TWI786209B - Composite sheet for forming protective film and method for manufacturing semiconductor chip - Google Patents

Abstract

A composite sheet for forming a protective film including a support sheet and an energy ray-curable protective film-forming film provided on the support sheet, wherein the protective film-forming film contains an energy ray-curable component (a0) and a non-energy ray-curable polymer (b), the layer in contact with the protective film-forming film of the support sheet contains the a resin component (X), the HSP distance R_23A between the energy ray-curable component (a0) and the non-energy ray-curable polymer (b) is 6.5 or less and the HSP distance R_13A between the energy ray-curable component (a0) and the resin component (X) is 2.2 or more.

Description

Composite sheet for forming protective film and method for manufacturing semiconductor wafer

This invention relates to the manufacturing method of the composite sheet for protective film formation, and a semiconductor wafer. This application is based on Japanese Patent Application No. 2017-208433 filed in Japan on October 27, 2017 as the basis for claiming priority, and the content thereof is incorporated herein.

In recent years, the manufacture of semiconductor devices to which a mounting method called a so-called face-down method has been developed has been developed. In the face-down method, a semiconductor wafer having electrodes such as bumps on a circuit surface is used, and the aforementioned electrodes are bonded to a substrate. Therefore, the back surface of the semiconductor wafer on the opposite side to the circuit surface is exposed.

A resin film containing an organic material is formed as a protective film on the exposed back surface of the semiconductor wafer to be assembled in a semiconductor device as a semiconductor wafer with a protective film. The protective film is used to prevent cracks from occurring in the semiconductor wafer after a dicing step or packaging.

In order to form such a protective film, for example, the composite sheet for protective film formation provided with the film for protective film formation for forming a protective film on a support sheet can be used. The film for protective film formation can form a protective film by hardening. In addition, when dividing the semiconductor wafer provided with the film for protective film formation or a protective film on the back surface into semiconductor wafers, a support sheet can be used for fixing a semiconductor wafer. In addition, the support sheet can also be used as a dicing sheet, and the composite sheet for protective film formation can also be used as a composite sheet which integrated the film for protective film formation and a dicing sheet.

The composite sheet for protective film formation is attached to the back surface of a semiconductor wafer through the film for protective film formation among them. Thereafter, the steps of forming a protective film by curing the film for forming a protective film, cutting the film for forming a protective film or the protective film, dividing the semiconductor wafer into semiconductor wafers, and dividing the semiconductor wafer into semiconductor wafers are appropriately performed at an appropriate time. Pick-up of a semiconductor wafer (semiconductor wafer with a film for forming a protective film or semiconductor wafer with a protective film) having a film for forming a protective film or a protective film after cutting on its surface from a support sheet (pick-up). Furthermore, in the case of picking up a semiconductor wafer with a film for forming a protective film, the semiconductor wafer with a protective film is formed by curing the film for forming a protective film, and finally a semiconductor device is manufactured using the semiconductor wafer with a protective film.

As such a composite sheet for forming a protective film, for example, a sheet provided with a film for forming a thermosetting protective film that is cured by heating to form a protective film is currently mainly used. However, heat curing of a film for forming a thermosetting protective film usually takes about several hours to as long as several hours, and therefore it is expected that the curing time can be shortened. On the other hand, it has been considered to use a film for protective film formation that is curable (energy ray curable) by irradiation of energy rays such as ultraviolet rays when forming a protective film (see Patent Document 1). [Prior art literature] [Patent Document]

[Patent Document 1] International Patent Publication No. 2016/068042

[Problems to be Solved by the Invention]

However, in the case of using a composite sheet for protective film formation using an energy ray curable protective film forming film, there is a possibility that the film for protective film formation or the adhesive force between the protective film and the support sheet may change significantly over time. question. Once the adhesive force changes as described above, even when the same composite sheet for forming a protective film is used, the semiconductor wafer with the film for forming a protective film or the semiconductor wafer with a protective film is removed from the support sheet. Reproducibility at pick-up also decreases, making the process unstable.

The object of the present invention is to provide a composite sheet for forming a protective film and a method for manufacturing a semiconductor wafer using the composite sheet for forming a protective film, wherein the composite sheet for forming a protective film is an energy ray curable film for forming a protective film A composite sheet for forming a protective film with a support sheet, and capable of suppressing changes in the adhesive force between the protective film and the support sheet over time of the film for forming a protective film or its cured product. [Means used to solve the problem]

In order to solve the above-mentioned problems, the present invention provides a composite sheet for forming a protective film, which is a composite sheet for forming a protective film that includes a support sheet and has an energy ray-curable film for forming a protective film on the support sheet, wherein the protective film The forming film contains an energy ray-curable component (a0) and a non-energy ray-curable polymer (b), the layer of the support sheet in contact with the protective film forming film contains a resin component (X), and the energy ray-curable The HSP distance R _23A between the active component (a0) and the non-energy ray-curable polymer (b) is 6.5 or less, and the HSP distance between the energy ray-curable component (a0) and the resin component (X) R _13A is 2.2 or more.

In the protective film-forming composite sheet of the present invention, it is preferable that the support sheet has a base material and an adhesive layer on the base material, and that the adhesive layer is a layer in contact with the protective film-forming film. Furthermore, the present invention provides a method of manufacturing a semiconductor wafer, which includes attaching the film for forming a protective film in the composite sheet for forming a protective film to a semiconductor wafer; The film forming film is irradiated with energy rays to form a protective film; the aforementioned semiconductor wafer is divided, and the aforementioned protective film or the aforementioned protective film forming film is cut to obtain the cut protective film or protective film forming film. a plurality of semiconductor wafers; and separating and picking up the semiconductor wafer having the protective film or the film for forming a protective film after cutting from the support sheet.

That is, the present invention includes the following aspects. [1] A composite sheet for forming a protective film, which is a composite sheet for forming a protective film comprising a support sheet and an energy ray-curable film for forming a protective film provided on the support sheet, wherein the film for forming a protective film contains The energy ray curable component (a0) and the non-energy ray curable polymer (b), the layer of the support sheet in contact with the protective film forming film contains a resin component (X), the energy ray curable component (a0 ) and the HSP distance R _23A between the non-energy ray-curable polymer (b) is 6.5 or less, and the HSP distance R _13A between the energy ray-curable component (a0) and the resin component (X) is 2.2 above. [2] The composite sheet for forming a protective film according to [1], wherein the support sheet includes a base material and an adhesive layer provided on the base material, and the adhesive layer is formed with the film for forming a protective film. contact layer. [3] A method of manufacturing a semiconductor wafer, comprising: attaching the film for forming a protective film in the composite sheet for forming a protective film described in [1] or [2] to a semiconductor wafer; The protective film forming film after the semiconductor wafer is irradiated with energy rays to form a protective film; the semiconductor wafer is divided, and the protective film or the protective film forming film is cut to obtain a protective film having a cut or a plurality of semiconductor wafers of the cut protective film-forming film; and separating and picking up the semiconductor wafer provided with the cut protective film or the cut protective film-forming film from the support sheet. [Effect of the present invention]

According to the present invention, there are provided a composite sheet for forming a protective film and a method for manufacturing a semiconductor wafer using the composite sheet for forming a protective film, wherein the composite sheet for forming a protective film is an energy ray curable film for forming a protective film A composite sheet for forming a protective film with a support sheet, and capable of suppressing changes in the adhesive force between the protective film and the support sheet over time of the film for forming a protective film or its cured product.

◇Composite sheet for forming a protective film The composite sheet for forming a protective film according to an embodiment of the present invention is a composite sheet for forming a protective film including a support sheet and an energy ray-curable film for forming a protective film provided on the support sheet , wherein the film for forming a protective film contains an energy ray curable component (a0) and a non-energy ray curable polymer (b), and the layer of the support sheet that is in contact with the film for forming a protective film contains a resin component (X) , the HSP distance R _23A (sometimes abbreviated as "R _23A " in this specification) between the aforementioned energy ray curable component (a0) and the aforementioned non-energy ray curable polymer (b) is 6.5 or less, and the aforementioned The HSP distance R _13A (which may be abbreviated as “R _13A ” in this specification) between the energy ray-curable component (a0) and the aforementioned resin component (X) is 2.2 or more.

In the composite sheet for forming a protective film, by setting R _23A and R _13A to values in the specific range as described above, changes in the adhesive force between the film for forming a protective film and the support sheet over time are suppressed, and similarly The adhesive force between the protective film and the support sheet of the cured product of the film for protective film formation changes with time.

The film for forming a protective film is cured by irradiation with energy rays to form a protective film. This protective film is used to protect the semiconductor wafer or the back surface (the surface opposite to the electrode formation surface) of the semiconductor wafer. The film for protective film formation is flexible and can be easily attached to an object to be attached.

In addition, in this specification, "the film for protective film formation" means the film before hardening, and "protective film" means the film obtained by hardening the film for protective film formation.

In the present invention, as long as it is a laminated structure that maintains the cured product of the support sheet and the protective film forming film (in other words, the support sheet and the protective film) even after the protective film forming film is cured, the laminated structure is called "" Composite sheet for protective film formation".

In this specification, "HSP" means Hansen solubility parameter (Hansen solubility parameter). HSP (sometimes represented by the symbol "δ") (MPa ^1/2 ) can be calculated by the following formula. δ=((δ _D ) ² + (δ _P ) ² + (δ _H ) ² ) ^1/2 (wherein, δ _D is the dispersion term, δ _P is the polar term, and δ _H is the hydrogen bond term)

In the composite sheet for protective film formation, 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 film for protective film formation. On the other hand, a resin component (X) is a component contained in the layer which contacts the film for protective film formation in a support sheet.

The HSPs of these target components can be obtained by known methods. Specifically, it is as follows. That is, first, various solvents for which HSPs are known are selected, and the solubility of the aforementioned target components in these solvents is confirmed.

The aforementioned solvent is not particularly limited as long as its HSP is known. Examples of the aforementioned solvent include chain or cyclic ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such as toluene; ethanol, 2-propanol, 1-butanol, and the like; Monohydric aliphatic alcohols such as alcohol and cyclohexanol; Polyhydric aliphatic alcohols such as propylene glycol; Monohydric or polyhydric aromatic alcohols such as benzyl alcohol; Amides such as dimethylformamide; Aromatic heterocycles such as quinoline Compounds (i.e., compounds having an aromatic heterocyclic group); chain aliphatic esters such as ethyl acetate (i.e., chain carboxylic acid esters); cyclic aliphatic esters such as γ-butyrolactone (i.e., i.e., lactones); aromatic esters such as ethyl benzoate (i.e., aromatic carboxylic acid esters); halogenated hydrocarbons such as tetrachloroethylene; dialkylene glycols such as diethylene glycol; Nitriles; nitro compounds such as nitrobenzene (compounds with a nitro group); orthosilicates such as tetraethyl orthosilicate, etc.

The solubility of a target component in a solvent can be confirmed, for example, by the following method. That is, in a container, 15 mg of the target component was added to 2 mL of a solvent whose temperature was stabilized at 23° C., and the container was capped and sealed. The contents were mixed by inverting the sealed container 50 times, then the container (in other words, the resulting intermediate mixture) was allowed to stand for 4 hours, and then the container was inverted 50 times in the same manner as above to mix the contents ( In other words, the intermediate mixture), the container (in other words, the resulting final mixture) was then allowed to stand for 1 day. During the above period, these steps of mixing and standing were carried out at a temperature of 23°C. Next, it is immediately confirmed whether the target components are dissolved in the final mixture. At this time, the method of confirming whether or not there is dissolution is not particularly limited as long as it can be confirmed accurately. For example, this can be confirmed by visual inspection of the final mixture, or the final mixture can be filtered and inspected for the presence of insoluble material. However, these are just one example. Furthermore, the usage amount of the target component and the solvent is not limited to the above usage amount, for example, as long as the usage ratio is the same as above (15 mg of the target component per 2 mL of solvent), the solvent and the target component can also be increased or decreased at the same time usage.

By the method described above, even when only a small amount of insoluble matter (undissolved residue) of the target component is observed in the aforementioned final mixture, the target component is still judged as "insoluble", while in the aforementioned final mixture When no insoluble matter of the target component is observed at all, the target component is judged as "dissolved". By the above method, the solubility of the target component in the solvent can be confirmed.

The solvent used to obtain the aforementioned 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 of only one.

The aforementioned solvents for confirming the solubility of the target component are preferably at least 20 types, and more preferably 21 to 30 types. When the kind of the said solvent is more than the said lower limit, the HSP of a target component can be obtained with higher precision. When the kind of the said solvent is below the said upper limit, the HSP of a target component can be calculated|required more efficiently.

After confirming the solubility of the target component in the solvent, use the analysis software "HSPiP" to obtain the target by inputting the HSP of the solvent and the judgment result of "insoluble" or "dissolution" of the target component when using this solvent. Component HSP.

When wanting to obtain the HSP of the target component, define the HSP space of the three-dimensional space composed of δ _D (dispersion item), δ _P (polarity item) and δ _H (hydrogen bond item). In this HSP space, draw (plot) The HSP of the solvent and the judgment result of the solubility of the target component. Afterwards, a sphere located in the HSP space is imagined such that the drawing of the solvent that has dissolved the target component exists on the surface and inside of the sphere, while the drawing of the solvent that does not dissolve the target component exists on the outside of the sphere to make a maximized sphere . On the surface of this sphere there must be a drawing of the solvent that has dissolved the target component. This sphere system is a Hansen Dissolving Sphere (also known as a Hansen 3D Sphere, a Hansen Interaction Sphere, etc.). Moreover, Hansen solubilized the HSP of the target component in the center of the spheres. Furthermore, the radius of the Hansen dissolved sphere is the interaction radius R ₀ , when R ₀ is large, it means that there are many kinds of solvents that can dissolve the target component; on the contrary, when R ₀ is small, it means that the target component can be dissolved There are few types of solvents in which ingredients are dissolved.

In the aforementioned composite sheet for forming a protective film, R _23A and R _13A is specified as a specific range of values. Specifically, it is as follows.

R _23A is the distance between the HSP of the energy ray-curable component (a0) and the HSP of the non-energy ray-curable polymer (b), that is, the distance between the HSPs of these components, which is a positive value (greater than zero value). In other words, R _23A is the distance between the center of the Hansen-dissolving sphere of the energy ray-curable component (a0) and the center of the Hansen-dissolve sphere of the non-energy ray-curable polymer (b).

R _23A is 6.5 or less, preferably 6.3 or less, more preferably 6.1 or less, and particularly preferably 5.9 or less. _{When R23A} is below the said upper limit, the mutual solubility of an energy ray curable component (a0) and a non-energy ray curable polymer (b) becomes high. Furthermore, in the composite sheet for protective film formation, the change with time of the adhesive force between the film for protective film formation and a support sheet, and the change with time of the adhesive force between a protective film and a support sheet are suppressed.

The lower limit of R _23A is not particularly limited as long as it is greater than 0. From the viewpoint of easier production of the protective film-forming composite sheet, R _23A is preferably 0.5 or more, and may be 1 or more, for example.

R _23A can be appropriately adjusted within a range set by arbitrarily combining the above-mentioned preferred lower limit and upper limit. For example, in one embodiment, R _23A is preferably 0.5-6.5, more preferably 0.5-6.3, more preferably 0.5-6.1, and particularly preferably 0.5-5.9. Furthermore, in one embodiment, R _23A is preferably 1-6.5, more preferably 1-6.3, more preferably 1-6.1, and particularly preferably 1-5.9. As still another state, it may also be 5.5~5.8. However, these are just one example.

R _13A is the distance between the HSP of the energy ray-curable component (a0) and the HSP of the resin component (X), that is, the distance between the HSPs of these components, and it is a positive value (a value greater than zero). In other words, R _13A is the distance between the center of the Hansen dissolution sphere of the energy ray-curable component (a0) and the center of the Hansen dissolution sphere of the resin component (X).

R _13A is 2.2 or more, preferably 2.3 or more, and more preferably 2.4 or more. When _R13A is more than the above-mentioned lower limit value, the miscibility between the energy ray curable component (a0) and the resin component (X) does not increase unnecessarily, and the adhesion between the film for protective film formation and the support sheet is suppressed The force changes over time, and the adhesion between the protective film and the support sheet changes over time.

The upper limit of R _13A is not particularly limited. R _13A is preferably 6 or less from the viewpoint of easier production of the protective film-forming composite sheet.

R _13A can be appropriately adjusted within the range set by arbitrarily combining the above-mentioned preferred lower limit and upper limit. For example, R _13A is preferably 2.2-6, more preferably 2.3-6, and particularly preferably 2.4-6. As yet another state, it may also be 2.5~4.0. However, these are just one example.

