JP7132938B2 - COMPOSITE SHEET FOR PROTECTIVE FILM FORMATION AND METHOD FOR MANUFACTURING SEMICONDUCTOR CHIP - Google Patents

Description

TECHNICAL FIELD The present invention relates to a composite sheet for forming a protective film and a method for manufacturing a semiconductor chip.
This application claims priority based on Japanese Patent Application No. 2017-208434 filed in Japan on October 27, 2017, the content of which is incorporated herein.

2. Description of the Related Art In recent years, semiconductor devices have been manufactured by applying a mounting method called a so-called face down method. In the face-down method, a semiconductor chip having electrodes such as bumps on a circuit surface is used, and the electrodes are joined to a substrate. Therefore, the back surface of the semiconductor chip on the side opposite to the circuit surface may be exposed.

A resin film containing an organic material is formed as a protective film on the exposed back surface of the semiconductor chip, and the semiconductor chip may be incorporated into a semiconductor device as a semiconductor chip with a protective film.
A protective film is used to prevent cracks from occurring in a semiconductor chip after a dicing process or packaging.

In order to form such a protective film, for example, a protective film-forming composite sheet comprising a protective film-forming film on a support sheet is used. The film for forming a protective film can form a protective film by curing. Further, the support sheet can be used for fixing the semiconductor wafer when the semiconductor wafer having the protective film forming film or the protective film on the back surface thereof is divided into semiconductor chips. Further, the support sheet can also be used as a dicing sheet, and the protective film-forming composite sheet can be used as a product in which a protective film-forming film and a dicing sheet are integrated.

The protective film-forming composite sheet is attached to the back surface of the semiconductor wafer with the protective film-forming film therein. After that, at a suitable timing, formation of a protective film by curing the protective film-forming film, cutting of the protective film-forming film or protective film, division of the semiconductor wafer into semiconductor chips, cutting of the protective film-forming film or A semiconductor chip having a protective film on its back surface (semiconductor chip with a film for forming a protective film or a semiconductor chip with a protective film) is picked up from the support sheet, or the like, as appropriate. When a semiconductor chip with a protective film-forming film is picked up, the protective film-forming film is cured to form a semiconductor chip with a protective film. Finally, the semiconductor chip with a protective film is used to manufacture a semiconductor device is manufactured.

As such a composite sheet for forming a protective film, for example, a sheet provided with a thermosetting film for forming a protective film that forms a protective film by being cured by heating has been mainly used so far. However, since heat curing of a thermosetting film for forming a protective film usually requires a long time of about several hours, shortening of the curing time is desired. On the other hand, the use of a protective film-forming film that can be cured by irradiation with energy rays such as ultraviolet rays (energy ray-curable) is being studied for forming a protective film (see Patent Document 1).

WO2016/068042

However, when a protective film-forming composite sheet having an energy ray-curable protective film-forming film is used, the adhesive force between the protective film-forming film or protective film and the support sheet decreases over time. There is a problem that it may change greatly depending on the If the adhesive force changes in this way, even if the same composite sheet for forming a protective film is used, it will be difficult to pick up the semiconductor chip with the film for forming a protective film or the semiconductor chip with a protective film from the support sheet. Reproducibility is lowered, and the process becomes unstable.

The present invention provides a protective film-forming composite sheet comprising an energy ray-curable protective film-forming film and a support sheet, wherein the protective film is the protective film-forming film or a cured product thereof; It is an object of the present invention to provide a composite sheet for forming a protective film in which a change over time in adhesive strength between a sheet and a sheet is suppressed, and a method for manufacturing a semiconductor chip using the composite sheet for forming a protective film.

In order to solve the above problems, the present invention provides a protective film-forming composite sheet comprising a support sheet and an energy ray-curable protective film-forming film on the support sheet, The film contains an energy ray-curable component (a0) and a non-energy ray-curable polymer (b), and the layer in the support sheet that is in contact with the protective film-forming film contains a resin component (X). and the polarity term _δP of the HSP of the resin component (X) is 7.5 MPa ^1/2 or less, and in the HSP space, the HSP of the energy ray-curable component (a0) is the non-energy ray-curable Provided is a composite sheet for forming a protective film, which is contained in the Hansen melting sphere region of the polymer (b).

In the protective film-forming composite sheet of the present invention, the support sheet comprises a base material, and a pressure-sensitive adhesive layer is provided on the base material, and the pressure-sensitive adhesive layer contacts the protective film-forming film. Layers are preferred.
The present invention also includes a step of attaching a protective film forming film in the protective film forming composite sheet to a semiconductor wafer, and irradiating the protective film forming film after being attached to the semiconductor wafer with an energy ray. dividing the semiconductor wafer, cutting the protective film or the film for forming a protective film, and forming a plurality of semiconductor chips having the protective film or the film for forming a protective film after cutting; and picking up the semiconductor chip provided with the cut protective film or protective film-forming film from the support sheet.

That is, the present invention includes the following aspects.
[1] A protective film-forming composite sheet comprising a support sheet and an energy ray-curable protective film-forming film provided on the support sheet,
The protective film-forming film contains an energy ray-curable component (a0) and a non-energy ray-curable polymer (b),
The layer of the support sheet that is in contact with the protective film-forming film contains a resin component (X),
The HSP polarity term _δP of the resin component (X) is 7.5 MPa ^1/2 or less,
When an HSP space is defined and Hansen melting spheres of the non-energy ray-curable polymer (b) are produced in the HSP space, the HSP of the energy ray-curable component (a0) becomes the non-energy ray-curable A composite sheet for forming a protective film, which is contained in the Hansen melting sphere region of the polymer (b).
[2] The support sheet includes a substrate and an adhesive layer provided on the substrate,
The composite sheet for forming a protective film according to [1], wherein the pressure-sensitive adhesive layer is a layer in contact with the film for forming a protective film.
[3] Affixing the film for forming a protective film in the composite sheet for forming a protective film according to [1] or [2] to a semiconductor wafer;
forming a protective film by irradiating the film for forming a protective film after being attached to the semiconductor wafer with an energy ray;
Dividing the semiconductor wafer and cutting the protective film or protective film forming film to obtain a plurality of semiconductor chips each having the protective film or protective film forming film after being cut;
A method for manufacturing a semiconductor chip, comprising separating and picking up the semiconductor chip provided with the cut protective film or protective film-forming film from the support sheet.

According to the present invention, a protective film-forming composite sheet comprising an energy ray-curable protective film-forming film and a support sheet, wherein the protective film-forming film or a cured product thereof; , a support sheet, and a protective film-forming composite sheet in which change with time is suppressed, and a method for manufacturing a semiconductor chip using the protective film-forming composite sheet.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention. 1A to 1C are cross-sectional views for schematically explaining a method for manufacturing a semiconductor chip according to an embodiment of the present invention; 1A to 1C are cross-sectional views for schematically explaining a method for manufacturing a semiconductor chip according to an embodiment of the present invention; 1A to 1C are cross-sectional views for schematically explaining a method for manufacturing a semiconductor chip according to an embodiment of the present invention;

◇ Protective Film-Forming Composite Sheet A protective film-forming composite sheet according to one embodiment of the present invention includes a support sheet and an energy ray-curable protective film-forming film provided on the support sheet. A film-forming composite sheet, wherein the protective film-forming film contains an energy ray-curable component (a0) and a non-energy ray-curable polymer (b), and the protective film-forming film in the support sheet The layer in contact with contains the resin component (X), and the polarity term δ _P of the HSP of the resin component (X) (in this specification, it may be particularly abbreviated as “δ _P1 ”) is 7. 5 MPa ^1/2 or less, an HSP space is defined, and in the HSP space, when Hansen melting spheres of the non-energy ray-curable polymer (b) are produced, the HSP of the energy ray-curable component (a0) is the protective film-forming composite sheet contained in the region of the Hansen melting sphere of the non-energy ray-curable polymer (b).

As described above, in the protective film-forming composite sheet, δ _P1 is a value within a specific range, and in the HSP space, the HSP of the energy ray-curable component (a0) is present in a specific region. , the change over time of the adhesive force between the protective film-forming film and the support sheet is suppressed, and similarly, the adhesive force between the protective film, which is a cured product of the protective film-forming film, and the support sheet. change over time is suppressed.

The film for forming a protective film is cured by irradiation with energy rays to form a protective film. This protective film is for protecting the back surface of the semiconductor wafer or semiconductor chip (the surface opposite to the electrode forming surface). The protective film-forming film is flexible and can be easily attached to an application target.

In addition, in this specification, the "film for forming a protective film" means a film before curing, and the "protective film" means a film obtained by curing a film for forming a protective film.

In the present invention, even after the protective film-forming film is cured, as long as the laminated structure of the support sheet and the cured product of the protective film-forming film (in other words, the support sheet and the protective film) is maintained. This laminated structure is called a "composite sheet for forming a protective film".

As used herein, "HSP" means Hansen solubility parameter.
HSP (sometimes represented by symbol “δ”) (MPa ^1/2 ) is calculated by the following formula.
δ = ((δ _D ) ² + (δ _P ) ² + (δ _H ) ² ) ^1/2
(Wherein, _δD is the dispersion term, _δP is the polar term, and _δH is the hydrogen bonding term.)

In the protective film-forming composite sheet, HSP is considered for the energy ray-curable component (a0), the non-energy ray-curable polymer (b), and the resin component (X).
Both the energy ray-curable component (a0) and the non-energy ray-curable polymer (b) are components contained in the protective film-forming film. On the other hand, the resin component (X) is a component contained in the layer in the support sheet that is in contact with the protective film-forming film.

HSPs of these target components are determined by known methods. Specifically, it is as follows.
That is, first, a plurality of solvents with known HSPs are selected, and the solubility of the target component in these solvents is confirmed.

The solvent is not particularly limited as long as the HSP is known.
Examples of the solvent include linear or cyclic ketones such as acetone, methyl ethyl ketone and cyclohexanone; aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such as toluene; monohydric aliphatic alcohols; polyhydric aliphatic alcohols such as propylene glycol; monohydric or polyhydric aromatic alcohols such as benzyl alcohol; amides such as dimethylformamide; linear aliphatic esters (ie linear carboxylic acid esters) such as ethyl acetate; cycloaliphatic esters (ie lactones) such as γ-butyrolactone; aromatic esters such as ethyl benzoate ( halogenated hydrocarbons such as tetrachloroethylene; dialkylene glycols such as diethylene glycol; nitriles such as acetonitrile; nitro compounds such as nitrobenzene (i.e., compounds having a nitro group); and acid esters.

Solubility of the target component in the solvent can be confirmed, for example, by the following method.
That is, in a container, 15 mg of the target component is added to 2 mL of solvent whose temperature is stabilized at 23° C., and the container is fitted with a lid and sealed. Mix the contents by inverting the sealed container 50 times, then allow the container (in other words, the resulting intermediate mixture) to stand for 4 hours, and then invert the container 50 times in the same manner as above. The contents (ie said intermediate mixture) are then mixed at , and the container (ie the final mixture obtained) is then allowed to stand for one day. During this time, these mixing and standing operations are all performed under the temperature condition of 23°C. The presence or absence of dissolution of the component of interest in the final mixture is then immediately checked. The method for confirming the presence or absence of dissolution at this time is not particularly limited as long as it can be accurately confirmed. For example, the presence or absence of insoluble matter may be confirmed by visually observing the final mixture, or by filtering the final mixture. However, these are only examples. In addition, the amount of the target component and the solvent used is not limited to the above. For example, if the above usage ratio (15 mg of the target component per 2 mL of solvent) is the same, the amount of both the solvent and the target component used is increased. You can let it go, or you can reduce it.

According to the above-described method, if even a small amount of insoluble matter (undissolved matter) of the target component is found in the final mixture, the target component is determined to be "insoluble", and insoluble matter of the target component in the final mixture is not observed at all, the target component is determined to be "dissolved".
As described above, the solubility of the target component in the solvent can be confirmed.

The solvent used to obtain the mixture, that is, the solvent to which the target component is added is not a mixed solvent obtained by mixing two or more solvents, but a single solvent.

The number of solvents for confirming the solubility of the target component is preferably 20 or more, more preferably 21 to 30. When the solvent species is at least the lower limit, the HSP of the target component can be obtained with higher accuracy. When the solvent species is equal to or less than the upper limit, the HSP of the target component can be obtained more efficiently.

After confirming the solubility of the target component in the solvent, the analysis software "HSPiP" is then used to determine the HSP of the solvent and the determination result of "insoluble" or "soluble" of the target component when using this solvent. , to determine the HSP of this target component.

When obtaining the HSP of the target component, the HSP space, which is a three-dimensional space of δ _D (dispersion term), δ _P (polar term) and δ _H (hydrogen bond term), is defined, and in this HSP space, the solvent HSP and , and the determination result of the solubility of the target component are plotted. Then, assuming a sphere in the HSP space, the plot of the solvent in which the target component is dissolved exists on the surface and inside of the sphere, and the plot of the solvent in which the target component is not dissolved exists on the outside of the sphere. Create a sphere with the maximum height. On the surface of this sphere there is always a plot of the solvent in which the component of interest is dissolved. This sphere is a Hansen lysing sphere (also called Hansen three-dimensional sphere, Hansen interaction sphere, etc.). The center of the Hansen sphere is the target component HSP. In addition, the radius of the Hansen dissolving _sphere is the interaction radius R ₀ , and when R ₀ is large, there are many solvent species that dissolve the target component It means less seeds.

In the protective film-forming composite sheet, δ _P (δ _P1 ) of the resin component (X) is 7.5 MPa ^1/2 or less, preferably 7.3 MPa ^1/2 or less. 0 MPa ^1/2 or less, 6.7 MPa ^1/2 or less, or 6.5 MPa ^1/2 or less. _Considering the type of the non-energy ray-curable polymer (b) that is normally used, the non-energy ray-curable polymer (b) and the resin component (X) are phase less soluble. On the other hand, in the present embodiment, the degree of compatibility of the energy ray-curable component (a0) with the non-energy ray-curable polymer (b) is defined, as will be described later. As a result, the compatibility of the energy ray-curable component (a0) with the resin component (X) becomes low when δ _P1 is equal to or less than the upper limit.

The lower limit of _δP1 is not particularly limited. δ _P1 is preferably 1 MPa ^1/2 or more, and may be 3 MPa ^1/2 or more, for example, from the viewpoint of easier production of the protective film-forming composite sheet.

δ _P1 can be appropriately adjusted within a range set by arbitrarily combining the preferred lower limit and upper limit values described above. For example, in one embodiment, δ _P1 is preferably 1-7.5 MPa ^1/2 , more preferably 1-7.3 MPa ^1/2 , such as 1-7 MPa ^1/2 , 1-6.7 MPa ^1/2 , and 1 to 6.5 MPa ^1/2 . Also, in one embodiment, δ _P1 is preferably 3-7.5 MPa ^1/2 , more preferably 3-7.3 MPa ^1/2 , for example 3-7 MPa ^1/2 , 3-6.7 MPa ^1/2 , and 3 to 6.5 MPa ^1/2 . However, these are only examples.
As another aspect, it may be ¹ MPa ^1/2 or more and 7.26 MPa ^1/2 or less, or 1 MPa 1/2 or more and 6.4 MPa ^1/2 or less.

In the protective film-forming composite sheet, in the HSP space, the HSP of the energy ray-curable component (a0) is contained in the Hansen melting sphere region of the non-energy ray-curable polymer (b). By satisfying these conditions, immediately after the production of the protective film-forming composite sheet, the energy ray-curable component (a0) present in the protective film-forming film is a non-energy ray-curable polymer ( High compatibility with b).
On the other hand, as described above, since δ _P1 is a specific value or less, the non-energy ray-curable polymer present in the protective film-forming film ( b) has low compatibility with the resin component (X) in the adjacent support sheet. Therefore, the energy ray-curable component (a0), which is highly compatible with the non-energy ray-curable polymer (b), also has low compatibility with the resin component (X).
As a result, in the protective film-forming composite sheet, the energy ray-curable component (a0) stably stays in the protective film-forming film and in the protective film, and is prevented from migrating to the adjacent support sheet.

Thus, in the protective film-forming composite sheet, the transfer of the energy ray-curable component (a0) to the support sheet is suppressed, and immediately after the production of the protective film-forming composite sheet, the protective film-forming film, the protective film and changes in the composition of the support sheet are suppressed. Therefore, each layer (protective film-forming film, protective film, and support sheet) is inhibited from changing properties over time, changes in adhesive strength between the protective film-forming film and the support sheet over time, and changes in the protective film and support sheet. Time-dependent change in adhesive strength between is suppressed.

Components that easily migrate from the protective film-forming film and the protective film to the support sheet include components that are not precipitated in these films and films, components with relatively small molecular weights, and the like. The energy ray-curable component (a0) whose HSP is not defined as described above corresponds to any of these, and when transferred to the support sheet, and the adhesion between the protective film and the backing sheet to a non-negligible extent. On the other hand, components other than the energy ray-curable component (a0) are difficult to migrate from the protective film-forming film and the protective film to the support sheet, or even if they migrate, they do not affect the adhesive strength. or have a negligible and very small effect.
In the present embodiment, by using the energy ray-curable component (a0) whose HSP is defined as described above, the composite sheet for forming a protective film exhibits excellent effects as described above. Play.

