anhydride of the above ethylenic unsaturated dicarboxylic acid; 2-carboxyethyl methacrylate, etc. Carboxyalkyl (meth)acrylate and so on. Among these, monomers containing hydroxyl groups and monomers containing carboxyl groups are preferred, and monomers containing hydroxyl groups are preferred.

Acrylic monomers that do not have the above functional group X, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( N-butyl meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, (meth) Hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate , Isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), (methyl ) Tridecyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate ((methyl ) Palmitoyl acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), etc. The alkyl group constituting the alkyl ester is C 1～ 18 chain structure of alkyl (meth) acrylate and so on. In addition, acrylic monomers that do not have the aforementioned functional group X, for example, methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, (methyl ) (Meth)acrylates containing alkoxyalkyl groups such as ethoxyethyl acrylate; (meth)acrylates containing aromatic groups such as aryl (meth)acrylates including phenyl (meth)acrylate Acrylate; non-crosslinkable (meth)acrylic amide and its derivatives; (meth)acrylic acid N,N-dimethylaminoethyl, (meth)acrylic acid N,N-dimethyl Non-crosslinkable (meth)acrylates with tertiary amino groups such as aminopropyl groups.　　The above non-acrylic monomers, for example, olefins such as ethylidene and norbornene; vinyl acetate; styrene, etc.

In the acrylic polymer (a11), the content of the structural unit produced by the acrylic monomer having the functional group X is preferably 0.1 to 50% by mass relative to the total amount of the structural units constituting these, and more preferably It is 1 to 40% by mass, and particularly preferably 3 to 30% by mass. When the content of the structural unit is within the above range, the content of the energy ray-curable double bond in the obtained acrylic resin (a1-1) can be easily adjusted to a preferred range.

・Energy ray-curable compound (a12) Energy ray-curable compound (a12) is a compound having a group Y capable of reacting with the functional group X and an energy ray-curable double bond. For the above-mentioned group Y, for example, one or more selected from the group consisting of isocyanate groups, epoxy groups, and carboxyl groups, among which isocyanate groups are preferred. When the energy ray-curable compound (a12) has an isocyanate group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group. The number of energy ray-curable double bonds possessed by the energy ray-curable compound (a12) in one molecule is preferably 1 to 5, more preferably 1 to 3.　　Energy ray hardening compound (a12) can be used alone or in combination of two or more.

Energy ray-curable compound (a12), for example, 2-methacryloyloxyethyl isocyanate, methyl-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl Isocyanate, 1,1-(bisacryloyloxymethyl) ethyl isocyanate; diisocyanate compound or polyisocyanate compound, an acrylic monoisocyanate compound obtained by reacting with hydroxy(meth)acrylate; diisocyanate compound Or a polyisocyanate compound, a polyalcohol compound, and a hydroxyethyl (meth) acrylate obtained by the reaction of acrylic monoisocyanate compound. Among these, 2-methacryl oxyethyl isocyanate is preferred.

In the acrylic resin (a1-1), the content of the energy ray-curable double bond produced by the energy ray-curable compound (a12) relative to the content of the functional group X produced by the acrylic polymer (a11) The ratio is preferably 20 to 120 mol%, more preferably 5 to 100 mol%, and particularly preferably 50 to 100 mol%. When the above ratio is within the above range, the adhesive force of the hardened resin layer (I') formed by hardening can be further increased. In addition, when the energy ray-curable compound (a12) is a monofunctional (having one of the above groups in one molecule) compound, the upper limit of the ratio of the content is 100 mol%, and the energy ray-curable compound (a12) is In the case of a polyfunctional (having two or more of the above groups in one molecule) compound, the upper limit of the ratio of the above content is more than 100 mol%.

The content of the acrylic resin (a1-1) relative to the total amount (100% by mass) of the active ingredient of the energy ray curable resin composition or the total amount (100% by mass) of the energy ray curable resin layer (I) is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, and particularly preferably 3 to 20% by mass.

The mass average molecular weight (Mw) of the polymer (a1) is preferably 100,000 to 2,000,000, and more preferably 300,000 to 1,500,000.

At least a part of the polymer (a1) may be cross-linked by a cross-linking agent (e) described below, or may be uncross-linked.

(Compound (a2)) Compound (a2) is a compound having an energy ray-hardening double bond and a molecular weight of 100 to 80,000. The energy ray-hardenable double bond possessed by the compound (a2) is preferably (meth)acryloyl, vinyl, etc.　　 compound (a2), for example, low molecular weight compound with energy ray hardening double bond, epoxy resin with energy ray hardening double bond, phenol resin with energy ray hardening double bond, etc.　　 Compound (a2) can be used alone or in combination of two or more.

The low-molecular-weight compound having an energy ray-curable double bond, for example, a multifunctional monomer, oligomer, etc., is preferably an acrylate compound having a (meth)acryloyl group. Acrylate compounds, for example, 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxylated bisphenol A Di(meth)acrylate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)benzene Radical] stilbene, 2,2-bis[4-((meth)acryloyloxypolypropyloxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate (tricyclodecane dihydroxy Methyl di(meth)acrylate), 1,10-decanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanedi Alcohol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylic acid Ester, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((methyl) Acryloyloxyethoxy)phenyl]propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth) Group) 2-functional (meth)acrylates such as acryloxypropane; tri(2-(meth)acryloxyethyl) isocyanurate, ε-caprolactone modified tri-(2 -(Meth)acryloyloxyethyl)isocyanurate, ethoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri( Methacrylate, di-trimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(methyl) Multifunctional (meth)acrylates such as acrylate and dipentaerythritol hexa(meth)acrylate; multifunctional (meth)acrylate oligomers such as urethane (meth)acrylate oligomer Wait.

For the epoxy resin having energy ray hardening double bonds and the phenol resin having energy ray hardening double bonds, for example, the contents described in paragraph 0043 of "JP-A-2013-194102" can be used. These resins may also correspond to resins constituting the thermosetting component (f) described later, and in the present invention, they are treated as compound (a2).

The mass average molecular weight (Mw) of the compound (a2) is preferably 100 to 30,000, more preferably 300 to 10,000.

The content of the compound (a2) is preferably 1 to 40 relative to the total amount (100% by mass) of the active ingredient of the energy ray curable resin composition or the total amount (100% by mass) of the energy ray curable resin layer (I) The mass% is more preferably 2-30 mass%, and particularly preferably 3-20 mass%.

[Polymer (b) without energy ray-curable double bonds] When the energy ray-curable resin composition contains the compound (a2), the polymer (b) without the energy ray-curable double bonds (b)( Hereinafter, it is also abbreviated as "polymer (b)").　　Polymer (b) can be used alone or in combination of two or more.

Polymer (b), for example, acrylic polymer, phenoxy resin, urethane resin, polyester, rubber-based resin, urethane acrylate resin, polyvinyl alcohol (PVA), butyral resin, Polyester urethane resin, etc. Among these, an acrylic polymer (hereinafter, "acrylic polymer (b-1)") is preferred.

The acrylic polymer (b-1) may be a well-known component. For example, it may be a homopolymer of one acrylic monomer or a copolymer of two or more acrylic monomers, or may be A copolymer composed of one or more acrylic monomers and a monomer (non-acrylic monomer) other than one or more acrylic monomers.

Acrylic monomers constituting the acrylic polymer (b-1), for example, alkyl (meth)acrylate, (meth)acrylate having a cyclic skeleton, (meth)acrylate containing epoxy groups, (Meth)acrylates containing hydroxyl groups, (meth)acrylates containing substituted amine groups, etc. The "substituted amine group" is as described previously.

Alkyl (meth)acrylate, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylic acid n-butyl ester, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, Heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, ( Isononyl meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), (meth)acrylic acid Tridecyl ester, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate ((meth)acrylic acid Palmyl), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), etc. The alkyl group constituting the alkyl ester is a C 1-18 chain Structure of alkyl (meth) acrylate and so on.

(Meth)acrylate having a cyclic skeleton, for example, isoalkyl (meth)acrylate, dicyclopentyl (meth)acrylate, etc., cycloalkyl (meth)acrylate; benzyl (meth)acrylate Aralkyl (meth)acrylates such as esters; (meth)acrylic acid cyclomethacrylates such as dicyclopentenyl (meth)acrylate; (meth)acrylic acid dicyclopentenyloxyethyl esters (meth) Group) cycloalkyloxy acrylate and the like.

Epoxy-containing (meth)acrylate, for example, (meth)acrylic epoxy. Hydroxy-containing (meth)acrylates, for example, hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-(meth)acrylic acid Hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.　　(Meth)acrylate containing substituted amine groups, for example, N-methylaminoethyl (meth)acrylate, etc.

The non-acrylic monomers constituting the acrylic polymer (b-1) are, for example, olefins such as vinyl and norbornene; vinyl acetate; styrene and the like.

The polymer (b) may be obtained by cross-linking at least a part of it with a cross-linking agent (e) or uncross-linked. At least a part of the polymer (b) obtained by crosslinking with the crosslinking agent (e), for example, the reactive functional group in the polymer (b) reacts with the crosslinking agent (e).　　The above reactive functional groups can be selected according to the type of crosslinking agent (e), etc., and there is no particular limitation. For example, when the crosslinking agent (e) is a polyisocyanate compound, the above-mentioned reactive functional groups, for example, hydroxyl groups, carboxyl groups, amine groups, etc., among these, a hydroxyl group having high reactivity with isocyanate groups is preferred. In addition, when the crosslinking agent (e) is an epoxy-based compound, the above-mentioned reactive functional group, for example, a carboxyl group, an amine group, an amide group, etc., among these, a carboxyl group having high reactivity with an epoxy group Better. Among them, from the viewpoint of preventing corrosion of semiconductor wafers and semiconductor wafer circuits, the reactive functional group is preferably a group other than a carboxyl group.