As described above, since R _23A is below a specific value, the energy ray-curable component (a0) present in the film for protective film formation and the non-energy ray-curable The polymers (b) have high mutual solubility and are easily retained in the film for protective film formation and in the protective film as they are. Furthermore, since _R13A is more than a specific value, the miscibility of the energy ray-curable component (a0) in the film for protective film formation and in the protective film with the resin component (X) in the adjacent support sheet is not unnecessarily high, Furthermore, it is the state which hardly moves to the adjacent support piece. As a result, in the composite sheet for protective film formation, the energy ray curable component (a0) remained stably in the film for protective film formation and in the protective film, and the movement to the adjacent support sheet was suppressed. Moreover, since the change in the composition of the film for forming a protective film, the protective film, and the support sheet is suppressed immediately after the composite sheet for forming a protective film is manufactured, changes in the characteristics of these layers over time are suppressed, and the film for forming a protective film is suppressed. The adhesive force between the protective film and the support sheet changes over time, and the adhesive force between the protective film and the support sheet changes over time. As an example, R _23A may be 5.5~5.8, and R _13A may also be 2.5~4.0.

Components that easily migrate from the film for protective film formation and the protective film to the support sheet are components that do not precipitate in these films for protective film formation and the protective film, components with relatively small molecular weight, and the like. In the energy ray-curable component (a0) whose R _23A and R _13A are not set within the above-mentioned range, when it corresponds to any of the above-mentioned components and moves to the support sheet, the film for protective film formation The adhesion between the film and the support sheet, and the adhesion between the protective film and the support sheet will have a large influence that cannot be ignored. On the other hand, components other than the energy ray-curable component (a0) hardly move from the film for forming a protective film and the protective film to the support sheet, or even if they have moved to the support sheet, they do not affect the above-mentioned Adhesion has an effect, or only negligible to a very small extent. In this embodiment, by using a component whose R _23A and R _13A are set within the above-mentioned range as the energy ray-curable component (a0), the composite sheet for forming a protective film can exhibit the excellent properties as described above. Effect.

For example, when the photopolymerization initiator (c) itself, which is an optional component described later, moves to the support sheet as described above, the adhesive force between the film for forming a protective film and the support sheet, and the protection Adhesion between the membrane and the support sheet can have significant effects that cannot be ignored. However, when using a photoinitiator (c), content of a photoinitiator (c) in the film for protective film formation and a protective film is very small normally. Therefore, even when the photopolymerization initiator (c) is used, since its content is extremely small, it usually does not affect the above-mentioned adhesive force, or only causes negligible and extremely small influence.

In order to suppress the change over time in the adhesive force between the film for protective film formation and the support sheet by using the photopolymerization initiator (c), similarly suppress the protective film and the support sheet which are cured products of the film for protective film formation The adhesive force between them changes with time, so the HSP distance R _23B between the photopolymerization initiator (c) and the non-energy ray-curable polymer (b) (sometimes referred to simply as "R _23B " in this specification ) can have the same setting as R _23A , and the HSP distance R _13B between the photopolymerization initiator (c) and the resin component (X) (sometimes referred to as "R _13B " in this specification) can be compared with R _13A has the same setting. That is, the composite sheet for forming a protective film according to one embodiment of the present invention is a composite sheet for forming a protective film which includes a support sheet and has an energy ray-curable film for forming a protective film on the support sheet. The film for forming a protective film may contain an energy ray-curable component (a0), a non-energy ray-curable polymer (b), and a photopolymerization initiator (c), and the film for forming a protective film may be combined with the film for forming a protective film on the support sheet. The contact layer contains a resin component (X), wherein R _23A and R _23B are 6.5 or less, and R _13A and R _13B are 2.2 or more. Composite sheet for forming a protective film.

R _23B is the distance between the HSP of the photopolymerization initiator (c) and the HSP of the non-energy ray curable polymer (b), that is, the distance between the HSPs of these components, which is a positive value (greater than zero value). In other words, R _23B is the distance between the center of the Hansen-dissolved sphere of the photopolymerization initiator (c) and the center of the Hansen-dissolved sphere of the non-energy ray-curable polymer (b).

R _23B is preferably not more than 6.5, more preferably not more than 6.3, more preferably not more than 6.1, and most preferably not more than 5.9. _{When R23B} is below the said upper limit, the mutual solubility of a photoinitiator (c) and a non-energy-ray curable polymer (b) becomes high. And, in the composite sheet for protective film formation, by using the photopolymerization initiator (c), the adhesive force between the film for protective film formation and the support sheet is suppressed from changing over time, and the adhesion between the protective film and the support sheet is suppressed. Adhesion changes over time.

The lower limit of R _23B is not particularly limited as long as it is greater than 0. From the viewpoint of easier production of the protective film-forming composite sheet, R _23B is preferably 0.5 or more, and may be 1 or more, for example.

R _23B can be appropriately adjusted within the range set by arbitrarily combining the above-mentioned preferred lower limit and upper limit. For example, in one embodiment, R _23B is preferably 0.5-6.5, more preferably 0.5-6.3, more preferably 0.5-6.1, and particularly preferably 0.5-5.9. Furthermore, in one embodiment, R _23B is preferably 1-6.5, more preferably 1-6.3, more preferably 1-6.1, and particularly preferably 1-5.9.

R _13B is the distance between the HSP of the photopolymerization initiator (c) and the HSP of the resin component (X), that is, the distance between the HSPs of these components, which is a positive value (a value greater than zero). In other words, R _13B is the distance between the center of the Hansen dissolved sphere of the photopolymerization initiator (c) and the center of the Hansen dissolved sphere of the resin component (X).

R _13B is preferably at least 2.2, more preferably at least 2.3, and more preferably at least 2.4. When _R13B is more than the said lower limit, the mutual solubility of a photoinitiator (c) and a resin component (X) will not become unnecessarily high. And, in the composite sheet for protective film formation, by using the photopolymerization initiator (c), the adhesive force between the film for protective film formation and the support sheet is suppressed from changing over time, and the adhesion between the protective film and the support sheet is suppressed. Adhesion changes over time.

The upper limit of R _13B is not particularly limited. From the viewpoint of easier production of the protective film-forming composite sheet, R _13B is preferably 6 or less.

R _13B can be appropriately adjusted within the range set by arbitrarily combining the above-mentioned preferred lower limit and upper limit. For example, R _13B is preferably 2.2-6, more preferably 2.3-6, and particularly preferably 2.4-6. However, these are just one example.

In the case of using the photopolymerization initiator (c), as described above, since R _23B is not more than a specific value, immediately after the composite sheet for forming a protective film is manufactured, the The photopolymerization initiator (c) has high compatibility with the non-energy ray curable polymer (b), and is in a state of being easily retained in the film for protective film formation and in the protective film as it is. Furthermore, since _R13B is more than a specific value, the compatibility between the photopolymerization initiator (c) in the protective film forming film and the protective film and the resin component (X) in the adjacent support sheet is not unnecessarily high. , and is in a state that hardly moves to the adjacent supporting piece. As a result, similar to the case of the energy ray-curable component (a0), in the composite sheet for forming a protective film, the photopolymerization initiator (c) remained stably in the film for forming a protective film and in the protective film, suppressing Movement of adjacent support sheets.

However, as described above, even when the photopolymerization initiator (c) is used, generally, as long as R _23A and R _13A satisfy the above-mentioned conditions, even if R _23B and R _13B do not satisfy the above-mentioned conditions, The said composite sheet for protective film formation can fully exhibit the effect of this invention.

By adjusting the type of energy ray curable component (a0) (for example, the structure of the main skeleton, the presence or absence of functional groups or their type, molecular weight, etc.), R _23A and R23A related to the energy ray curable component (a0) can be adjusted Any of _13A . Furthermore, R _23A can also be adjusted by adjusting the type of the non-energy ray curable polymer (b) (for example, the structure of the structural unit, the presence or absence of a functional group or its type, molecular weight, etc.). Furthermore, R _13A can also be adjusted by adjusting the type of the resin component (X) (for example, the structure of the structural unit, the presence or absence of a functional group or its type, molecular weight, etc.).

By adjusting the type of photopolymerization initiator (c) (for example, the structure of the main skeleton, whether there is a functional group or its type, molecular weight, etc.), it is possible to adjust R _23B and R related to the photopolymerization initiator (c). Either of _13B . Furthermore, R _23B can also be adjusted by adjusting the type of the non-energy ray curable polymer (b) (for example, the structure of the structural unit, the presence or absence of a functional group or its type, molecular weight, etc.). Furthermore, R _13B can also be adjusted by adjusting the type of the resin component (X) (for example, the structure of the structural unit, the presence or absence of a functional group or its type, molecular weight, etc.).

In the aforementioned composite sheet for forming a protective film, the rate of change in the adhesive force between the protective film and the support sheet before and after the lapse of time obtained by the following method is preferably 30% or less, more preferably 27.5% or less , and more preferably 25% or less, for example, either 22.5% or less and 20% or less. In addition, the change rate of the adhesive force between a protective film and a support sheet may be 23% or less, or may be 14% or less. The lower limit of the rate of change of the aforementioned adhesive force is not particularly limited. For example, a composite sheet for forming a protective film having a change rate of the above-mentioned adhesive force of 5% or more can be more easily produced. As one of them, the change rate of the adhesive force between the protective film and the support sheet may be 5% to 30%, may be 5% to 27.5%, may be 5% to 25%, or may be It may be not less than 5% and not more than 23%, may be not less than 5% and not more than 22.5%, or may be not less than 5% and not more than 20%, or may be not less than 5% and not more than 14%. One aspect of the protective film-forming composite sheet of the present invention contains the protective film-forming film and the chemical components contained in the support sheet, respectively, which are the same as the adhesion between the protective film and the support sheet when evaluated by the following method The chemical composition of the protective film forming film and the support sheet in the protective film forming composite sheet in which the rate of change in force is 5% to 30% and preferably 5% to 20%. That is, as long as it is a composite sheet for protective film formation containing a film for protective film formation and a support sheet having the same chemical composition as described above, it may have the same width and thickness as the composite sheet for protective film formation in the following method. Film thickness varies in width and thickness.

<How to obtain the change rate of the adhesive force between the protective film and the support sheet>

The width of all layers in the composite sheet for protective film formation is 25mm, and the composite sheet for protective film formation with a film thickness of 25 μm is attached to a silicon wafer through the film for protective film formation. . Next, under the conditions of illuminance of 200mW/cm ² and light intensity of 200mJ/cm ² , by irradiating ultraviolet rays to the attached protective film-forming film, the protective film-forming film was cured into a protective film and used as a test piece. , and further, test pieces before time elapsed (before time elapsed) and after time elapsed were produced. Next, for the test piece before and after time, under the condition of 23°C, at a peeling speed of 300mm/min, the support sheet was peeled off from the protective film attached to the aforementioned silicon wafer so that the surface where the protective film and the support sheet contact each other The peeling is pulled apart by forming an angle of 180°, that is, the so-called 180° peeling is performed. Then, using the peeling force (N/25mm) at this time as the adhesive force, the adhesive force before the passage of time to the test piece before the passage of time and the adhesion after the passage of time to the test piece after the passage of time were obtained, and based on From these adhesive forces, the change rate of the adhesive force between the protective film and the support sheet was calculated by the following formula.

[Change rate of adhesion (%)]={[adhesion before time (N/25mm)]-[adhesion after time (N/25mm)]}/[adhesion before time (N/25mm) ]x100(%)

The composite sheet for protective film formation 1 hour after preparation of the composite sheet for protective film formation was used as the test piece before time elapsed. Use the composite sheet for protective film formation after 48 hours after making the composite sheet for protective film formation, as the test piece after the passage of time, and until the adhesive force after the passage of time is measured as the test piece, at 21 Store statically at ~25°C, relative humidity 45~65%.

In addition, in this specification, "thickness" is the value which measured the thickness at arbitrary 5 places with the contact type thickness meter, and expressed it as an average.

Hereinafter, the structure of the composite sheet for protective film formation will be explained in detail.

◎Support sheet In a support sheet composed of two or more layers, these layers may be the same or different from each other, and the combination of these layers is not particularly limited as long as it does not impair the effect of the present invention.

In addition, in this specification, not limited to the case of a support sheet, "a plurality of layers may be the same or different from each other" means "all layers may be the same, or all layers may be different." , or only a part of the layers may be the same", and "a plurality of layers are different from each other" means "at least one of the constituent materials and thickness of each layer is different from each other".

As a preferable support sheet, for example, a support sheet provided with a base material and an adhesive layer directly contacted with the aforementioned base material and laminated thereon (the base material and the adhesive agent are laminated in direct contact in this order) support sheet); the base material, the intermediate layer and the adhesive are in direct contact with the thickness direction of these film layers in this order, and the support sheet obtained by lamination, etc.

FIG. 1 is a schematic cross-sectional view of a composite sheet for forming a protective film according to an embodiment of the present invention. In addition, in the following drawings used in conjunction with the description, for the sake of easy understanding of the characteristics of the present invention and for convenience, the main parts may be enlarged and shown, and the size ratio of each component may not be the same as the actual one.

The composite sheet 1A for protective film formation shown here is provided with the base material 11, the adhesive agent layer 12 is provided on the base material 11, and the film 13 for protective film formation is provided on the adhesive agent layer 12. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12. In other words, the composite sheet 1A for forming a protective film has a surface (referred to as "the first surface" in this specification) 10a on one side of the support sheet 10. The film 13 for protective film formation is laminated|stacked. In addition, 1 A of composite sheets for protective film formation are equipped with the peeling film 15 further on the film 13 for protective film formation.

In the protective film forming composite sheet 1A, the adhesive layer 12 is laminated on one surface (in this specification, sometimes referred to as "the first surface") 11a of the substrate 11, and the protective film forming film 13 is laminated. The adhesive layer 16 for jigs is laminated on one side of the protective film forming film 13 on the entire surface (in this specification, sometimes referred to as "the first surface") 12a of one side of the adhesive layer 12 (in this specification, sometimes referred to as "the first surface") 13a (that is, the region near the edge), and the release film 15 is laminated on the first surface 13a of the protective film forming film 13 On the part where the adhesive agent layer 16 for jigs is not laminated|stacked and the surface 16a (upper surface and side surface) of the adhesive agent layer 16 for jigs.

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

The jig adhesive layer 16 may have, for example, a single-layer structure containing an adhesive component, or may have a multi-layer structure in which film layers containing an adhesive component are laminated on both surfaces of a core sheet. .

In the composite sheet 1A for forming a protective film shown in FIG. 1 , the back surface of a semiconductor wafer (not shown) is attached to the first surface 13a of the film 13 for forming a protective film with the release film 15 removed, and The upper side of the surface 16 a of the jig adhesive layer 16 is attached to a jig such as a ring-frame for use.

Fig. 2 is a schematic cross-sectional view of a composite sheet for forming a protective film according to another embodiment of the present invention. In addition, in the drawings after FIG. 2 , the same constituent elements as those shown in the already described drawings are assigned the same reference numerals as those shown in the already described drawings, and detailed description thereof will be omitted.

The composite sheet 1B for protective film formation shown here is the same as the composite sheet 1A for protective film formation shown in FIG. 1 except not having the adhesive agent layer 16 for jigs. That is, in the protective film forming composite sheet 1B, the adhesive layer 12 is laminated on the first surface 11a of the substrate 11, and the protective film forming film 13 is laminated on the entire first surface 12a of the adhesive layer 12. , and the release film 15 is laminated on the entire surface of the first surface 13a of the film 13 for protective film formation.

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

In the protective film forming composite sheet 1B shown in FIG. 2 , the back surface of a semiconductor wafer (not shown) is attached to the center of the first surface 13a of the protective film forming film 13 with the release film 15 removed. Part of the side area, and the area near the edge portion is attached to a jig such as a ring frame for use.

3 is a schematic cross-sectional view of a composite sheet for forming a protective film according to another embodiment of the present invention. The composite sheet 1C for protective film formation shown here is the same as the composite sheet 1B for protective film formation shown in FIG. 2 except the shape of the film for protective film formation being different. That is, 1 C of composite sheets for protective film formation are equipped with the base material 11, are equipped with the adhesive agent layer 12 on the base material 11, and are equipped with the film 23 for protective film formation on the adhesive agent layer 12. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12 , in other words, the protective film forming composite sheet 1C has a structure in which the protective film forming film 23 is laminated on the first surface 10 a of the support sheet 10 . In addition, 1 C of composite sheets for protective film formation are equipped with the peeling film 15 on the film 23 for protective film formation further.

In the protective film forming composite sheet 1C, the adhesive layer 12 is laminated on the first surface 11a of the substrate 11, and the protective film forming film 23 is laminated on a part of the first surface 12a of the adhesive layer 12 (that is, area on the central side). And the peeling film 15 is laminated|stacked on the area|region which does not have the film 23 for laminated|stacked protective film formations among the 1st surface 12a of the adhesive layer 12, and the surface 23a (upper surface and side surface) of the film 23 for protective film formations.