For example, the photopolymerization initiator (c) itself, which is an optional component described later, when transferred to the support sheet as described above, has an adhesive strength between the protective film-forming film and the support sheet, and a protective film and the support. It may have a non-negligible impact on the adhesive force between sheets. However, when the photopolymerization initiator (c) is used, the content of the photopolymerization initiator (c) in the protective film-forming film and the protective film is usually extremely small. Therefore, even when the photopolymerization initiator (c) is used, it itself usually has no effect on the above adhesive strength, or has only a negligible and extremely small effect. .

By using the photopolymerization initiator (c), it suppresses the change over time of the adhesive force between the protective film-forming film and the support sheet, and similarly, the protective film which is a cured product of the protective film-forming film and the support sheet, in the same way as in the case of the energy ray-curable component (a0), in the HSP space, the HSP of the photopolymerization initiator (c) should be included in the Hansen melting sphere region of the non-energy ray-curable polymer (b).
That is, a protective film-forming composite sheet according to one embodiment of the present invention is a protective film-forming composite sheet comprising a support sheet and an energy ray-curable protective film-forming film provided on the support sheet. The protective film-forming film contains an energy ray-curable component (a0), a non-energy ray-curable polymer (b) and a photopolymerization initiator (c), and the protective film in the support sheet The layer in contact with the forming film contains the resin component (X), the HSP polarity term _δP of the resin component (X) is 7.5 MPa ^1/2 or less, defines an HSP space, and In, when the Hansen melting sphere of the non-energy ray-curable polymer (b) is produced, the HSP of the energy ray-curable component (a0) and the HSP of the photopolymerization initiator (c) are the non- It may be included in the Hansen melting sphere region of the energy ray-curable polymer (b).

In the protective film-forming composite sheet, in the HSP space, when the HSP of the photopolymerization initiator (c) is contained in the region of the Hansen melting sphere of the non-energy ray-curable polymer (b), the protective film is formed. The photopolymerization initiator (c) present in the protective film-forming film has high compatibility with the non-energy ray-curable polymer (b) immediately after the production of the composite sheet.
On the other hand, as described above, since δ _P1 is a specific value or less, the non-energy ray-curable polymer present in the protective film-forming film ( b) has low compatibility with the resin component (X) in the adjacent support sheet. Therefore, the photopolymerization initiator (c), which has high compatibility with the non-energy ray-curable polymer (b), also has low compatibility with the resin component (X).
As a result, when the photopolymerization initiator (c) is used, as in the case of the energy ray-curable component (a0), the photopolymerization initiator (c) is added to the protective film-forming composite sheet in the protective film-forming composite sheet. It stays stably in the forming film and in the protective film and is inhibited from migrating to the adjacent support sheet.

However, as described above, even when the photopolymerization initiator (c) is used, usually, if the energy ray-curable component (a0) satisfies the above-described HSP conditions, photopolymerization Even if the initiator (c) does not satisfy the above-described HSP conditions, the protective film-forming composite sheet sufficiently exhibits the effects of the present invention.

In the present embodiment, the value of δ _P1 can be adjusted by adjusting the type of resin component (X) (for example, the structure of the structural unit, the presence or absence or type of functional group, the molecular weight, etc.).

In the present embodiment, by adjusting the type of the energy ray-curable component (a0) (for example, the structure of the main skeleton, the presence or absence or type of functional groups, the molecular weight, etc.), the HSP of the energy ray-curable component (a0) can be adjusted so as to be included in the region of the Hansen melting sphere of the non-energy ray-curable polymer (b). Also, by adjusting the type of the non-energy ray-curable polymer (b) (for example, the structure of the structural unit, the presence or absence or type of functional groups, the molecular weight, etc.), the HSP of the energy ray-curable component (a0) can be It can be adjusted so as to be included in the region of the Hansen melting sphere of the non-energy ray-curable polymer (b).

In the present embodiment, by adjusting the type of the photopolymerization initiator (c) (for example, the structure of the main skeleton, the presence or absence or type of functional groups, the molecular weight, etc.), the HSP of the photopolymerization initiator (c) is It can be adjusted so as to be included in the region of the Hansen melting sphere of the non-energy ray-curable polymer (b). Then, by adjusting the type of the non-energy ray-curable polymer (b) (for example, the structure of the structural unit, the presence or absence or type of functional groups, the molecular weight, etc.), the HSP of the photopolymerization initiator (c) can It can be adjusted so as to be included in the region of the Hansen melting sphere of the energy ray-curable polymer (b).

In the protective film-forming composite sheet, the rate of change in adhesive strength between the protective film and the support sheet before and after aging, calculated by the method described below, is preferably 30% or less, and is 27.5. % or less, more preferably 25% or less, for example, it may be either 22.5% or less or 20% or less. Also, the rate of change in adhesive strength between the protective film and the support sheet may be 23% or less, or may be 14% or less.
The lower limit of the rate of change in adhesive strength is not particularly limited. For example, a protective film-forming composite sheet having a rate of change in adhesive strength of 5% or more can be produced more easily.
As one aspect, the rate of change in adhesive strength between the protective film and the support sheet may be 5% or more and 30% or less, may be 5% or more and 27.5% or less, or may be 5% or more. 25% or less, 5% or more and 23% or less, 5% or more and 22.5% or less, 5% or more and 20% or less, 5% or more It may be 14% or less.
One aspect of the present invention is a protective film having a rate of change in adhesive force between the protective film and the support sheet of 5% or more and 30% or less, preferably 5% or more and 20% or less, when evaluated by the following method. A protective film-forming composite sheet including a protective film-forming film and a support sheet having the same chemical compositions as those of the protective film-forming film and the support sheet in the forming composite sheet. That is, if the protective film-forming composite sheet includes the protective film-forming film and the support sheet having the same chemical composition, the width of the protective film-forming composite sheet and the thickness of the protective film-forming film in the following method are different. It may have a width and a thickness.

<Method for calculating rate of change in adhesive force between protective film and support sheet>
A protective film-forming composite sheet in which all layers in the protective film-forming composite sheet have a width of 25 mm and a protective film-forming film has a thickness of 25 μm is attached to a silicon wafer by the protective film-forming film. . Next, under the conditions of an illuminance of 200 mW/cm ² and a light amount of 200 mJ/cm ² , the protective film-forming film after being attached is irradiated with ultraviolet rays to cure the protective film-forming film to form a protective film, which is a test piece. As, to prepare test pieces before and after aging. Next, for the test pieces before and after aging, under the condition of 23 ° C., the support sheet was removed from the protective film attached to the silicon wafer, and the surfaces of the protective film and the support sheet that were in contact with each other were placed at an angle of 180 °. , so-called 180° peeling is performed at a peeling speed of 300 mm/min. Then, the peel strength (N / 25 mm) at this time is adopted as the adhesive strength, and the adhesive strength before aging for the test piece before aging and the adhesive strength after aging for the test piece after aging are obtained, and from these adhesive strengths The rate of change in adhesive force between the protective film and the support sheet is calculated by the following formula.
[Adhesive strength change rate (%)] = {[adhesive strength before aging (N / 25 mm)] - [adhesive strength after aging (N / 25 mm)]} / [adhesive strength before aging (N / 25 mm)] × 100
As the pre-aged test piece, one hour after the production of the protective film-forming composite sheet is used. The test piece after aging was 48 hours after the composite sheet for forming a protective film was prepared, and after the test piece was made, it was kept at 21 to 25 ° C. until the adhesive strength was measured after the passage of time. , and stored at a relative humidity of 45 to 65%.
In this specification, the term “thickness” means an average value obtained by measuring the thickness at any five points with a contact-type thickness gauge.

The configuration of the protective film-forming composite sheet will be described in detail below.

⊚ Supporting sheet In the supporting sheet comprising two or more layers, these layers may be the same or different, and the combination of these layers is not particularly limited as long as the effects of the present invention are not impaired.

In the present specification, not only in the case of the support sheet, "the plurality of layers may be the same or different" means "all the layers may be the same or all the layers may be different." Only some of the layers may be the same", and further, "multiple layers are different from each other" means "at least one of the constituent material and thickness of each layer is different from each other" means

A preferable support sheet is, for example, a sheet comprising a base material and a pressure-sensitive adhesive layer laminated on the base material in direct contact (a base material and a pressure-sensitive adhesive layer laminated in this order in direct contact). ); a substrate, an intermediate layer and an adhesive layer are laminated in this order in direct contact with each other in the thickness direction.

FIG. 1 is a cross-sectional view schematically showing a protective film-forming composite sheet according to one embodiment of the present invention.
In the drawings used in the following description, in order to make it easier to understand the features of the present invention, there are cases where the main parts are enlarged for convenience, and the dimensional ratio of each component is the same as the actual one. not necessarily.

The protective film-forming composite sheet 1A shown here includes a substrate 11, an adhesive layer 12 on the substrate 11, and a protective film-forming film 13 on the adhesive layer 12. FIG. The support sheet 10 is a laminate of a substrate 11 and an adhesive layer 12, and the protective film-forming composite sheet 1A is, in other words, one surface of the support sheet 10 (in this specification, the "first surface"). ) 10a and a protective film forming film 13 is laminated thereon. In addition, the protective film-forming composite sheet 1A further includes a release film 15 on the protective film-forming film 13 .

In the protective film-forming composite sheet 1A, the pressure-sensitive adhesive layer 12 is laminated on one surface 11a of the substrate 11 (which may be referred to herein as the “first surface”). The protective film-forming film 13 is laminated on the entire surface of one surface (in this specification, sometimes referred to as the “first surface”) 12a, and one surface of the protective film-forming film 13 (in this specification, may be referred to as a "first surface") 13a, that is, a jig adhesive layer 16 is laminated on a region near the peripheral edge, and the first surface 13a of the protective film forming film 13 Of these, the release film 15 is laminated on the surface where the jig adhesive layer 16 is not laminated and the surface 16a (upper surface and side surface) of the jig adhesive layer 16 .

In the protective film-forming composite sheet 1A, the protective film-forming film 13 is energy ray-curable and contains an energy ray-curable component (a0) and a non-energy ray-curable polymer (b).
In addition, the layer in the support sheet 10 that contacts the protective film-forming film 13, that is, the pressure-sensitive adhesive layer 12 contains the resin component (X).

The jig adhesive layer 16 may have, for example, a single-layer structure containing an adhesive component, or a plurality of layers in which layers containing an adhesive component are laminated on both sides of a sheet serving as a core material. It may be structural.

The composite sheet 1A for forming a protective film shown in FIG. The upper surface of the surface 16a of the tool adhesive layer 16 is used by being attached to a tool such as a ring frame.

FIG. 2 is a cross-sectional view schematically showing a protective film-forming composite sheet according to another embodiment of the present invention.
In the drawings after FIG. 2, the same constituent elements as those shown in already explained figures are given the same reference numerals as in the already explained figures, and detailed explanations thereof will be omitted.

The protective film-forming composite sheet 1B shown here is the same as the protective film-forming composite sheet 1A shown in FIG. 1 except that the jig adhesive layer 16 is not provided. That is, in the protective film-forming composite sheet 1B, the adhesive layer 12 is laminated on the first surface 11a of the base material 11, and the protective film-forming film 13 is laminated on the entire first surface 12a of the adhesive layer 12. , a release film 15 is laminated on the entire surface of the first surface 13 a of the protective film forming film 13 .

In the protective film-forming composite sheet 1B, the protective film-forming film 13 is energy ray-curable and contains an energy ray-curable component (a0) and a non-energy ray-curable polymer (b).
In addition, the layer in the support sheet 10 that contacts the protective film-forming film 13, that is, the pressure-sensitive adhesive layer 12 contains the resin component (X).

In the protective film-forming composite sheet 1B shown in FIG. 2, a semiconductor wafer (not shown) is attached to a central portion of the first surface 13a of the protective film-forming film 13 in a state where the release film 15 is removed. ), and the area near the periphery is attached to a jig such as a ring frame for use.

FIG. 3 is a cross-sectional view schematically showing a protective film-forming composite sheet according to still another embodiment of the present invention.
The protective film-forming composite sheet 1C shown here is the same as the protective film-forming composite sheet 1B shown in FIG. 2 except that the shape of the protective film-forming film is different. That is, the protective film-forming composite sheet 1</b>C comprises a substrate 11 , an adhesive layer 12 on the substrate 11 , and a protective film-forming film 23 on the adhesive layer 12 . The support sheet 10 is a laminate of a substrate 11 and an adhesive layer 12. In other words, the protective film-forming composite sheet 1C is formed by laminating a protective film-forming film 23 on the first surface 10a of the support sheet 10. configuration. In addition, the protective film-forming composite sheet 1</b>C further includes a release film 15 on the protective film-forming film 23 .

In the protective film-forming composite sheet 1C, the pressure-sensitive adhesive layer 12 is laminated on the first surface 11a of the base material 11, and the protective film is formed on a part of the first surface 12a of the pressure-sensitive adhesive layer 12, that is, the central region. film 23 is laminated. Then, of the first surface 12a of the adhesive layer 12, the release film 15 is placed on the area where the protective film forming film 23 is not laminated and on the surface 23a (upper surface and side surface) of the protective film forming film 23. Laminated.

When the protective film-forming composite sheet 1C is viewed from above in a plan view, the protective film-forming film 23 has a smaller surface area than the adhesive layer 12 and has, for example, a circular shape.

In the protective film-forming composite sheet 1C, the protective film-forming film 23 is energy ray-curable and contains an energy ray-curable component (a0) and a non-energy ray-curable polymer (b).
The layer in the support sheet 10 that contacts the protective film-forming film 23, that is, the pressure-sensitive adhesive layer 12 contains the resin component (X).

In the protective film-forming composite sheet 1C shown in FIG. 3, the back surface of a semiconductor wafer (not shown) is adhered to the surface 23a of the protective film-forming film 23 in a state in which the release film 15 is removed. A region of the first surface 12a of 12 where the protective film forming film 23 is not laminated is used by being attached to a jig such as a ring frame.

In addition, in the protective film-forming composite sheet 1C shown in FIG. 3, the first surface 12a of the pressure-sensitive adhesive layer 12, in the region where the protective film-forming film 23 is not laminated, is the same as that shown in FIG. A jig adhesive layer may be laminated (not shown). The protective film-forming composite sheet 1C provided with such a jig adhesive layer is similar to the protective film-forming composite sheet shown in FIG. Affixed to tools and used.

As described above, the protective film-forming composite sheet may be provided with an adhesive layer for a jig, regardless of the form of the support sheet and the protective film-forming film. However, as shown in FIG. 1, the protective film-forming composite sheet having the jig adhesive layer preferably has the jig adhesive layer on the protective film-forming film.

The composite sheet for forming a protective film according to one embodiment of the present invention is not limited to those shown in FIGS. 1 to 3, and some of those shown in FIGS. may be modified or deleted, or other configurations may be added to those described above.

For example, in the protective film-forming composite sheet shown in FIGS. 1 to 3, an intermediate layer may be provided between the substrate 11 and the pressure-sensitive adhesive layer 12 . That is, in the protective film-forming composite sheet of the present invention, the support sheet may be formed by laminating a base material, an intermediate layer and an adhesive layer in this order in the thickness direction thereof. Any intermediate layer can be selected according to the purpose.
In the protective film-forming composite sheet shown in FIGS. 1 to 3, layers other than the intermediate layer may be provided at arbitrary locations.
Further, in the protective film-forming composite sheet, a partial gap may be formed between the release film and the layer in direct contact with the release film.
In the protective film-forming composite sheet, the size and shape of each layer can be arbitrarily adjusted according to the purpose.

In the protective film-forming composite sheet shown in FIGS. 1 to 3, the layer in contact with the protective film-forming film in the support sheet is the pressure-sensitive adhesive layer. When the layer to be applied is a layer other than the pressure-sensitive adhesive layer, this other layer contains the resin component (X).

In the protective film-forming composite sheet of the present invention, as described later, the layer such as the pressure-sensitive adhesive layer that is in direct contact with the protective film-forming film in the support sheet is non-energy ray-curable. preferable. Such a composite sheet for forming a protective film makes it possible to easily pick up a semiconductor chip having a protective film on its back surface (a semiconductor chip with a protective film) from the support sheet after being cut.

The support sheet may be transparent, opaque, or colored depending on the purpose.
Among others, in the present invention in which the protective film-forming film is energy ray-curable, the support sheet is preferably one that allows energy rays to pass therethrough.

For example, in the support sheet, the transmittance of light with a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the protective film-forming film is irradiated with energy rays (ultraviolet rays) through the support sheet, the degree of curing of the protective film-forming film is further improved when the light transmittance is within such a range.
On the other hand, the upper limit of the transmittance of light having a wavelength of 375 nm is not particularly limited in the support sheet. For example, the light transmittance may be 95% or less.
As one aspect, the transmittance of light with a wavelength of 375 nm in the support sheet is preferably 30% or more and 95% or less, more preferably 50% or more and 95% or less, and 70% or more and 95% or less. is particularly preferred.

Further, in the support sheet, the transmittance of light having a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more.
When the protective film-forming film or the protective film is irradiated with a laser beam through the support sheet and the light transmittance is within such a range, the printing can be performed more clearly.
On the other hand, in the support sheet, the upper limit of the transmittance of light with a wavelength of 532 nm is not particularly limited. For example, the light transmittance may be 95% or less.
As one aspect, the transmittance of light having a wavelength of 532 nm in the support sheet is preferably 30% or more and 95% or less, more preferably 50% or more and 95% or less, and 70% or more and 95% or less. is particularly preferred.