The polymer (b) having a reactive functional group is obtained, for example, by polymerizing at least the monomer having a reactive functional group. In the case of the acrylic polymer (b-1), any or both of the above-mentioned acrylic monomers and non-acrylic monomers listed as the monomers constituting the acrylic polymer may be given as Reactive functional groups may be used. For example, a polymer (b) having a hydroxyl group as a reactive functional group, for example, a polymer obtained by polymerizing a (meth)acrylate containing a hydroxyl group, etc. Other examples include the above-mentioned acrylic monomers or non- Among acrylic monomers, monomers in which one or more hydrogen atoms are substituted with the above-mentioned reactive functional groups are obtained by polymerization.

In the polymer (b), the content of the structural unit derived from the monomer having a reactive functional group is preferably 1 to 25% by mass, more preferably 2 to 20 with respect to the total amount of the structural units constituting the polymer quality%. When the content of the above-mentioned structural unit is within the above-mentioned range, in the polymer (b), the degree of crosslinking is within a preferable range.

The mass average molecular weight (Mw) of the polymer (b) is preferably from 10,000 to 2,000,000, and more preferably from 100,000 to 1,500,000 from the viewpoint of improving the film-forming property of the energy ray-curable resin composition.

An energy ray-curable resin composition, for example, a composition containing either or both of the polymer (a1) and the compound (a2), and when the compound (a2) is contained, the polymer (b) is contained as good.

The total content of the energy ray-curable component (a) and the polymer (b) is relative to the total amount (100% by mass) of the active component of the energy-ray-curable resin composition or the total amount of the energy-ray-curable resin layer (I) ( 100% by mass), preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and particularly preferably 15 to 70% by mass. When the total content is within the above range, the energy ray hardening property can be further improved.

When the energy ray-curable resin composition or the energy ray-curable resin layer (I) contains the energy ray-curable component (a) and the polymer (b), the content of the polymer (b) is relative to the energy ray-curable The component (a) is 100 parts by mass, preferably 3 to 160 parts by mass, more preferably 6 to 130 parts by mass. When the content of the polymer (b) is within the above range, the energy ray hardening property can be further improved.

The energy ray-curable resin composition, in addition to the energy ray-curable component (a) and the polymer (b), can be blended for the purpose and contains a photopolymerization initiator (c), a coupling agent (d), and a crosslinking agent (e), one or more selected from the group consisting of colorant (g), thermosetting component (f), hardening accelerator (g), filler (h), and general additive (z). For example, when an energy ray-curable resin composition containing an energy ray-curable component (a) and a thermosetting component (f) is used, the energy ray-curable resin layer (I) formed can be improved by heating The adhesion force of the adherend can also increase the strength of the cured resin layer (I′) formed by the energy ray-curable resin layer (I).

等的9-氧硫𠮿

化合物；二苯甲酮、2-(二甲基胺基)-1-(4-嗎啉基苯基)-2-苄基-1-丁酮、乙酮、1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-、1-(O-乙醯肟)等的二苯甲酮化合物；過氧化物化合物；二乙醯基等的二酮化合物；苄基；二苄基；2,4-二乙基氧硫𠮿

；1,2-二苯基甲烷；2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮；2-氯蒽醌等。又，1-氯蒽醌等的醌化合物；胺等的光増感劑等。    　　光聚合起始劑(c)，可單獨使用亦可、將2種以上合併使用亦可。    　　能量線硬化性樹脂組成物或能量線硬化性樹脂層(I)中，光聚合起始劑(c)之含量，相對於能量線硬化性化合物(a)100質量份，較佳為0.01～20質量份，更佳為0.03～10質量份，特佳為0.05～5質量份。[Photopolymerization initiator (c)] Photopolymerization initiator (c), for example, benzine, benzine methyl ether, benzin ether, benzin isopropyl ether, benzin isobutyl Benzoin compounds such as ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal, etc.; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane Acetophenone compounds such as -1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis(2,4,6-trimethylbenzoyl)oxy ) Phenylene phosphine (phosphine), 2,4,6-trimethylbenzyl diphenyl phosphine oxide and other phosphinium oxide compounds; benzyl phenyl sulfide, tetramethyl thiuram single Thioether compounds such as thioether; α-keto alcohol compounds such as 1-hydroxycyclohexyl benzophenone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; 9-oxysulfur 𠮿

9-Oxygen Sulfur 𠮿

Compounds; benzophenone, 2-(dimethylamino)-1-(4-morpholinylphenyl)-2-benzyl-1-butanone, ethyl ketone, 1-[9-ethyl- 6-(2-methylbenzyl)-9H-carbazol-3-yl]-, 1-(O-acetoxime) and other benzophenone compounds; peroxide compounds; diethyl acetyl And other diketone compounds; benzyl; dibenzyl; 2,4-diethyl oxysulfide 𠮿

; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 2-chloroanthraquinone, etc. Also, quinone compounds such as 1-chloroanthraquinone; photo-sensitizing agents such as amine. The photopolymerization initiator (c) may be used alone or in combination of two or more. The content of the photopolymerization initiator (c) in the energy ray-curable resin composition or the energy ray-curable resin layer (I) is preferably 0.01-20 based on 100 parts by mass of the energy ray-curable compound (a). The part by mass is more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.

[Coupling agent (d)] Coupling agent (d), when used with functional groups that can react with inorganic compounds or organic compounds, can improve the adhesion of the energy ray-curable resin layer (I). The cured resin layer (I') formed by curing the energy ray-curable resin layer (I) does not impair heat resistance and improve water resistance.　　Coupling agent (d) can be used alone or in combination of two or more.

The coupling agent (d) is preferably a compound having a functional group capable of reacting with a functional group possessed by the energy ray-curable component (a), polymer (b), etc., and a silane coupling agent is more preferable. Silane coupling agent, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxy Methyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane Silane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino) )Propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-acetylureidopropyltriethoxysilane, 3-hydrothiopropyltrimethoxysilane, 3-hydrothiopropyl Methyldimethoxysilane, bis(3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxy Acetyloxysilane, imidazole silane, etc.

In the energy ray-curable resin composition or the energy ray-curable resin layer (I), the content of the coupling agent (d) is 100 parts by mass relative to the total of 100 parts by mass of the energy ray-curable component (a) and the polymer (b). It is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass. When the content of the coupling agent (d) is more than the above lower limit, the effects of improving the dispersibility of the resin to the filler and improving the adhesiveness of the energy ray-curable resin layer (I) are more significant. Below the limit, the generation of outgassing can be suppressed.

[Crosslinking agent (e)] When the crosslinking agent (e) is used to crosslink the energy ray curable component (a), polymer (b), etc., the initial stage of the energy ray curable resin layer (I) can be adjusted Then force and cohesion.　　Crosslinking agent (e) can be used alone or in combination of two or more.

Crosslinking agent (e), for example, organic polyvalent isocyanate compound, organic polyvalent imine compound, metal chelate-based crosslinking agent (crosslinking agent with metal chelate structure), aziridine (aziridine) system Crosslinking agent (crosslinking agent with acrylcyclopropane) and the like.

Organic polyvalent isocyanate compounds, for example, aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, and alicyclic polyvalent isocyanate compounds (hereinafter, these compounds are also collectively referred to as "aromatic polyvalent isocyanate compounds, etc."); Terpolymers, isocyanurate bodies and adducts of aromatic polyvalent isocyanate compounds, etc.; terminal isocyanate urethane prepolymers obtained by reacting the above-mentioned aromatic polyvalent isocyanate compounds with polyalcohol compounds Wait. The above-mentioned "adduct" means the above-mentioned aromatic polyvalent isocyanate compound, aliphatic polyvalent isocyanate compound or alicyclic polyvalent isocyanate compound, and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or Low molecular weight reactants containing active hydrogen compounds such as castor oil are, for example, xylene diisocyanate adducts of trimethylolpropane described later. In addition, "terminal isocyanate urethane prepolymer" means a prepolymer having an isocyanate group at the molecular terminal while having a urethane bond.

Organic polyvalent isocyanate compounds, more specifically, for example, in 2,4-tolyl diisocyanate; 2,6-tolyl diisocyanate; 1,3-xylene diisocyanate; 1,4-xylene diisocyanate Isocyanates; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone Diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; all or part of the hydroxyl groups in the polyhydric alcohols such as trimethylolpropane, additional Compounds derived from any one or more of xylylene diisocyanate, hexamethyl diisocyanate, and xylene diisocyanate; diamine diisocyanate, etc.

Organic polyvalent imine compounds, for example, N,N'-diphenylmethane-4,4'-bis(1-azridine carboxyl amide), trimethylolpropane-tri-β-acridine Cyclopropanyl propionate, tetramethylolmethane-tris-beta-acrylcyclopropane propionate, N,N'-toluene-2,4-bis(1-azcyclopropane carboxyamide) triethylene melamine Wait.