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

In 1 C of composite sheets for protective film formation, the film 23 for protective film formation has energy ray curability, and contains an energy ray curable component (a0) and a non-energy ray curable polymer (b). In addition, the layer which contacts the film 23 for protective film formation in the support sheet 10, that is, the adhesive layer 12 contains a resin component (X).

In the composite sheet 1C for forming a protective film shown in FIG. 3 , the back surface of a semiconductor wafer (not shown) is attached to the surface 23a of the film 23 for forming a protective film with the peeling film 15 removed, and the adhesive In the first surface 12a of the layer 12, the area where the film 23 for forming a laminated protective film is not present is attached to a jig such as a ring frame for use.

In addition, in the composite sheet 1C for forming a protective film shown in FIG. 3 , in the first surface 12 a of the adhesive layer 12 where the film 23 for forming a protective film is not laminated, the same structure as that shown in FIG. 1 may be laminated. There is an adhesive layer (not shown). The composite sheet 1C for forming a protective film having the adhesive layer for a jig as described above is the same as the composite sheet for forming a protective film shown in FIG. Fixtures for use.

As mentioned above, in the composite sheet for protective film formation, even if a support sheet and the film for protective film formation are any form, you may be provided with the adhesive agent layer for jigs. However, as shown in FIG. 1, as a composite sheet for protective film formation provided with the adhesive agent layer for jigs, it is usually preferable to provide the adhesive agent layer for jigs on the film for protective film formation.

The composite sheet for forming a protective film according to an embodiment of the present invention is not limited to the composite sheet for forming a protective film shown in FIGS. Part of the structure of the protective film-forming composite sheet shown in FIGS. 1 to 3 may be changed or deleted, or other structures may be added to the structures described so far.

For example, an intermediate layer may be provided between the base material 11 and the adhesive layer 12 in the composite sheet for protective film formation shown in FIGS. 1 to 3 . That is, in the composite sheet for forming a protective film of the present invention, the support sheet may be a support sheet in which a substrate, an intermediate layer, and an adhesive layer are laminated in this order in the thickness direction of these film layers. Here, any film layer can be selected as the intermediate layer according to the purpose. In addition, in the composite sheet for protective film formation shown in FIGS. 1-3, the film layer other than the said intermediate|middle layer may be provided in arbitrary positions. In addition, in the composite sheet for protective film formation, some gaps may be formed between the peeling film and the film layer directly contacting this peeling film. In addition, in the composite sheet for protective film formation, the size and shape of each layer can be adjusted arbitrarily according to the purpose.

In addition, in the composite sheet for protective film formation shown in FIGS. When the layer is other than the adhesive layer, the other layer contains the resin component (X).

In the composite sheet for forming a protective film of the present invention, as described later, the layers such as the adhesive layer that are in direct contact with the film for forming a protective film in the support sheet are preferably non-energy ray curable. Such a composite sheet for forming a protective film can make it easier to pick up a semiconductor wafer (semiconductor wafer with a protective film) having a cut protective film on the back surface from the support sheet.

The support sheet may be transparent or opaque, or may be colored according to the purpose. Among them, in the present invention in which the film for protective film formation has energy ray curability, it is preferable that the support sheet allows energy ray transmission.

For example, in the support sheet, the light transmittance to light having a wavelength of 375 nm is preferably at least 30%, preferably at least 50%, and particularly preferably at least 70%. When the light transmittance is in such a range, when the film for protective film formation is irradiated with energy rays (ultraviolet rays) via the support sheet, the degree of curing of the film for protective film formation can be further increased. On the other hand, in the support sheet, the upper limit value of the light transmittance of light having a wavelength of 375 nm is not particularly limited. For example, the aforementioned light transmittance may be 95% or less. As one of the aspects, in the support sheet, the light transmittance for light having a wavelength of 375 nm is preferably not less than 30% and not more than 95%, preferably not less than 50% and not more than 95%, and is preferably not less than 70% and not more than 95%. Below % is especially good.

Furthermore, in the support sheet, the light transmittance of light having a wavelength of 532 nm is preferably at least 30%, more preferably at least 50%, and particularly preferably at least 70%. When the said light transmittance exists in such a range, when irradiating laser light to the film for protective film formation or a protective film via a support sheet, and marking on these films, marking can be made more clearly. On the other hand, in the support sheet, the upper limit value of the light transmittance of light having a wavelength of 532 nm is not particularly limited. For example, the aforementioned light transmittance may be 95% or less. As one of the aspects, in the support sheet, the light transmittance for light having a wavelength of 532 nm is preferably not less than 30% and not more than 95%, preferably not less than 50% and not more than 95%, and is preferably not less than 70% and not more than 95%. Below % is especially good.

Furthermore, in the support sheet, the light transmittance of light having a wavelength of 1064 nm is preferably at least 30%, more preferably at least 50%, and particularly preferably at least 70%. When the said light transmittance exists in such a range, when irradiating laser light to the film for protective film formation or a protective film via a support sheet, and engraves on these films, engraving can be made clearer. On the other hand, in the support sheet, the upper limit value of the light transmittance of light having a wavelength of 1064 nm is not particularly limited. For example, the aforementioned light transmittance may be 95% or less. As one of the aspects, in the support sheet, the light transmittance for light having a wavelength of 1064 nm is preferably not less than 30% and not more than 95%, preferably not less than 50% and not more than 95%, and is preferably not less than 70% and not more than 95%. Below % is especially good.

As one of the methods of dividing a semiconductor wafer to obtain semiconductor wafers, for example, the following method is known: irradiating laser light in a manner focused on a focal point set inside the semiconductor wafer to form a modified layer inside the semiconductor wafer, Next, the semiconductor wafer on which the modified layer is formed and the film for forming a protective film or the protective film is attached on the back surface is expanded in the surface direction of the film layers together with these film layers, and these A method of cutting the film layer and at the same time dividing and singulating the semiconductor wafer at the position of the modified layer, and then obtaining the semiconductor wafer. When the above-mentioned composite sheet for forming a protective film is suitable for this method, in the support sheet, the light transmittance for light having a wavelength of 1342 nm is preferably 30% or more, preferably 50% or more, and More than 70% is especially good. When the light transmittance is in such a range, when the semiconductor wafer is irradiated with laser light through the support sheet and the film for forming a protective film or the protective film, the modified layer can be formed on the semiconductor wafer more easily. On the other hand, in the support sheet, the upper limit value of the light transmittance of light having a wavelength of 1342 nm is not particularly limited. For example, the aforementioned light transmittance may be 95% or less. As one of the aspects, in the supporting sheet, the light transmittance for light having a wavelength of 1342 nm is preferably not less than 30% and not more than 95%, preferably not less than 50% and not more than 95%, and is preferably not less than 70% and not more than 95%. Below % is especially good.

It is preferable that the said support sheet has a base material and an adhesive layer is provided on the said base material. In addition, in the composite sheet for forming a protective film, the support sheet includes a base material and an adhesive layer is provided on the base material, and the adhesive layer is a layer in contact with the film for forming a protective film (the protective film It is preferable that the film for formation is in direct contact with the above-mentioned pressure-sensitive adhesive layer and laminated thereon).

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

○Substrate The aforementioned base material is in the form of a sheet or a film, and various resins are exemplified as its constituent material. Examples of the aforementioned resins include polyethylenes 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); Polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene - Ethylene-based copolymers (copolymers obtained by using ethylene as a monomer) such as (meth)acrylate copolymers and ethylene-norbornene copolymers; vinyl chloride-based resins such as polyvinyl chloride and vinyl chloride copolymers (resins obtained using vinyl chloride as a monomer); polystyrene; polycycloolefins; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly Polyethylene isophthalate, polyethylene 2,6-naphthalate, polyesters whose structural units are wholly aromatic polyesters having aromatic cyclic groups, etc.; two or more of the aforementioned polyethers Copolymer of ester; poly(meth)acrylate; polyurethane; polyurethane acrylate; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; Polyester; Polyetherketone, etc. In addition, as said resin, the polymer alloy (polymer alloy), such as the mixture of the said polyester and another resin, is also mentioned, for example. In the aforementioned polymer blend such as a mixture of polyester and other resins, it is preferable that the amount of resin other than polyester is relatively small. Furthermore, as the above-mentioned resin, for example, a cross-linked resin obtained by cross-linking one or two or more of the aforementioned resins listed above; using one or more of the aforementioned resins listed above Modified resins such as two or more ionomers.

In addition, in this specification, "(meth)acryl" means the concept including both "acryl" and "methacryl". The same applies to other terms similar to (meth)acrylic acid.

The resin constituting the base material may be used only by one type, or two or more types may be used, and when two or more types are used, the combination and ratio thereof may be selected arbitrarily.

The substrate may be composed of one layer (single layer), or may be composed of multiple layers of two or more layers, and in the case of multiple layers, these multiple layers may be the same or different from each other, and these multiple layers The combination of 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 composite sheet for forming a protective film and the adhesion to a semiconductor wafer or a semiconductor wafer can be further improved. Here, the "thickness of the substrate" refers to the thickness of the entire substrate, for example, the thickness of a substrate composed of a plurality of layers refers to the total thickness of all the layers constituting the substrate.

It is preferable that the thickness of the base material has high accuracy, that is, it is preferable that the thickness variation in any part can be suppressed. Among the above-mentioned constituent materials, examples of materials that can be used to form such a base material having a high-precision thickness include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, Ethylene-vinyl acetate copolymer, etc.

In addition to the above-mentioned main constituent materials such as resins, the substrate may contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers).

It is preferable that the optical properties of the substrate satisfy the optical properties of the support sheet described above. For example, the substrate can be transparent or opaque, or it can also be colored according to the purpose, or other layers can also be deposited. Furthermore, in the present invention in which the film for forming a protective film has energy ray curability, it is preferable that the substrate allows energy ray transmission.

In order to improve the adhesion between the substrate and other layers such as an adhesive layer provided on the substrate, roughening treatment by sand blasting, solvent treatment, etc. may be applied to the surface of the substrate. , Corona (corona) discharge treatment, electron beam irradiation treatment, plasma treatment, ozone and ultraviolet irradiation treatment, flame treatment, chromic acid treatment, oxidation treatment such as hot air treatment, etc. In addition, the base material may be a base material treated with a primer (primer) on the surface. Furthermore, the substrate may also have an antistatic coating; it is used to prevent the substrate from sticking to other sheets or the film layer of the adsorption table when the protective film forming composite sheets are stacked for storage.

The substrate can be produced by a known method. For example, the resin-containing substrate can be produced by molding a resin composition containing the aforementioned resin.

○Adhesive layer The aforementioned adhesive layer is in the form of a sheet or film and contains an adhesive. Examples of the aforementioned adhesive include adhesives such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins. resin, preferably acrylic resin. When the adhesive layer contains the resin component (X), it is preferable to contain the resin component (X) as the aforementioned adhesive. That is, as one of them, the resin component (X) is selected from acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates and esters at least one of the group consisting of resinoids. Furthermore, as another aspect, the resin component (X) is selected from the group consisting of an adhesive resin (I-1a), an energy ray curable compound, and an adhesive resin (I-2a) described later. Preferably at least 1 ingredient.

In addition, in the present invention, the term "adhesive resin" is a concept that includes both adhesive resins and adhesive resins. A resin that exhibits adhesiveness due to other ingredients, a resin that exhibits adhesiveness due to the presence of a trigger such as heat or water, etc.

The adhesive layer may consist of one layer (single layer), or may consist of plural layers of two or more layers, and in the case of plural layers, these plural layers may be the same as or different from each other. The combination of layers is not particularly limited. When the adhesive layer is composed of multiple layers and the adhesive layer contains the resin component (X), it is preferable that at least the layer in direct contact with the film for forming a protective film among these multiple layers contains the resin component (X). All the 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 adhesive layer" refers to the thickness of the entire adhesive layer, for example, the thickness of the adhesive layer composed of a plurality of layers refers to the total thickness of all the layers constituting the adhesive layer.

It is preferable that the optical properties of the adhesive layer satisfy the optical properties of the support sheet described above. The adhesive layer may be transparent or opaque, or may be colored according to the purpose. Furthermore, in the present invention in which the film for protective film formation has energy ray curability, it is preferable that the pressure-sensitive adhesive layer is permeable to energy ray.

The adhesive layer may be formed using an energy ray-curable adhesive, or may be formed using a non-energy ray-curable adhesive. An adhesive layer formed using an energy ray-curable 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 adhesive layer is formed on the target position by applying the adhesive composition on the surface where the adhesive layer is to be formed, and drying it as necessary. The more specific method for forming the adhesive layer will be described in detail later together with the methods for forming other layers. In the adhesive composition, the content ratio of the components that do not evaporate at normal temperature is usually the same as the content ratio of the aforementioned components in the adhesive layer. In addition, in this specification, "normal temperature" means the temperature which is not particularly cold or hot, that is, the normal temperature, For example, the temperature of 15-25 degreeC etc. are mentioned.

The coating of the adhesive composition can be performed by a known method, for example, the use of an air knife coater (Air-knife-coater), a blade coater (Blade-coater), a rod coater ( Bar-coater), Gravure-coater, Roll-coater, Roll-knife-coater, Curtain-coater , Die-Coater, Knife-coater, Screen-coater, Mayer bar coater, Kiss-coater ) and other methods of coating machines.

The drying conditions of the adhesive composition are not particularly limited, but when the adhesive composition contains a solvent described later, it is preferable to heat and dry it. It is preferable to dry the solvent-containing adhesive composition at 70-130° C. for 10 seconds to 5 minutes.

In the case where the adhesive layer has energy ray curability, as an adhesive composition containing an energy ray curable adhesive, that is, as an energy ray curable adhesive composition, for example, non-energy ray curable Adhesive composition (I-1) consisting of an adhesive resin (I-1a) (hereinafter sometimes referred to simply as "adhesive resin (I-1a)") and an energy ray-curable compound; Adhesion of energy ray-curable adhesive resin (I-2a) (hereinafter sometimes referred to simply as "adhesive resin (I-2a)") in which unsaturated groups are introduced into the side chains of permanent adhesive resin (I-1a) an adhesive composition (I-2); an adhesive composition (I-3) containing the aforementioned adhesive resin (I-2a) and an energy ray-curable compound; and the like.

＜Adhesive composition (I-1)＞ As mentioned above, the said adhesive composition (I-1) contains the non-energy ray curable adhesive resin (I-1a) and an energy ray curable compound. In addition, as another aspect, the adhesive composition (I-1) contains a non-energy ray-curable adhesive resin (I-1a), an energy ray-curable compound, and a crosslinking agent, a photopolymerizable At least one component of the group consisting of initiators, other additives, and solvents.

[Adhesive resin (I-1a)] The aforementioned adhesive resin (I-1a) is preferably an acrylic resin. As said acrylic resin, the acrylic polymer which has the structural unit derived from an alkyl (meth)acrylate at least is mentioned, for example. The structural unit of the said acrylic resin may be used only by 1 type, or may use 2 or more types, and when using 2 or more types, the combination and ratio can be chosen arbitrarily.

As the above-mentioned alkyl (meth)acrylate, for example, an alkyl (meth)acrylate having 1 to 20 carbon atoms in the alkyl group constituting the alkyl ester can be mentioned, and the above-mentioned alkyl group is a straight chain or Branched chains are preferred. Examples of the alkyl (meth)acrylate include, more specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate base) hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-(meth)acrylate Nonyl, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate (also known as lauryl (meth)acrylate ), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as (myristyl (meth)acrylate), pentadecyl (meth)acrylate, (meth) Cetyl 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, etc.

From the viewpoint of improving the adhesive force of the adhesive layer, the acrylic polymer preferably has a structural unit derived from an alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms. Furthermore, from the viewpoint of further improving the adhesive force of the adhesive layer, the number of carbon atoms in the alkyl group is preferably 4-12, and more preferably 4-8. Furthermore, the alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms is preferably an alkyl methacrylate.

The aforementioned acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate. As the aforementioned functional group-containing monomer, for example, the reaction of the aforementioned functional group with the later-described crosslinking agent as the starting point of crosslinking, the reaction of the aforementioned functional group with the later-described unsaturated group-containing compound A monomer that can introduce unsaturated groups into the side chains of acrylic polymers by reacting with unsaturated groups, etc.

As said functional group in a functional group containing monomer, a hydroxyl group, a carboxyl group, an amino group, an epoxy group etc. are mentioned, for example. That is, as a functional group containing monomer, a hydroxyl group containing monomer, a carboxyl group containing monomer, an amino group containing monomer, an epoxy group containing monomer etc. are mentioned, for example.