Further, in the support sheet, the transmittance of light having a wavelength of 1064 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the protective film-forming film or the protective film is irradiated with a laser beam through the support sheet and the light transmittance is within such a range, the printing can be performed more clearly.
On the other hand, in the support sheet, the upper limit of the transmittance of light with a wavelength of 1064 nm is not particularly limited. For example, the light transmittance may be 95% or less.
As one aspect, the transmittance of light having a wavelength of 1064 nm in the support sheet is preferably 30% or more and 95% or less, more preferably 50% or more and 95% or less, and 70% or more and 95% or less. is particularly preferred.

As one method for obtaining semiconductor chips by dividing a semiconductor wafer, for example, a laser beam is irradiated so as to be focused on a focal point set inside the semiconductor wafer to form a modified layer inside the semiconductor wafer, Next, the semiconductor wafer having the modified layer formed thereon and the protective film-forming film or protective film attached to the back surface is expanded together with the film or film in the surface direction of the film or film, A method of obtaining semiconductor chips is known by cutting a film or membrane and dividing a semiconductor wafer at the site of a modified layer to separate the semiconductor wafer into individual pieces.
When the protective film-forming composite sheet is applied to such a method, the support sheet preferably has a transmittance of 30% or more, more preferably 50% or more, for light having a wavelength of 1342 nm. 70% or more is particularly preferred. When the light transmittance is in such a range, the semiconductor wafer is irradiated with a laser beam through the support sheet and the protective film forming film or protective film to form a modified layer on the semiconductor wafer. Easy to form.
On the other hand, the upper limit of the transmittance of light having a wavelength of 1342 nm is not particularly limited in the support sheet. For example, the light transmittance may be 95% or less.
As one aspect, the transmittance of light having a wavelength of 1342 nm in the support sheet is preferably 30% or more and 95% or less, more preferably 50% or more and 95% or less, and 70% or more and 95% or less. is particularly preferred.

The support sheet preferably comprises a base material and a pressure-sensitive adhesive layer on the base material.
In the protective film-forming composite sheet, the support sheet includes a substrate and an adhesive layer provided on the substrate, and the adhesive layer is in contact with the protective film-forming film. (The protective film-forming film is laminated in direct contact with the pressure-sensitive adhesive layer).

Next, each layer constituting the support sheet will be described in more detail.

○ Substrate The substrate is sheet-like or film-like, and examples of its constituent materials include various resins. Examples of the resin include polyethylene such as low-density polyethylene (sometimes abbreviated as LDPE), linear low-density polyethylene (sometimes abbreviated as LLDPE), and high-density polyethylene (sometimes abbreviated as HDPE); polypropylene; Polyolefins other than polyethylene such as polybutene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic ester copolymer, ethylene- Ethylene copolymers such as norbornene copolymers (copolymers obtained using ethylene as a monomer); vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (obtained using vinyl chloride as a monomer) polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, all structural units having an aromatic cyclic group Polyesters such as aromatic polyesters; Copolymers of two or more of the above polyesters; Poly(meth)acrylic acid esters; Polyurethanes; Polyurethane acrylates; Polyimides; ; polyether ketone and the like.
Examples of the resin include polymer alloys such as mixtures of the polyester and other resins. The polymer alloy of the polyester and the resin other than polyester is preferably one in which the amount of the resin other than the polyester is relatively small.
Further, as the resin, for example, a crosslinked resin in which one or more of the resins exemplified above are crosslinked; Resins may also be mentioned.

In this specification, "(meth)acrylic acid" is a concept that includes both "acrylic acid" and "methacrylic acid". The same is true for (meth)acrylic acid and similar terms.

The resin constituting the substrate may be of one type or two or more types, and when two or more types are used, the combination and ratio thereof can be arbitrarily selected.

The substrate may consist of one layer (single layer), or may consist of a plurality of layers of two or more layers. A combination of layers is not particularly limited.

The thickness of the substrate is preferably 50-300 μm, more preferably 60-150 μm. When the thickness of the base material is within such a range, the flexibility of the protective film-forming composite sheet and the adhesion to a semiconductor wafer or a semiconductor chip are further improved.
Here, the "thickness of the base material" means the thickness of the entire base material. means.

It is preferable that the base material has a high thickness accuracy, that is, a material in which variations in thickness are suppressed irrespective of parts. Among the constituent materials described above, examples of materials that can be used to form such a substrate with high thickness accuracy include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, and the like. is mentioned.

The substrate contains various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, softeners (plasticizers), etc., in addition to the main constituent materials such as the resins. may

The optical properties of the substrate are preferably such that they satisfy the optical properties of the support sheet described above. For example, the substrate may be transparent, opaque, colored according to purpose, or may be deposited with other layers.
In the present invention in which the protective film-forming film is energy ray-curable, the substrate preferably transmits energy rays.

In order to improve adhesion with other layers such as the pressure-sensitive adhesive layer provided thereon, the substrate is subjected to roughening treatment such as sandblasting or solvent treatment, corona discharge treatment, electron beam irradiation treatment, or plasma treatment. , ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, or other oxidation treatment may be applied to the surface.
Further, the substrate may have a primer-treated surface.
In addition, the base material has an antistatic coating layer; prevents the base material from adhering to other sheets and the base material from adhering to the adsorption table when the protective film-forming composite sheet is stacked and stored. It may have layers or the like.

A base material can be manufactured by a well-known method. For example, a substrate containing a resin can be produced by molding a resin composition containing the resin.

O Adhesive Layer The adhesive layer is sheet-like or film-like and contains an adhesive. Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins, with acrylic resins being preferred. .
When the pressure-sensitive adhesive layer contains the resin component (X), it preferably contains the resin component (X) as the pressure-sensitive adhesive.
That is, as one aspect, the resin component (X) is at least selected from the group consisting of acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates and ester resins. One is preferred.
In another aspect, the resin component (X) is at least one selected from the group consisting of adhesive resins (I-1a), energy ray-curable compounds, and adhesive resins (I-2a) described below. It is preferably a component.

In the present invention, the term "adhesive resin" is a concept that includes both a resin having adhesiveness and a resin having adhesiveness. Also included are resins that exhibit adhesiveness when used in combination with other components such as additives, and resins that exhibit adhesiveness due to the presence of a trigger such as heat or water.

The pressure-sensitive adhesive layer may consist of one layer (single layer) or may consist of two or more layers. The combination of multiple layers is not particularly limited.
When the pressure-sensitive adhesive layer is composed of multiple layers and the pressure-sensitive adhesive layer contains the resin component (X), among these multiple layers, at least the layer that is in direct contact with the protective film-forming film contains the resin component ( X) is preferably contained, and all layers may contain the resin component (X).

The thickness of the adhesive layer is preferably 1-100 μm, more preferably 1-60 μm, and particularly preferably 1-30 μm.
Here, the "thickness of the pressure-sensitive adhesive layer" means the thickness of the entire pressure-sensitive adhesive layer. means the thickness of

The optical properties of the pressure-sensitive adhesive layer preferably satisfy the optical properties of the support sheet described above. For example, the pressure-sensitive adhesive layer may be transparent, opaque, or colored depending on the purpose.
In the present invention in which the protective film-forming film is energy ray-curable, the pressure-sensitive adhesive layer preferably transmits energy rays.

The adhesive layer may be formed using an energy ray-curable adhesive, or may be formed using a non-energy ray-curable adhesive. A pressure-sensitive adhesive layer formed using an energy ray-curable pressure-sensitive adhesive can easily adjust physical properties before and after curing.

<<Adhesive Composition>>
The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, the pressure-sensitive adhesive layer can be formed on the target site by applying the pressure-sensitive adhesive composition to the surface on which the pressure-sensitive adhesive layer is to be formed, and drying it as necessary. A more specific method for forming the pressure-sensitive adhesive layer will be described later in detail together with methods for forming other layers. The content ratio of the components that do not vaporize at room temperature in the pressure-sensitive adhesive composition is usually the same as the content ratio of the components in the pressure-sensitive adhesive layer. In this specification, the term "ordinary temperature" means a temperature at which no particular cooling or heating is applied, that is, a normal temperature.

Coating of the pressure-sensitive adhesive composition may be performed by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater. , Meyer bar coater, kiss coater and the like.

Drying conditions for the pressure-sensitive adhesive composition are not particularly limited, but when the pressure-sensitive adhesive composition contains a solvent to be described later, it is preferable to dry by heating. The solvent-containing pressure-sensitive adhesive composition is preferably dried, for example, at 70 to 130° C. for 10 seconds to 5 minutes.

When the pressure-sensitive adhesive layer is energy-ray-curable, the pressure-sensitive adhesive composition containing the energy-ray-curable pressure-sensitive adhesive, i.e., the energy-ray-curable pressure-sensitive adhesive composition includes, for example, non-energy-ray-curable pressure-sensitive adhesive Adhesive composition (I-1) containing a resin (I-1a) (hereinafter sometimes abbreviated as "adhesive resin (I-1a)") and an energy ray-curable compound; non-energy An energy ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the radiation-curable adhesive resin (I-1a) (hereinafter referred to as “adhesive resin (I-2a)”) a pressure-sensitive adhesive composition (I-2) containing the adhesive resin (I-2a); and a pressure-sensitive adhesive composition (I-3) containing the adhesive resin (I-2a) and an energy ray-curable compound, etc. is mentioned.

<Adhesive composition (I-1)>
The adhesive composition (I-1) contains, as described above, a non-energy ray-curable adhesive resin (I-1a) and an energy ray-curable compound.
In another aspect, the pressure-sensitive adhesive composition (I-1) comprises a non-energy ray-curable pressure-sensitive adhesive resin (I-1a), an energy ray-curable compound, optionally a cross-linking agent, and a photopolymerization initiator. and at least one component selected from the group consisting of agents, other additives, and solvents.

[Adhesive resin (I-1a)]
The adhesive resin (I-1a) is preferably an acrylic resin.
Examples of the acrylic resin include an acrylic polymer having at least a structural unit derived from a (meth)acrylic acid alkyl ester.
The structural units of the acrylic resin may be of one type or two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

Examples of the (meth)acrylic acid alkyl ester include those in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is linear or branched. is preferred.
(Meth)acrylic acid alkyl esters, more specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylic acid n-butyl, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (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, (meth) ) undecyl acrylate, dodecyl (meth)acrylate (also referred to as lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also referred to as myristyl (meth)acrylate), (meth)acrylic Pentadecyl acid, hexadecyl (meth)acrylate (also known as palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (also known as stearyl (meth)acrylate), nonadecyl (meth)acrylate , eicosyl (meth)acrylate, and the like.

From the viewpoint of improving the adhesive strength of the pressure-sensitive adhesive layer, the acrylic polymer preferably has a structural unit derived from a (meth)acrylic acid alkyl ester in which the alkyl group has 4 or more carbon atoms. The number of carbon atoms in the alkyl group is preferably 4 to 12, more preferably 4 to 8, from the viewpoint of further improving the adhesive strength of the adhesive layer. In addition, the (meth)acrylic acid alkyl ester in which the alkyl group has 4 or more carbon atoms is preferably a methacrylic acid alkyl ester.

It is preferable that the acrylic polymer further has a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from the (meth)acrylic acid alkyl ester.
As the functional group-containing monomer, for example, the functional group reacts with a cross-linking agent described later to become a starting point for cross-linking, or the functional group reacts with an unsaturated group in the unsaturated group-containing compound described later. and those capable of introducing an unsaturated group into the side chain of the acrylic polymer.

Examples of the functional group in the functional group-containing monomer include hydroxyl group, carboxyl group, amino group, epoxy group and the like.
That is, examples of functional group-containing monomers include hydroxyl group-containing monomers, carboxy group-containing monomers, amino group-containing monomers, and epoxy group-containing monomers.

Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth) Hydroxyalkyl (meth)acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; Saturated alcohol (that is, unsaturated alcohol having no (meth)acryloyl skeleton) and the like can be mentioned.

Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (i.e., monocarboxylic acids having an ethylenically unsaturated bond) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, and maleic acid; , ethylenically unsaturated dicarboxylic acids (i.e., dicarboxylic acids having an ethylenically unsaturated bond) such as citraconic acid; anhydrides of said ethylenically unsaturated dicarboxylic acids; carboxyalkyl (meth)acrylates such as 2-carboxyethyl methacrylate Ester etc. are mentioned.

The functional group-containing monomer is preferably a hydroxyl group-containing monomer or a carboxy group-containing monomer, more preferably a hydroxyl group-containing monomer.

The functional group-containing monomers constituting the acrylic polymer may be of one type or two or more types, and when two or more types are used, the combination and ratio thereof can be arbitrarily selected.

In the acrylic polymer, the content of structural units derived from functional group-containing monomers is preferably 1 to 40% by mass, and 2 to 37% by mass, based on the total amount (total mass) of the structural units. is more preferable, and 3 to 34% by mass is particularly preferable.

The acrylic polymer may further have structural units derived from other monomers in addition to the structural units derived from the (meth)acrylic acid alkyl ester and the structural units derived from the functional group-containing monomer.
The other monomer is not particularly limited as long as it is copolymerizable with (meth)acrylic acid alkyl ester or the like.
Examples of the other monomers include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile and acrylamide.

The other monomers constituting the acrylic polymer may be of one type or two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

The acrylic polymer can be used as the above non-energy ray-curable adhesive resin (I-1a).
On the other hand, the functional group in the acrylic polymer is reacted with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group (energy ray-polymerizable group), and the above-mentioned energy ray-curable adhesiveness It can be used as resin (I-2a).

The pressure-sensitive adhesive resin (I-1a) contained in the pressure-sensitive adhesive composition (I-1) may be of only one type, or may be of two or more types. You can choose.

In the adhesive composition (I-1), the content of the adhesive resin (I-1a) is preferably 5 to 99% by mass relative to the total mass of the adhesive composition (I-1). , more preferably 10 to 95% by mass, particularly preferably 15 to 90% by mass.

[Energy ray-curable compound]
Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) include monomers or oligomers having energy ray-polymerizable unsaturated groups and curable by energy ray irradiation.
Among energy ray-curable compounds, monomers include, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4 -polyvalent (meth)acrylates such as butylene glycol di(meth)acrylate, 1,6-hexanediol (meth)acrylate; urethane (meth)acrylates; polyester (meth)acrylates; polyether (meth)acrylates; meth)acrylate and the like.
Among energy ray-curable compounds, oligomers include, for example, oligomers obtained by polymerizing the above-exemplified monomers.
Urethane (meth)acrylates and urethane (meth)acrylate oligomers are preferred as the energy ray-curable compound because they have relatively large molecular weights and are less likely to reduce the storage modulus of the pressure-sensitive adhesive layer.

The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) may be of one type or two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. .

In the pressure-sensitive adhesive composition (I-1), the content of the energy ray-curable compound is preferably 1 to 95% by mass with respect to the total weight of the pressure-sensitive adhesive composition (I-1). , more preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass.

[Crosslinking agent]
As the adhesive resin (I-1a), in addition to the structural unit derived from the (meth)acrylic acid alkyl ester, when using the acrylic polymer having a structural unit derived from a functional group-containing monomer, the adhesive composition ( I-1) preferably further contains a cross-linking agent.

The cross-linking agent is, for example, one that reacts with the functional group to cross-link the adhesive resins (I-1a).
Examples of cross-linking agents include tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and isocyanate-based cross-linking agents (i.e., cross-linking agents having an isocyanate group) such as adducts of these diisocyanates; epoxy-based cross-linking agents such as ethylene glycol glycidyl ether; agents (that is, cross-linking agents having a glycidyl group); aziridine-based cross-linking agents such as hexa[1-(2-methyl)-aziridinyl]triphosphatriazine (that is, cross-linking agents having an aziridinyl group); metals such as aluminum chelates chelate-based cross-linking agents (ie, cross-linking agents having a metal chelate structure); isocyanurate-based cross-linking agents (ie, cross-linking agents having an isocyanuric acid skeleton);
The cross-linking agent is preferably an isocyanate-based cross-linking agent because it improves the cohesive force of the pressure-sensitive adhesive to improve the adhesive strength of the pressure-sensitive adhesive layer and is easily available.

The pressure-sensitive adhesive composition (I-1) may contain one type of cross-linking agent, or two or more types thereof.

In the adhesive composition (I-1), the content of the cross-linking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the adhesive resin (I-1a), It is more preferably 0.1 to 20 parts by mass, particularly preferably 0.3 to 15 parts by mass.

[Photoinitiator]
The adhesive composition (I-1) may further contain a photopolymerization initiator. The adhesive composition (I-1) containing a photopolymerization initiator undergoes a sufficient curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone, 2-hydroxy -Acetophenone compounds such as 2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethan-1-one; bis(2,4,6-trimethylbenzoyl)phenylphosphine acylphosphine oxide compounds such as oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexylphenyl ketone; azo compounds such as bisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; 2-chloroanthraquinone and the like.
As the photopolymerization initiator, for example, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as an amine;

The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-1) may be of one type or two or more types, and when two or more types are used, the combination and ratio thereof can be arbitrarily selected.

In the adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the energy ray-curable compound. It is more preferably from 0.03 to 10 parts by mass, and particularly preferably from 0.05 to 5 parts by mass.