When an organic polyvalent isocyanate compound is used as the crosslinking agent (e), it is preferable to use a polymer containing a hydroxyl group for the energy ray hardening component (a) and/or the polymer (b). When the crosslinking agent (e) has an isocyanate group and the energy ray hardening component (a) and/or the polymer (b) has a hydroxyl group, the crosslinking agent (e) and the energy ray hardening component (a) and/or The reaction of the polymer (b) can be easily introduced into the crosslinked structure in the energy ray-curable resin layer (I).

In the energy ray-curable resin composition or the energy ray-curable resin layer (I), the content of the crosslinking agent (e) is 100 parts by mass relative to the total of the energy ray-curable component (a) and the polymer (b), It is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass.

[Thermosetting component (f)] The thermosetting component (f), for example, epoxy thermosetting resin, thermosetting polyimide, polyurethane, unsaturated polyester, polysilicon Oxygen resins, etc. Among these, epoxy-based thermosetting resins are preferred.　　The thermosetting component (f) can be used alone or in combination of two or more.

(Epoxy-based thermosetting resin) The epoxy-based thermosetting resin contains epoxy resin (f1) and may further contain a thermosetting agent (f2).

Epoxy resin (f1), for example, well-known resins, for example, multifunctional epoxy resin, bisphenol A diepoxy ether and its hydride, o-cresol novolac epoxy resin, dicyclopentadiene type ring Oxygen resins, biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins, and other bifunctional epoxy compounds.　　Epoxy resin (f1) can be used alone or in combination of two or more.

For the epoxy resin (f1), vinyl (ethenyl) (vinyl), 2-propenyl (allyl), (meth)acryloyl, (meth)acryloylamide, etc. can be used. Hydrocarbon-based epoxy resin. Epoxy resins with unsaturated hydrocarbon groups have higher compatibility with acrylic resins than epoxy resins without unsaturated hydrocarbon groups. Therefore, when an epoxy resin having an unsaturated hydrocarbon group is used, the reliability of the resulting package can be improved.

The number average molecular weight of the epoxy resin (f1) is preferably 300 to 30,000, and more preferably from the viewpoint of the curability of the energy ray-curable resin layer (I) and the strength and heat resistance of the cured resin layer (I′). It is 400～10000, and especially good is 500～3000. The epoxy equivalent of the epoxy resin (f1) is preferably 100 to 1000 g/eq, and more preferably 150 to 800 g/eq.

The thermal hardener (f2) has a function as a hardener for the epoxy resin (f1).　　Thermosetting agent (f2), for example, a compound having more than two functional groups that can react with epoxy groups in one molecule. The above-mentioned functional groups, for example, phenolic hydroxyl groups, alcoholic hydroxyl groups, amine groups, carboxyl groups, acid groups, etc. are anhydrified groups, and the phenolic hydroxyl groups, amine groups, or acid groups are anhydride groups, preferably, Phenolic hydroxyl or amine groups are preferred.　　Thermal hardener (f2) can be used alone or in combination of two or more.

Among the thermosetting agents (f2), phenolic curing agents having phenolic hydroxyl groups are, for example, polyfunctional phenol resins, bisphenols, novolac type phenol resins, dicyclopentadiene phenol resins, aralkyl phenol resins, and the like. Among the thermal hardeners (f2), there are amine-based hardeners with an amine group, such as dicyandiamide. The content of the thermosetting agent (f2) is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the epoxy resin (f1).

The content of the thermosetting component (f) (for example, the total content of the epoxy resin (f1) and the thermosetting agent (f2)) is preferably 1 to 500 parts by mass relative to 100 parts by mass of the polymer (b).

[Curing accelerator (g)] The curing accelerator (g) is a component that can adjust the curing speed of the energy ray-curable resin layer (I). Preferred hardening accelerators (g), for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, etc. ; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 -Imidazoles such as hydroxymethylimidazole; organic phosphinates such as tributylphosphinium, diphenylphosphinium, and triphenylphosphinium; tetraphenylphosphonium tetraphenylboronate, triphenylphosphinium tetrachloride Tetraphenyl boron salts such as phenyl borate. When using a hardening accelerator (g), the content of the hardening accelerator (g) is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the thermosetting component (f).

[General additive (z)] The general additive (z) can use well-known additives, which can be arbitrarily selected according to the purpose without any special restrictions, such as fillers, colorants, plasticizers, antistatic Agents, antioxidants, absorbents, etc. Among the widely used additives (z), they can be used alone or in combination of two or more.

Examples of fillers include inorganic fillers and organic fillers. When these components are used, the coefficient of thermal expansion of the cured resin layer (I') can be adjusted. The energy ray-curable resin layer (I) may or may not contain fillers. When the filler is contained, its content is more effective in suppressing the occurrence of deformation. Compared to the energy ray-curable resin composition The total amount of the active ingredient (100% by mass) or the total amount (100% by mass) of the energy ray-curable resin layer (I) is preferably 5 to 87% by mass, and more preferably 7 to 78% by mass.　　Filling material, for example, made of thermally conductive material. Inorganic fillers, such as powders of silica, alumina, talc, calcium carbonate, titanium white, iron oxide red, silicon carbide, boron nitride, etc.; particles obtained by spheroidizing these inorganic fillers; these Surface modified products of inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc. The average particle size of the filler is preferably 0.01-20 μm, more preferably 0.1-15 μm, and particularly preferably 0.3-10 μm. When the average particle diameter of the filler is within the above range, the adhesiveness of the cured resin layer (I') can be maintained, and the decrease in the penetration rate of the energy ray-curable resin layer (I) can be suppressed.

The energy ray-curable resin composition may or may not contain a coloring agent. When the coloring agent is contained, the content is as small as possible. Specifically, it is effective relative to the energy ray-curable resin composition The total amount of the ingredients (100% by mass) or the total amount of the energy ray-curable resin layer (I) (100% by mass) is preferably less than 5% by mass, more preferably less than 0.1% by mass, and particularly preferably less than 0.01 Mass%, the best is less than 0.001 mass%.

＜<Production method of energy ray curable resin composition>＞ 　　The energy ray curable resin composition can be prepared by blending the components constituting the composition.　　The order of addition when blending the ingredients is not particularly limited, it can add more than two kinds of ingredients at the same time. When using a solvent, you can first mix the solvent with any additive component other than the solvent. The additive component can be diluted before storage and use, or any additive component other than the solvent can be diluted and stored beforehand. These additional ingredients can also be mixed and used. At the time of blending, the mixing method of each component is not particularly limited. For example, a known method such as a method of rotating and mixing a stirrer or a stirring wing, a method of mixing using a kneading machine, and a method of applying ultrasonic waves to mix them are known. It can be selected and used appropriately. The temperature and time of the addition and mixing of the ingredients are not particularly limited as long as they do not cause the deterioration of the added ingredients, as long as they are properly adjusted, and the temperature is preferably 15 to 30°C.

The above solvents, for example, hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropane-1-ol), 1-butanol; ethyl acetate, etc. Esters; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds with amide bond) such as dimethylformamide and N-methylpyrrolidone. Among these, from the viewpoint that the components contained in the energy ray-curable resin composition can be more uniformly mixed, it is preferable to use methyl ethyl ketone, toluene, and ethyl acetate. The solvent may be used alone or in combination of two or more.

The energy ray-curable resin layer (I) may be composed of a single layer, or may be composed of plural layers of two or more layers. The energy ray-curable resin layer (I) composed of two or more layers includes, for example, an energy ray-curable resin layer (Ii) capable of imparting a cured resin layer (I′) with high storage elasticity E′, and has The resin layer of the energy-curable resin layer (I-ii) with high adhesion. With these structures, when the energy ray-curable resin layer (I-ii) is disposed on the surface on the side where the sealing object is placed, in addition to being able to firmly fix the sealing object, after curing, the energy rays The cured resin layer (I') obtained by curing the curable resin layer (Ii) has the function of effectively suppressing deformation, so that the performance of the temporary fixing layer and the performance of the anti-deformation layer can be further improved. The preferred composition and physical properties of the energy ray-curable resin layer (Ii) and (I-ii) can be combined with the desired function in the above preferred composition content and physical properties of the energy ray-curable resin layer (I). Appropriate choice can be used.

The thickness of the energy ray-curable resin layer (I) is preferably 1 to 500 μm, more preferably 5 to 300 μm, particularly preferably 10 to 200 μm, most preferably 15 to 100 μm, and most preferably 20 to 50 μm. When the thickness of the energy ray-curable resin layer (I) is more than the above lower limit, a hardened sealing body that can more effectively suppress deformation can be produced, and below the above upper limit, in addition to suppressing the increase in cost, it can also Get excellent hardenability. The "thickness of the energy ray-curable resin layer (I)" refers to the thickness of the entire energy ray-curable resin layer (I), for example, the energy ray-curable resin layer (I) composed of two or more layers ) Means the total thickness of all layers constituting the energy ray-curable resin layer (I).

The storage elastic modulus E'of the cured resin layer (I') formed by curing the energy ray-curable resin layer (I) at 23°C is obtained as a cured resin layer with a flat surface that can suppress deformation and have a flat surface From the viewpoint of curing the laminate of the sealing body, it is preferably 1.0×10 ⁷ Pa or more, more preferably 1.0×10 ⁸ Pa or more, particularly preferably 5.0×10 ⁸ Pa or more, and most preferably 1.0×10 ⁹ or more, and, It is preferably 1.0×10 ¹³ Pa or less, more preferably 1.0×10 ¹² Pa or less, particularly preferably 5.0×10 ¹¹ Pa or less, and most preferably 1.0×10 ¹¹ Pa or less.