Examples of the aforementioned hydroxyl-containing monomers include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, Hydroxyalkyl (meth)acrylates such as hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; vinyl alcohol , non-(meth)acrylic unsaturated alcohols such as acrylic alcohol (that is, unsaturated alcohols that do not contain a (meth)acrylic acid skeleton), etc.

As the aforementioned carboxyl group-containing monomers, for example, ethylenically unsaturated monocarboxylic acids (that is, monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid can be cited; Ethylenically unsaturated dicarboxylic acids (that is, dicarboxylic acids having ethylenically unsaturated bonds), such as fumaric acid, itaconic acid, maleic acid, citraconic acid; the aforementioned ethylenically unsaturated Anhydrides of dicarboxylic acids; carboxyalkyl (meth)acrylates such as 2-carboxyethyl methacrylate, etc.

The functional group-containing monomers are preferably hydroxyl-containing monomers and carboxyl-containing monomers, and more preferably hydroxyl-containing monomers.

The functional group-containing monomer constituting the acrylic polymer may be used alone, or two or more of them may be used, and when two or more are used, the combination and ratio thereof may be selected arbitrarily.

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

The aforementioned acrylic polymer may have a structural unit derived from other monomers in addition to the structural unit derived from an alkyl (meth)acrylate and the structural unit derived from a functional group-containing monomer. The aforementioned other monomers are not particularly limited as long as they can be copolymerized with an alkyl (meth)acrylate or the like. Examples of other monomers include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide and the like.

The aforementioned other monomers constituting the aforementioned acrylic polymer may be used alone, or may be used in combination of two or more, and when using two or more, combinations and ratios thereof may be selected arbitrarily.

The aforementioned acrylic polymer can be used as the aforementioned non-energy ray curable adhesive resin (I-1a). On the other hand, a product obtained by reacting a functional group in the aforementioned acrylic polymer with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group (energy ray polymerizable group) can be used as the aforementioned energy ray polymer. Curable adhesive resin (I-2a) is used.

The adhesive resin (I-1a) contained in the adhesive composition (I-1) may be used only by one type, or two or more types may be used, and when two or more types are used, any combination thereof may be selected and Proportion.

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

[Energy ray curable compound] Examples of the aforementioned energy ray-curable compound contained in the adhesive composition (I-1) include monomers or oligomers (oligomers) that have an energy ray polymerizable unsaturated group and are curable by energy ray irradiation. . In energy ray curable compounds, as monomers, for example, trimethylolpropane tri(meth)acrylate, neopentylthritol (meth)acrylate, neopentylthritol tetra(meth)acrylate, di Polyvalent (meth)acrylates such as neopentylitol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate, etc. ; Urethane (meth)acrylate; Polyester (meth)acrylate; Polyether (meth)acrylate; Epoxy (meth)acrylate, etc. Among the energy ray-curable compounds, examples of the oligomer include oligomers obtained by polymerizing the monomers listed above, and the like. From the point of view that the molecular weight is relatively large and the storage modulus of the adhesive layer hardly decreases, the energy ray-curable compound is urethane (meth)acrylate, urethane (meth)acrylate Oligomers are preferred.

The aforementioned energy ray-curable compounds contained in the adhesive composition (I-1) may be used alone, or may be used in two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be selected arbitrarily.

In the aforementioned adhesive composition (I-1), the content of the aforementioned energy ray-curable compound relative to the total mass of the adhesive composition (I-1) is preferably 1 to 95% by mass, and preferably 5 to 90% by mass. The mass % is preferable, and 10-85 mass % is especially preferable.

[Crosslinking agent] In the case of using the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate as the adhesive resin (I-1a) In this case, the adhesive composition (I-1) preferably further contains a crosslinking agent.

The aforementioned crosslinking agent is, for example, a crosslinking agent capable of reacting with the aforementioned functional group to crosslink the adhesive resins (I-1a) to each other. As the crosslinking agent, for example, toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and isocyanate-based crosslinking agents such as adducts of the above-mentioned diisocyanates (that is, those having isocyanate groups) crosslinking agent); epoxy-based crosslinking agent such as ethylene glycol glycidyl ether (that is, a crosslinking agent having a glycidyl group); hexa[1-(2-methyl)-aziridine] Aziridine-based cross-linking agents such as triphosphatriazine (that is, cross-linking agents having an aziridine group); metal chelate-based cross-linking agents such as aluminum chelates (that is, having a metal chelate cross-linking agent with combined structure); isocyanurate cross-linking agent (that is, cross-linking agent with isocyanuric acid skeleton) and so on. From the standpoint of improving the cohesive force of the adhesive to increase the adhesive force of the adhesive layer and being easy to obtain, the crosslinking agent is preferably an isocyanate crosslinking agent.

The crosslinking agent contained in the adhesive composition (I-1) may be used alone, or may be used in two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be selected arbitrarily.

In the aforementioned adhesive composition (I-1), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the content of the adhesive resin (I-1a). It is preferable, and it is especially preferable to use 0.3-15 mass parts.

[Photopolymerization Initiator] The adhesive composition (I-1) may further contain a photopolymerization initiator. The adhesive composition (I-1) containing a photopolymerization initiator can sufficiently perform a curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

Examples of the aforementioned photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. Benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, etc. acetophenone compounds; acyl oxidation of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Phosphine compounds; sulfides such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile Compounds; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxides; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2, 4-Diethylthioxanthone; 1,2-Diphenylmethane; 2-Hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 2-Chloroanthraquinone Wait. In addition, as said photoinitiator, the quinone compound, such as 1-chloroanthraquinone, the photosensitizer, such as an amine, etc. can be used, for example.

The photopolymerization initiator contained in the adhesive composition (I-1) may be used only by 1 type, or may use 2 or more types, and when using 2 or more types, the combination and ratio can be selected arbitrarily.

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

[Other additives] The adhesive composition (I-1) may contain other additives that do not correspond to any of the above-mentioned components within the range that does not impair the effect of the present invention. The aforementioned other additives include, for example, antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, tackifiers, reactive Known additives such as inhibitors and crosslinking accelerators (catalysts). In addition, as a reaction inhibitor, for example, an unexpected crosslinking reaction of the adhesive composition (I-1) in storage due to the action of the catalyst mixed in the adhesive composition (I-1) can be suppressed. As a reaction inhibitor, for example, a reaction inhibitor of a chelate complex formed by chelating with a catalyst, and more specifically, a reaction inhibitor having two or more carbonyl groups (—C( =O)—) reaction inhibitor.

The other additives contained in the adhesive composition (I-1) may be used only by one type, or two or more types may be used, and when two or more types are used, the combination and ratio thereof may be selected arbitrarily.

In the adhesive composition (I-1), the content of other additives is not particularly limited, and can be appropriately selected according to the type.

[solvent] The adhesive composition (I-1) may also contain a solvent. Since the adhesive composition (I-1) contains a solvent, the coatability to the surface to be coated can be improved.

The aforementioned solvent is preferably an organic solvent, and as the aforementioned organic solvent, for example, ketones such as methyl ethyl ketone and acetone; esters (carboxylates) such as ethyl acetate; tetrahydrofuran, dioxane, etc. Ethers; aliphatic hydrocarbons such as cyclohexane and n-hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol, etc.

As the aforementioned solvent, for example, the solvent used when preparing the adhesive resin (I-1a) may not be removed from the adhesive resin (I-1a) and directly used in the adhesive composition (I-1), Alternatively, when preparing the adhesive composition (I-1), the same or different solvent as that used for the preparation of the adhesive resin (I-1a) may be added separately.

The solvent contained in the adhesive composition (I-1) may be used alone, or two or more kinds may be used, and when two or more kinds are used, the combination and ratio thereof may be selected arbitrarily.

In the adhesive composition (I-1), the content of the solvent is not particularly limited, and may be appropriately adjusted.

In the adhesive composition (I-1), examples of the resin component (X) include an adhesive resin (I-1a) and an energy ray-curable compound.

＜Adhesive composition (I-2)＞ As described above, the aforementioned adhesive composition (I-2) contains the energy ray-curable adhesive resin (I- 2a). Furthermore, as another aspect, the aforementioned adhesive composition (I-2) contains the aforementioned adhesive resin (I-2a), and optionally a crosslinking agent, a photopolymerization initiator, other additives, and a solvent. at least 1 ingredient in the group of .

[Adhesive resin (I-2a)] The aforementioned adhesive resin (I-2a) can be 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 aforementioned unsaturated group-containing compound reacts with the functional group in the adhesive resin (I-1a) in addition to the aforementioned energy ray polymerizable unsaturated group, so the aforementioned unsaturated group-containing compound has the ability to be compatible with the adhesive The compound of the group to which the resin (I-1a) is bonded. As the aforementioned energy ray polymerizable unsaturated group, for example, (meth)acryl, vinyl (ethenyl, also called vinyl), allyl (allyl, also called 2-propenyl (2- propenyl)), etc., preferably (meth)acryl. As the group that can be bonded to the functional group in the adhesive resin (I-1a), for example, an isocyanate group and a glycidyl group that can be bonded to a hydroxyl group or an amine group, and an isocyanate group that can be bonded to a hydroxyl group or an epoxy group Bonded hydroxyl and amine groups, etc.

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

The adhesive resin (I-2a) contained in the adhesive composition (I-2) may be used only by one type, or two or more types may be used, and when two or more types are used, any combination thereof may be selected and Proportion.

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

[Crosslinking agent] In the case of using, for example, the same adhesive resin (I-1a) as the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer as the adhesive resin (I-2a), the adhesive composition (I-2) preferably further contains a crosslinking agent.

Examples of the crosslinking agent in the adhesive composition (I-2) include the same crosslinking agents as in the adhesive composition (I-1). The crosslinking agent contained in the adhesive composition (I-2) may be used alone, or may be used in two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be selected arbitrarily.

In the aforementioned adhesive composition (I-2), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the content of the adhesive resin (I-2a). It is preferable, and it is especially preferable to use 0.3-15 mass parts.

[Photopolymerization Initiator] The adhesive composition (I-2) may further contain a photopolymerization initiator. The adhesive composition (I-2) containing a photopolymerization initiator can sufficiently perform a curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator in the adhesive composition (I-2) include the same photopolymerization initiators as in the adhesive composition (I-1). The photopolymerization initiator contained in the adhesive composition (I-2) may be used only by 1 type, or may use 2 or more types, and when using 2 or more types, the combination and ratio 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, preferably 0.03 to 10 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-2a). 1 part is preferred, and 0.05 to 5 parts by mass is particularly preferred.

[Other additives] The adhesive composition (I-2) may contain other additives that do not correspond to any of the above-mentioned components within the range that does not impair the effect of the present invention. Examples of other additives in the adhesive composition (I-2) include the same ones as those in the adhesive composition (I-1). As for other additives contained in the adhesive composition (I-2), only one type may be used, or two or more types may be used, and when two or more types are used, the combination and ratio thereof may be selected arbitrarily.

In the adhesive composition (I-2), the content of other additives is not particularly limited, and can be appropriately selected according to the type.

[solvent] The adhesive composition (I-2) may contain a solvent for the same purpose as that of 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 solvent contained in the adhesive composition (I-2) may be used alone, or two or more kinds may be used, and when two or more kinds are used, the combination and ratio thereof may be selected arbitrarily. In the adhesive composition (I-2), the content of the solvent is not particularly limited, and can be appropriately adjusted.

In the adhesive composition (I-2), the resin component (X) includes, for example, an adhesive resin (I-2a).

＜Adhesive composition (I-3)＞ As described above, the adhesive composition (I-3) contains the aforementioned adhesive resin (I-2a) and an energy ray-curable compound. In addition, as another aspect, the adhesive composition (I-3) contains the adhesive resin (I-2a), an energy ray-curable compound, and a crosslinking agent, a photopolymerization initiator, At least one component of the group consisting of other additives and solvents.

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

[Energy ray curable compound] Examples of the energy ray-curable compound contained in the adhesive composition (I-3) include monomers and oligomers that have an energy ray polymerizable unsaturated group and are curable by irradiation with energy rays, and can be The same energy ray-curable compounds contained in the adhesive composition (I-1) are listed. The aforementioned energy ray-curable compounds contained in the adhesive composition (I-3) may be used alone, or may be used in two or more kinds. When two or more kinds are used, the combination and ratio thereof may be selected arbitrarily.

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

[Photopolymerization Initiator] The adhesive composition (I-3) may further contain a photopolymerization initiator. The adhesive composition (I-3) containing a photopolymerization initiator can sufficiently perform a curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator in the adhesive composition (I-3) include the same photopolymerization initiators as in the adhesive composition (I-1). The photopolymerization initiator contained in the adhesive composition (I-3) may be used only by 1 type, or may use 2 or more types, and when using 2 or more types, the combination and ratio can be selected arbitrarily.

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

[Other additives] The adhesive composition (I-3) may contain other additives that do not correspond to any of the above-mentioned components within the range that does not impair the effect of the present invention. Examples of the aforementioned other additives include the same ones as in the adhesive composition (I-1). The other additives contained in the adhesive composition (I-3) may be used only by 1 type, or 2 or more types may be used, and when 2 or more types are used, the combination and ratio can be chosen arbitrarily.

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

[solvent] The adhesive composition (I-3) may contain a solvent for the same purpose as that of 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 solvent contained in the adhesive composition (I-3) may be used alone, or two or more kinds may be used, and when two or more kinds are used, the combination and ratio thereof may be selected arbitrarily. In the adhesive composition (I-3), the content of the solvent is not particularly limited, and can be appropriately adjusted.

In the adhesive composition (I-3), examples of the resin component (X) include 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), adhesive composition (I-2) and adhesive composition (I-3) have been mainly described, and the components contained in these adhesive compositions have been described, Similarly, general adhesive compositions other than these three adhesive compositions (referred to as "adhesive compositions other than adhesive compositions (I-1) to (I-3)" in this specification can be used. ).

Adhesive compositions other than the adhesive compositions (I-1) to (I-3) include non-energy ray curable adhesive compositions in addition to energy ray curable adhesive compositions. thing. Examples of non-energy ray-curable adhesive compositions include acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, The adhesive composition (I-4) containing a non-energy ray-curable adhesive resin (I-1a) such as an ester resin preferably contains an acrylic resin. Moreover, the adhesive composition (I-4) which is a non-energy-ray-curable adhesive composition does not contain the energy-ray-curable compound in the said adhesive composition (I-1).

Adhesive compositions other than adhesive compositions (I-1) to (I-3) preferably contain one or more cross-linking agents, and the content of the cross-linking agent can be the same as that of the above-mentioned adhesives. In the case of agent composition (I-1) and the like.

＜Adhesive composition (I-4)＞ As a preferable example of an adhesive composition (I-4), the adhesive composition containing the said adhesive resin (I-1a) and a crosslinking agent is mentioned, for example. As another aspect, a composition containing the above-mentioned adhesive resin (I-1a), a crosslinking agent, and at least one component selected from the group consisting of other additives and solvents as needed, as an adhesive Composition (I-4).

[Adhesive resin (I-1a)] Examples of the adhesive resin (I-1a) in the adhesive composition (I-4) include the same adhesive resin (I-1a) as in the adhesive composition (I-1). The adhesive resin (I-1a) contained in the adhesive composition (I-4) may be used only by one type, or two or more types may be used, and when two or more types are used, any combination thereof may be selected and Proportion.

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

[Crosslinking agent] In the case of using the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate as the adhesive resin (I-1a) In this case, the adhesive composition (I-4) preferably further contains a crosslinking agent.

Examples of the crosslinking agent in the adhesive composition (I-4) include the same crosslinking agents as in the adhesive composition (I-1). The crosslinking agent contained in the adhesive composition (I-4) may be used alone, or may be used in two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be selected arbitrarily.

In the aforementioned adhesive composition (I-4), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the content of the adhesive resin (I-1a). It is preferable, and it is especially preferable to use 0.3-15 mass parts.

[Other additives] The adhesive composition (I-4) may contain other additives that do not correspond to any of the above-mentioned components within the range that does not impair the effect of the present invention. Examples of the aforementioned other additives include the same ones as in the adhesive composition (I-1). The other additives contained in the adhesive composition (I-4) may be used only by 1 type, or 2 or more types may be used, and when 2 or more types are used, the combination and ratio can be chosen arbitrarily.

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

[solvent] The adhesive composition (I-4) may contain a solvent for the same purpose as that of the adhesive composition (I-1). Examples of the solvent in the adhesive composition (I-4) include the same solvents as those in the adhesive composition (I-1). The solvent contained in the adhesive composition (I-4) may be used alone, or two or more kinds may be used, and when two or more kinds are used, the combination and ratio thereof may be selected arbitrarily. In the adhesive composition (I-4), the content of the solvent is not particularly limited, and can be appropriately adjusted.