[Other additives]
The pressure-sensitive adhesive composition (I-1) may contain other additives that do not correspond to any of the above-described components, as long as they do not impair the effects of the present invention.
Examples of other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers, rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers. , a reaction retardant, a cross-linking accelerator (catalyst), and other known additives.
The reaction retarder is, for example, an unintended cross-linking reaction in the PSA composition (I-1) during storage due to the action of a catalyst mixed in the PSA composition (I-1). It suppresses progression. Examples of the reaction retarder include those that form a chelate complex by chelating the catalyst, more specifically those having two or more carbonyl groups (-C(=O)-) in one molecule. mentioned.

The other additives contained in the pressure-sensitive adhesive composition (I-1) may be of one type or two or more types, and when two or more types are used, their combination and ratio can be arbitrarily selected.

The content of other additives in the pressure-sensitive adhesive composition (I-1) is not particularly limited, and may be appropriately selected according to the type.

[solvent]
The adhesive composition (I-1) may contain a solvent. Since the pressure-sensitive adhesive composition (I-1) contains a solvent, the coating suitability to the surface to be coated is improved.

The solvent is preferably an organic solvent, and examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; esters such as ethyl acetate (that is, carboxylic acid esters); ethers such as tetrahydrofuran and dioxane; Aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such as toluene and xylene; and alcohols such as 1-propanol and 2-propanol.

As the solvent, for example, the solvent used in the production of the adhesive resin (I-1a) may be used as it is in the adhesive composition (I-1) without removing it from the adhesive resin (I-1a). However, a solvent of the same or different type as that used in the production of the adhesive resin (I-1a) may be added separately in the production of the adhesive composition (I-1).

The pressure-sensitive adhesive composition (I-1) may contain only one kind of solvent, or two or more kinds of solvents.

In the pressure-sensitive adhesive composition (I-1), the solvent content is not particularly limited and may be adjusted as appropriate.

In the adhesive composition (I-1), what can be the resin component (X) includes, for example, an adhesive resin (I-1a) and an energy ray-curable compound.

<Adhesive composition (I-2)>
As described above, the pressure-sensitive adhesive composition (I-2) is an energy-ray-curable adhesive resin in which an unsaturated group is introduced into the side chain of the non-energy-ray-curable adhesive resin (I-1a). Contains (I-2a).
In another aspect, the pressure-sensitive adhesive composition (I-2) includes the pressure-sensitive adhesive resin (I-2a) and, optionally, a cross-linking agent, a photopolymerization initiator, other additives, and a solvent. and at least one component selected from

[Adhesive resin (I-2a)]
The adhesive resin (I-2a) is obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group.

The unsaturated group-containing compound is capable of bonding with the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a) in addition to the energy ray-polymerizable unsaturated group. It is a compound having a group.
Examples of the energy ray-polymerizable unsaturated group include a (meth)acryloyl group, a vinyl group (also referred to as an ethenyl group), an allyl group (also referred to as a 2-propenyl group), etc., and a (meth)acryloyl group is preferred. .
Groups capable of bonding with functional groups in the adhesive resin (I-1a) include, for example, an isocyanate group and a glycidyl group capable of bonding with a hydroxyl group or an amino group, and a hydroxyl group and an amino group capable of bonding with a carboxy group or an epoxy group. etc.

Examples of the unsaturated group-containing compound include (meth)acryloyloxyethyl isocyanate, (meth)acryloylisocyanate, glycidyl (meth)acrylate, and the like.

The pressure-sensitive adhesive resin (I-2a) contained in the pressure-sensitive adhesive composition (I-2) may be of only one type, or may be of two or more types. You can choose.

In the adhesive composition (I-2), the content of the adhesive resin (I-2a) is preferably 5 to 99% by mass with respect to the total mass of the adhesive composition (I-2). , more preferably 10 to 95% by mass, particularly preferably 10 to 90% by mass.

[Crosslinking agent]
As the adhesive resin (I-2a), for example, when using the acrylic polymer having the same structural unit derived from a functional group-containing monomer as in the adhesive resin (I-1a), the adhesive composition ( I-2) may further contain a cross-linking agent.

Examples of the cross-linking agent in the pressure-sensitive adhesive composition (I-2) include the same cross-linking agents as in the pressure-sensitive adhesive composition (I-1).
The pressure-sensitive adhesive composition (I-2) may contain one type of cross-linking agent, or two or more types thereof.

In the adhesive composition (I-2), the content of the cross-linking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the adhesive resin (I-2a), It is more preferably 0.1 to 20 parts by mass, particularly preferably 0.3 to 15 parts by mass.

[Photoinitiator]
The adhesive composition (I-2) may further contain a photopolymerization initiator. The adhesive composition (I-2) containing a photopolymerization initiator undergoes a sufficient curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-2) include the same photopolymerization initiators as in the pressure-sensitive adhesive composition (I-1).
The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-2) may be of one type or two or more types, and when two or more types are used, the combination and ratio thereof can be arbitrarily selected.

In the adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the adhesive resin (I-2a). , more preferably 0.03 to 10 parts by mass, particularly preferably 0.05 to 5 parts by mass.

[Other additives]
The pressure-sensitive adhesive composition (I-2) may contain other additives that do not fall under any of the above-mentioned components, as long as they do not impair the effects of the present invention.
Examples of the other additives in the adhesive composition (I-2) include the same additives as the other additives in the adhesive composition (I-1).
The other additives contained in the pressure-sensitive adhesive composition (I-2) may be of one type or two or more types, and when there are two or more types, their combination and ratio can be arbitrarily selected.

The content of other additives in the pressure-sensitive adhesive composition (I-2) is not particularly limited, and may be appropriately selected according to the type.

[solvent]
The adhesive composition (I-2) may contain a solvent for the same purpose as the adhesive composition (I-1).
Examples of the solvent in the adhesive composition (I-2) include the same solvents as in the adhesive composition (I-1).
The pressure-sensitive adhesive composition (I-2) may contain only one kind of solvent, or two or more kinds of solvents.
In the pressure-sensitive adhesive composition (I-2), the solvent content is not particularly limited and may be adjusted as appropriate.

In the adhesive composition (I-2), what can be the resin component (X) is, for example, the adhesive resin (I-2a).

<Adhesive composition (I-3)>
The adhesive composition (I-3) contains the adhesive resin (I-2a) and an energy ray-curable compound, as described above.
In another aspect, the pressure-sensitive adhesive composition (I-3) comprises the pressure-sensitive adhesive resin (I-2a), an energy ray-curable compound, and optionally a cross-linking agent, a photopolymerization initiator, other and at least one component selected from the group consisting of additives and solvents.

In the adhesive composition (I-3), the content of the adhesive resin (I-2a) is preferably 5 to 99% by mass relative to the total mass of the adhesive composition (I-3). , more preferably 10 to 95% by mass, particularly preferably 15 to 90% by mass.

[Energy ray-curable compound]
Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) include monomers and oligomers that have an energy-ray-polymerizable unsaturated group and can be cured by irradiation with an energy ray. The same energy ray-curable compound contained in the product (I-1) can be mentioned.
The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) may be of one type or two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. .

In the adhesive composition (I-3), the content of the energy ray-curable compound is 0.01 to 300 parts by mass with respect to 100 parts by mass of the adhesive resin (I-2a). preferably 0.03 to 200 parts by mass, particularly preferably 0.05 to 100 parts by mass.

[Photoinitiator]
The adhesive composition (I-3) may further contain a photopolymerization initiator. The adhesive composition (I-3) containing a photopolymerization initiator undergoes a sufficient curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-3) include the same photopolymerization initiators as in the pressure-sensitive adhesive composition (I-1).
The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-3) may be of one type or two or more types, and when two or more types are used, the combination and ratio thereof can be arbitrarily selected.

In the adhesive composition (I-3), the content of the photopolymerization initiator is 0.01 to 0.01 with respect to 100 parts by mass of the total content of the adhesive resin (I-2a) and the energy ray-curable compound. It is preferably 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.

[Other additives]
The pressure-sensitive adhesive composition (I-3) may contain other additives that do not fall under any of the above-mentioned components, as long as they do not impair the effects of the present invention.
Examples of the other additives include the same as the other additives in the adhesive composition (I-1).
The other additives contained in the pressure-sensitive adhesive composition (I-3) may be of one type or two or more types, and when two or more types are used, their combination and ratio can be selected arbitrarily.

In the pressure-sensitive adhesive composition (I-3), the content of other additives is not particularly limited, and may be appropriately selected according to the type.

[solvent]
The adhesive composition (I-3) may contain a solvent for the same purpose as the adhesive composition (I-1).
Examples of the solvent in the adhesive composition (I-3) include the same solvents as in the adhesive composition (I-1).
The pressure-sensitive adhesive composition (I-3) may contain only one kind of solvent, or two or more kinds of solvents.
In the pressure-sensitive adhesive composition (I-3), the solvent content is not particularly limited and may be adjusted as appropriate.

In the adhesive composition (I-3), what can be the resin component (X) includes, for example, an adhesive resin (I-2a) and an energy ray-curable compound.

<Adhesive Compositions Other than Adhesive Compositions (I-1) to (I-3)>
So far, the adhesive composition (I-1), the adhesive composition (I-2) and the adhesive composition (I-3) have been mainly described, but the components described as these components are A general adhesive composition other than these three adhesive compositions (herein referred to as "adhesive compositions other than adhesive compositions (I-1) to (I-3)") But you can use it as well.

The pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) include not only energy-ray-curable pressure-sensitive adhesive compositions but also non-energy-ray-curable pressure-sensitive adhesive compositions.
Examples of non-energy ray-curable pressure-sensitive adhesive compositions include acrylic resins, urethane-based resins, rubber-based resins, silicone-based resins, epoxy-based resins, polyvinyl ethers, polycarbonates, ester-based resins, and the like. adhesive composition (I-4) containing a flexible adhesive resin (I-1a), and those containing an acrylic resin are preferred.

The pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) preferably contain one or more cross-linking agents, the content of which is the same as the pressure-sensitive adhesive composition described above. It can be the same as the case of (I-1) or the like.

<Adhesive composition (I-4)>
Preferable adhesive compositions (I-4) include, for example, those containing the adhesive resin (I-1a) and a cross-linking agent. The pressure-sensitive adhesive composition (I-4), which is a non-energy ray-curable pressure-sensitive adhesive composition, does not contain the energy ray-curable compound in the pressure-sensitive adhesive composition (I-1).
In another aspect, the pressure-sensitive adhesive composition (I-4) is at least selected from the group consisting of the pressure-sensitive adhesive resin (I-1a), a cross-linking agent, and optionally other additives and solvents. containing one component;

[Adhesive resin (I-1a)]
The adhesive resin (I-1a) in the adhesive composition (I-4) includes the same adhesive resin (I-1a) in the adhesive composition (I-1).
The pressure-sensitive adhesive resin (I-1a) contained in the pressure-sensitive adhesive composition (I-4) may be of only one type, or may be of two or more types. You can choose.

In the adhesive composition (I-4), the content of the adhesive resin (I-1a) is preferably 5 to 99% by mass relative to the total mass of the adhesive composition (I-4). , more preferably 10 to 95% by mass, particularly preferably 15 to 90% by mass.

[Crosslinking agent]
As the adhesive resin (I-1a), in addition to the structural unit derived from the (meth)acrylic acid alkyl ester, when using the acrylic polymer having a structural unit derived from a functional group-containing monomer, the adhesive composition ( I-4) preferably further contains a cross-linking agent.

Examples of the cross-linking agent in the pressure-sensitive adhesive composition (I-4) include the same cross-linking agents as in the pressure-sensitive adhesive composition (I-1).
The pressure-sensitive adhesive composition (I-4) may contain one type of cross-linking agent, or two or more types thereof.

In the adhesive composition (I-4), the content of the cross-linking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the adhesive resin (I-1a), It is more preferably 0.1 to 20 parts by mass, particularly preferably 0.3 to 15 parts by mass.

[Other additives]
The pressure-sensitive adhesive composition (I-4) may contain other additives that do not fall under any of the above-mentioned components, as long as they do not impair the effects of the present invention.
Examples of the other additives include the same as the other additives in the adhesive composition (I-1).
The other additives contained in the pressure-sensitive adhesive composition (I-4) may be of one type or two or more types, and when two or more types are used, their combination and ratio can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-4), the content of other additives is not particularly limited, and may be appropriately selected according to the type.

[solvent]
The adhesive composition (I-4) may contain a solvent for the same purpose as the adhesive composition (I-1).
Examples of the solvent in the adhesive composition (I-4) include the same solvents as in the adhesive composition (I-1).
The pressure-sensitive adhesive composition (I-4) may contain only one solvent, or two or more solvents.
In the pressure-sensitive adhesive composition (I-4), the solvent content is not particularly limited and may be adjusted as appropriate.

In the adhesive composition (I-4), what can be the resin component (X) is, for example, the adhesive resin (I-1a).

In the protective film-forming composite sheet, the pressure-sensitive adhesive layer is preferably non-energy ray-curable. This is because if the pressure-sensitive adhesive layer is energy ray-curable, simultaneous curing of the pressure-sensitive adhesive layer may not be suppressed when the protective film-forming film is cured by irradiation with energy rays. If the pressure-sensitive adhesive layer is cured at the same time as the protective film-forming film, the protective film-forming film after curing and the pressure-sensitive adhesive layer may stick to each other at their interface to such an extent that they cannot be peeled off. In that case, it becomes difficult to peel off the protective film-forming film after curing, that is, the semiconductor chip having the protective film on the back surface (semiconductor chip with protective film) from the support sheet having the adhesive layer after curing, A semiconductor chip with a protective film cannot be normally picked up. By using a non-energy ray-curable adhesive layer in the support sheet, such problems can be reliably avoided, and the protective film-attached semiconductor chip can be picked up more easily.

Here, the effect in the case where the pressure-sensitive adhesive layer is non-energy ray-curable has been described. A similar effect can be obtained if the layer is non-energy ray curable.

<<Method for producing pressure-sensitive adhesive composition>>
Adhesive compositions other than the adhesive compositions (I-1) to (I-3) such as the adhesive compositions (I-1) to (I-3) and the adhesive composition (I-4) , the pressure-sensitive adhesive and, if necessary, each component for constituting the pressure-sensitive adhesive composition, such as components other than the pressure-sensitive adhesive.
There are no particular restrictions on the order of addition of each component when blending them, and two or more components may be added at the same time.
When a solvent is used, the solvent may be mixed with any compounding component other than the solvent and used by diluting this compounding component in advance, or any compounding component other than the solvent may be diluted in advance. You may use by mixing a solvent with these compounding ingredients, without preserving.
The method of mixing each component at the time of blending is not particularly limited, and may be selected from known methods such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves. It can be selected as appropriate.
The temperature and time at which each component is added and mixed are not particularly limited as long as each compounded component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30°C.

◎ Protective film-forming film The protective film-forming film is energy ray-curable and contains an energy ray-curable component (a0) and a non-energy ray-curable polymer (b), as described above. .
The energy ray-curable component (a0) is preferably uncured, preferably tacky, more preferably uncured and tacky.

Since the film for forming a protective film is energy ray-curable, the protective film can be formed by curing in a shorter time than a thermosetting film for forming a protective film.

In the present invention, the term "energy ray" means an electromagnetic wave or charged particle beam that has an energy quantum, and examples thereof include ultraviolet rays, radiation, electron beams, and the like.
Ultraviolet rays can be applied by using, for example, a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, a black light, an LED lamp, or the like as an ultraviolet light source. The electron beam can be generated by an electron beam accelerator or the like.
In the present invention, "energy ray-curing" means the property of curing by irradiation with energy rays, and "non-energy ray-curing" means the property of not curing even when irradiated with energy rays. .

The protective film-forming film may consist of one layer (single layer), or may consist of two or more layers, and when it consists of multiple layers, these multiple layers may be the same or different from each other. , the combination of these multiple layers is not particularly limited.
When the film for forming a protective film is composed of multiple layers, at least the layer in direct contact with the support sheet among these multiple layers comprises the energy ray-curable component (a0) and the non-energy ray-curable polymer (b). and all layers may contain the energy ray-curable component (a0) and the non-energy ray-curable polymer (b).

The thickness of the protective film-forming film is preferably 1 to 100 μm, more preferably 3 to 75 μm, particularly preferably 5 to 50 μm. When the thickness of the film for forming a protective film is at least the lower limit, a protective film with higher protective ability can be formed. In addition, when the thickness of the protective film-forming film is equal to or less than the upper limit, excessive thickness is suppressed.
Here, the "thickness of the protective film-forming film" means the thickness of the entire protective film-forming film. means the total thickness of all the layers that make up the

The transmittance of the protective film-forming film to light having a wavelength of 350 nm is preferably 0% or more and 20% or less, more preferably 0% or more and 15% or less, and 0% or more and 8% or less. is more preferable, and it is particularly preferably 0% or more and 5% or less, and may be 0%. When the light transmittance is equal to or less than the upper limit, the ultraviolet curable component is cured unintendedly by the action of ultraviolet light contained in the light emitted from a fluorescent lamp or the like in the protective film-forming film during storage. It can suppress the progress of the reaction.