The visible light (wavelength: 380 nm to 750 nm) transmittance of the energy ray-curable resin layer (I) is preferably 5% or more, more preferably 10% or more, particularly preferably 30% or more, and most preferably 50% or more. When the visible light transmittance is within the above range, sufficient energy ray hardening can be obtained. The upper limit of the visible light transmittance is not limited, for example, it can be 95% or less. The above-mentioned transmittance can be measured by a known method using a spectrophotometer.

<Manufacturing method of laminate> The laminate of one aspect of the present invention can, for example, have various expectations that an adhesive layer (X), a base material (Y) and an energy ray-curable resin layer (I) can be formed separately The content of the composition is made by fitting. The formation of each layer can be formed, for example, by applying a resin composition used to form each layer on a release material and drying it. However, the manufacturing method of the laminate of one aspect of the present invention is not limited to the above method, for example, it can be coated on the adhesive layer (X) formed on the release material to form the substrate (Y) The resin composition (y), and then apply the energy ray-curable resin composition on it, as shown in the method, on a specific layer, apply the resin composition in sequence to form a layer to form a multilayer Method. In this case, the multiple layers can be coated simultaneously using, for example, a multi-layer coater (Coater).

[Manufacturing method of hardened sealing body] The manufacturing method of the hardened sealing body of one aspect of the present invention is a method of manufacturing a hardened sealing body using the laminate of one aspect of the present invention, which has the following steps (i) to (iv). Step (i): Step of placing the sealing object on a part of the surface of the energy ray-curable resin layer (I) of the laminate, Step (ii): irradiating the energy ray-curable resin layer with energy rays (I), a step of forming a cured resin layer (I') formed by curing an energy ray-curable resin layer (I) Step (iii): the aforementioned sealing object, and at least the peripheral part of the sealing object is hardened The surface of the resin layer (I') is covered with a thermosetting sealing material, and the sealing material is thermally hardened to form a hardened sealing body including the sealing object. Step (iv): After expanding the thermally expandable particles Treatment to separate the hardened resin layer (I') and the supporting layer (II) at the interface, and the step of preparing a hardened sealing body with a hardened resin layer, and the hardened sealing body in one aspect of the present invention , Refers to the object obtained by hardening the sealing material after covering the sealing object with the sealing material, which is composed of the sealing object and the hardened material of the sealing material.

FIG. 4 is a schematic cross-sectional view illustrating a step of manufacturing a hardened seal using the laminate 1a shown in FIG. 1(a). Hereinafter, each step described above will be described with reference to FIG. 4 as appropriate.

<Step (i)> Step (i) is a step of placing a sealing object on a part of the surface of the energy ray-curable resin layer (I) included in the laminate of one aspect of the present invention. FIG. 4(a) illustrates that in the laminate 1a in this step, the adhesive surface of the adhesive layer (X) of the support layer (II) is attached to the support 50 to make the energy ray-curable resin layer (I) Part of the surface of the surface, the state of the sealing object 60 is placed. In addition, in FIG. 4(a), in order to explain the example of using the laminate 1a shown in FIG. 1(a), when a laminate having an aspect of the present invention having another configuration is used, it is similarly a support, The laminate and the object to be sealed are laminated or placed in this order.

The temperature condition in step (i) is preferably performed at a temperature at which the thermally expandable particles are not expanded, for example, under an environment of 0 to 80°C (wherein the expansion initiation temperature (t) is 60 to 80°C) In this case, it is better to perform under the environment where the expansion start temperature (t) is not reached.

The support is preferably the whole surface of the adhesive surface attached to the adhesive layer (X) of the laminate.　　 Therefore, the support is preferably plate-shaped. In addition, as shown in FIG. 4, the surface area of the support attached to the side of the adhesive surface of the adhesive layer (X) is preferably equal to or greater than the adhesive surface area of the adhesive layer (X).

The material constituting the support body may be appropriately selected in accordance with the type of sealing object, the type of sealing material used in step (ii), etc., and considering the required characteristics such as mechanical strength and heat resistance. Specifically, the materials constituting the support, for example, metallic materials such as SUS; non-metallic inorganic materials such as glass and silicon wafers; epoxy resin, ABS resin, acrylic resin, engineering plastics, high-end engineering plastics, polyacrylic acid Resin materials such as amine resins and polyimide resins; composite materials such as glass epoxy resins; among these, SUS, glass, and silicon wafers are preferred. In addition, from the viewpoint that the energy ray-curable resin layer (I) can be irradiated with energy rays through a support, the support is preferably a transparent material such as glass. In addition, engineering plastics can be exemplified by nylon, polycarbonate (PC), and polyethylene terephthalate (PET). High-end engineering plastics can be exemplified by polyphenylene sulfide (PPS), polyether sock (PES), and polyether-ether ketone (PEEK).

The thickness of the support can be appropriately selected in accordance with the type of sealing object, the type of sealing material used in step (ii), etc., and is preferably 20 μm or more and 50 mm or less, and more preferably 60 μm or more and 20 mm or less.

On the other hand, the energy rays are placed on a part of the sealing object on the surface of the curable resin layer (I), for example, semiconductor wafers, semiconductor wafers, compound semiconductors, semiconductor packages, electronic parts, sapphire substrates, displays , Flat substrates, etc.

When the object to be sealed is a semiconductor wafer, when the laminate of one aspect of the present invention is used, a semiconductor wafer with a cured resin layer can be manufactured. As the semiconductor wafer, a conventionally known one can be used, and on its circuit surface, an integrated circuit composed of circuit elements such as transistors, resistors, and condensers is formed. Afterwards, the semiconductor wafer is preferably placed on the inner surface opposite to the circuit surface by being covered with the surface of the energy ray-curable resin layer (I). In this case, after mounting, the circuit surface of the semiconductor wafer is exposed. Mounting of semiconductor wafers can be carried out using well-known devices such as flip chip bonders and die bonders.　　Semiconductor chip configuration layout, configuration number, etc., can be made according to the purpose of the package form, production quantity, etc. can make appropriate decisions.

Among them, like the laminate of one aspect of the present invention, the sealing material is used to cover a larger area of the semiconductor wafer than FOWLP, FOPLP and other semiconductor wafers, forming not only the circuit surface of the semiconductor wafer, but also the sealing material In the surface area of the package, a package that can also form a wire redistribution layer (RDL) is preferred. Therefore, the semiconductor wafer is a part of the surface on which the energy ray is placed on the curable resin layer (I). The plural semiconductor wafers are formed in rows and columns at a specific distance. It is preferred that a plurality of semiconductor wafers are placed on the surface at a specific distance, with the entire column as a plurality of rows and in a matrix of a plurality of columns.　　The spacing between semiconductor chips can be appropriately determined in accordance with the intended packaging form.

<Step (ii)> Step (ii) is a step of irradiating the energy ray curable resin layer (I) with energy rays to form a cured resin layer (I′) formed by curing the energy ray curable resin layer (I) . FIG. 4(b) illustrates the state in which the energy ray-curable resin layer (I) is cured to form a cured resin layer (I′) in this step. The type and conditions of the energy ray are not particularly limited as long as the type and conditions of the energy ray-curable resin layer (I) can be cured to the extent that they can fully exert their functions. Choose and use according to the expected process. When the energy ray-curable resin layer (I) is cured, the illuminance of the energy ray is preferably 4 to 280 mW/cm ² , and during the aforementioned curing, the light quantity of the energy ray is preferably 5 to 1000 mJ/cm ² , 100 to 500mJ/cm ² is preferable. The types of energy rays and irradiation devices are as described above. The energy beam can be irradiated in any direction as long as the energy beam curable resin layer (I) is irradiated by the energy beam, for example, the support body (II) and the support body 50 have excellent light penetration when used In the case of transmissivity, it can pass through the support (II) and the support 50 (that is, in FIG. 4(b), it is injected from the surface opposite to the adhesive layer (X) of the support 50, through the support The body 50, the adhesive layer (X) and the base material (Y)) irradiate the energy ray to the energy ray-curable resin layer (I).

<Step (iii)> Step (iii) is to cover the sealing object with a thermosetting sealing material (hereinafter, also referred to as "coating process"), and the hardened resin layer (at least the peripheral portion of the sealing object) ( I') the step of thermally hardening the sealing material to form a hardened sealing body including the object to be sealed. In the coating process, first, in order to coat the object to be sealed with a sealing material, at least the peripheral portion of the object is sealed with at least the surface of the hardened resin layer (I'). The sealing material covers the entire exposed surface of the object to be sealed, and also fills the gaps between multiple semiconductor wafers. For example, FIG. 4(c) illustrates a state where the entire surface of the sealing object 60 and the cured resin layer (I') is covered with the sealing material 70.

The sealing material has the function of sealing the object and its additional requirements by external environmental protection. The sealing material used in the manufacturing method of one aspect of the present invention is a thermosetting sealing material containing a thermosetting resin. In addition, the sealing material may be solid, such as granular, granular, or film-like at room temperature, or liquid in the form of a composition. From the viewpoint of workability, the sealing resin is a film-like sealing material Film is better.

The coating method can be selected according to the type of sealing material used in the conventional sealing steps, for example, the rolling layer method, vacuum pressing method, vacuum layer method, spin coating method, die coating can be used Distribution method, transfer molding method, compression molding die method, etc.