In the adhesive composition (I-4), the resin component (X) includes, for example, an adhesive resin (I-1a).

In the above composite sheet for forming a protective film, the adhesive layer is preferably non-energy ray curable. This is because if the adhesive layer has energy ray curability, when the film for protective film formation is hardened by the irradiation of an energy ray, it cannot suppress that an adhesive layer also hardens|cures simultaneously. When the adhesive layer and the film for protective film formation are hardened simultaneously, the film for protective film formation after hardening, and an adhesive layer may adhere mutually at the interface between them so that they cannot be peeled off. In this case, the semiconductor wafer (semiconductor wafer with a protective film) provided with a cured protective film-forming film (that is, protective film) on the back surface becomes difficult to change from the cured adhesive layer The support sheet peels off, and then it becomes impossible to pick up the semiconductor wafer with the protective film normally. By making the adhesive layer in the support sheet non-energy ray curable, such a problem can be reliably avoided, and the semiconductor wafer with the protective film can be picked up more easily.

Here, the effect in the case where the adhesive layer is non-energy ray curable has been described, but even if the film layer directly in contact with the protective film forming film of the support sheet is a film layer other than the adhesive layer, The same effect can be exhibited as long as this film layer is non-energy ray curable.

＜＜Manufacturing method of adhesive composition＞＞ Adhesive compositions (I-1) to (I-3) can be obtained by preparing the above-mentioned adhesive and, if necessary, components other than the above-mentioned adhesive, etc., which are used to constitute the adhesive composition. Adhesive compositions other than the adhesive compositions (I-1) to (I-3) such as the , adhesive composition (I-4), and the like. The order of addition when preparing each component is not specifically limited, You may add 2 or more types of components at the same time. In the case of using a solvent, it can be used by mixing the solvent with any of the formulation components other than the solvent and diluting the formulation components in advance, or by not mixing any of the formulation components other than the solvent. It is used by mixing the solvent and this preparation component as it is diluted beforehand. The mixing method of each component is not particularly limited at the time of preparation, and can be appropriately 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, and a method of mixing using ultrasonic waves. . The temperature and time during the addition and mixing of each component are not particularly limited as long as they do not cause deterioration of each compounded component, and can be appropriately adjusted, but the temperature is preferably 15-30°C.

◎Film for protective film formation As mentioned above, the said film for protective film formation has energy ray curability, and contains an energy ray curable component (a0) and a non-energy ray curable polymer (b). The energy ray curable component (a0) is preferably uncured, preferably has adhesiveness, and is more preferably uncured and has adhesiveness.

Since the film for forming a protective film has energy ray curability, it can form a protective film by curing in a shorter time than a film for forming a thermosetting protective film.

In the present invention, the term "energy ray" refers to a ray having energy quanta in electromagnetic waves or charged particle beams, and examples thereof include ultraviolet rays, radiation rays, and electron beams. For example, ultraviolet rays may be irradiated by using a high-pressure mercury lamp, a fusion-H lamp, a xenon lamp, a black-light, an LED lamp, or the like as an ultraviolet source. The electron beam may be irradiated with an electron beam generated by an electron beam accelerator or the like. In the present invention, "energy ray curability" refers to the property of being cured by irradiating energy ray, and "non-energy ray curability" refers to the property of not curing even when irradiated with energy ray.

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

The thickness of the film for protective film formation is preferably 1 to 100 μm, more preferably 3 to 75 μm, and particularly preferably 5 to 50 μm. By making the thickness of the film for protective film formation more than the said lower limit, the protective film which has higher protective ability can be formed. Furthermore, by making the thickness of the film for protective film formation below the said upper limit, it can suppress that a protective film becomes thick too much. Here, the "thickness of the film for forming a protective film" refers to the thickness of the entire film for forming a protective film. For example, the thickness of a film for forming a protective film consisting of multiple layers refers to all the layers constituting the film for forming a protective film. total thickness.

The light transmittance of the film for forming a protective film at a wavelength of 350 nm is preferably from 0% to 20%, preferably from 0% to 15%, more preferably from 0% to 8%, and more than 0%. Less than 5% is especially good, and it can also be 0%. By setting the light transmittance below the upper limit, unexpected curing reactions of the ultraviolet curable components by ultraviolet rays contained in light sources such as fluorescent lamps can be suppressed in the film for protective film formation during storage.

The film for protective film formation and a protective film are mutually almost or completely the same in light transmittance with respect to the same wavelength. For example, for a protective film formed by curing a film for forming a protective film having a light transmittance at a wavelength of 350 nm in the above range, the light transmittance at a wavelength of 350 nm is preferably 0% to 20%, and preferably 0% to 15%. % or less is preferable, more preferably 0% or more and 8% or less, and particularly preferably 0% or more and 5% or less, and may be 0%.

The curing conditions for curing the protective film-forming film to form the protective film are not particularly limited as long as the degree of curing allows the protective film to fully perform its function, and can be appropriately selected according to the type of protective film-forming film. For example, when curing the film for forming a protective film, the illuminance of energy rays is preferably 4 to 280 mW/cm ² . Furthermore, during the aforementioned curing, the light quantity of the energy rays is preferably 3 to 1000 mJ/cm ² .

＜＜Protective film forming composition＞＞ The above-mentioned film for forming a protective film can be formed using a composition for forming a protective film containing the constituent materials thereof. For example, the protective film-forming film is formed on the target position by applying the protective film-forming composition on the surface where the protective film-forming film is to be formed, and drying as necessary. In the composition for forming a protective film, the ratio of the content of the component that does not evaporate at normal temperature is usually the same as the ratio of the content of the above-mentioned components in the film for forming a protective film.

Coating of the composition for forming a protective film can be performed by a known method, for example, use of an air knife coater, a knife coater, a rod coater, a gravure coater, or a roll coater can be used. , Roller knife coater, shower curtain coater, die coater, knife coater, screen coater, Mailer rod coater, kiss coater and other coating machine methods.

The drying conditions of 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 it. For example, it is preferable to dry the protective film-forming composition containing a solvent at 70 to 130° C. for 10 seconds to 5 minutes.

＜Protective film forming composition (IV-1)＞ Examples of the composition for forming a protective film include the composition for forming a protective film (IV-1) containing the aforementioned 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 is cured by irradiation of energy rays, that is, a component for imparting film-forming properties, flexibility, and the like to the film for forming a protective 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 80000.

As the aforementioned energy ray curable group in the energy ray curable component (a0), a group containing an energy ray curable double bond can be mentioned, and a (meth)acryl group, a vinyl group, etc. can be mentioned as comparative examples. good example.

The energy ray curable component (a0) is not particularly limited as long as it satisfies the above conditions, and examples thereof include low molecular weight compounds having energy ray curable groups, epoxy resins having energy ray curable groups, and energy ray curable groups. Radiation-curable phenolic resin, etc.

Among the energy ray curable components (a0), examples of low molecular weight compounds having energy ray curable groups include polyfunctional monomers or oligomers, etc. Acrylic compounds are preferred. Examples of the aforementioned acrylate compounds include 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethylene Oxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di( Meth)acrylate, 2,2-bis[4-((meth)acryloxyethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloxy ethoxy)phenyl]fluorene, 2,2-bis[4-((meth)acryloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate ( Tricyclodecane dimethylol 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 ( 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-1,3- Difunctional (meth)acrylates such as di(meth)acryloxypropane; Tris(2-(meth)acryloxyethyl)isocyanurate, ε-caprolactone modified tris-(2-(meth)acryloxyethyl)isocyanurate , Ethoxylated Glycerin Tri(meth)acrylate, Neopentylthritol Tri(meth)acrylate, Trimethylolpropane Tri(meth)acrylate, Ditrimethylolpropane Tetra(meth)acrylate Acrylates, Ethoxylated Neopentylthritol Tetra(meth)acrylates, Neopentylthritol Tetra(meth)acrylates, Dineopentylthritol Poly(meth)acrylates, Dineopentylthritol Hexa Multifunctional (meth)acrylates such as (meth)acrylates; Polyfunctional (meth)acrylate oligomers such as urethane (meth)acrylate oligomers, etc.

Among the energy ray curable components (a0), as an epoxy resin having an energy ray curable group and a phenolic resin having an energy ray curable group, for example, "Japanese Patent Laid-Open No. 2013-194102 The materials described in paragraph 0043, etc., of the Gazette. This resin also corresponds to the resin constituting the thermosetting component (h) described later, but in the present invention, it is handled as the energy ray curing component (a0).

The molecular weight of the energy ray-curable component (a0) is preferably from 100 to 30,000, and more preferably from 300 to 10,000.

The energy ray-curable component (a0) contained in the composition for forming a protective film (IV-1) and the film for forming a protective film may be used only by one type, or two or more types may be used, and in the case of using two or more types The combination and ratio can be selected arbitrarily.

[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) depending on the purpose (in this specification, sometimes It is abbreviated as "energy ray curable component (a1)").

The energy ray-curable component (a1) is a component that is cured by irradiation of energy rays, that is, a component for imparting film-forming properties, flexibility, and the like to the film for forming a protective film.

Examples of the energy ray curable component (a1) include polymers having an energy ray curable group and having a weight molecular weight of 80,000 to 2,000,000. At least a part of the energy ray-curable component (a1) may already be cross-linked by the cross-linking agent (f) described later, or may not be cross-linked. In addition, in this specification, the so-called "weight average molecular weight" means a standard polystyrene equivalent value measured by gel-permeation-chromatography (GPC) unless otherwise specified.

As the energy ray curable component (a1), for example, an acrylic polymer (a11) having a functional group capable of reacting with a group possessed by another compound, and an acrylic polymer having a group capable of reacting with the aforementioned functional group and having An acrylic resin (a1-1) obtained by polymerizing both energy ray curable compounds (a12) having energy ray curable groups such as energy ray curable double bonds.

Examples of the aforementioned functional groups that can react with groups possessed by other compounds include hydroxyl groups, carboxyl groups, amino groups, and substituted amino groups (for example, one or two hydrogen atoms of the amino group are replaced by groups other than hydrogen atoms. The group substituted by the group), epoxy group, etc. However, from the viewpoint of preventing corrosion of circuits such as semiconductor wafers and semiconductor wafers, the aforementioned functional groups are preferably groups other than carboxyl groups. Among the above, the aforementioned functional group is preferably a hydroxyl group.

・Acrylic polymer with functional groups (a11) Examples of the acrylic polymer (a11) having a functional group include polymers obtained by copolymerizing an acrylic monomer having the functional group and an acrylic monomer not having the functional group, or It is a polymer obtained by copolymerizing a monomer other than an acrylic monomer (that is, a non-acrylic monomer) in addition to these monomers. In addition, the aforementioned acrylic polymer (a11) may be a random (random) copolymer or a block (block) copolymer.

Examples of the acrylic monomer having the aforementioned functional groups include hydroxyl-containing monomers, carboxyl-containing monomers, amino-containing monomers, substituted amino-containing monomers, and epoxy-containing monomers. Wait.

Examples of the aforementioned hydroxyl-containing monomers include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, Hydroxyalkyl (meth)acrylates such as hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; vinyl alcohol , non-(meth)acrylic unsaturated alcohols such as acrylic alcohol (that is, unsaturated alcohols that do not contain a (meth)acrylic acid skeleton), etc.

Examples of the aforementioned carboxyl group-containing monomers include ethylenically unsaturated monocarboxylic acids (that is, monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; fumaric acid , itaconic acid, maleic acid, citraconic acid, etc., ethylenically unsaturated dicarboxylic acids (that is, dicarboxylic acids having ethylenically unsaturated bonds); the aforementioned ethylenically unsaturated dicarboxylic acids Anhydrides; carboxyalkyl (meth)acrylates such as 2-carboxyethyl methacrylate, etc.

The acrylic monomers having the aforementioned functional groups are preferably hydroxyl-containing monomers and carboxyl-containing monomers, and more preferably hydroxyl-containing monomers.

The acrylic monomers having the aforementioned functional groups constituting the aforementioned acrylic polymer (a11) may be used alone or in combination of two or more. .

Examples of acrylic monomers having no functional group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. , n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth) ) hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate (also known as lauryl (meth)acrylate) , tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as (myristyl (meth)acrylate), pentadecyl (meth)acrylate, (meth)acrylic acid Cetyl (also known as palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (also known as stearyl (meth)acrylate), etc. The alkyl group constituting the alkyl ester is an alkyl (meth)acrylate with a chain structure of 1 to 18 carbon atoms.

Furthermore, examples of acrylic monomers that do not have the aforementioned functional groups include methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxy (meth)acrylate, (meth)acrylic acid esters containing alkoxyalkyl groups such as methoxymethyl esters, ethoxyethyl (meth)acrylates, etc.; aryl (meth)acrylates containing phenyl (meth)acrylates, etc. (Meth)acrylates with aromatic groups; non-crosslinkable (meth)acrylamide and its derivatives; N,N-dimethylaminoethyl (meth)acrylate, (methyl) ) Non-crosslinkable tertiary amino (meth)acrylates such as N,N-dimethylaminopropyl acrylate, etc.

The acrylic monomers not having the aforementioned functional groups constituting the aforementioned acrylic polymer (a11) may be used alone or in combination of two or more. When using two or more types, combinations thereof and Proportion.

Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; and styrene. The non-acrylic monomer constituting the acrylic polymer (a11) may be used alone or in two or more types. When two or more types are used, the combination and ratio thereof may be selected arbitrarily.

In the aforementioned acrylic polymer (a11), the amount of structural units derived from the aforementioned functional group-containing acrylic monomer relative to the total amount (total mass) of the structural units constituting the acrylic polymer (a11) is The ratio (content) is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and particularly preferably 3 to 30% by mass. Since the aforementioned ratio is within such a range, energy rays in the aforementioned acrylic resin (a1-1) obtained by copolymerization of the aforementioned acrylic polymer (a11) and the aforementioned energy ray-curable compound (a12) The content of curable groups becomes easily adjustable within the range in which the protective film has a preferable degree of curing.

The above-mentioned acrylic polymer (a11) constituting the above-mentioned acrylic resin (a1-1) may be used alone, or two or more kinds may be used, and when two or more kinds are used, the combination and ratio thereof may be selected arbitrarily .

In the case of using the acrylic resin (a1-1), in the protective film forming composition (IV-1), the acrylic resin (a1 The content of -1) is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, and particularly preferably 3 to 20% by mass.

・Energy ray curable compound (a12) The energy ray-curable compound (a12) has one or more kinds selected from the group consisting of isocyanate group, epoxy group, and carboxyl group as the functional A group that reacts with a group is preferable, and it is more preferable to have an isocyanate group as the aforementioned group. For example, when the energy ray-curable compound (a12) has an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.

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

Examples of the energy ray-curable compound (a12) include 2-methacryloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, methacrylyl isocyanate, Allyl isocyanate, 1,1-(bisacryloxymethyl)ethyl isocyanate; Acryl monoisocyanate compounds obtained by reacting diisocyanate compounds or polyisocyanate compounds with hydroxyethyl (meth)acrylate; An acryl monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with a polyol compound and hydroxyethyl (meth)acrylate. Among the above, the aforementioned energy ray curable compound (a12) is preferably 2-methacryloxyethyl isocyanate.

The aforementioned energy ray-curable compound (a12) constituting the aforementioned acrylic resin (a1-1) may be used alone or in combination of two or more. Proportion.

In the aforementioned acrylic resin (a1-1), the energy ray-curable group derived from the aforementioned energy ray-curable compound (a12) is less than the content of the aforementioned functional group derived from the aforementioned acrylic polymer (a11). The content ratio of the agglomerates is preferably 20-120 mol%, more preferably 35-100 mol%, and particularly preferably 50-100 mol%. Since the ratio of the foregoing content is within such a range, the adhesive force of the protective film formed by curing becomes greater. In addition, when the aforementioned energy ray-curable compound (a12) is a monofunctional (having one aforementioned group in 1 molecule) compound, the upper limit of the ratio of the aforementioned content is 100 mole %, while the aforementioned energy When the radiation curable compound (a12) is a polyfunctional (has two or more of the above-mentioned groups in one molecule) compound, the upper limit of the ratio of the above-mentioned content exceeds 100 mol%.

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

In the case where at least a part of the energy ray-curable component (a1) has been crosslinked by the crosslinking agent (f), the energy ray-curable component (a1) does not belong to the already described acrylic polymer (a11 ), any one of the above-mentioned monomers of the constituents of the cross-linking agent (f), but may be a monomer having a group reactive with the cross-linking agent (f) after polymerization to cross-link the group reactive with the cross-linking agent (f) A polymer, or a polymer derived from the aforementioned energy ray curable compound (a12) and cross-linked at a group reactive with the aforementioned functional group may be used.