The film for forming a protective film and the protective film have substantially or completely the same transmittance for light having the same wavelength.
For example, in a protective film formed by curing a protective film-forming film having a transmittance of light at a wavelength of 350 nm within the above range, the transmittance of light at a wavelength of 350 nm is preferably 0% or more and 20% or less, and more It is preferably 0% or more and 15% or less, more preferably 0% or more and 8% or less, particularly preferably 0% or more and 5% or less, and may be 0%.

The curing conditions for forming the protective film by curing the protective film-forming film are not particularly limited as long as the degree of curing is such that the protective film sufficiently exhibits its function. It may be selected as appropriate.
For example, the illuminance of the energy beam during curing of the protective film-forming film is preferably 4 to 280 mW/cm ² . It is preferable that the light quantity of the energy beam during the curing is 3 to 1000 mJ/cm ² .

<<Composition for Forming Protective Film>>
The protective film-forming film can be formed using a protective film-forming composition containing its constituent materials. For example, the protective film-forming film can be formed on the target site by applying the protective film-forming composition to the surface to be formed of the protective film-forming film and drying it as necessary.
The content ratio of the components that do not vaporize at room temperature in the protective film-forming composition is usually the same as the content ratio of the components in the protective film-forming film.

The protective film-forming composition may be applied by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, A method using various coaters such as a screen coater, a Meyer bar coater, and a kiss coater can be used.

Drying conditions for the composition for forming a protective film are not particularly limited, but when the composition for forming a protective film contains a solvent described later, it is preferable to heat and dry the composition. The protective film-forming composition containing a solvent is preferably dried, for example, at 70 to 130° C. for 10 seconds to 5 minutes.

<Protective film-forming composition (IV-1)>
Examples of the protective film-forming composition include protective film-forming composition (IV-1) containing the energy ray-curable component (a0) and the non-energy ray-curable polymer (b).

[Energy ray-curable component (a0)]
The energy ray-curable component (a0) is a component that cures when irradiated with an energy ray, and is also a component that imparts film-forming properties, flexibility, and the like to the protective film-forming film.
Examples of the energy ray-curable component (a0) include compounds having an energy ray-curable group and having a molecular weight of 100 to 80,000.

Examples of the energy ray-curable group in the energy ray-curable component (a0) include groups containing an energy ray-curable double bond, and preferred examples include a (meth)acryloyl group and a vinyl group. .

The energy ray-curable component (a0) is not particularly limited as long as it satisfies the above conditions. phenolic resin having a group, and the like.

Among the energy ray-curable component (a0), low-molecular-weight compounds having energy ray-curable groups include, for example, polyfunctional monomers or oligomers, and acrylate compounds having (meth)acryloyl groups are preferred.
Examples of the acrylate compounds include 2-hydroxy-3-(meth)acryloyloxypropyl 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)acryloxydiethoxy)phenyl]propane, 9,9-bis [4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 2,2-bis[4-((meth)acryloxypolypropoxy)phenyl]propane, tricyclodecanedimethanol di(meth)acrylate (tri cyclodecanedimethylol di(meth)acrylate), 1,10-decanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dipropylene glycol Di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acryloxyethoxy)phenyl]propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy- Bifunctional (meth)acrylates such as 1,3-di(meth)acryloxypropane;
tris(2-(meth)acryloxyethyl)isocyanurate, ε-caprolactone-modified tris-(2-(meth)acryloxyethyl)isocyanurate, ethoxylated glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, Trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, dipentaerythritol hexa( Polyfunctional (meth)acrylates such as meth)acrylates;
Examples include polyfunctional (meth)acrylate oligomers such as urethane (meth)acrylate oligomers.

Among the energy ray-curable component (a0), the epoxy resin having an energy ray-curable group and the phenolic resin having an energy ray-curable group are described, for example, in paragraph 0043 of "JP-A-2013-194102". can be used. Such a resin corresponds to a resin constituting a thermosetting component (h) described later, but is treated as an energy ray-curable component (a0) in the present invention.

The energy ray-curable component (a0) preferably has a molecular weight of 100 to 30,000, more preferably 300 to 10,000.

The energy ray-curable component (a0) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be of only one type, or may be of two or more types. Any combination and ratio thereof can be selected.

[Energy ray-curable component (a1)]
The composition for forming a protective film (IV-1) and the film for forming a protective film may contain an energy ray-curable component (a1) other than the energy ray-curable component (a0) (in this specification, simply may be referred to as "energy ray-curable component (a1)").

The energy ray-curable component (a1) is a component that cures when irradiated with an energy ray, and is also a component that imparts film-forming properties, flexibility, and the like to the protective film-forming film.

Examples of the energy ray-curable component (a1) include polymers having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000. At least part of the energy ray-curable component (a1) may or may not be crosslinked with a crosslinking agent (f) described later.
As used herein, the term "weight average molecular weight" means a polystyrene equivalent value measured by a gel permeation chromatography (GPC) method, unless otherwise specified.

Examples of the energy ray-curable component (a1) include, for example, an acrylic polymer (a11) having a functional group that can react with a group possessed by another compound, a group that reacts with the functional group, and an energy ray-curable two An energy ray-curable compound (a12) having an energy ray-curable group such as a double bond and an acrylic resin (a1-1) obtained by polymerization can be mentioned.

Examples of the functional group capable of reacting with a group possessed by another compound include a hydroxyl group, a carboxy group, an amino group, and a substituted amino group (for example, one or two hydrogen atoms in the amino group are groups other than hydrogen atoms). substituted groups), epoxy groups, and the like. However, from the viewpoint of preventing corrosion of circuits such as semiconductor wafers and semiconductor chips, the functional group is preferably a group other than the carboxyl group.
Among these, the functional group is preferably a hydroxyl group.

- Acrylic polymer having a functional group (a11)
Examples of the acrylic polymer (a11) having the functional group include those obtained by copolymerizing an acrylic monomer having the functional group and an acrylic monomer having no functional group. In addition to the monomers, monomers other than acrylic monomers (that is, non-acrylic monomers) may be copolymerized.
Further, the acrylic polymer (a11) may be a random copolymer or a block copolymer.

Examples of acrylic monomers having functional groups include hydroxyl group-containing monomers, carboxy group-containing monomers, amino group-containing monomers, substituted amino group-containing monomers, and epoxy group-containing monomers.

Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth) Hydroxyalkyl (meth)acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; Saturated alcohol (that is, unsaturated alcohol having no (meth)acryloyl skeleton) and the like can be mentioned.

Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (i.e., monocarboxylic acids having an ethylenically unsaturated bond) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, and maleic acid; , ethylenically unsaturated dicarboxylic acids (i.e., dicarboxylic acids having an ethylenically unsaturated bond) such as citraconic acid; anhydrides of said ethylenically unsaturated dicarboxylic acids; carboxyalkyl (meth)acrylates such as 2-carboxyethyl methacrylate Ester etc. are mentioned.

The acrylic monomer having the functional group is preferably a hydroxyl group-containing monomer or a carboxy group-containing monomer, more preferably a hydroxyl group-containing monomer.

The acrylic monomer having a functional group, which constitutes the acrylic polymer (a11), may be of only one type, or may be of two or more types. You can choose.

Examples of acrylic monomers having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n (meth) acrylate. -butyl, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (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, (meth)acrylate undecyl acrylate, dodecyl (meth)acrylate (also referred to as lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, Alkyl groups that constitute alkyl esters, such as hexadecyl (meth)acrylate (also referred to as palmityl (meth)acrylate), heptadecyl (meth)acrylate, and octadecyl (meth)acrylate (also referred to as stearyl (meth)acrylate) However, (meth)acrylic acid alkyl esters having a chain structure having 1 to 18 carbon atoms can be mentioned.

Examples of acrylic monomers having no functional group include alkoxy groups such as methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, and ethoxyethyl (meth)acrylate. Alkyl group-containing (meth)acrylic acid esters; (meth)acrylic acid esters having an aromatic group, including (meth)acrylic acid aryl esters such as phenyl (meth)acrylate; non-crosslinkable (meth)acrylamides and Derivatives thereof; (meth)acrylic acid esters having a non-crosslinkable tertiary amino group such as N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate; .

The acrylic monomer having no functional group, which constitutes the acrylic polymer (a11), may be only one kind, or may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof are arbitrary. can be selected to

Examples of the non-acrylic monomers include olefins such as ethylene and norbornene; vinyl acetate; and styrene.
The non-acrylic monomers constituting the acrylic polymer (a11) may be of one type or two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

In the acrylic polymer (a11), the ratio (content) of the amount of structural units derived from the acrylic monomer having the functional group to the total amount (total mass) of the structural units constituting the acrylic polymer (a11) is 0. It is preferably 1 to 50% by mass, more preferably 1 to 40% by mass, and particularly preferably 3 to 30% by mass. When the ratio is within such a range, in the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12), energy The content of the radiation-curable group makes it possible to easily adjust the degree of curing of the protective film within a preferred range.

The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be of only one type, or may be of two or more types. You can choose.

When the acrylic resin (a1-1) is used, the content of the acrylic resin (a1-1) in the protective film-forming composition (IV-1) is the total of the protective film-forming composition (IV-1). It is preferably from 1 to 40% by mass, more preferably from 2 to 30% by mass, and particularly preferably from 3 to 20% by mass.

- Energy ray-curable compound (a12)
In the energy ray-curable compound (a12), one or two selected from the group consisting of an isocyanate group, an epoxy group and a carboxy group as a group capable of reacting with a functional group possessed by the acrylic polymer (a11). Those having the above are preferable, and those having an isocyanate group as the group are more preferable. For example, when the energy ray-curable compound (a12) has an isocyanate group as the group, the isocyanate group readily reacts with the hydroxyl group of the acrylic polymer (a11) having the hydroxyl group as the functional group.

The energy ray-curable compound (a12) preferably has 1 to 5, more preferably 1 to 3, energy ray-curable groups in one molecule.

Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1,1-(bisacryloyloxymethyl) ethyl isocyanate;
An acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth)acrylate;
An acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or polyisocyanate compound, a polyol compound, and hydroxyethyl (meth)acrylate, and the like.
Among these, the energy ray-curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.

The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be of only one type, or may be of two or more types. can be selected to

In the acrylic resin (a1-1), energy ray curability derived from the energy ray-curable compound (a12) with respect to the content (number of moles) of the functional group derived from the acrylic polymer (a11) The group content (number of moles) is preferably 20 to 120 mol %, more preferably 35 to 100 mol %, and particularly preferably 50 to 100 mol %. When the proportion of the content is within such a range, the adhesive strength of the protective film formed by curing is increased. When the energy ray-curable compound (a12) is a monofunctional compound (having one group per molecule), the upper limit of the content ratio is 100 mol%. When the energy ray-curable compound (a12) is a polyfunctional compound (having two or more of the above groups in one molecule), the upper limit of the content ratio may exceed 100 mol %.

The weight average molecular weight (Mw) of the energy ray-curable component (a1) is preferably 100,000 to 2,000,000, more preferably 300,000 to 1,500,000.

When the energy ray-curable component (a1) is at least partially crosslinked by the crosslinking agent (f), the energy ray-curable component (a1) constitutes the acrylic polymer (a11). A monomer that does not correspond to any of the above-mentioned monomers and has a group that reacts with the cross-linking agent (f) is polymerized and cross-linked at the group that reacts with the cross-linking agent (f). Alternatively, the groups derived from the energy ray-curable compound (a12) and reactive with the functional groups may be crosslinked.

The protective film-forming composition (IV-1) and the energy ray-curable component (a1) contained in the protective film-forming film may be of only one type, or may be of two or more types. Any combination and ratio thereof can be selected.

In the composition for forming a protective film (IV-1), the content of the energy ray-curable component (a0) is the total content of the energy ray-curable component (a1) and the non-energy ray-curable polymer (b) of 100. It is preferably 10 to 400 parts by mass, more preferably 30 to 350 parts by mass.

[Non-energy ray-curable polymer (b)]
The non-energy ray-curable polymer (b) is a polymer having no energy ray-curable group.
At least part of the polymer (b) may be crosslinked with a crosslinking agent (f) described later, or may not be crosslinked.

Examples of the non-energy ray-curable polymer (b) include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, acrylic urethane resins, polyvinyl alcohol (sometimes abbreviated as PVA), butyral resins, A polyester urethane resin etc. are mentioned.

Among these, the polymer (b) is preferably an acrylic polymer (hereinafter sometimes abbreviated as "acrylic polymer (b-1)"). A combination of the polymer (b), which is an acrylic polymer, and the resin component (X) having a _δP of 7.5 MPa ^1/2 or less is particularly preferable in the present embodiment, and such a combination is selected. In this case, changes over time in adhesive strength between the protective film-forming film and the support sheet and changes in adhesive strength over time between the protective film and the support sheet are more significantly suppressed.
Further, when the polymer (b) is an acrylic polymer, particularly when it is a highly polar acrylic polymer, the adhesion between the protective film forming film and the semiconductor wafer, and the protective film forming The adhesion between the film and the semiconductor chip is further improved, and the adhesion between the protective film and the semiconductor wafer and the adhesion between the protective film and the semiconductor chip are further improved. Here, the "highly polar acrylic polymer" includes, for example, an acrylic polymer having a polarized structure, an acrylic polymer having a high SP value (Solubility Parameter), and the like.

The acrylic polymer (b-1) may be a known one, and may be, for example, a homopolymer of one acrylic monomer or a copolymer of two or more acrylic monomers. Alternatively, it may be a copolymer of one or more acrylic monomers and one or more monomers other than acrylic monomers (that is, non-acrylic monomers).

Examples of the acrylic monomer constituting the acrylic polymer (b-1) include (meth)acrylic acid alkyl esters, (meth)acrylic acid esters having a cyclic skeleton, glycidyl group-containing (meth)acrylic acid esters, Examples include hydroxyl group-containing (meth)acrylic acid esters and substituted amino group-containing (meth)acrylic acid esters. Here, the "substituted amino group" is as described above.

Examples of the (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-(meth)acrylate. Butyl, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (meth)acrylate ) 2-ethylhexyl acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, (meth)acrylic Undecyl acid, dodecyl (meth)acrylate (also called lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also called myristyl (meth)acrylate), pentadecyl (meth)acrylate , hexadecyl (meth)acrylate (also referred to as palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (also referred to as stearyl (meth)acrylate), etc. Examples thereof include (meth)acrylic acid alkyl esters in which the group has a chain structure of 1 to 18 carbon atoms.

Examples of (meth)acrylic acid esters having a cyclic skeleton include (meth)acrylic acid cycloalkyl esters such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate;
(meth)acrylic acid aralkyl ester such as benzyl (meth)acrylate;
(meth)acrylic acid cycloalkenyl esters such as (meth)acrylic acid dicyclopentenyl ester;
(Meth)acrylic acid cycloalkenyloxyalkyl esters such as (meth)acrylic acid dicyclopentenyloxyethyl ester and the like.

Examples of the glycidyl group-containing (meth)acrylic acid ester include glycidyl (meth)acrylate.
Examples of the hydroxyl group-containing (meth)acrylic acid ester include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxy (meth)acrylate. propyl, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and the like.
Examples of the substituted amino group-containing (meth)acrylic acid ester include N-methylaminoethyl (meth)acrylate.

Examples of the non-acrylic monomers constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; vinyl acetate; and styrene.

As the non-energy ray-curable polymer (b) at least partially crosslinked by the crosslinking agent (f), for example, a reactive functional group in the polymer (b) reacted with the crosslinking agent (f) is mentioned.
The reactive functional group may be appropriately selected according to the type of the cross-linking agent (f) and is not particularly limited. For example, when the cross-linking agent (f) is a polyisocyanate compound, the reactive functional group includes a hydroxyl group, a carboxyl group, an amino group, etc. Among them, a hydroxyl group having high reactivity with the isocyanate group is preferred. When the cross-linking agent (f) is an epoxy-based compound, examples of the reactive functional group include a carboxy group, an amino group, an amide group, and the like. groups are preferred. However, the reactive functional group is preferably a group other than the carboxy group from the viewpoint of preventing corrosion of the circuits of the semiconductor wafer or semiconductor chip.

Examples of the non-energy ray-curable polymer (b) having a reactive functional group include those obtained by polymerizing a monomer having at least the reactive functional group. In the case of the acrylic polymer (b-1), one or both of the acrylic monomer and the non-acrylic monomer exemplified as monomers constituting the acrylic polymer (b-1) are those having the reactive functional group. You can use it. Examples of the polymer (b) having a hydroxyl group as a reactive functional group include those obtained by polymerizing a hydroxyl group-containing (meth)acrylic acid ester. Examples thereof include those obtained by polymerizing a monomer in which one or more hydrogen atoms are substituted with the reactive functional groups in the acrylic monomers or non-acrylic monomers.

In the non-energy ray-curable polymer (b) having a reactive functional group, the ratio of the amount of structural units derived from a monomer having a reactive functional group to the total amount (total mass) of the structural units constituting this ( content) is preferably 1 to 25% by mass, more preferably 2 to 20% by mass. When the ratio is within such a range, the degree of cross-linking in the polymer (b) is in a more preferable range.

The weight average molecular weight (Mw) of the non-energy ray-curable polymer (b) is preferably 10,000 to 2,000,000 from the viewpoint of better film-forming properties of the protective film-forming composition (IV-1). , 100,000 to 1,500,000.