Then, after the coating process, the sealing material is thermally hardened to obtain a hardened sealing body in which the sealing object is sealed by the sealing material. In addition, the thermosetting treatment in step (iii) is performed at a temperature at which the thermally expandable particles do not expand. For example, when a laminate having a layer containing thermally expandable particles is used, the expansion may not start until the thermally expandable particles are expanded. It is better to proceed under the temperature conditions of the initial temperature (t).

In the manufacturing method according to one aspect of the present invention, as shown in FIG. 4(c), the surface of the object to be sealed 60 sealed by the sealing material 70 is provided with a cured resin layer (I′). Heat hardening treatment. Since the hardened resin layer (I’) is provided, the difference in shrinkage stress between the surfaces of the two hardened sealing bodies obtained can be reduced, and deformation caused by the hardened sealing body can be effectively suppressed.

<Step (iv)> Step (iv) is that the above-mentioned thermally expandable particles undergo expansion treatment to separate the hardened resin layer (I') and the support layer (II) at the interface to produce a hardened resin layer The steps of hardening the sealing body. Fig. 4(d) is an illustration to show that the thermally expandable particles undergo expansion treatment and form a separated state at the interface P between the hardened resin layer (I') and the support layer (II). As shown in FIG. 4(d), a separation result is formed at the interface P, and a cured resin with a cured sealing body 80 and a cured resin layer (I′) formed by sealing the object 60 to be sealed can be prepared.层的形状封体100。 Hardened sealing body 100. In addition, the presence of the hardened resin layer (I’) not only has the function of effectively suppressing the deformation caused by the hardened sealing body, but also protects the sealed object and improves the reliability of the sealed object.

"Expansion treatment" in step (iv) refers to heating the thermally expandable particles above the expansion start temperature (t), subjecting the thermally expandable particles to expansion treatment, and then curing the resin layer (I') through this treatment The surface of the supporting layer (II) on the side is uneven. As a result, the interface P can be easily separated as a whole when a little force is used. When the thermally expandable particles are expanded, "the temperature at which the expansion initiation temperature (t) or more" means "the expansion initiation temperature (t) + 10°C" or more, and the "expansion initiation temperature (t) + 60°C" or less Preferably, "expansion onset temperature (t) + 15°C" or more and "expansion onset temperature (t) + 40°C" or less are preferable. In addition, the heating method is not particularly limited. For example, a heating method such as a hot plate, an oven, a sintering furnace, an infrared lamp, a hot air blower, etc. may be used to make the interface between the support layer (II) and the hardened resin layer (I′) From the viewpoint of easy separation of P, the heat source during heating is preferably a method that can be provided on the support 50 side.

The hardened sealing body with a hardened resin layer obtained by this method can then be subjected to necessary processing. An example of this is the following description. In the following description, the object to be sealed 60 will be described as the semiconductor wafer 60 is used.

<First Grinding Step> In FIG. 5(a), it is a hardened sealing body 100 with a hardened resin layer obtained according to the above-mentioned manufacturing method, and in FIG. 5(b), for illustrating the use of grinding means 110 to pair with the hardened sealing body 80 The hardened resin layer (I') is ground for the opposite side surface 100a to expose the circuit surface 60a of the semiconductor wafer 60 in the first grinding step. The grinding means 110 is not particularly limited. For example, a well-known grinding device such as a grinder can be used. When implementing the first grinding step, from the viewpoint of workability, it is better to fix the surface of the hardened sealing body on the side of the hardened resin layer (I’) to another support. From the viewpoint of workability, before the first grinding step, it can be cut to a specific size containing one or more wafers.

<Steps for redistributing the wire (RDL) and forming external terminal electrodes> In FIG. 5(c), the circuit surface 60a of the semiconductor wafer 60 exposed on the surface of the hardened sealing body 80 is formed as a circuit through the first grinding step The connected wire redistribution layer (RDL) 200, and the steps of forming the wire redistribution layer (RDL) of the external terminal electrode 300 and forming the external terminal electrode. The material of RDL 200 is not particularly limited as long as it is a conductive material. For example, it can be metals such as gold, silver, copper, aluminum, and alloys containing these metals. The wire redistribution layer (RDL) 200 can be formed by a known method such as subtractive process or semi-additive process, and if necessary, one or more insulating layers can be provided. The external terminal electrode 300 is electrically connected to the external electrode pad of the wire redistribution layer (RDL) 200. The external electronic electrode 300 can be formed by welding, for example, solder balls (Solder balls).

<Cutting Step> In FIG. 5(d), a step of cutting the hardened sealing body 100 with a hardened resin layer connected to the external terminal electrode 300 is explained.　　Slicing can be carried out according to the method of one unit of semiconductor wafer, or a specific size including a plurality of semiconductor wafers. The method of cutting the hardened sealing body 100 with a hardened resin layer is not particularly limited, and it can be implemented using cutting means such as a dicing saw.

<Second Grinding Step> In FIG. 5(e), in order to illustrate the use of grinding means 110 to grind the hardened resin layer (I′) on the opposite side of the wire redistribution layer (RDL) 200 disposed to the hardened sealing body 80 The second grinding step. At this time, the surface on the RDL 200 side of the hardened sealing body 80 is preferably fixed using an inner surface grinding machine (BACK GRINDING TABLE) or the like. The grinding means 110 is the same as the first grinding step, for example. In the second grinding step, it is possible to grind a part of the hardened resin layer (I’) or grind all the hardened resin layers (I’). The method of grinding hardened resin layer (I’) can make the resulting semiconductor package more compact. Therefore, from this point of view, it is preferred that all of the cured resin layer (I') be ground. On the other hand, in the case where the second grinding step is not performed or only part of the hardened resin layer (I') is performed, the hardened resin layer (I') also has the function of protecting the inner surface of the semiconductor wafer 60. [Example]

This embodiment will be specifically described using the following examples, but the present invention is not limited to the following examples. In the following description, the curable resin layer (I) means both "energy ray curable resin layer (I)" and "thermosetting resin layer".　　 Furthermore, the physical property values in each case are the values measured according to the following methods.

<Mass average molecular weight (Mw)> Using a gel permeation chromatography analyzer (manufactured by Tosoh Corporation, product name "HLC-8020"), the measurement is performed under the following conditions, and the measurement is converted using standard polystyrene value. (Measurement conditions) Columns: Connect "TSK guard column HXL-L", "TSK gel G2500HXL", "TSK gel G2000HXL", "TSK gel G1000HXL" (both are manufactured by Tosoh Corporation) in this order　　・Column temperature: 40 ℃ 　　・Development solvent: tetrahydrofuran 　　・Flow rate: 1.0mL/min

<Measurement of the thickness of each layer> 　　Measured using a constant pressure thickness measuring device (model: "PG-02J", standard specifications: JIS K6783, Z 1702, Z 1709) manufactured by TECLOCK Corporation.

<Measurement method of the initial expansion temperature (t) of the thermally expandable particles and the maximum expansion temperature> The initial expansion temperature (t) of the thermally expandable particles used in each example was measured according to the following method. A sample made of an aluminum cup with a diameter of 6.0 mm (inner diameter of 5.65 mm) and a depth of 4.8 mm was added with 0.5 mg of thermally expandable particles to be measured, and an aluminum cover (diameter of 5.6 mm and thickness of 0.1 mm) was added.　　Using a dynamic viscoelasticity measuring device, the height of the sample is measured from the top of the aluminum cover of the sample with a force of 0.01N applied by a pressurizer. Subsequently, with a force of 0.01 N applied to the pressurizer, from 20 °C to 300 °C, heating is performed at a heating rate of 10 °C/min, and the amount of displacement in the vertical direction of the pressurizer is measured. The initial temperature of displacement in the direction is set as the initial temperature of expansion (t). The maximum expansion temperature is the temperature at which the displacement measured by the above method reaches the maximum.

<Evaluation of deformation> The curable resin layer (I) of the sheet for forming the curable resin layer (I) prepared in each example was attached to a silicon wafer (size: 12 inches, thickness: 100 μm). Subsequently, a resin composition prepared by mixing an epoxy resin (manufactured by STRUERS, product name "EPO-FIX resin") and a hardener (manufactured by STRUERS company, product name "EPO-FIX hardener") as a thermosetting property The resin composition was applied to the surface of the silicon wafer on the opposite side to the curable resin layer (I) with a thickness of 30 μm. In this way, a measurement sample before curing in the order of the curable resin layer (I)/silicon wafer/thermosetting resin composition layer was prepared. Subsequently, when the curable resin layer (I) is an energy ray-curable resin layer (I), the ultraviolet irradiation device RAD-2000 (manufactured by Linde Co., Ltd.) was used to adjust the ultraviolet ray according to the degree of 215mW/cm ² and the amount of light 187mJ/ Irradiation 3 times under the condition of cm ^{2 to} harden the energy ray-curable resin layer (I) to form a cured resin layer (I′). When the curable resin layer (I) is a thermosetting resin layer (I), it can be heated at 180°C for 60 minutes to form a cured resin layer (I′). Thereafter, the above thermosetting resin composition is heated and hardened to form a thermosetting resin layer, and a measurement sample after curing in the order of hardening resin layer (I′)/silicon wafer/thermosetting resin layer is prepared. After placing the measured sample after hardening on a horizontal bed, visually observe and evaluate whether it is deformed according to the following criteria. In addition, the part of the "silicon wafer/thermosetting resin layer" in the measurement sample after curing is equivalent to the structure of the hardened sealing body formed by sealing the semiconductor wafer with thermosetting resin, so this evaluation result can be used as Evaluation of the performance of the anti-deformation layer of the hardened resin layer (I'). A: The amount of deformation is 3 mm or less. B: The amount of deformation is greater than 3 mm and less than 15 mm. C: The amount of deformation is 15 mm or more. In addition, when the curable resin layer (I) is not attached, the deformation amount of the silicon wafer/thermosetting resin layer in the same order as above is 15 mm.