The energy ray-curable component (a1) contained in the composition for forming a protective film (IV-1) and the film for forming a protective film may be used only by one type, or two or more types may be used, and in the case of using two or more types The combination and ratio can be selected arbitrarily.

In the protective film forming composition (IV-1), the energy ray curable component (a0) is The content of is preferably 10 to 400 parts by mass, and more preferably 30 to 350 parts by mass.

[Non-energy ray curable polymer (b)] The non-energy ray curable polymer (b) is a polymer that does not have an energy ray curable group. At least a part of the aforementioned polymer (b) may already be cross-linked by a cross-linking agent (f) described later, or may not be cross-linked.

Examples of the non-energy ray curable polymer (b) include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber-based resins, acrylate urethane resins, polyvinyl alcohol ( Can be referred to as PVA), butyral resin, polyester urethane resin, etc.

Among the above, the polymer (b) is preferably an acrylic polymer (hereinafter, sometimes simply referred to as "acrylic polymer (b-1)"). For example, when the aforementioned polymer (b) is an acrylic polymer, especially when it is a highly polar acrylic polymer, the adhesion between the film for forming a protective film and the semiconductor wafer, and the The adhesiveness between the film for formation and a semiconductor wafer improves further, and the adhesiveness between a protective film and a semiconductor wafer, and the adhesiveness between a protective film and a semiconductor wafer also improve further. Here, examples of the "highly polar acrylic polymer" include 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 known, for example, may be a homopolymer of one type of acrylic monomer, or may be a copolymer of two or more types of acrylic monomers, or 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 monomers constituting the acrylic polymer (b-1) include alkyl (meth)acrylates, (meth)acrylates having a cyclic skeleton, and glycidyl group-containing (meth)acrylates. ) acrylates, hydroxyl-containing (meth)acrylates, substituted amino-containing (meth)acrylates, etc. Here, the "substituted amino group" is as described above.

Examples of the aforementioned alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth) Hexyl acrylate, Heptyl (meth)acrylate, 2-Ethylhexyl (meth)acrylate, Isooctyl (meth)acrylate, n-Octyl (meth)acrylate, n-Nonyl (meth)acrylate , isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (also known as lauryl (meth)acrylate), Tridecyl (meth)acrylate, Myristyl (meth)acrylate (also known as myristyl ((meth)acrylate), Pentadecyl (meth)acrylate, Decyl (meth)acrylate Hexadecyl (also known as palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (also known as stearyl (meth)acrylate), etc. The alkyl group constituting the alkyl ester is an alkyl (meth)acrylate with a chain structure of 1 to 18 carbon atoms.

Examples of (meth)acrylates having a cyclic skeleton include cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentyl (meth)acrylate. ; Aralkyl (meth)acrylates such as benzyl (meth)acrylate; Cycloalkenyl (meth)acrylates such as dicyclopentenyl (meth)acrylate; Cycloalkenyloxyalkyl (meth)acrylate, such as dicyclopentenyloxyethyl (meth)acrylate, etc.

As said glycidyl group containing (meth)acrylate, glycidyl (meth)acrylate etc. are mentioned, for example. Examples of the hydroxyl group-containing (meth)acrylate include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylate, Base) 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Examples of the substituted amino group-containing (meth)acrylate include N-methylaminoethyl (meth)acrylate and the like.

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

Examples of the non-energy ray-curable polymer (b) that is at least partially crosslinked by the crosslinking agent (f) include reactive functional groups in the aforementioned polymer (b) that react with the crosslinking agent (f). after the polymer. The above-mentioned reactive functional group can be appropriately selected according to the type of crosslinking agent (f), and is not particularly limited. For example, when the crosslinking agent (f) is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxyl group, and an amino group, among which a hydroxyl group having high reactivity with an isocyanate group is preferred. Furthermore, when the crosslinking agent (f) is an epoxy compound, examples of the reactive functional groups include carboxyl groups, amino groups, amido groups, and the like, among which those having high reactivity with epoxy groups Carboxyl is preferred. However, the aforementioned reactive functional group is preferably a group other than a carboxyl group from the viewpoint of preventing corrosion of a semiconductor wafer, a circuit of a semiconductor wafer, or the like.

Examples of the non-energy ray-curable polymer (b) having the reactive functional group include polymers obtained by polymerizing monomers having at least the reactive functional group. In the case of the acrylic polymer (b-1), any one of the aforementioned acrylic monomers and non-acrylic monomers listed as monomers constituting the acrylic polymer (b-1) or Both, monomers having the aforementioned reactive functional groups can be used. Examples of the polymer (b) having a hydroxyl group as a reactive functional group include polymers obtained by polymerizing a hydroxyl group-containing (meth)acrylate. In addition, the above-mentioned acrylic monomers or non-acrylic monomers exemplified by polymerizing a monomer in which one or more hydrogen atoms are replaced by the above-mentioned reactive functional groups obtained polymer.

In the non-energy ray-curable polymer (b) having a reactive functional group, the total amount (total mass) of structural units constituting the non-energy ray-curable polymer (b) is composed of The ratio (content) of the amount of the structural unit derived from the monomer is preferably 1 to 25% by mass, more preferably 2 to 20% by mass. With this ratio being within such a range, the degree of crosslinking in the aforementioned polymer (b) can become a more preferable range.

From the viewpoint of improving the film-forming properties of the composition for forming a protective film (IV-1), the weight average molecular weight (Mw) of the non-energy ray curable polymer (b) is preferably 10,000 to 2,000,000, And preferably 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 used alone or in two or more kinds. In the above cases, the combination and ratio can be selected arbitrarily.

In the composition for forming a protective film (IV-1), the energy ray-curable component (a0), the energy ray-curable component (a1), and the non-energy ray-curable The ratio of the total content of the polymer (b) (that is, the ratio of the energy ray curable component (a0), the energy ray curable component (a1) and the non-energy ray curable polymer (b) in the protective film forming film total content), 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 and 25 to 50% by mass, Any of 25 to 39% by mass. When the ratio of the said total content exists in such a range, the energy-beam curability of the film for protective film formation becomes more favorable.

In the composition for forming a protective film (IV-1) and the film for forming a protective film, the non-energy ray-curable The content of the non-toxic polymer (b) is preferably 50 to 400 parts by mass, more preferably 100 to 350 parts by mass, particularly preferably 150 to 300 parts by mass, and most preferably 150 to 280 parts by mass. When the said content of the said polymer (b) exists in such a range, the energy-beam curability of the film for protective film formation becomes more favorable.

[other ingredients] The composition for forming a protective film (IV-1) and the film for forming a protective film may further contain a non-energy ray-curable component (a0), an energy ray-curable component (a1), and a non-energy ray-curable polymer other ingredients of any of the substance (b).

The compound (IV-1) for forming a protective film and the above-mentioned other components contained in the film for forming a protective film may be used alone, or two or more kinds may be used, and in the case of using two or more kinds, they can be selected arbitrarily its combination and proportion.

Examples of the aforementioned other components include photopolymerization initiators (c), fillers (d), coupling (coupling) agents (e), crosslinking agents (f), colorants (g), thermosetting components (h ), curing accelerator (i), general additives (z), etc. For example, by using the protective film-forming composition (IV-1) containing the thermosetting component (h), the formed protective film-forming film can be heated to increase the adhesive force to the adherend, and can also improve Thus, the strength of the protective film formed by the film for protective film formation is obtained.

(Photopolymerization initiator (c)) Examples of the photopolymerization initiator (c) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. Benzoin compounds such as; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1- Acetophenone compounds such as ketones; Acyls such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide phosphine oxide compounds; sulfides such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; Azo compounds; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; benzophenone, 2-(dimethylamino)-1-(4-morpholinophenyl) -2-Benzyl-1-butanone, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O - benzophenone compounds such as acetyl oxime); peroxides; diketone compounds such as diacetyl; benzyl; dibenzyl; 2,4-diethylthioxanthone; 1,2- Diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 2-chloroanthraquinone, etc. In addition, as a photoinitiator (c), for example, a quinone compound, such as 1-chloroanthraquinone; a photosensitizer, such as an amine, etc. can be used.

The photopolymerization initiator (c) contained in the composition for forming a protective film (IV-1) and the film for forming a protective film may be used alone, or may be used in two or more kinds, and in the case of using two or more kinds The combination and ratio can be selected arbitrarily.

In the case of using the photopolymerization initiator (c), relative to the total content of the energy ray curable component (a0) and the energy ray curable component (a1) in the protective film forming composition (IV-1) 100 parts by mass, the content of the photopolymerization initiator (c) is preferably 0.01-20 parts by mass, more preferably 0.03-15 parts by mass, and most preferably 0.05-10 parts by mass.

(Filler (d)) When the film for protective film formation contains the filler (d), it becomes easy to adjust the thermal expansion coefficient of the protective film obtained by hardening the film for protective film formation. Furthermore, 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 can be further improved. Furthermore, when the film for protective film formation contains a filler (d), the moisture absorption rate of a protective film can be reduced, and heat dissipation can also be improved. As the filler (d), for example, a filler made of a heat-conducting material is exemplified.

The filler (d) may be either an organic filler or an inorganic filler, and an inorganic filler is preferable. Preferable inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride, etc.; beads obtained by spheroidizing the above inorganic fillers. ; Surface modified products of the above-mentioned inorganic fillers; Single crystal fibers of the above-mentioned inorganic fillers; Glass fibers, etc. Among the above, silica or alumina is preferred as the inorganic filler.

The average particle size of the filler (d) is not particularly limited, but is preferably 0.01-20 μm, more preferably 0.1-15 μm, and particularly preferably 0.3-10 μm. When the average particle size of the filler (d) is in such a range, the adhesiveness of the protective film to the object on which the protective film is to be formed can be maintained, and at the same time, the decrease in light transmittance of the protective film can be suppressed. In addition, in this specification, "average particle diameter" means the particle diameter (D50) value of 50% cumulative value in the particle size distribution curve obtained by the 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 used only by one type, or two or more types may be used, and when two or more types are used, any Choose its combination and proportion.

In the case of using the filler (d), in the composition for forming a protective film (IV-1), the ratio of the content of the filler (d) to the total content (total mass) of all components other than the solvent (that is, , 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, and particularly preferably 30 to 75% by mass, for example, 40 to 80% by mass. Either 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 becomes easier.

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

The coupling agent (e) has one of functional groups capable of reacting with functional groups contained in the energy ray curable component (a0), energy ray curable component (a1), non-energy ray curable polymer (b), etc. Compounds are preferred, and silane coupling agents are preferred. As a preferred example of the aforementioned silane coupling agent, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidyloxy Propyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyl Trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyl Methyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyl Trimethoxysilane, 3-Mercaptopropylmethyldimethoxysilane, Bis(3-triethoxysilylpropyl)tetrasulfane, Methyltrimethoxysilane, Methyltriethoxy Silane, Vinyltrimethoxysilane, Vinyltriacetyloxysilane, Imidazolesilane, etc.

The coupling agent (e) contained in the protective film forming composition (IV-1) and the protective film forming film may be used only by 1 type, or may use 2 or more types, and when 2 or more types are used, The combination and proportion thereof can be selected arbitrarily.

In the case of using the coupling agent (e), in the composition for forming a protective film (IV-1) and the film for forming a protective film, relative to the energy ray-curable component (a0), the energy ray-curable component (a1 ) and the total content of non-energy ray curable polymer (b) is 100 parts by mass, the content of coupling agent (e) is preferably 0.03-20 parts by mass, more preferably 0.05-10 parts by mass, and 0.1 ~5 parts by mass is particularly preferred. By making the above-mentioned content of the coupling agent (e) more than the above-mentioned lower limit value, the dispersibility of the filler (d) in the resin can be improved, and the adhesiveness of the film for forming a protective film to the adherend can be improved, so it can be more prominent. The effect brought by the use of the coupling agent (e) can be effectively obtained. Furthermore, since the said content of the coupling agent (e) is below the said upper limit, the generation|occurrence|production of outgassing (outgas) is suppressed further.

(Crosslinking agent (f)) By crosslinking the aforementioned energy ray curable component (a0), energy ray curable component (a1) or non-energy ray curable polymer (b) using a crosslinking agent (f), the protective film formation can be adjusted. The initial adhesion and cohesion of the film.

Examples of the crosslinking agent (f) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (that is, crosslinking agents having a metal chelate structure), aziridine An aridine type crosslinking agent (that is, a crosslinking agent having an aziridine group) and the like.

Examples of the aforementioned organic polyvalent isocyanate compounds include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, and alicyclic polyvalent isocyanate compounds (hereinafter, these compounds may be collectively referred to as "aromatic polyvalent isocyanate compounds, etc." ); trimers of the aforementioned aromatic polyvalent isocyanate compounds, etc.; isocyanurates and adducts; terminal isocyanate urethane prepolymers obtained by reacting the aforementioned aromatic polyvalent isocyanate compounds, etc., with polyol compounds Wait. The aforementioned "adduct" refers to aromatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, or alicyclic polyvalent isocyanate compounds with ethylene glycol, propylene glycol, neopentyl glycol, trimethylol Reactants of low-molecular-weight active hydrogen-containing compounds such as propane and castor oil. As an example of the aforementioned adduct, a xylylene diisocyanate adduct of trimethylolpropane as described later, etc. are mentioned. Furthermore, the term "isocyanate-terminated urethane prepolymer" refers to a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.

As the aforementioned organic polyvalent isocyanate compound, more specifically, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylene diisocyanate; 1,4-xylene diisocyanate; Isocyanate; Diphenylmethane-4,4'-diisocyanate; Diphenylmethane-2,4'-diisocyanate; 3-Methyldiphenylmethane diisocyanate; Hexamethylene diisocyanate; Isophorone Diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; polyols such as trimethylolpropane added toluene di Any one or two or more compounds of isocyanate, hexamethylene diisocyanate and xylylene diisocyanate; lysine diisocyanate, etc.

Examples of the aforementioned organic polyvalent imine compounds include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β -Aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, N,N'-toluene-2,4-bis(1-aziridinylamide)tri extended melamine, etc.

In the case of using an organic polyvalent isocyanate compound as the crosslinking agent (f), use a hydroxyl group-containing polymer as the energy ray curable component (a0), energy ray curable component (a1) or non-energy ray curable polymer Object (b) is preferred. When the crosslinking agent (f) has an isocyanate group and the energy ray curable component (a0), energy ray curable component (a1) or non-energy ray curable polymer (b) has a hydroxyl group, the crosslinking agent (f) Reaction with energy ray curable component (a0), energy ray curable component (a1) or non-energy ray curable polymer (b), can easily introduce a crosslinked structure into the film for protective film formation middle.

The crosslinking agent (f) contained in the composition for forming a protective film (IV-1) and the film for forming a protective film may be used only by 1 type, or may use 2 or more types, and when 2 or more types are used, The combination and proportion thereof can be selected arbitrarily.

In the case of using the crosslinking agent (f), in the protective film forming composition (IV-1), relative to the energy ray curable component (a0), the energy ray curable component (a1) and the non-energy ray curable The total content of the permanent polymer (b) is 100 parts by mass, and the content of the crosslinking agent (f) is preferably 0.01-20 parts by mass, more preferably 0.1-10 parts by mass, and particularly 0.5-5 parts by mass. good. Since the said content of a crosslinking agent (f) is more than the said lower limit, the effect by using a crosslinking agent (f) can be acquired more notably. Furthermore, when the said content of a crosslinking agent (f) is below the said upper limit, excessive use of a crosslinking agent (f) can be suppressed.

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

Examples of the aforementioned organic pigments and organic dyes include ammonium (Aminium) pigments, cyanine (Cyanine) pigments, merocyanine (Merocyanine) pigments, Croconium (Croconium) pigments, Squarylium pigments, Azulenium pigments, Polymethine pigments, Naphthoquinone pigments, Pyrylium pigments, Phthalocyanine pigments, Naphthalocyanine pigments, Naphthalactam pigments, Azo pigments, condensed azo pigments, Indigo pigments, Perinone pigments, Perylene pigments ) pigments, Dioxazine pigments, Quinacridone pigments, Isoindolinone pigments, Quinophthalone pigments, Pyrrole pigments, Thioindigo pigments, metal complex pigments (metal complex salt pigments), dithiol metal complex pigments, indole phenol pigments, triallyl methane ) pigments, Anthraquinone pigments, Naphthol pigments, Azomethine pigments, Benzimidazolone pigments, Pyranthrone pigments and Shilin (Threne) pigments, etc.

Examples of the aforementioned 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, and ruthenium-based pigments. , platinum pigments, ITO (indium tin oxide) pigments, ATO (antimony tin oxide) pigments, etc.