The protective film-forming composition (IV-1) and the non-energy ray-curable polymer (b) contained in the protective film-forming film may be one kind, two or more kinds, or two or more kinds. In that case, their combination and ratio can be arbitrarily selected.

In the protective film-forming composition (IV-1), the energy ray-curable component (a0), the energy ray-curable component (a1), and the non-energy ray-curable component with respect to the total content (total mass) of components other than the solvent The ratio of the total content of the polymer (b) (that is, the energy ray-curable component (a0), the energy ray-curable component (a1), and the non-energy ray-curable polymer (b) of the protective film-forming film total content) is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, particularly preferably 15 to 70% by mass, for example, 20 to 60% by mass, 25 It may be up to 50% by mass or 25 to 39% by mass. When the ratio of the total content is within such a range, the energy ray curability of the film for forming a protective film becomes better.

In the protective film-forming composition (IV-1) and the protective film-forming film, the content of the non-energy ray-curable polymer (b) is the energy ray-curable component (a0) and the energy ray-curable component (a1 ) with respect to 100 parts by mass of the total content, preferably 50 to 400 parts by mass, more preferably 100 to 350 parts by mass, particularly preferably 150 to 300 parts by mass, 150 to 280 parts by mass Parts by mass are highly preferred. When the content of the polymer (b) is in such a range, the energy ray curability of the film for forming a protective film becomes better.

[Other ingredients]
The composition for forming a protective film (IV-1) and the film for forming a protective film may contain an energy ray-curable component (a0), an energy ray-curable component (a1) and a non-energy ray-curable polymer ( It may further contain other components that do not correspond to any of b).

The other components contained in the protective film-forming composition (IV-1) and the protective film-forming film may be one type or two or more types, and when there are two or more types, combinations thereof and Any ratio can be selected.

Examples of the other components include a photopolymerization initiator (c), a filler (d), a coupling agent (e), a cross-linking agent (f), a colorant (g), a thermosetting component (h), Curing accelerator (i), general-purpose additive (z), and the like are included.
For example, by using the protective film-forming composition (IV-1) containing the thermosetting component (h), the protective film-forming film formed has improved adhesion to the adherend by heating, The strength of the protective film formed from this protective film-forming film is also improved.

(Photoinitiator (c))
The photopolymerization initiator (c) includes, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin compounds such as benzoin dimethyl ketal; - Acetophenone compounds such as hydroxy-2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethan-1-one; bis(2,4,6-trimethylbenzoyl)phenyl acylphosphine oxide compounds such as phosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexylphenyl ketone azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; benzophenone, 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone, Benzophenone compounds such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); peroxide compounds; diketone compounds such as diacetyl benzyl; dibenzyl; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone;
As the photopolymerization initiator (c), for example, quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines; and the like can also be used.

The protective film-forming composition (IV-1) and the photopolymerization initiator (c) contained in the protective film-forming film may be of one type or two or more types. can be selected arbitrarily.

When the photopolymerization initiator (c) is used, the content of the photopolymerization initiator (c) in the protective film-forming composition (IV-1) is the energy ray-curable compound (a0) and the energy ray-curable component With respect to 100 parts by mass of the total content of (a1), it is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 15 parts by mass, and 0.05 to 10 parts by mass. is particularly preferred.

(Filler (d))
By including the filler (d) in the protective film-forming film, the thermal expansion coefficient of the protective film obtained by curing the protective film-forming film can be easily adjusted. By optimizing the coefficient of thermal expansion for the object on which the protective film is to be formed, the reliability of the package obtained using the protective film-forming composite sheet is further improved. In addition, by including the filler (d) in the protective film-forming film, the moisture absorption rate of the protective film can be reduced and the heat dissipation can be improved.
Examples of the filler (d) include those made of thermally conductive materials.

The filler (d) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
Preferable inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, iron oxide, silicon carbide, boron nitride; beads obtained by spheroidizing these inorganic fillers; and surface modification of these inorganic fillers. products; single crystal fibers of these inorganic fillers; glass fibers and the like.
Among these, the inorganic filler is preferably silica or alumina.

The average particle size of the filler (d) is not particularly limited, but is preferably 0.01 to 20 μm, more preferably 0.1 to 15 μm, and particularly preferably 0.3 to 10 μm. . When the average particle size of the filler (d) is within such a range, it is possible to suppress a decrease in the light transmittance of the protective film while maintaining the adhesion of the protective film to the object to be formed.
In the present specification, the "average particle size" means the value of the particle size ( _D50 ) at an integrated value of 50% in a particle size distribution curve obtained by a laser diffraction scattering method, unless otherwise specified. .

The filler (d) contained in the composition for forming a protective film (IV-1) and the film for forming a protective film may be of only one type, or may be of two or more types. and ratio can be selected arbitrarily.

When the filler (d) is used, the ratio of the content of the filler (d) to the total content (total mass) of all components other than the solvent in the protective film-forming composition (IV-1) (i.e., The content of the filler (d) in the protective film-forming film) is preferably 10 to 85% by mass, more preferably 20 to 80% by mass, particularly 30 to 75% by mass. Preferably, for example, it may be either 40 to 70% by mass or 45 to 65% by mass. When the content of the filler (d) is within such a range, the adjustment of the coefficient of thermal expansion described above becomes easier.

(Coupling agent (e))
By using a coupling agent (e) having a functional group capable of reacting with an inorganic compound or an organic compound, the adhesiveness and adhesion of the protective film-forming film to the adherend can be improved. Moreover, by using the coupling agent (e), the protective film obtained by curing the film for forming a protective film has improved water resistance without impairing heat resistance.

The coupling agent (e) is a compound having a functional group capable of reacting with a functional group possessed by the energy ray-curable component (a0), the energy ray-curable component (a1), the non-energy ray-curable polymer (b), etc. and more preferably a silane coupling agent.
Preferred silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-amino ethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyl dimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane and the like.

The coupling agent (e) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be one kind or two or more kinds. Any combination and ratio can be selected.

When the coupling agent (e) is used, the content of the coupling agent (e) in the protective film-forming composition (IV-1) and the protective film-forming film is the energy ray-curable component (a0), the energy It is preferably 0.03 to 20 parts by mass, preferably 0.05 to 10 parts by mass, based on 100 parts by mass of the total content of the radiation-curable component (a1) and the non-energy ray-curable polymer (b). more preferably 0.1 to 5 parts by mass. When the content of the coupling agent (e) is at least the lower limit, the dispersibility of the filler (d) in the resin is improved, and the adhesion of the protective film-forming film to the adherend is improved. etc., the effect of using the coupling agent (e) can be obtained more remarkably. Moreover, generation|occurrence|production of outgassing is suppressed more because the said content of a coupling agent (e) is below the said upper limit.

(Crosslinking agent (f))
Using a crosslinking agent (f), the energy ray-curable component (a0), the energy ray-curable component (a1), or the non-energy ray-curable polymer (b) is crosslinked to obtain a protective film-forming film The initial adhesive strength and cohesive strength of the can be adjusted.

Examples of the cross-linking agent (f) include an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate-based cross-linking agent (i.e., a cross-linking agent having a metal chelate structure), an aziridine-based cross-linking agent (i.e., having an aziridinyl group cross-linking agent) and the like.

Examples of the organic polyisocyanate compounds include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds and alicyclic polyisocyanate compounds (hereinafter collectively referred to as "aromatic polyisocyanate compounds, etc."). trimers, isocyanurates and adducts of the aromatic polyvalent isocyanate compounds; terminal isocyanate urethane prepolymers obtained by reacting the aromatic polyvalent isocyanate compounds and the like with polyol compounds. etc. The "adduct" is a mixture of the aromatic polyisocyanate compound, the aliphatic polyisocyanate compound or the alicyclic polyisocyanate compound and a low molecular weight compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. It means a reactant with a compound containing molecularly active hydrogen. Examples of the adduct include a xylylene diisocyanate adduct of trimethylolpropane as described later. The term "terminal isocyanate urethane prepolymer" means a prepolymer having urethane bonds and an isocyanate group at the end of the molecule.

More specifically, the organic polyvalent isocyanate compound includes, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylylene diisocyanate; diphenylmethane-4 ,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; Compounds in which one or more of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate are added to all or part of the hydroxyl groups of polyols such as propane; lysine diisocyanate and the like.

Examples of the organic polyvalent imine compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, and tetramethylolmethane. -tri-β-aziridinylpropionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide) triethylene melamine, and the like.

When an organic polyvalent isocyanate compound is used as the cross-linking agent (f), the energy ray-curable component (a0), the energy ray-curable component (a1), or the non-energy ray-curable polymer (b) is a hydroxyl group-containing polymer is preferably used. When the cross-linking agent (f) has an isocyanate group and the energy ray-curable component (a0), the energy ray-curable component (a1) or the non-energy ray-curable polymer (b) has a hydroxyl group, the cross-linking agent (f ) and the energy ray-curable component (a0), the energy ray-curable component (a1) or the non-energy ray-curable polymer (b) can easily introduce a crosslinked structure into the protective film-forming film.

The cross-linking agent (f) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be of one type or two or more types, and when two or more types are used, a combination thereof. and ratio can be selected arbitrarily.

When the cross-linking agent (f) is used, the content of the cross-linking agent (f) in the protective film-forming composition (IV-1) is the energy ray-curable component (a0), the energy ray-curable component (a1) and It is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the total content of the non-energy ray-curable polymer (b). 5 to 5 parts by mass is particularly preferred. When the content of the cross-linking agent (f) is at least the lower limit, the effect of using the cross-linking agent (f) can be obtained more remarkably. Moreover, excessive use of a crosslinking agent (f) is suppressed because the said content of a crosslinking agent (f) is below the said upper limit.

(Colorant (g))
Examples of the coloring agent (g) include known ones such as inorganic pigments, organic pigments, and organic dyes.

Examples of the organic pigments and organic dyes include aminium dyes, cyanine dyes, merocyanine dyes, croconium dyes, squalium dyes, azulenium dyes, polymethine dyes, naphthoquinone dyes, pyrylium dyes, and phthalocyanines. dyes, naphthalocyanine dyes, naphtholactam dyes, azo dyes, condensed azo dyes, indigo dyes, perinone dyes, perylene dyes, dioxazine dyes, quinacridone dyes, isoindolinone dyes, quinophthalone dyes , pyrrole dyes, thioindigo dyes, metal complex dyes (metal complex salt dyes), dithiol metal complex dyes, indolephenol dyes, triallylmethane dyes, anthraquinone dyes, naphthol dyes, azomethine dyes, benzimidazo Examples include ron-based dyes, pyranthrone-based dyes, and threne-based dyes.

Examples of the inorganic pigments include carbon black, cobalt-based pigments, iron-based pigments, chromium-based pigments, titanium-based pigments, vanadium-based pigments, zirconium-based pigments, molybdenum-based pigments, ruthenium-based pigments, platinum-based pigments, ITO ( indium tin oxide) dyes, ATO (antimony tin oxide) dyes, and the like.

The colorant (g) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be one kind or two or more kinds, and in the case of two or more kinds, combinations thereof. and ratio can be selected arbitrarily.

When the colorant (g) is used, the content of the colorant (g) in the protective film-forming composition (IV-1) and the protective film-forming film may be appropriately adjusted depending on the purpose. For example, when adjusting the print visibility by adjusting the content of the coloring agent (g) and adjusting the light transmittance of the protective film, in the protective film-forming composition (IV-1), The ratio of the content of the colorant (g) to the total content (total mass) of all components (that is, the content of the colorant (g) of the protective film-forming film) is 0.1 to 10% by mass. preferably 0.4 to 7.5% by mass, particularly preferably 0.8 to 5% by mass. When the content of the coloring agent (g) is at least the lower limit, the effect of using the coloring agent (g) can be obtained more remarkably. Moreover, excessive use of the coloring agent (g) is suppressed because the content of the coloring agent (g) is equal to or less than the upper limit.

(Thermosetting component (h))
The thermosetting component (h) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be of one type or two or more types. can be selected arbitrarily.

Examples of the thermosetting component (h) include epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, and silicone resins, with epoxy thermosetting resins being preferred.

*Epoxy thermosetting resin The epoxy thermosetting resin consists of an epoxy resin (h1) and a thermosetting agent (h2).
The epoxy thermosetting resin contained in the protective film-forming composition (IV-1) and the protective film-forming film may be of one type or two or more types. Any combination and ratio can be selected.

・Epoxy resin (h1)
Examples of the epoxy resin (h1) include known ones, such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, ortho-cresol novolak epoxy resins, dicyclopentadiene type epoxy resins, Biphenyl-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, phenylene skeleton-type epoxy resins, and other epoxy compounds having a functionality of two or more can be used.

As the epoxy resin (h1), an epoxy resin having an unsaturated hydrocarbon group may be used. Epoxy resins having unsaturated hydrocarbon groups have higher compatibility with acrylic resins than epoxy resins having no unsaturated hydrocarbon groups. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of a package obtained using a composite sheet for forming a protective film is improved.

Epoxy resins having unsaturated hydrocarbon groups include, for example, compounds obtained by converting part of the epoxy groups of polyfunctional epoxy resins into groups having unsaturated hydrocarbon groups. Such a compound can be obtained, for example, by addition reaction of (meth)acrylic acid or a derivative thereof to an epoxy group.
Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like that constitutes the epoxy resin.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethenyl group (also referred to as a vinyl group), a 2-propenyl group (also referred to as an allyl group), and a (meth)acryloyl group. , (meth)acrylamide group and the like, and acryloyl group is preferred.

The number average molecular weight of the epoxy resin (h1) is not particularly limited. 1 is more preferable, and 500 to 3,000 is particularly preferable.
As used herein, the term "number average molecular weight" means a number average molecular weight measured by gel permeation chromatography (GPC) and converted to standard polystyrene, unless otherwise specified.
The epoxy equivalent of the epoxy resin (h1) is preferably 100-1000 g/eq, more preferably 150-800 g/eq.
As used herein, "epoxy equivalent" means the number of grams (g/eq) of an epoxy compound containing one equivalent of an epoxy group, and can be measured according to the method of JIS K 7236:2001.

Epoxy resin (h1) may be used alone or in combination of two or more. When two or more are used in combination, the combination and ratio thereof can be arbitrarily selected.

・Heat curing agent (h2)
The thermosetting agent (h2) functions as a curing agent for the epoxy resin (h1).
Examples of the thermosetting agent (h2) include compounds having two or more functional groups capable of reacting with epoxy groups in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an anhydrided group of an acid group. is preferably a group, more preferably a phenolic hydroxyl group or an amino group.

Among thermosetting agents (h2), phenolic curing agents having phenolic hydroxyl groups include, for example, polyfunctional phenolic resins, biphenols, novolac type phenolic resins, dicyclopentadiene phenolic resins, and aralkylphenolic resins.
Among the thermosetting agents (h2), amine-based curing agents having an amino group include, for example, dicyandiamide.

The thermosetting agent (h2) may have an unsaturated hydrocarbon group.
Examples of the thermosetting agent (h2) having an unsaturated hydrocarbon group include, for example, a compound obtained by substituting a portion of the hydroxyl groups of a phenol resin with a group having an unsaturated hydrocarbon group; Examples thereof include compounds in which a group having a saturated hydrocarbon group is directly bonded.
The unsaturated hydrocarbon group in the thermosetting agent (h2) is the same as the unsaturated hydrocarbon group in the above epoxy resin having an unsaturated hydrocarbon group.

When a phenol-based curing agent is used as the heat curing agent (h2), the heat curing agent (h2) preferably has a high softening point or glass transition temperature in terms of improving the peelability of the protective film from the support sheet. .

Among the thermosetting agents (h2), the number average molecular weight of resin components such as polyfunctional phenol resins, novolak phenol resins, dicyclopentadiene phenol resins, and aralkyl phenol resins is preferably 300 to 30,000. 400 to 10,000 is more preferred, and 500 to 3,000 is particularly preferred. Among the thermosetting agent (h2), the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.

The thermosetting agent (h2) may be used alone or in combination of two or more. When two or more are used in combination, the combination and ratio thereof can be arbitrarily selected.

When the thermosetting component (h) is used, the content of the thermosetting agent (h2) in the composition for forming a protective film (IV-1) and the film for forming a protective film is equal to the content of the epoxy resin (h1) of 100. It is preferably 0.01 to 20 parts by mass.

When the thermosetting component (h) is used, the content of the thermosetting component (h) (e.g., epoxy resin (h1) and heat The total content of the curing agent (h2)) is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the non-energy ray-curable polymer (b).

(Curing accelerator (i))
The curing accelerator (i) is a component for adjusting the curing speed of the protective film-forming film.
Preferred curing accelerators (i) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole. , 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; tributylphosphine, diphenylphosphine, triphenylphosphine, etc. organic phosphines; tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate;

The curing accelerator (i) may be used alone or in combination of two or more. When two or more are used in combination, the combination and ratio thereof can be arbitrarily selected.
When the curing accelerator (i) is used, the content of the curing accelerator (i) in the protective film-forming composition (IV-1) and the protective film-forming film is not particularly limited, depending on the components used in combination. It can be selected as appropriate.

(General purpose additive (z))
The general-purpose additive (z) may be a known one, can be arbitrarily selected according to the purpose, and is not particularly limited, but preferable examples include plasticizers, antistatic agents, antioxidants, gettering agents, and the like. are mentioned.