<Evaluation of Separability> After the silicon wafer is attached to the surface of the curable resin layer (I) of the laminate obtained in each example, the curable resin layer (I) is cured by energy rays or thermal energy to form a cured resin layer (I'). Subsequently, the expandable base material layer (Y1) was expanded via a heat expansion process to separate the hardened resin layer (I') from the support layer (II), and then the separation properties were evaluated based on the following criteria. In addition, the curing conditions of the curable resin layer (I) prepared in each example and the heat expansion treatment conditions of the support layer (II) are the same as those described in Examples 1 to 5 and Reference Example 1 described later. .　　A: Separation can be formed, and the appearance of the hardened resin layer (I’) is good, and no paste remains.　　B: Separation can be formed, although the appearance of the hardened resin layer (I’) is good, but some of the paste remains.　　C: Separation could not be formed, or paste remained on the cured resin layer (I’), or the appearance of the cured resin layer (I’) was poor.

<Storage elastic modulus E'of the expandable base material layer (Y1)> The 200 μm thick expandable base material layer (Y1) for measuring the storage elastic modulus E'obtained was cut into 5 mm in length×30 mm in width×200 μm in thickness After the size, remove the peeling material as a test sample. Using a dynamic viscoelasticity measuring device (manufactured by TA Instruments, product name "DMAQ800"), under the conditions of test start temperature 0 °C, test end temperature 300 °C, heating rate 3 °C/min, vibration number 1 Hz, amplitude 20 μm, At a specific temperature, the storage elastic modulus E'of the test sample is measured.

＜Storage shear elastic modulus G'of the first adhesive layer (X1) and the second adhesive layer (X2)＞ Cut the first adhesive layer (X1) and the second adhesive layer (X2) to diameter For the 8mm round shape, remove the peeling material and stack it to form a thickness of 3mm as the test sample. Using a viscoelasticity measuring device (manufactured by Anton Paar, device name "MCR300"), spiral shear was used under the conditions of test start temperature 0°C, test end temperature 300°C, heating rate 3°C/min, vibration number 1 Hz Method to determine the storage shear elastic modulus G'of the test sample at a specific temperature.

<Storage elastic modulus E'of the cured resin layer (I')> The cured resin layer (I) obtained in each example after curing was used as a test piece, and a dynamic viscoelasticity measuring device (manufactured by TA Instruments, product name "DMAQ800" was used "), under the conditions of the test start temperature of 0 °C, the test end temperature of 300 °C, the heating rate of 3 °C/min, the number of vibrations of 11 Hz, and the amplitude of 20 μm, at 23 °C, the formed hardened resin layer (I') was measured The storage elasticity E'. In addition, in the test piece, when the curable resin layer (I) is an energy ray curable resin layer (I), the ultraviolet irradiation device RAD-2000 (manufactured by Linde Co., Ltd.) is used, and the ultraviolet ray is 215 mW/cm ² 3. If the light intensity is 187mJ/cm ^{2 and} the condition is irradiated three times to harden it, when the curable resin layer (I) is a thermosetting resin layer (I), it is used for heat curing at 180°C for 60 minutes.

Synthesis Example 1 (Synthesis of "urethane acrylate resin" used for the expandable base layer (Y1)) In a reaction vessel under a nitrogen atmosphere, relative to polycarbonate diol (carbonic acid) with a mass average molecular weight of 1,000 (Ester type diol) 100 parts by mass, isophorone diisocyanate is added in such a way that the equivalent ratio of the hydroxyl group of the polycarbonate diol to the isocyanate group of isophorone diisocyanate is 1/1, and then 160 mass parts of toluene is added , Stir under a nitrogen atmosphere, and then perform the reaction at 80°C for more than 6 hours to bring the isocyanate group concentration to the theoretical amount. Next, a solution obtained by diluting 1.44 parts by mass of 2-hydroxyethyl methacrylate (2-HEMA) in 30 parts by mass of toluene was added, and then the reaction was carried out at 80°C for 6 hours until the isocyanate groups at both ends disappeared, and A urethane prepolymer with a mass average molecular weight of 29,000 was prepared. Subsequently, 100 parts by mass of the urethane prepolymer obtained above, 117 parts by mass of methyl methacrylate (MMA), and 2-hydroxyethyl methacrylate (2- HEMA) 5.1 parts by mass, 1.1 thioglycerol 1.1 parts by mass, and 50 parts by mass of toluene, while stirring, the temperature was raised to 105 ℃. Subsequently, 2.2 parts by mass of toluene diluted with 2.2 parts by mass of free radical initiator (manufactured by Japan Finechem Co., Ltd., product name "ABN-E") was maintained in the reaction vessel at 105°C for 4 hours. The resulting solution was dropped into it. After the dripping was completed, the reaction was carried out at 105°C for 6 hours to prepare a solution of urethane acrylate resin with a mass average molecular weight of 105,000.

[Fabrication of the supporting layer (II) forming sheet] Manufacturing Example 1 (Supporting layer (II-A)) Fabricating the supporting layer (II-A) sheet in the following order (1-1) to (1-4) . The details of the materials used to form each layer are shown below.

<Adhesive resin> ・Acrylic copolymer (i): It has a raw material list formed by 2-ethylhexyl acrylate (2EHA)/2-hydroxyethyl acrylate (HEA)=80.0/20.0 (mass ratio) Acrylic copolymer with a structural unit Mw of 600,000.・Acrylic copolymer (ii): with n-butyl acrylate (BA)/methyl methacrylate (MMA)/2-hydroxyethyl acrylate (HEA)/acrylic acid=86.0/8.0/5.0/1.0 (Mass ratio) An acrylic copolymer having a structural unit Mw of 600,000 by the raw material monomer formed. <Additive> ・Isocyanate crosslinking agent (i): manufactured by Tosoh Corporation, product name "CORONATE L", solid content concentration: 75% by mass. <Thermally expandable particles> ・Thermally expandable particles A: manufactured by KUREHA Corporation, product name "S2640", expansion initiation temperature (t) = 208°C, average particle diameter (D ₅₀ ) = 24 μm, 90% particle diameter (D ₉₀ )=49μm. <Peeling material> ・Heavy peeling film: manufactured by Linde Co., Ltd., product name "SP-PET382150", one side of polyethylene terephthalate (PET) film, equipped with silicone-based peeling agent The thickness of the stripper layer formed: 38 μm.・Light release film: The product name "SP-PET381031" manufactured by Linde Co., Ltd., one side of the PET film is provided with a release agent layer formed of a polysiloxane-based release agent, thickness: 38 μm.

(1-1) The first adhesive layer (X1) is formed in 100 parts by mass of the solid content of the acrylic copolymer (i) as an adhesive resin, and 5.0 parts by mass of the isocyanate-based crosslinking agent (i) is added After dilution with toluene and uniform stirring, an adhesive composition with a solid content concentration (effective component concentration) of 25% by mass was prepared. Subsequently, the adhesive composition was applied to the surface of the release agent layer (hereinafter, "peeling treatment surface") of the heavy peeling film to form a coating film, and the coating film was dried at 100°C for 60 seconds to form The first adhesive layer (X1) of a non-thermally expandable adhesive layer with a thickness of 5 μm. In addition, at 23° C., the storage shear elastic modulus G′ (23) of the first adhesive layer (X1) was 2.5×10 ⁵ Pa. In addition, the first adhesive layer (X1) measured in accordance with the above method had an adhesive force at 23° C. of 0.3 N/25 mm.

(1-2) The second adhesive layer (X2) is formed on 100 parts by mass of the solid content of the acrylic copolymer (ii) as an adhesive resin, and 0.8 part by mass of the isocyanate-based crosslinking agent (i) is added After dilution with toluene and uniform stirring, an adhesive composition with a solid content concentration (effective component concentration) of 25% by mass was prepared. Subsequently, the adhesive composition was applied to the peeling treatment surface of the light peeling film to form a coating film, and the coating film was dried at 100° C. for 60 seconds to form a second adhesive layer (X2) with a thickness of 10 μm. ). In addition, at 23° C., the storage shear elastic modulus G′ (23) of the second adhesive layer (X2) was 9.0×10 ⁴ Pa. In addition, the adhesive force of the second adhesive layer (X2) measured according to the above method at 23°C was 1.0 N/25 mm.