The coloring agent (g) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be used only by 1 type, or may use 2 or more types, and when using 2 or more types, you may use Any combination and proportion thereof can be selected arbitrarily.

When using a coloring agent (g), content of the coloring agent (g) in the protective film forming composition (IV-1) and the protective film forming film can be adjusted suitably according to the objective. For example, in the case of adjusting the printing visibility by controlling the content of the colorant (g) and controlling the light transmittance of the protective film, in the protective film forming composition (IV-1), relative to all the solvents The ratio of the total content (total mass) of the components to the content of the colorant (g) (that is, the content of the colorant (g) in the protective film forming film) is preferably 0.1 to 10% by mass, and 0.4 to 7.5% by mass % is preferable, and 0.8-5 mass % is especially preferable. When the said content of a coloring agent (g) is more than the said lower limit, the effect by using a coloring agent (g) can be acquired more notably. Furthermore, when the said content of a coloring agent (g) is below the said upper limit, excessive use of a coloring agent (g) can be suppressed.

(thermosetting component (h)) The thermosetting component (h) contained in the composition for forming a protective film (IV-1) and the film for forming a protective film may be used alone, or may be used in two or more kinds, and in the case of using two or more kinds, it may be Any combination and proportion thereof can be selected arbitrarily.

The thermosetting component (h) includes, for example, epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, silicone resins, etc., and epoxy thermosetting resins are preferred.

＊Epoxy thermosetting resin Epoxy thermosetting resin is composed of epoxy resin (h1) and thermosetting agent (h2). The epoxy-based thermosetting resins contained in the composition for forming a protective film (IV-1) and the film for forming a protective film may be used only by one type, or two or more types may be used, and when two or more types are used, it may be Any combination and proportion thereof can be selected arbitrarily.

・Epoxy resin (h1) Examples of the epoxy resin (h1) include known epoxy resins such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydride, o-cresol novolak epoxy resin , dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, epoxy compound with more than two functions Wait.

An epoxy resin having an unsaturated hydrocarbon group can also be used as the epoxy resin (h1). An epoxy resin having an unsaturated hydrocarbon group has higher miscibility with an acrylic resin than an epoxy resin not having an unsaturated hydrocarbon group. Therefore, by using the epoxy resin which has an unsaturated hydrocarbon group, the reliability of the package obtained using the composite sheet for protective film formation can be improved.

As an epoxy resin which has an unsaturated hydrocarbon group, the compound obtained by converting a part of the epoxy group of a polyfunctional epoxy resin into the group which has an unsaturated hydrocarbon group is mentioned, for example. Such a compound can be obtained, for example, by an addition reaction of (meth)acrylic acid or a derivative thereof with an epoxy group. In addition, as an epoxy resin which has an unsaturated hydrocarbon group, the compound which the group which has an unsaturated hydrocarbon group and the aromatic ring etc. which comprise an epoxy resin are directly bonded is mentioned, for example. The unsaturated hydrocarbon group is a polymerizable unsaturated group. As its specific example, vinyl (ethenyl, also known as vinyl), 2-propenyl (2-propenyl, also known as allyl), (formyl base) acryl group, (meth)acrylamide group, etc., preferably acryl group.

The number average molecular weight of the epoxy resin (h1) is not particularly limited, but is preferably 300 to 30,000, and preferably 400 to 10,000 from the viewpoint of the curability of the protective film forming film, and the strength and heat resistance of the protective film. Preferably, 500-3000 is particularly preferred. In this specification, unless otherwise specified, "number average molecular weight" refers to the number average molecular weight represented by the standard polystyrene equivalent value measured by gel permeation chromatography (GPC) method. The epoxy equivalent of the epoxy resin (h1) is preferably 100-1000 g/eq, more preferably 150-800 g/eq. In this specification, the so-called "epoxy equivalent" means the number of grams (g/eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and can be measured according to the method of JIS K 7236:2001.

One type of epoxy resin (h1) may be used alone, or two or more types may be used, and when two or more types are used, the combination and ratio thereof may be selected arbitrarily.

・Heat curing agent (h2) The thermal curing agent (h2) functions as a curing agent for the epoxy resin (h1). As a thermosetting agent (h2), the compound which has 2 or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. As the aforementioned functional groups, for example, phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups, and acid groups are functional groups of acid anhydrides. Phenolic hydroxyl or amino groups are preferred.

Among the thermosetting agents (h2), examples of phenolic curing agents having phenolic hydroxyl groups include polyfunctional phenolic resins, biphenols, novolak-type phenolic resins, dicyclopentadiene-type phenolic resins, arane phenolic resin, etc. Among the thermosetting agents (h2), examples of the amine curing agent having an amine group include dicyandiamide and the like.

The thermosetting agent (h2) may have an unsaturated hydrocarbon group. The thermal curing agent (h2) having an unsaturated hydrocarbon group includes, for example, a compound in which a part of the hydroxyl groups of a phenolic resin is substituted by a group having an unsaturated hydrocarbon group, an aromatic compound in which a group having an unsaturated hydrocarbon group is directly bonded to a phenolic resin. Compounds on the ring, etc. The aforementioned unsaturated hydrocarbon group in the thermosetting agent (h2) is the same as the unsaturated hydrocarbon group in the above-mentioned epoxy resin having an unsaturated hydrocarbon group.

In the case of using a phenolic curing agent as the thermal curing agent (h2), from the viewpoint of improving the peelability of the protective film from the support sheet, the thermal curing agent (h2) should have a high softening point or a high glass transition temperature. good.

In the thermosetting agent (h2), for example, the number average molecular weight of resin components such as polyfunctional phenolic resin, novolac type phenolic resin, dicyclopentadiene type phenolic resin, and aralkylphenol resin is 300 to 30,000. Preferably, 400-10000 is more preferable, and 500-3000 is especially preferable. The molecular weight of non-resin components such as bisphenol and dicyandiamide in the thermosetting agent (h2) is not particularly limited, and is preferably 60-500, for example.

The thermosetting agent (h2) can be used individually by 1 type, or 2 or more types can also be used, and when using 2 or more types, the combination and ratio can be chosen arbitrarily.

In the case of using a thermosetting component (h), in the composition for forming a protective film (IV-1) and the film for forming a protective film, the thermosetting agent (h2 ) content is preferably 0.01 to 20 parts by mass.

In the case of using a thermosetting component (h), in the composition for forming a protective film (IV-1) and the film for forming a protective film, the thermosetting The content of the component (h) (for example, the total content of the epoxy resin (h1) and the thermosetting agent (h2)) is preferably 1 to 500 parts by mass.

(curing accelerator (i)) The curing accelerator (i) is a component for adjusting the curing rate of the film for protective film formation. Preferred examples of the curing accelerator (i) include triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol. Class amines; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4- Imidazoles such as methyl-5-hydroxymethylimidazole; organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenylphosphonium tetraphenylborate and triphenylphosphine Tetraphenylboron salts such as tetraphenylborate and the like.

The curing accelerator (i) may be used alone or in two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be selected arbitrarily. In the case of using the curing accelerator (i), 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, and can be determined according to the content of the curing accelerator (i) used together. The ingredients are properly selected.

(General additive (z)) The general-purpose additive (z) can be a known additive, and can be arbitrarily selected according to the purpose, and is not particularly limited. For example, plasticizers, antistatic agents, antioxidants, and gettering agents can be listed as preferred ones. example.

The general-purpose additive (z) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be used only by one type, or two or more types may be used, and when two or more types are used, it may be Any combination and proportion thereof can be selected arbitrarily. In the case of using the general-purpose additive (z), 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 can be appropriately selected according to the purpose.

(solvent) The protective film forming composition (IV-1) preferably further contains a solvent. The protective film-forming composition (IV-1) containing a solvent has good handling properties. The aforementioned solvents are not particularly limited, and examples include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (also called 2-methylpropan-1-ol), 1- Alcohols such as butanol; 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) as a preferred example. The solvent contained in the protective film forming composition (IV-1) may be used alone or in two or more kinds. When two or more kinds are used, the combination and ratio thereof may be selected arbitrarily.

From the viewpoint that the components contained in the composition for forming a protective film (IV-1) can be mixed more uniformly, the solvent contained in the composition for forming a protective film (IV-1) is based on methyl ethyl ketone, toluene Or ethyl acetate is preferred.

In the protective film forming composition (IV-1), the total amount of all components not belonging to any one of the solvent, the non-energy ray curable polymer (b), the filler (d), and the colorant (g) content (total mass), the ratio of the total content of the energy ray-curable component (a0) and the photopolymerization initiator (c) (that is, in the film for protective film formation, relative to the non-energy ray-curable polymerization (b), filler (d) and coloring agent (g) of any one of the total content of all components, energy ray curable component (a0) and the ratio of the total content of the photopolymerization initiator (c)), It is preferably 85 mass % to 100 mass %, more preferably 90 mass % to 100 mass %, more preferably 95 mass % to 100 mass %, and may be 100 mass %. By setting the ratio of the above-mentioned total content to such a value, in the composite sheet for forming a protective film, it is possible to further suppress a change in the adhesive force between the film for forming a protective film and the support sheet over time, and a change in the adhesion between the protective film and the support sheet. Adhesion changes over time.

＜<Manufacturing method of protective film forming composition>> A composition for forming a protective film such as the composition for forming a protective film (IV-1) can be obtained by preparing each component for constituting the composition for forming a protective film. The order of addition when preparing each component is not specifically limited, You may add 2 or more types of components at the same time. In the case of using a solvent, it can be used by mixing the solvent with any of the formulation components other than the solvent and diluting the formulation components in advance, or by not mixing any of the formulation components other than the solvent. It is used by mixing the solvent and this preparation component as it is diluted beforehand. The mixing method of each component is not particularly limited at the time of preparation, and can be appropriately 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, and a method of mixing using ultrasonic waves. The temperature and time during the addition and mixing of each component are not particularly limited as long as they do not cause deterioration of each compounded component, and can be appropriately adjusted, but the temperature is preferably 15-30°C.

◇Manufacture of composite sheets for protective film formation The aforementioned composite sheet for protective film formation can be produced by laminating each of the above-mentioned layers in a corresponding positional relationship. The method of forming each layer is as described above. For example, in the case of laminating an adhesive layer on a substrate when producing a support sheet, the above-mentioned adhesive composition can be applied to the substrate and dried if necessary.

On the other hand, for example, when a film for forming a protective film is further laminated on an adhesive layer already laminated on a substrate, the composition for forming a protective film can be applied on the adhesive layer to form a protective film directly. Form a film. The film layer other than the film for protective film formation can be laminated|stacked on the adhesive layer by the same method using the composition for forming this film layer. As described above, when using any one of the compositions to form a continuous two-layer laminated structure, the composition may be further coated on the film layer formed from the aforementioned composition to form a new layer. However, the film layer laminated later among these two layers is formed in advance on the other release film using the aforementioned composition, and the exposed surface of the formed film layer on the side opposite to the side contacting the aforementioned release film and the It is preferable that the exposed surfaces of another film layer that has been formed in advance are attached to each other to form a continuous two-layer laminated structure. In this case, the composition is preferably applied to the release-treated surface of the release film. After forming the laminated structure, the release film can be removed as required.

For example, in the production of a composite sheet for forming a protective film formed by laminating an adhesive layer on a substrate and laminating a film for forming a protective film on the adhesive layer (the support sheet is a laminate of the substrate and the adhesive layer) In the case of a composite sheet for forming a protective film), the adhesive composition is applied to the base material and dried as required, and the adhesive layer is laminated on the base material first, and then a protective film is additionally coated on the release film. The composition is used and dried as necessary, and the film for protective film formation is formed on the peeling film first. Next, the exposed surface of the film for forming a protective film and the exposed surface of the adhesive layer laminated on the substrate are attached to each other, so that the film for forming a protective film is laminated on the adhesive layer, and a composite sheet for forming a protective film is obtained. .

In addition, in the case of laminating the adhesive layer on the substrate, instead of applying the adhesive composition on the substrate as described above, the adhesive composition may be applied on the release film and dried as required. , and then firstly form the adhesive layer on the release film, and then attach the exposed surface of this layer to the surface of the substrate side to laminate the adhesive layer on the substrate. In either method, the release film can be removed at any time after forming the desired laminated structure.

As described above, since any layer other than the base material constituting the protective film forming composite sheet can be formed in advance on the release film and bonded to the surface of the target layer, it can be laminated according to needs. By selecting a film layer that can be used in this way, a composite sheet for forming a protective film can be produced.

In addition, the protective film forming composite sheet is usually stored in a state where a release film is bonded to the surface of the outermost layer (eg, protective film forming film) opposite to the support sheet of the protective film forming composite sheet. Therefore, it is also possible to apply a composition for forming the outermost layer constituting a composition for forming a protective film, etc. on the release film (preferably a release-treated surface of the release film), and dry it as required, and then Firstly, the outermost film layer is formed on the release film, and then on the exposed surface on the opposite side to the release film contacting this layer, other layers are laminated by any of the above methods, and the release film is not removed. In the directly bonded state, a composite sheet for protective film formation is further obtained.

◇Manufacturing method of semiconductor wafer The above-mentioned composite sheet for forming a protective film can be applied to the manufacture of semiconductor wafers. As a method of manufacturing a semiconductor wafer at this time, for example, a manufacturing method including the step of attaching the film for forming a protective film in the composite sheet for forming a protective film to a semiconductor wafer (hereinafter sometimes referred to as "attaching step"); a step of irradiating energy rays to the protective film forming film attached to the semiconductor wafer to form a protective film (hereinafter sometimes simply referred to as "protective film forming step"); The semiconductor wafer is divided, and the above-mentioned protective film or the film for forming the protective film is cut to obtain a plurality of semiconductor wafers provided with the protective film after cutting or the film for forming the protective film after cutting (hereinafter sometimes referred to simply as "dividing step") ”); separating and picking up the semiconductor wafer provided with the cut-off protective film or the cut-off protective-film-forming film from the support sheet (hereinafter sometimes simply referred to as “pick-up step”). In the aforementioned manufacturing method, the aforementioned protective film forming step, the dividing step, and the picking-up step are performed after the aforementioned attaching step. Also, the order of performing the protective film forming step, the dividing step, and the picking-up step can be arbitrarily set according to purposes, except that the picking-up step is performed after the dividing step. That is, the aforementioned semiconductor wafer manufacturing method, as one of the modes, may be performed in the order of the aforementioned protective film forming step, the aforementioned dividing step, and the aforementioned picking-up step after the aforementioned attaching step, or may be performed in the order of the aforementioned attaching step after the aforementioned attaching step. The dividing step, the aforementioned picking-up step, and the aforementioned protective film forming step may be performed in that order, or may be performed in the order of the aforementioned dividing step, the aforementioned protective film forming step, and the aforementioned picking-up step after the aforementioned attaching step.

The thickness of the semiconductor wafer to be used as the protective film forming composite sheet is not particularly limited, but from the viewpoint of easier division into semiconductor wafers described later, it is preferably 30 to 1000 μm, and 100 to 400 μm. is better.

Hereinafter, the above-mentioned manufacturing method will be described with reference to the drawings. 4 is a schematic cross-sectional view of a method for manufacturing a semiconductor wafer according to an embodiment of the present invention. Here, the manufacturing method in the case of the composite sheet for protective film formation shown in FIG. 1 is demonstrated as an example. The manufacturing method of this embodiment (in this specification, may be referred to as "manufacturing method (1)") includes the step of attaching the film for forming a protective film in the composite sheet for forming a protective film to a semiconductor wafer. step (attaching step); step of irradiating energy rays to the protective film forming film attached to the semiconductor wafer to form a protective film (protective film forming step); dividing the aforementioned semiconductor wafer, and The protective film is cut to obtain a plurality of semiconductor wafers having the cut protective film (dividing step); the semiconductor wafer having the cut protective film is separated from the support sheet and picked up (pick-up step).

In the aforementioned attaching step of manufacturing method (1), as shown in FIG. 4( a ), protective film forming film 13 in protective film forming composite sheet 1A is attached to back surface 9 b of semiconductor wafer 9 . The protective film forming composite sheet 1A is used after removing the peeling film 15 . In the aforementioned attaching step, the film for forming a protective film may be softened by heating and attached to the semiconductor wafer 9 . In addition, here, the illustration of the bumps etc. on the surface of the circuit in the semiconductor wafer 9 is abbreviate|omitted.

After the attaching step of the manufacturing method (1), in the aforementioned protective film forming step, the protective film forming film 13 attached to the semiconductor wafer 9 is irradiated with energy rays to form a protective film 13 ′, as shown in FIG. 4(b). At this time, energy rays are irradiated to the film 13 for protective film formation via the support sheet 10 . In addition, here, the composite sheet for protective film formation after the film 13 for protective film formation becomes the protective film 13' is shown by the code|symbol 1A'. This also applies to the subsequent schemas.