The general-purpose additive (z) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be one kind or two or more kinds. Any combination and ratio can be selected.
When the general-purpose additive (z) is used, the content of the general-purpose additive (z) in the protective film-forming composition (IV-1) and the protective film-forming film is not particularly limited, and is appropriately selected according to the purpose. do it.

(solvent)
The protective film-forming composition (IV-1) preferably further contains a solvent. The protective film-forming composition (IV-1) containing a solvent is easy to handle.
The solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutyl alcohol (also referred to as 2-methylpropan-1-ol), 1-butanol, and the like. esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (ie, compounds having an amide bond).
The protective film-forming composition (IV-1) may contain only one kind of solvent, or two or more kinds of solvents.

The solvent contained in the protective film-forming composition (IV-1) is methyl ethyl ketone, toluene, ethyl acetate, or the like, since the components contained in the protective film-forming composition (IV-1) can be more uniformly mixed. is preferred.

Total content of all components other than solvent, non-energy ray-curable polymer (b), filler (d) and colorant (g) in protective film-forming composition (IV-1) The ratio of the total content of the energy ray-curable component (a0) and the photopolymerization initiator (c) to the (total mass) (that is, the non-energy ray-curable polymer (b) in the protective film-forming film, filling The ratio of the total content of the energy ray-curable component (a0) and the photopolymerization initiator (c) to the total content of all components that do not fall under either the material (d) or the colorant (g)) is It is preferably 85% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, even more preferably 95% by mass or more and 100% by mass or less, or may be 100% by mass. When the ratio of the total content is such a numerical value, in the protective film-forming composite sheet, the change over time of the adhesive strength between the protective film-forming film and the support sheet, and the adhesive strength between the protective film and the support sheet is more suppressed.

<<Method for Producing Composition for Forming Protective Film>>
A composition for forming a protective film such as the composition for forming a protective film (IV-1) is obtained by blending each component for constituting the composition.
There are no particular restrictions on the order of addition of each component when blending, and two or more components may be added at the same time.
When a solvent is used, the solvent may be mixed with any compounding component other than the solvent and used by diluting this compounding component in advance, or any compounding component other than the solvent may be diluted in advance. You may use by mixing a solvent with these compounding ingredients, without preserving.
The method of mixing each component at the time of blending is not particularly limited, and may be selected from known methods such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves. It can be selected as appropriate.
The temperature and time at which each component is added and mixed are not particularly limited as long as each compounded component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30°C.

<Method for Producing Protective Film-Forming Composite Sheet> The protective film-forming composite sheet can be produced by laminating the above-described layers so as to have corresponding positional relationships. The method for forming each layer is as described above.
For example, when a pressure-sensitive adhesive layer is laminated on a substrate when producing a support sheet, the above-described pressure-sensitive adhesive composition may be applied onto the substrate and dried as necessary.

On the other hand, for example, when a protective film-forming film is laminated on the adhesive layer already laminated on the substrate, the protective film-forming composition is applied onto the adhesive layer to form a protective film. It is possible to form the forming film directly. Layers other than the protective film-forming film can also be laminated on the pressure-sensitive adhesive layer in the same manner using the composition for forming this layer. Thus, when forming a continuous two-layer laminated structure using either composition, the composition is further applied on the layer formed from the composition to form a new layer. It is possible to form
However, of these two layers, the layer to be laminated later is formed in advance using the composition on another release film, and the side of the formed layer that is in contact with the release film is Preferably, the opposite exposed surface is laminated to the exposed surface of the remaining layer that has already been formed to form a continuous two-layer laminate structure. At this time, the composition is preferably applied to the release-treated surface of the release film. The release film may be removed as necessary after the laminated structure is formed.

For example, a composite sheet for forming a protective film in which a pressure-sensitive adhesive layer is laminated on a base material and a film for forming a protective film is laminated on the pressure-sensitive adhesive layer (the support sheet is a laminate of the base material and the pressure-sensitive adhesive layer). In the case of manufacturing a composite sheet for forming a protective film), the adhesive composition is applied on the substrate, and dried as necessary to laminate the adhesive layer on the substrate, and a separate A protective film-forming film is formed on the release film by applying a protective film-forming composition onto the release film and drying it as necessary. Then, the exposed surface of the film for forming a protective film is laminated to the exposed surface of the adhesive layer already laminated on the substrate, and the film for forming a protective film is laminated on the adhesive layer to form a protective film. A composite sheet for use is obtained.

In the case of laminating the adhesive layer on the substrate, as described above, instead of coating the adhesive composition on the substrate, the adhesive composition is coated on the release film. , By drying as necessary, an adhesive layer is formed on the release film, and the exposed surface of this layer is attached to one surface of the base material to attach the adhesive layer to the base material. May be laminated.
In either method, the peeling film may be removed at any timing after forming the intended laminated structure.

In this way, all layers other than the base material constituting the protective film-forming composite sheet can be formed in advance on a release film and laminated by a method of bonding them to the surface of the desired layer. A composite sheet for forming a protective film may be produced by appropriately selecting a layer that employs such a step as leverage.

The protective film-forming composite sheet is usually stored in a state in which a release film is attached to the surface of the outermost layer (for example, protective film-forming film) opposite to the support sheet. Therefore, on this release film (preferably its release-treated surface), a composition for forming a layer constituting the outermost layer, such as a composition for forming a protective film, is applied and dried as necessary. Then, a layer constituting the outermost layer is formed on the release film, and the remaining layers are laminated on the exposed surface of this layer opposite to the side in contact with the release film by any of the above methods. Alternatively, the composite sheet for forming a protective film can be obtained by leaving the laminated state without removing the release film.

<Method for Manufacturing Semiconductor Chip> The composite sheet for forming a protective film can be used for manufacturing a semiconductor chip.
At this time, the method for manufacturing a semiconductor chip includes, for example, a step of attaching the protective film forming film in the protective film forming composite sheet to a semiconductor wafer (hereinafter, sometimes abbreviated as "attaching step"). , a step of forming a protective film by irradiating the film for forming a protective film after being attached to the semiconductor wafer with an energy ray (hereinafter sometimes abbreviated as a “protective film forming step”); A step of dividing the wafer and cutting the protective film or the protective film forming film to obtain a plurality of semiconductor chips provided with the protective film after cutting or the protective film forming film after cutting (hereinafter referred to as "dividing A step of picking up the semiconductor chip provided with the protective film after cutting or the protective film forming film after cutting from the support sheet (hereinafter referred to as “pickup step”). may be abbreviated as) and a method including. In the manufacturing method, the protective film forming step, the dividing step and the picking up step are performed after the attaching step. The pick-up process is performed after the dividing process, but except for this point, the order of performing the protective film forming process, the dividing process, and the pick-up process can be arbitrarily set according to the purpose.
That is, as one aspect of the semiconductor chip manufacturing method, the protective film forming step, the dividing step, and the pick-up step may be performed in this order after the bonding step, or the dividing step, The pick-up step and the protective film forming step may be performed in this order, or the dividing step, the protective film forming step, and the pick-up step may be performed in this order after the attaching step.

The thickness of the semiconductor wafer to be used for the composite sheet for forming a protective film is not particularly limited. 400 μm is more preferred.

The above manufacturing method will be described below with reference to the drawings. FIG. 4 is a cross-sectional view for schematically explaining a method of manufacturing a semiconductor chip according to one embodiment of the present invention. Here, the manufacturing method in the case where the protective film-forming composite sheet is the one shown in FIG. 1 will be described as an example.
The production method of the present embodiment (in this specification, may be referred to as "production method (1)") is a step of attaching the protective film-forming film in the protective film-forming composite sheet to a semiconductor wafer. (Attaching step); A step of irradiating the film for forming a protective film after being attached to the semiconductor wafer with an energy beam to form a protective film (Protective film forming step); A step of cutting the protective film to obtain a plurality of semiconductor chips having the cut protective film (dividing step), and separating the semiconductor chips having the cut protective film from the support sheet and picking them up. and a step (pickup step).

In the attaching step of the manufacturing method (1), the protective film forming film 13 in the protective film forming composite sheet 1A is attached to the back surface 9b of the semiconductor wafer 9, as shown in FIG. 4(a).
The protective film-forming composite sheet 1A is used after removing the release film 15 .
In the attaching step, the protective film-forming film may be heated to be softened and attached to the semiconductor wafer 9 .
Here, in the semiconductor wafer 9, illustration of bumps and the like on the circuit surface is omitted.

After the attaching step of the manufacturing method (1), in the protective film forming step, the protective film forming film 13 attached to the semiconductor wafer 9 is irradiated with energy rays, and as shown in FIG. 4(b), A protective film 13' is formed. At this time, the protective film-forming film 13 is irradiated with the energy rays through the support sheet 10 .
Here, the protective film-forming composite sheet after the protective film-forming film 13 becomes the protective film 13' is denoted by reference numeral 1A'. This also applies to subsequent figures.

In the protective film forming step, the illuminance and the amount of light of the energy beam with which the protective film forming film 13 is irradiated are as described above.

In the protective film-forming composite sheet 1A, as described above, the energy ray-curable component (a0) stably stays in the protective film-forming film 13, and this component migrates to the adjacent support sheet 10. is suppressed. Therefore, changes in the composition of the protective film-forming film 13 are suppressed from immediately after the production of the protective film-forming composite sheet 1A to the start of the protective film-forming step. In the protective film forming step, the protective film forming film 13 is sufficiently cured to form a protective film 13' having a high degree of curing.

In the dividing step of the manufacturing method (1), the semiconductor wafer 9 is divided, the protective film 13' is cut, and as shown in FIG. to obtain a semiconductor chip 9'. At this time, the protective film 13' is cut (divided) along the periphery of the semiconductor chip 9'.

In the dividing step, the method for dividing the semiconductor wafer 9 and cutting the protective film 13' may be a known method.
As such a method, for example, a dicing blade is used to divide (cut) the semiconductor wafer 9 together with the protective film 13′; Then, the semiconductor wafer 9 having the modified layer formed thereon and the protective film 13' attached to the rear surface 9b is placed together with the protective film 13'. , a method of expanding in the surface direction of the protective film 13 ′, cutting the protective film 13 ′, and dividing the semiconductor wafer 9 at the portion of the modified layer.

In the pick-up step of the manufacturing method (1), as shown in FIG. 4D, the semiconductor chip 9' provided with the cut protective film 130' is separated from the support sheet 10 and picked up. Here, the pick-up direction is indicated by an arrow I, which also applies to subsequent figures. As the separating means 8 for separating the semiconductor chip 9' together with the protective film 130' from the supporting sheet 10, a vacuum collet or the like can be used.
As described above, the target semiconductor chip 9' is obtained as a semiconductor chip with a protective film.

In the protective film-forming composite sheet 1A used in the manufacturing method (1), as described above, the change over time in the adhesive force between the protective film-forming film 13 and the support sheet 10 is suppressed, and similarly, Change over time in the adhesive force between the protective film 13' (protective film 130' after cutting) and the support sheet 10 is suppressed. Therefore, in the manufacturing method (1), the reproducibility is improved when picking up the protective film-attached semiconductor chip (semiconductor chip 9′ having the protective film 130′ after cutting) from the support sheet 10 in the pick-up step. , the process stabilizes.

In the manufacturing method (1), the dividing step is performed after the protective film forming step. A forming step may also be performed (this embodiment may be referred to as “manufacturing method (2)”).
That is, the manufacturing method of the present embodiment (manufacturing method (2)) comprises a step of attaching a protective film forming film in the protective film forming composite sheet to a semiconductor wafer (attaching step), and dividing the semiconductor wafer. a step of cutting the protective film forming film to obtain a plurality of semiconductor chips having the protective film forming film after cutting (dividing step); A step of irradiating the film for forming a protective film (film for forming a protective film after cutting) to form a protective film (protective film forming step); and a step of picking up by separating from the substrate (hereinafter sometimes abbreviated as a “pickup step”).
FIG. 5 is a cross-sectional view for schematically explaining an embodiment of such a semiconductor chip manufacturing method.

The sticking step of manufacturing method (2) can be performed in the same manner as the sticking step of manufacturing method (1), as shown in FIG. 5(a) (as shown in FIG. 4(a)).

In the dividing step of the manufacturing method (2), the semiconductor wafer 9 is divided, the protective film forming film 13 is cut, and as shown in FIG. A plurality of semiconductor chips 9' are obtained. At this time, the protective film forming film 13 is cut (divided) along the periphery of the semiconductor chip 9'. Reference numeral 130 denotes the protective film forming film 13 after being cut.

In the protective film-forming composite sheet 1A used in the manufacturing method (2), as described above, the change over time in the adhesive force between the protective film-forming film 13 and the support sheet 10 is suppressed. Therefore, in the manufacturing method (2), in the dividing step, peeling of the semiconductor chip with the protective film forming film (semiconductor chip 9′ equipped with the protective film forming film 130 after cutting) from the support sheet 10 is suppressed. The reproducibility of the division is improved and the process is stabilized.

In the protective film forming step of the manufacturing method (2), the protective film forming film 130 is irradiated with energy rays through the support sheet 10 to protect the semiconductor chip 9' as shown in FIG. 5(c). A membrane 130' is formed.
The protective film forming step in the manufacturing method (2) can be performed by the same method as the protective film forming step in the manufacturing method (1) described above. In this step, the cut protective film forming film 130 is sufficiently cured to form a protective film 130' with a high degree of curing.
By performing this step, a semiconductor chip with a protective film in the same state as that shown in FIG.

In the pick-up step of the manufacturing method (2), as shown in FIG. 5(d), the semiconductor chip 9' provided with the cut protective film 130' is separated from the support sheet 10 and picked up.
The pick-up step in manufacturing method (2) can be performed in the same manner as the pick-up step in manufacturing method (1) described above (as shown in FIG. 4(d)). In this process, the reproducibility is improved when the protective film-attached semiconductor chip (semiconductor chip 9' having the protective film 130' after cutting) is picked up from the support sheet 10, and the process is stabilized.
As described above, the target semiconductor chip 9' is obtained as a semiconductor chip with a protective film.

In the manufacturing methods (1) and (2), the pick-up process is performed after the protective film forming process, but in the manufacturing method of the semiconductor chip according to the present embodiment, the pick-up process is performed without performing the protective film forming process, A protective film forming step may be performed after the pick-up step (this embodiment may be referred to as “manufacturing method (3)”).
That is, the manufacturing method of the present embodiment (manufacturing method (3)) comprises a step of attaching a protective film forming film in the protective film forming composite sheet to a semiconductor wafer (attaching step), and dividing the semiconductor wafer. a step of cutting the protective film forming film to obtain a plurality of semiconductor chips provided with the cut protective film forming film (dividing step); A step of picking up the semiconductor chips by separating them from the support sheet (pickup step), and irradiating the protective film forming film after being attached to the semiconductor wafer (the protective film forming film after cutting and picking up) with an energy ray. and a step of forming a protective film (protective film forming step).
FIG. 6 is a cross-sectional view for schematically explaining an embodiment of such a semiconductor chip manufacturing method.

As shown in FIGS. 6(a) to 6(b), the attaching step and the dividing step of the manufacturing method (3) are performed in the same manner as the attaching step and the dividing step of the manufacturing method (2) (FIG. 5 ( a) to FIG. 5(b)).

In the pick-up step of the manufacturing method (3), as shown in FIG. 6C, the semiconductor chip 9' provided with the cut protective film forming film 130 is separated from the support sheet 10 and picked up.
The pick-up step in manufacturing method (3) can be performed in the same manner as the pick-up step in manufacturing methods (1) and (2) described above (as shown in FIGS. 4(d) and 5(d)). . In this step, the reproducibility when picking up the semiconductor chip with the protective film forming film (the semiconductor chip 9 ′ having the protective film forming film 130 after cutting) from the support sheet 10 is improved, and the process is improved. stabilize.

In the protective film forming step of the manufacturing method (3), the protective film forming film 130 after being picked up is irradiated with an energy beam to form a protective film 130' on the semiconductor chip 9' as shown in FIG. 6(d). to form
The protective film forming step in the manufacturing method (3) is the same as the manufacturing methods (1) and (2) described above, except that it is not necessary to irradiate the protective film forming film 130 with the energy beam through the support sheet 10. ) can be carried out in the same manner as the protective film forming step in ). In this step, the cut protective film forming film 130 is sufficiently cured to form a protective film 130' with a high degree of curing.
As described above, the target semiconductor chip 9' is obtained as a semiconductor chip with a protective film.

In the manufacturing methods (1) to (3), as described above, the semiconductor wafer 9 is divided into semiconductor chips 9′ by forming a modified layer inside the semiconductor wafer 9 without using a dicing blade. is formed and the semiconductor wafer 9 is divided at the site of this modified layer. In this case, among the dividing steps, the step of forming the modified layer inside the semiconductor wafer 9 may be performed at any stage before the step of dividing the semiconductor wafer 9 at the portion of the modified layer. For example, it can be performed at any stage such as before the sticking process or between the sticking process and the protective film forming process.

So far, the method of manufacturing a semiconductor chip using the protective film-forming composite sheet 1A shown in FIG. 1 has been described, but the method of manufacturing a semiconductor chip of the present invention is not limited to this.
For example, the method for manufacturing a semiconductor chip of the present invention includes the protective film forming composite sheets 1B to 1C shown in FIGS. A semiconductor chip can be similarly manufactured by using a material other than the film-forming composite sheet 1A.
As described above, when the protective film-forming composite sheet of another embodiment is used, steps may be appropriately added, changed, deleted, etc. in the above-described manufacturing method based on the difference in the structure of these sheets. , to manufacture semiconductor chips.