(1-3) Preparation of base material (Y) To 100 parts by mass of the solid content of the urethane acrylate resin obtained in Synthesis Example 1, 6.3 parts by mass of the isocyanate-based crosslinking agent (i) was added As a catalyst, 1.4 parts by mass of dioctyltin bis(2-ethylhexanoate) and the above-mentioned thermally expandable particles A were diluted with toluene and stirred uniformly to obtain a solid content concentration (effective component concentration) of 30% by mass Resin composition. The content of the heat-expandable particles A is 20% by mass relative to the total amount (100% by mass) of the effective ingredients in the resulting resin composition. Subsequently, this resin composition was applied to a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., product name "COSMO-SHUNE A4100") with a thickness of 50 μm as a non-expandable substrate, stretched Strength value: 0 mN/5 mmφ) A coating film was formed on the surface, and the coating film was dried at 100° C. for 120 seconds to form an expandable substrate layer (Y1) with a thickness of 50 μm. Among them, the PET film of the above non-expandable substrate is equivalent to the non-expandable substrate layer (Y2). According to the above method, a base material (Y) formed of an expandable base material layer (Y1) with a thickness of 50 μm and a non-expandable base material layer (Y2) with a thickness of 50 μm is prepared.

In addition, the sample for measuring the storage elastic modulus E′ and the tensile strength value of the expandable base material layer (Y1) is to apply the resin composition to form a coating film on the peeling treatment surface of the light peeling film, and make the The coating film was dried at an atmospheric temperature of 100°C for 120 seconds to similarly form an expandable substrate layer (Y1) with a thickness of 200 μm. Subsequently, the storage elastic modulus and the tensile strength value at each temperature of the expandable base material layer (Y1) were measured based on the above measurement method. The measurement results are shown below.・Storage elasticity E'(23)=23×10 ⁸ Pa at 23℃・Storage elasticity E′(100)=3.0×10 ⁶ Pa at 100℃・Storage elasticity E′(208) at 208℃ )=5.0×10 ⁵ Pa ・Tensile strength value=0mN／5mmφ

(1-4) Lamination of each layer The non-expandable base material layer (Y2) of the base material (Y) prepared according to (1-3) above, and the second formed by (1-2) above While bonding the adhesive layer (X2), the expandable base material layer (Y1) is bonded to the first adhesive layer (X1) formed in (1-1) above. Subsequently, in order of light peeling film/second adhesive layer (X2)/non-expandable substrate layer (Y2)/expandable substrate layer (Y1)/first adhesive layer (X1)/heavy peeling film Together, a sheet for forming the support layer (II-A) was prepared.

Production Example 2 (Support Layer (II-B)) In Production Example 1, the drying conditions after forming the coating film by changing the thermally expandable particles A to the following thermally expandable particles B and applying the resin composition were changed to atmospheric temperature The sheet for forming the support layer (II-B) was prepared in the same manner as in Production Example 1 except that the treatment was performed at 100°C for 1 minute.　　 Heat-expandable particles B: manufactured by Japan FERRITE Co., Ltd., product name "031-40DU", expansion starting temperature (t) = 80°C.

Production Example 3 (Supporting layer (II-C)) In Production Example 1, the drying conditions after the heat-expandable particles A were changed to the following heat-expandable particles C and the coating resin composition was formed into a coating film were changed to atmospheric temperature The sheet for forming the support layer (II-C) was prepared in the same manner as in Production Example 1 except that the treatment was performed at 100°C for 1 minute.　　 Heat-expandable particles C: manufactured by Japan FERRITE Co., Ltd., product name "053-40DU", expansion starting temperature (t) = 100°C.

In addition, in Production Examples 2 and 3, when the sheet for forming the support layer (II) was formed, although the drying temperature after forming the coating film by applying the resin composition, the expansion starting temperature (t) of the thermally expandable particles was It is high, but because the above drying temperature is atmospheric temperature, no foaming phenomenon is found on the formed support layer (II).

Manufacturing Example 4 (Supporting layer (II-D)) In Manufacturing Example 1, except that the thermally expandable particles A were changed to the following thermally expandable particles D, and the drying conditions after forming the coating film by applying the resin composition were changed to atmospheric temperature The sheet for forming the support layer (II-D) was prepared in the same manner as in Production Example 1 except that the treatment was performed at 100°C for 1 minute.　　 Heat-expandable particles D: manufactured by Japan FERRITE Co., Ltd., product name "920-40DU", expansion starting temperature (t) = 120°C.

[Preparation of the sheet for forming the hardenable resin layer (I)] Manufacturing example 5 (Energy line hardenable resin layer (IA)) The following types and addition amounts are blended (any one is the "effective ingredient ratio") Each component of the product was diluted with methyl ethyl ketone and stirred uniformly to prepare a solution of a hardenable composition with a solid content concentration (effective component concentration) of 61% by mass. [(a2) Ingredients] Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., product name "KAYARAD DPHA"): 17.6 parts by mass [(b) Ingredients] Acrylic polymer: Butyl acrylate (BA) (55 parts by mass), methyl acrylate (MA) (10 parts by mass), epoxy methacrylate (GMA) (20 parts by mass) and 2-hydroxyethyl acrylate (HEA) (15 parts by mass) Acrylic resin formed (glass transition temperature: -28°C, Mw: 800,000): 17 parts by mass [(c) ingredient] phenyl 1-hydroxycyclohexanone (manufactured by BASF, product name "IRGACURE-184" ): 0.5 parts by mass [(d) ingredients] oligomer type silane coupling agent containing epoxy groups (Mitsubishi Chemical Co., Ltd., product name "MSEP2"): 0.6 parts by mass [(e) ingredients] TDI Crosslinking agent (Toyo Chemical Co., Ltd., product name "BHS-8515"): 0.5 parts by mass [(f) ingredient] Liquid bisphenol A epoxy resin (manufactured by Japan Catalyst Co., Ltd., product name) "BPA328"): 16 parts by mass · Dicyclopentadiene-type epoxy resin (manufactured by Japan Catalyst Co., Ltd., product name "XD-1000L"): 18 parts by mass · Dicyclopentadiene-type epoxy resin ( DIC Co., Ltd., product name "HP-7200HH"): 27 parts by mass · Dicyandiamide (made by ADEKA Co., Ltd., product name "ADEKA Partner 3636AS"): 1.5 parts by mass ((g) Ingredient] 　　Imidazole (manufactured by Shikoku Chemical Industry Co., Ltd., product name "2PH-Z"): 1.5 parts by mass

The solution of the curable composition prepared according to the above method is applied to the peeling treatment surface of the light peeling film to form a coating film, and the coating film is dried at 120°C for 2 minutes to form an energy line with a thickness of 25 μm For the curable resin layer (IA), a sheet for forming the energy ray curable resin layer (IA) formed of the energy ray curable resin layer (IA) and the lightly peelable film is prepared.

Production Example 6 (Energy ray-curable resin layer (IB)) Blended with the following types and addition amounts (each of which is the "effective ingredient ratio"), and then diluted with methyl ethyl ketone, evenly Stir to prepare a solution of a hardenable composition with a solid content concentration (effective component concentration) of 61% by mass. [(a2) Ingredient] 　　 ε-caprolactone modified tri-(2-acryloyloxyethyl)isocyanurate (manufactured by Shin Nakamura Chemical Industry Co., Ltd., product name "A-9300-1CL" , 3-functional UV-curable compound): 10 parts by mass [(b) ingredient] Acrylic resin: methyl acrylate (MA) (85 parts by mass) / 2-hydroxyethyl acrylate (HEA) (15 parts by mass) Acrylic resin formed by copolymerization: 28 parts by mass [(c) composition] 　　·2-(dimethylamino)-1-(4-morpholino(phenyl)-2-benzyl-1- Butanone (manufactured by BASF, product name "Irgacure (registered trademark) 369"): 0.6 parts by mass [(d) ingredients] 3-methacryloxy (methacryloxy) propyl trimethoxysilane (Shin-Etsu Chemical Industry) Co., Ltd., product name "KBM-503"): 0.4 parts by mass [(h) ingredients] Silicon dioxide filler (fused silica filler, average particle size 8 μm): 57 parts by mass [(z) ingredients] 　　Phthalocyanine-based cyan pigment (Pigment Blue 15: 3) 32 parts by mass, with indolinone-based yellow pigment (Pigment Yellow 139) 18 parts by mass, and anthraquinone-based red pigment (Pigment Red 177) 50 parts by mass Pigments obtained by mixing so that the total amount of the above three pigments/styrene acrylic resin amount = 1/3 (mass ratio): 4 parts by mass

The solution of the curable composition prepared by the above method was applied to the peeling surface of the light peeling film to form a coating film, and the coating film was dried at 120°C for 2 minutes to form a thickness of 25 μm The energy ray-curable resin layer (IB) is formed into a sheet for forming the energy ray-curable resin layer (IB) formed of the energy ray-curable resin layer (IB) and the lightly peelable film.