◇Method for manufacturing a semiconductor device After obtaining a semiconductor chip with a protective film by the manufacturing method described above, the semiconductor chip is flip-chip connected to the circuit surface of a substrate by a known method, and then a semiconductor package is obtained. A target semiconductor device may be manufactured using the package (not shown).

In one aspect of the present invention, the protective film-forming composite sheet includes a support sheet and an energy ray-curable protective film-forming film provided on the support sheet,
The film for forming a protective film is
As the energy ray-curable component (a0), an acrylate compound having a (meth)acryloyl group, preferably ε-caprolactone-modified tris-(2-(meth)acryloxyethyl)isocyanurate (content: protective film-forming composition (preferably 5 to 15% by mass relative to the total mass of components other than the solvent of substance (IV-1));
As the non-energy ray-curable polymer (b), an acrylic polymer, preferably an acrylic polymer obtained by copolymerizing methyl acrylate and 2-hydroxyethyl acrylate (content: protective film-forming composition ( preferably 25 to 30% by mass relative to the total mass of components other than the solvent in IV-1);
The layer in contact with the protective film-forming film in the support sheet is
As the resin component (X), an acrylic polymer having at least a (meth)acrylic acid alkyl ester-derived structural unit, preferably a (meth)acrylic acid alkyl ester-derived structural unit and a functional group-containing monomer-derived structural unit. acrylic polymer, more preferably a copolymer of 2-ethylhexyl methacrylate and 2-hydroxyethyl acrylate (content: of the components constituting the layer in contact with the protective film-forming film in the support sheet relative to the total mass, preferably 100% by mass),
including.
Further, in the composite sheet for forming a protective film, the rate of change in adhesive force between the protective film and the support sheet is preferably 5% or more and 30% or less, more preferably 5% or more and 23% or less. may be 14 to 23%.

The present invention will be described in more detail below with reference to specific examples. However, the present invention is by no means limited to the examples shown below.

<Monomer>
Full names for abbreviated monomers are shown below.
MA: methyl acrylate HEA: 2-hydroxyethyl acrylate MMA: methyl methacrylate 2EHMA: 2-ethylhexyl methacrylate 2EHA: 2-ethylhexyl acrylate AAc: acrylic acid HEMA: 2-hydroxyethyl methacrylate Vac: vinyl acetate

<Raw materials for manufacturing protective film-forming composition>
Raw materials used for producing the composition for forming a protective film are shown below.
[Energy ray-curable component (a0)]
(a0)-1: ε-caprolactone-modified tris-(2-acryloxyethyl) isocyanurate ("A-9300-1CL" manufactured by Shin-Nakamura Chemical Co., Ltd., trifunctional UV-curable compound)
[Non-energy ray-curable polymer (b)]
(b)-1: Acrylic polymer (weight average molecular weight 300,000, glass transition temperature 6° C.) obtained by copolymerizing MA (85 parts by mass) and HEA (15 parts by mass).
[Photoinitiator (c)]
(c) -1: 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone (manufactured by BASF "Irgacure (registered trademark) 369")
[Filler (d)]
(d)-1: Silica filler (fused silica filler, average particle size 8 μm)
[Coupling agent]
(e) -1:3-methacryloxypropyltrimethoxysilane ("KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent)
[Colorant (g)]
(g)-1: 32 parts by mass of phthalocyanine blue pigment (Pigment Blue 15:3), 18 parts by mass of isoindolinone yellow pigment (Pigment Yellow 139), and 50 parts by mass of anthraquinone red pigment (Pigment Red 177) and pigmented so that the total amount of the above three dyes/the amount of styrene acrylic resin=1/3 (mass ratio).

[Example 1]
<Production of composite sheet for forming protective film>
(Production of protective film-forming composition (IV-1))
Energy ray-curable component (a0)-1, polymer (b)-1, photopolymerization initiator (c)-1, filler (d)-1, coupling agent (e)-1 and colorant (g )-1 is dissolved or dispersed in methyl ethyl ketone so that these contents (solid content, parts by mass) are the values shown in Table 1, and stirred at 23 ° C. to obtain a solid content concentration of 50% by mass. A protective film-forming composition (IV-1) was prepared.

(Production of adhesive composition (I-4))
Acrylic polymer (X)-1 (100 parts by mass, solid content), and an isocyanate cross-linking agent ("Coronate L" manufactured by Tosoh Corporation, tolylene diisocyanate trimer adduct of trimethylolpropane) (5 parts by mass, solid content) and further containing methyl ethyl ketone as a solvent, a non-energy ray-curable pressure-sensitive adhesive composition (I-4)-1 having a solid content concentration of 30% by mass was prepared. The acrylic polymer (X)-1 is a polymer having a weight average molecular weight of 600,000, which is obtained by copolymerizing 2EHMA (80 parts by mass) and HEA (20 parts by mass).

(Manufacturing of support sheet)
The pressure-sensitive adhesive composition (I-4 )-1 and dried by heating at 120° C. for 2 minutes to form a non-energy ray-curable pressure-sensitive adhesive layer with a thickness of 10 μm.
Next, a polypropylene film (thickness: 80 μm) as a base material is attached to the exposed surface of the pressure-sensitive adhesive layer, whereby the base material, the pressure-sensitive adhesive layer and the release film are laminated in this order in the thickness direction. A support sheet was obtained.

(Manufacture of Composite Sheet for Protective Film Formation)
The protective film obtained above is formed on the release-treated surface of the release film (second release film, "SP-PET382150" manufactured by Lintec Corporation, thickness 38 μm) in which one side of the polyethylene terephthalate film is release-treated by silicone treatment. A 25 μm-thick energy ray-curable protective film-forming film was produced by applying the composition (IV-1) for protective film formation and drying at 100° C. for 2 minutes.
Furthermore, the exposed surface of the obtained film for forming a protective film on the side not provided with the second release film is treated with a release film (first release film, “SP-PET381031” manufactured by Lintec Corporation, thickness 38 μm). By bonding the surfaces together, a laminated film was obtained in which one surface of the film for forming a protective film was provided with the first release film and the other surface was provided with the second release film.

Then, the release film was removed from the adhesive layer of the support sheet obtained above. Also, the first release film was removed from the laminated film obtained above. Then, by bonding the exposed surface of the adhesive layer produced by removing the release film and the exposed surface of the protective film forming film produced by removing the first release film, the base material and the adhesive A protective film-forming composite sheet having a structure shown in FIG. 2 was prepared by laminating an agent layer, a protective film-forming film, and a second release film in this order in the thickness direction.

<Evaluation of Composite Sheet for Protective Film Formation>
(Calculation of HSP of energy ray-curable component (a0), non-energy ray-curable polymer (b) and resin component (X), and preparation of Hansen melting spheres of non-energy ray-curable polymer (b))
Energy ray-curable component (a0)-1 and non-energy ray-curable polymer (b)-1, which are components of the protective film-forming film, and acrylic polymer (X), which is a component of the pressure-sensitive adhesive layer HSP was calculated for -1. More specifically, it is as follows.
Acetone, cyclohexanone, toluene, 2-propanol, propylene glycol, dimethylformamide, quinoline, benzyl alcohol, ethyl benzoate, hexane, tetrachloroethylene, diethylene glycol, acetonitrile, cyclo Hexanol, nitrobenzene, 1-butanol, ethanol, ethyl acetate, methyl ethyl ketone, tetraethyl orthosilicate and γ-butyrolactone were used.
These solvents are placed in a container one by one, the target component (15 mg) is added to these solvents (2 mL) whose temperature has been stabilized at a temperature of 23 ° C., and the container is fitted with a lid and sealed. did.
The contents are mixed by inverting the sealed container 50 times, then the container (in other words, the intermediate mixture) is left to stand for 4 hours, and then the contents are mixed by inverting the container 50 times in the same manner as above. The material (ie said intermediate mixture) was mixed and then the container (ie the final mixture obtained) was allowed to stand for 1 day. During this period, the mixing and standing operations were all performed under the temperature condition of 23°C.
Then, the presence or absence of dissolution of the component of interest in the final mixture was immediately confirmed visually. Then, if even a small amount of insoluble matter (undissolved matter) of the target component is found in the final mixture, the target component is judged to be "insoluble", and no insoluble matter of the target component is found in the final mixture. If not, the component of interest was determined to be "dissolved".

Then, using the analysis software "HSPiP (version 4.1)", for all solvents, input the HSP and the above determination result, calculate the HSP of the target component, and further, non-energy ray curable For the polymer (b)-1, a Hansen melting sphere was produced in the HSP space. Then, it was confirmed whether or not the HSP of the energy ray-curable component (a0)-1 was included in the Hansen melting sphere region of this non-energy ray-curable polymer (b)-1 in the HSP space. Table 1 shows the results. Table 1 also shows δ _P (δ _P1 ) of the acrylic polymer (X)-1.

(Calculation of rate of change in adhesive force between protective film and support sheet)
The protective film-forming composite sheet obtained above was cut into strips having a width of 25 mm for all layers.
Next, the second release film was removed from the protective film-forming film in the protective film-forming composite sheet after this cutting, and the exposed surface of the protective film-forming film thus produced was transferred to a 6-inch silicon wafer (thickness: 300 µm). ) on the #2000 polished surface. At this time, the protective film-forming film was heated to 70° C. and attached.

Then, using an ultraviolet irradiation device ("RAD2000m/8" manufactured by Lintec), the film for forming a protective film was applied to the film for forming a protective film through the base material and the pressure-sensitive adhesive layer under the conditions of an illuminance of 200 mW/cm ² and a light amount of 200 mJ/cm ² . By irradiating ultraviolet rays three times, the film for forming a protective film was cured to form a protective film, and the resulting film was used as a test piece.

One hour after the protective film-forming composite sheet was produced, the adhesive strength between the protective film and the support sheet (adhesive layer) before aging was measured for this test piece.
The pre-aging adhesive strength between the protective film and the support sheet (adhesive layer) was measured by the following method. That is, under conditions of 23 ° C., using a precision universal testing machine ("Autograph AG-IS" manufactured by Shimadzu Corporation), the support sheet is removed from the protective film attached to the silicon wafer, and the protective film and the support sheet ( In other words, so-called 180° peeling was performed by peeling off at a peeling speed of 300 mm/min so that the surfaces of the adhesive layer) that were in contact with each other formed an angle of 180°. Then, the peel force (N/25 mm) at this time was measured, and this measured value was defined as the pre-aging adhesive force between the protective film and the support sheet.

Furthermore, in the same manner as above, a separate test piece was prepared, and 48 hours after the protective film-forming composite sheet was prepared, the post-time adhesive strength between the protective film and the support sheet (adhesive layer) was measured as follows: It was measured by the same method as in the case of the adhesive strength before aging described above. The prepared test pieces were stored under conditions of 21 to 25° C. and relative humidity of 45 to 65% until the adhesive strength was measured after the lapse of time.

Next, the rate of change (%) in adhesive strength between the protective film and the support sheet (adhesive layer) was calculated according to the following formula. Table 1 shows the results.
[Adhesive strength change rate (%)] = {[adhesive strength before aging (N / 25 mm)] - [adhesive strength after aging (N / 25 mm)]} / [adhesive strength before aging (N / 25 mm)] × 100

<Production and Evaluation of Protective Film-Forming Composite Sheet>
[Example 2, Comparative Examples 1 and 2]
A composite sheet for forming a protective film was produced and evaluated in the same manner as in Example 1, except that the type of pressure-sensitive adhesive composition was changed as shown in Table 1. Table 1 shows the results.

In Table 1, "Adhesive composition (I-4)-2" refers to acrylic polymer (X)-2 (100 parts by mass, solid content), and an isocyanate cross-linking agent (manufactured by Tosoh Corporation " Coronate L", a tolylene diisocyanate trimer adduct of trimethylolpropane) (5 parts by mass, solid content), further containing methyl ethyl ketone as a solvent, non-energy ray-curable with a solid content concentration of 30 mass% is a pressure-sensitive adhesive composition. The acrylic polymer (X)-2 is a polymer having a weight average molecular weight of 600,000, which is obtained by copolymerizing 2EHMA (70 parts by mass) and HEA (30 parts by mass).
In addition, the "adhesive composition (I-4)-3" includes an acrylic polymer (X)-3 (100 parts by mass, solid content), and an isocyanate cross-linking agent (manufactured by Tosoh Corporation "Coronate L", Tolylene diisocyanate trimer adduct of trimethylolpropane) (5 parts by mass, solid content), further containing methyl ethyl ketone as a solvent, non-energy ray-curable pressure-sensitive adhesive composition having a solid content concentration of 30 mass% It is a thing. The acrylic polymer (X)-3 is a polymer having a weight average molecular weight of 600,000, which is obtained by copolymerizing 2EHA (40 parts by mass), Vac (40 parts by mass) and HEA (20 parts by mass).
Further, the "adhesive composition (I-4)-4" includes an acrylic polymer (X)-4 (100 parts by mass, solid content), and an isocyanate cross-linking agent ("Coronate L" manufactured by Tosoh Corporation, Tolylene diisocyanate trimer adduct of trimethylolpropane) (5 parts by mass, solid content), further containing methyl ethyl ketone as a solvent, non-energy ray-curable pressure-sensitive adhesive composition having a solid content concentration of 30 mass% It is a thing. The acrylic polymer (X)-4 is obtained by copolymerizing 2EHA (20 parts by mass), MMA (78 parts by mass), AAc (1 part by mass) and HEMA (1 part by mass), and has a weight average molecular weight of 600,000 polymer.

As is clear from the above results, in Examples 1 and 2, the polarity term δ _P (δ _P1 ) of the resin component (X) is 7.26 MPa ^1/2 or less (6.4 to 7.26 MPa ^1/2 ). Met. Also, the HSP of the energy ray-curable component (a0)-1 was contained in the Hansen melting sphere region of the non-energy ray-curable polymer (b)-1 in the HSP space. In addition, the rate of change in the adhesive force between the protective film and the support sheet (adhesive layer) was as low as 23% or less (14 to 23%), and the change in the adhesive force over time was suppressed.

On the other hand, in Comparative Examples 1 and 2, the polar term δ _P (δ _P1 ) of the resin component (X) is 7.9 MPa ^1/2 or more (7.9 to 9.8 MPa ^1/2 ), In these comparative examples, the rate of change in adhesive force between the protective film and the support sheet (adhesive layer) was as high as 34% or more (34 to 39%), and the change in adhesive force over time was not suppressed. .
Such results were obtained in Comparative Example 1, probably because the use of the acrylic polymer (X)-3 was inappropriate.
On the other hand, it is considered that the reason why such results were obtained in Comparative Example 2 was that the use of the acrylic polymer (X)-4 was inappropriate.

From the results of these examples and comparative examples, it was confirmed that the change over time in the adhesive strength between the protective film and the support sheet is affected by the polarity term δ _P of the resin component (X).

INDUSTRIAL APPLICABILITY The present invention is industrially very useful because it can be used for manufacturing semiconductor devices.

1A, 1A', 1B, 1C... protective film forming composite sheet, 10... support sheet, 10a... surface (first surface) of support sheet, 11... substrate, 11a... Surface of substrate (first surface) 12 Adhesive layer 12a Surface of adhesive layer (first surface) 13, 23 Protective film forming film 130 Cut Later protective film forming film, 13a, 23a... surface of protective film forming film (first surface), 13b... surface of protective film forming film (second surface), 13'... protection Film 130′ Protective film after cutting 15 Peeling film 16 Adhesive layer for jig 16a Surface of adhesive layer for jig 9 Semiconductor wafer , 9b... back surface of semiconductor wafer, 9'... semiconductor chip

Claims (3)

A protective film-forming composite sheet comprising a support sheet and an energy ray-curable protective film-forming film provided on the support sheet,
The protective film-forming film contains an energy ray-curable component (a0) and a non-energy ray-curable polymer (b),
The layer in the support sheet that is in contact with the protective film-forming film contains a resin component (X),
The HSP polarity term _δP of the resin component (X) is 7.5 MPa ^1/2 or less,
When an HSP space is defined and Hansen melting spheres of the non-energy ray-curable polymer (b) are produced in the HSP space, the HSP of the energy ray-curable component (a0) becomes the non-energy ray-curable A composite sheet for forming a protective film, which is contained in the Hansen melting sphere region of the polymer (b). The support sheet comprises a substrate and an adhesive layer provided on the substrate,
The composite sheet for forming a protective film according to claim 1, wherein the pressure-sensitive adhesive layer is a layer that contacts the film for forming a protective film. Affixing the film for forming a protective film in the composite sheet for forming a protective film according to claim 1 or 2 to a semiconductor wafer;
forming a protective film by irradiating the film for forming a protective film after being attached to the semiconductor wafer with an energy ray;
Dividing the semiconductor wafer and cutting the protective film or the protective film forming film to obtain a plurality of semiconductor chips provided with the cut protective film or the protective film forming film after cutting;
A method for manufacturing a semiconductor chip, comprising separating and picking up the semiconductor chip provided with the cut protective film or the cut protective film forming film from the support sheet.

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