Manufacturing Example 7 (Thermosetting resin layer (IC)) Blended with the following types and addition amounts (either one is the "effective ingredient ratio") of each component, and then diluted with methyl ethyl ketone and evenly stirred , And a solution of a curable composition with a solid content concentration (effective component concentration) of 61% by mass is prepared.・Acrylic polymer: composed of butyl acrylate (BA) (1 part by mass), acrylic acid methyl (MA) (74 parts by mass), methacrylic epoxy (GMA) (15 parts by mass) and acrylic acid 2-hydroxy Acrylic resin formed by copolymerization of ethyl (HEA) (10 parts by mass) (glass transition temperature: 8°C, Mw: 440,000): 18 parts by mass • Liquid bisphenol A epoxy resin (Japan Catalyst Co., Ltd. limited Company-made, product name "BPA328"): 3 parts by mass · Solid bisphenol A epoxy resin (Mitsubishi Chemical Co., Ltd., product name "EPIKOTE 1055"): 20 parts by mass Dicyclopentadiene-type epoxy resin Resin (manufactured by Nippon Kayaku Co., Ltd., product name "XD-1000L"): 1.5 parts by mass · dicyandiamide (manufactured by ADEKA, product name "ADEKA partner 3636AS"): 0.5 parts by mass Mizole (Shikoku Product name "2PH-Z" manufactured by the Chemical Industry Co., Ltd.): 0.5 parts by mass · An oligomer type silane coupling agent containing epoxy groups (Mitsubishi Chemical Co., Ltd., product name "MSEP2"): 0.5 parts by mass・Spherical silica filler (manufactured by ADMATECHS Co., Ltd., product name "SC2050MA"): 6 parts by mass・Spherical silica filler (Rongsen Co., Ltd., product name "SV-10"): 50 parts by mass

The solution of the curable composition prepared according to the above method is applied to the peeling surface of the light peeling film to form a coating film, and the coating film is dried at 120°C for 2 minutes to form a thickness of 25 μm A thermosetting resin layer (IC), and then a sheet for forming a thermosetting resin layer (IC) formed of a thermosetting resin layer (IC) and a lightly peelable film.

[Fabrication of the laminate] Examples 1 to 5, Reference Example 1 The heavy peeling film of the support layer (II) forming sheet shown in Table 1 was removed, so that the exposed first adhesive layer (X1), as shown in Table 1. The surface of the curable resin layer (I) for forming the curable resin layer (I) shown is bonded together to obtain a laminate. In addition, in Example 5, the product name "REVALPHA 3195" (expansion onset temperature (t) = 170°C) manufactured by Nitto Denko Corporation was used as the support layer (II-E) forming sheet. The separation and deformation evaluation results of the laminates obtained in each case are shown in Table 1.

[Preparation of hardened sealing body] Then, using the laminate obtained in each case, a hardened sealing body was produced in the following order.

(1) Mounting of semiconductor wafers The light peeling film on the support layer (II) side of the laminate is removed, and the exposed adhesive surface of the second adhesive layer (X2) of the support layer (II) is attached to the support Body (glass). Subsequently, the lightly peelable film on the side of the curable resin layer (I) is also removed, and the curable resin layer is contacted with the inner surface on the opposite side to the circuit surface of each semiconductor wafer on the surface of the exposed curable resin layer (I) (I) As for the surface method, 9 semiconductor wafers (each having a wafer size of 6.4 mm×6.4 mm and a wafer thickness of 200 μm (♯2000)) are placed at necessary intervals.

(2) Formation of the cured resin layer (I') in Examples 1 to 5, after (1) above and before (3) below, ultraviolet (UV) irradiation is used as the energy ray of the curable resin layer (I) The curable resin layer (I) forms a cured resin layer (I′) on which a semiconductor wafer is placed. In addition, ultraviolet rays were irradiated three times under the conditions of illuminance 215 mW/cm ² and light quantity 187 mJ/cm ² from the support (glass) side using an ultraviolet irradiation device RAD-2000 (manufactured by Linde Co., Ltd.). In addition, in Reference Example 1, the step (2) is not carried out, and in the step (3) described later, the thermosetting resin layer as the curable resin layer (I) is simultaneously cured during the process of curing the sealing material .

(3) Formation of hardened sealing body The above-mentioned nine semiconductor wafers are covered with a thermosetting sealing resin film using a sealing material, and the hardened resin layer (I') of at least the periphery of the semiconductor wafer (refer to Example 1, On the surface of the thermosetting resin layer), a vacuum heat and pressure laminator (manufactured by ROHM and HAAS, product name "7024HP5") was used to thermally harden the sealing resin film to obtain a cured sealing body. The sealing conditions are as follows.・Preheating temperature: both bed and diaphragm are 100℃・Vacuum stretching: 60 seconds・Dynamic compression mode: 30 seconds・Static compression mode: 10 seconds・Sealing temperature: 180℃× 60 minutes

(4) Separation of the interface P After (3) above, the thermally expandable particles contained in the support layer (II) of each laminate are heated and expanded for 3 minutes at the temperature of the initial expansion temperature (t) + 30°C To separate the interface P between the first adhesive layer (X1) of the support layer (II) and the cured resin layer (I′). In this way, a hardened sealing body with a hardened resin layer is produced.

From the results in Table 1, it is known that in Examples 1 to 5 using the laminate of one aspect of the present invention, the cured seal body formed was not deformed, and the support layer (II) had excellent releasability. On the other hand, in Reference Example 1 where a thermosetting resin layer is used as the curable resin layer, the cured resin layer (I’) cannot be separated from the support layer (II).

1a, 1b, 2a, 2b, 3: Laminate (I): Energy ray-curable resin layer (I'): Cured resin layer (II): Support layer (X): Adhesive layer (X1): 1st adhesion Adhesive layer (X2): Second adhesive layer (Y): Base material (Y1): Expandable base material layer (Y2): Non-expandable base material layer 50: Support body 60: Sealing object (semiconductor wafer) 70 : Sealing material 80: Hardened seal body 100: Hardened seal body with hardened resin layer 100a: Hardened seal body surface 110: Grinding method 200: Lead wire redistribution layer (RDL) 300: External terminal electrode

[Fig. 1] A schematic cross-sectional view of the laminated body that describes the structure of the laminated body according to the first aspect of the present invention. [FIG. 2] A schematic cross-sectional view of the laminated body which constitutes the laminated body of the second aspect of the present invention. [FIG. 3] A schematic cross-sectional view of the laminated body that constitutes the laminated body of the third aspect of the present invention. [FIG. 4] A cross-sectional schematic diagram illustrating the steps of manufacturing a cured seal body with a cured resin layer using the laminate 1a shown in FIG. 1(a).　　 [Figure 5] A cross-sectional model diagram illustrating the processing method of the hardened sealing body.

1a, 1b: laminate

P: Interface

(X): Adhesive layer

(Y): substrate

(Y1): Intumescent substrate layer

(Y2): Non-expandable substrate layer

(I): Energy ray curable resin layer

(II): Support layer

Claims (11)

A laminate characterized by having an energy ray-curable resin layer (I) and a support layer (II) supporting the energy ray-curable resin layer (I); an energy line-curable resin layer (I), having Adhesive surface, the supporting layer (II) has a base material (Y) and an adhesive layer (X), at least one of the base material (Y) and the adhesive layer (X) contains heat-expandable particles, and it is due to Between the cured resin layer (I') formed by curing the energy ray-curable resin layer (I) and the support layer (II), the aforementioned thermally expandable particles are expanded to form a separation at this interface. The laminate according to claim 1, wherein the storage elastic modulus E′ at 23° C. of the cured resin layer (I′) formed by curing the energy ray-curable resin layer (I) is 1.0×10 ⁷ to 1.0×10 ¹³ Pa. The laminate according to claim 1 or 2, wherein the thickness of the energy ray-curable resin layer (I) is 1 to 500 μm. The laminate according to any one of claims 1 to 3, wherein the visible light transmittance of the energy ray-curable resin layer (I) is 5% or more. The laminate according to any one of claims 1 to 4, wherein the base material (Y) is an expandable base material layer (Y1) containing the aforementioned thermally expandable particles. The laminate according to claim 5, wherein the adhesive layer (X) is a non-expandable adhesive layer. The laminate according to claim 5 or 6, wherein the adhesive layer (X) and the energy ray-curable resin layer (I) are directly laminated. Such as the laminate of any one of claims 5 to 7, wherein the base material (Y) has a non-expandable base material layer (Y2) and an expandable base material layer (Y1), and the support layer (II) is in order It has a non-expandable base material layer (Y2), an expandable base material layer (Y1), and an adhesive layer (X). The adhesive layer (X) and the energy ray-curable resin layer (I) are directly laminated. The laminated body according to any one of claims 1 to 8, which is used to form a hardened sealing body including the aforementioned sealing object, which is placed on a part of the surface of the energy ray-curable resin layer (I) The object to be sealed is irradiated with energy rays to the energy ray-curable resin layer (I) to form a hardened resin layer (I') formed by curing the energy ray-curable resin layer (I), and the object to be sealed is sealed The surface of the hardened resin layer (I') of at least the peripheral part of the object is covered with a thermosetting sealant, and after the sealant is thermally hardened, the heat-expandable particles are expanded to cure the hardened resin layer (I' ) And the support layer (II) form a separation at this interface. The laminated body according to claim 9, which is used to prevent the warpage of the aforementioned hardened sealing body. A method for manufacturing a hardened sealing body, which is a method for manufacturing a hardened sealing body using the laminate according to any one of claims 1 to 10, characterized by having the following steps (i) to (iv): Step (i) : Step of placing the object to be sealed on a part of the surface of the energy ray-curable resin layer (I) of the aforementioned laminated body Step (ii): irradiating the energy ray-curable resin layer (I) with energy rays, Step of forming a cured resin layer (I') formed by curing an energy ray-curable resin layer (I) Step (iii): the aforementioned sealed object and the hardened resin layer (I ') The surface is covered with a thermosetting sealing material, and the sealing material is thermally hardened to form a hardened sealing body containing the sealing object. Step (iv): After the thermally expandable particles are expanded, the hardening is cured The resin layer (I') and the support layer (II) form a separation at this interface, and a step of producing a hardened sealing body with a hardened resin layer.

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