In the protective film forming step, the illuminance and light quantity of the energy rays irradiating the film 13 for protective film formation are as described above.

In the protective film forming composite sheet 1A, as described above, the energy ray curable component (a0) remains stably in the protective film forming film 13 , and the movement of this component to the adjacent supporting sheet 10 is suppressed. . Therefore, the change in the composition of the film 13 for protective film formation is suppressed from the moment after 1 A of composite sheets for protective film formation are manufactured until the protective film formation process is started. Also, in the protective film forming step, the film 13 for protective film formation is sufficiently cured, and further, the protective film 13' having a high degree of curing is formed.

In the aforementioned dividing step of the manufacturing method (1), the semiconductor wafer 9 is diced and the protective film 13' is cut, as shown in FIG. 4(c), a plurality of semiconductor wafers 9 having the cut protective film 130' are obtained. '. At this time, the protective film 13' is cut (divided) at a position along the edge portion of the semiconductor wafer 9'.

In the aforementioned dividing step, a method of dicing the semiconductor wafer 9 and cutting the protective film 13' may be a known method. As such a method, for example, a method of dividing (cutting) the semiconductor wafer 9 together with the protective film 13 ′ using a dicing blade; Laser light is irradiated to form a modified layer inside the semiconductor wafer 9, and then, the semiconductor wafer 9 with the modified layer formed and the protective film 13' attached on the back surface, 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 at the same time dividing the semiconductor wafer 9 at the position of the modified layer, etc.

In the picking-up process of manufacturing method (1), as shown in FIG.4(d), the semiconductor wafer 9' provided with the cut|disconnected protective film 130' is separated from the support sheet 10, and is picked up. Here, the pick-up direction is indicated by arrow I, which also applies to the following figures. Examples of the separation tool 8 for separating the semiconductor wafer 9 ′ from the support sheet 10 together with the protective film 130 ′ include a vacuum collet and the like. In the above manner, the target semiconductor wafer 9' can be obtained as a semiconductor wafer with a protective film.

As described above, in the protective film-forming composite sheet 1A used in the production method (1), the adhesive force between the protective film-forming film 13 and the support sheet 10 is suppressed from changing over time, and the protective film is also suppressed in the same way. The adhesive force between the film 13' (cut protective film 130') and the support sheet 10 changes with time. Therefore, in the manufacturing method (1), in the aforementioned pick-up step, the reproducibility when picking up the semiconductor wafer with the protective film (semiconductor wafer 9 ′ having the cut protective film 130 ′) from the support sheet 10 is improved, And the process is stable.

In the manufacturing method (1), the dividing step is performed after the protective film forming step, but in the semiconductor wafer manufacturing method according to this embodiment, the dividing step may be performed without the protective film forming step, and After the dividing step, a protective film forming step is performed (the present embodiment may be referred to as "manufacturing method (2)"). That is, the manufacturing method (manufacturing method (2)) of this embodiment includes the following steps: a step of attaching the film for forming a protective film in the composite sheet for forming a protective film to a semiconductor wafer (attaching step); The aforementioned semiconductor wafer is divided, and the aforementioned protective film forming film is cut to obtain a plurality of semiconductor wafers having the cut protective film forming film (dividing step); the aforementioned protective film after being attached to the aforementioned semiconductor wafer Step of forming a protective film by irradiating the film for film formation (film for forming a protective film after cutting) with energy rays (protective film forming step); separating and picking up the semiconductor wafer with the protective film after cutting from the support sheet (picking step). FIG. 5 is a schematic cross-sectional view illustrating an embodiment of such a method of manufacturing a semiconductor wafer.

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

In the aforementioned dividing step of the manufacturing method (2), the semiconductor wafer 9 is diced and the protective film forming film 13 is cut, as shown in FIG. A plurality of semiconductor wafers 9'. At this time, the film 13 for protective film formation is cut|disconnected (segmented) at the position along the edge part of the semiconductor wafer 9'. The film 13 for forming a protective film after dicing is denoted by reference numeral 130 .

As described above, in the composite sheet 1A for protective film formation used in the manufacturing method (2), the adhesive force between the film 13 for protective film formation and the support sheet 10 is suppressed from changing over time. Therefore, in the manufacturing method (2), in the aforementioned dividing step, the semiconductor wafer with the film for forming a protective film (semiconductor wafer 9 ′ provided with the film for forming a protective film 130 after cutting) is suppressed from peeling off from the support sheet 10, etc. , the reproducibility of segmentation is improved, and the process is stable.

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, as shown in FIG. 5(c), and the protective film 130 is further formed on the semiconductor wafer 9'. '. The protective film forming step of the manufacturing method (2) can be performed in the same method as the protective film forming step of the above-mentioned manufacturing method (1). Also, in this step, the film 130 for forming a protective film after cutting can be sufficiently cured, thereby forming the protective film 130' having a high degree of curing. By performing this step, it is possible to obtain a semiconductor wafer with a protective film in the same state as after completion of the dividing step of the manufacturing method (1) (ie, FIG. 4( c )).

In the picking-up process of manufacturing method (2), as shown in FIG.5(d), the semiconductor wafer 9' provided with the cut|disconnected protective film 130' is separated from the support sheet 10, and is picked up. The picking-up step of the manufacturing method (2) can be performed in the same way as the picking-up step of the above-mentioned manufacturing method (1) (as shown in FIG. 4( d )). Therefore, in this step, the reproducibility when picking up the semiconductor wafer with the protective film (semiconductor wafer 9 ′ having the cut protective film 130 ′) from the support sheet 10 is improved, and the process is stable. In the above manner, the target semiconductor wafer 9' can be obtained as a semiconductor wafer with a protective film.

In the manufacturing methods (1) and (2), the pick-up step is performed after the protective film forming step, but in the semiconductor wafer manufacturing method according to this embodiment, the protective film forming step may not be performed until the pick-up step is performed. , and a protective film forming step is performed after the pick-up step (the present embodiment may be referred to as "manufacturing method (3)"). That is, the manufacturing method (manufacturing method (3)) of this embodiment includes the following steps: a step of attaching the film for forming a protective film in the composite sheet for forming a protective film to a semiconductor wafer (attaching step); The aforementioned semiconductor wafer is divided, and the aforementioned protective film forming film is cut to obtain a plurality of semiconductor wafers having the cut protective film forming film (dividing step); the semiconductor wafer having the aforementioned cut protective film forming film The wafer is separated from the support sheet and picked up (pick-up step); the film for forming a protective film after being attached to the semiconductor wafer (the film for forming a protective film after cutting and picking up) is irradiated with energy rays to form a protective film step (protective film formation step). FIG. 6 is a schematic cross-sectional view illustrating an embodiment of such a method of manufacturing a semiconductor wafer.

The aforementioned attaching step and dividing step of manufacturing method (3) can be performed in the same way as the attaching step and dividing step of manufacturing method (2) (as shown in Figure 5(a) to Figure 5(b)), Figure 6 (a) ~ Figure 6 (b) shown.

In the picking-up process of manufacturing method (3), as shown in FIG.6(c), the semiconductor wafer 9' provided with the cut|disconnected protective film 130 is separated from the support sheet 10, and is picked up. The picking-up step of the manufacturing method (3) can be performed in the same way as the picking-up step of the manufacturing methods (1) and (2) (as shown in FIG. 4( d ) and FIG. 5( d )). In addition, in this step, the reproducibility of picking up the semiconductor wafer with the protective film forming film (semiconductor wafer 9 ′ having the cut protective film forming film 130 ) from the support sheet 10 is improved, and the process is stabilized.

In the protective film forming step of the manufacturing method (3), the picked-up protective film forming film 130 is irradiated with energy rays to form a protective film 130 ′ on the semiconductor wafer 9 ′ as shown in FIG. 6( d ). The protective film forming step of the production method (3) can be formed in the same manner as in the above-mentioned production methods (1) and (2), except that it is not necessary to irradiate the protective film forming film 130 with energy rays through the support sheet 10 . step by step method. Also, in this step, the film 130 for forming a protective film after cutting can be sufficiently cured, thereby forming the protective film 130' having a high degree of curing. In the above manner, the target semiconductor wafer 9' can be obtained as a semiconductor wafer with a protective film.

In the manufacturing methods (1) to (3), as described above, as a method of dividing the semiconductor wafer 9 to obtain the semiconductor wafer 9', it is applicable to form a modified layer inside the semiconductor wafer 9, and A method of dividing the semiconductor wafer 9 at the position of the modified layer without using a dicing knife. In this case, in the aforementioned dividing step, the step of forming the modified layer inside the semiconductor wafer 9 may be performed at any stage as long as it is before the step of dividing the semiconductor wafer 9 at the position of the modified layer, For example, it can be performed at any stage such as before the sticking step, between the sticking step and the protective film forming step.

Although the manufacturing method of the semiconductor wafer in the case of using the composite sheet 1A for protective film formation shown in FIG. 1 was demonstrated so far, the manufacturing method of the semiconductor wafer of this invention is not limited to this. For example, the method for manufacturing a semiconductor wafer of the present invention can also use the composite sheets 1B to 1C for forming protective films shown in FIGS. 2 to 3 , or the composite sheets for forming protective films shown in FIGS. Semiconductor wafers are produced in the same manner for protective film forming composite sheets other than the shown protective film forming composite sheet 1A. As described above, in the case of using the protective film-forming composite sheet of other embodiments, steps may be appropriately added, changed, deleted, etc. in the above-mentioned production method based on the structural differences of these sheets to produce semiconductor wafer.

◇Manufacturing method of semiconductor device After the semiconductor wafer with protective film is obtained by the above-mentioned manufacturing method, the semiconductor wafer is flip-chip connected to the circuit surface of the substrate by a known method, and it is used as a semiconductor package. (package), and then using the semiconductor package, a target semiconductor device (not shown) can be manufactured.

One aspect of the protective film-forming composite sheet of the present invention includes a support sheet and an energy ray-curable protective film-forming film provided on the support sheet, The aforementioned protective film-forming film comprising an acrylate compound having a (meth)acryl group as an energy ray-curable component (a0), and tris-(2-(meth)propene) modified with ε-caprolactone Acyloxyethyl) isocyanurate is preferable (with respect to the total mass of components other than the solvent in the protective film forming composition (IV-1), the content is preferably 5 to 15% by mass), and contains Acrylic polymer The non-energy ray curable polymer (b) is selected from acrylic polymers formed by copolymerizing methyl acrylate and 2-hydroxyethyl acrylate, n-butyl acrylate, methyl acrylate , glycidyl methacrylate, 2-hydroxyethyl acrylate, and acrylic polymers formed by copolymerization of butyl acrylate are preferably at least one component (relative to the protective film forming composition ( The total mass of components other than the solvent in IV-1), the content of which is preferably 25 to 30% by mass), The layer in contact with the protective film-forming film in the support sheet contains at least an acrylic polymer having a structural unit derived from an alkyl (meth)acrylate as a resin component (X) having a composition consisting of (form Base) acrylic polymers with structural units derived from alkyl acrylate and structural units derived from monomers containing functional groups are preferred, and 2-ethylhexyl methacrylate and 2-hydroxyethyl acrylate A copolymer of ester is preferred (with respect to the total mass of the components constituting the layer in contact with the protective film forming film in the aforementioned support sheet, its content is preferably 100% by mass), In addition, in the composite sheet for forming a protective film, the change rate of the adhesive force between the protective film and the support sheet is preferably 5% to 30%, may be 5% to 23%, or may be 14-23%.

[Example] Hereinafter, the present invention will be described in more detail by means of specific examples. However, this invention is not limited to the Example shown below.

＜Single＞ The formal names of the abbreviated monomers are as follows. MA: methyl acrylate HEA: 2-Hydroxyethyl Acrylate BA: n-butyl acrylate GMA: glycidyl methacrylate MMA: methyl methacrylate 2 EHMA: 2-ethylhexyl methacrylate 2 EHA: 2-ethylhexyl acrylate AAc: acrylic acid HEMA: 2-Hydroxyethyl methacrylate

<Materials for the preparation of protective film-forming composition> The raw materials used to prepare the composition for protective film formation are as follows. [Energy ray curable component (a0)] (a0)-1: ε-caprolactone-modified tris-(2-acryloxyethyl)isocyanurate ("A-9300-1CL" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trifunctional based UV curable compounds).

[Non-energy ray curable polymer (b)]

(b)-1: Acrylic polymer obtained by copolymerizing MA (85 parts by mass) and HEA (15 parts by mass) (weight average molecular weight: 300,000, glass transition temperature: 6° C.).

(b)-2: Acrylic polymer obtained by copolymerizing BA (10 parts by mass), MA (70 parts by mass), GMA (5 parts by mass) and HEA (15 parts by mass) The glass transition temperature is -1°C).

(b)-3: an acrylic polymer obtained by copolymerizing BA (52 parts by mass), MMA (20 parts by mass) and HEA (28 parts by mass) (weight average molecular weight: 300,000, glass transition temperature: -22°C ).

[Photopolymerization initiator (c)]

(c)-1: 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone ("Irgacure (registered trademark) 369 manufactured by BASF Corporation) ").

[Filler (d)]

(d)-1: Silica filler (fused silica filler, average particle diameter: 8 μm).

[Coupling agent (e)]

(e)-1: 3-methacryloxypropyl trimethoxysilane ("KBM-503" by Shin-Etsu Chemical Co., Ltd., silane coupling agent).

[coloring agent (g)]

(g)-1: 32 parts by mass of phthalocyanine blue pigment (blue pigment 15:3), 18 parts by mass of isoindolinone yellow pigment (yellow pigment 139), 50 parts by mass of anthraquinone A type of red pigment (red pigment 177) is mixed so that the total amount of the above three pigments/the amount of styrene acrylic resin=1/3 (mass ratio).

[Example 1]

＜Manufacture of composite sheet for protective film formation＞ (Preparation 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 coloring agent (g)-1 is dissolved or dispersed in methyl ethyl ketone so that the content of the above components (solid content, parts by mass) becomes the value shown in Table 1, and stirred at 23°C to adjust the concentration of solid components 50% by mass of the composition for forming a protective film (IV-1). In addition, "-" described in the column containing a component in Table 1 means that the composition for protective film formation (IV-1) does not contain this component.

(Preparation of Adhesive Composition (I-4)) Toluene disulfide containing acrylic polymer (X)-1 (100 parts by mass, solid content), an isocyanate crosslinking agent ("Coronate L" manufactured by Tosoh Corporation), and trimethylolpropane were prepared. isocyanate trimer adduct) (5 parts by mass, solid content), and a non-energy ray-curable adhesive composition (I-4 )-1. The acrylic polymer (X)-1 is obtained by copolymerizing 2 EHMA (80 parts by mass) and HEA (20 parts by mass), and has a weight average molecular weight of 600,000.

(Manufacture of support sheet) In the release film ("SP-PET 381031" manufactured by Lintec Corporation, thickness 38μm) obtained by peeling one surface of a polyethylene terephthalate film with silicone treatment On the aforementioned release-treated surface, the adhesive composition (I-4)-1 obtained above was coated, and dried by heating at 120° C. for 2 minutes to form a non-energy ray curable adhesive with a thickness of 10 μm. Adhesive layer. Next, a polypropylene-based film (80 μm in thickness) as a base material was attached to the exposed surface of the adhesive layer to obtain a base material, an adhesive layer, and a release film in this order in the thickness direction of these film layers. A support sheet composed of laminated layers.

(Manufacture of composite sheets for protective film formation) A peeling film obtained by peeling one surface of a polyethylene terephthalate film with silicone treatment (the second peeling film, "SP-PET" manufactured by Lintec Co., Ltd. -382150", thickness of 38 μm) on the aforementioned release-treated surface, the protective film-forming composition (IV-1) obtained above was coated, and dried by heating at 100°C for 2 minutes to produce a thickness of It is a film for forming an energy ray curable protective film with a thickness of 25 μm. Next, the peeling-treated surface of the peeling film (the first peeling film, "SP-PET 381031" manufactured by Lintec Co., Ltd., 38 μm in thickness) was attached to the obtained film for forming a protective film without the second peeling film. 2 On the exposed surface on the side of the release film, a laminated film having a first release film on one surface of the film for forming a protective film and a second release film on the other surface is obtained.

Next, the release film was removed from the adhesive layer of the support sheet obtained above. In addition, the first release film was removed from the laminated film obtained above. Thereafter, the surface exposed by removing the above-mentioned release film in the adhesive layer and the surface exposed by removing the above-mentioned first release film in the film for forming a protective film are bonded to each other to manufacture a substrate, an adhesive The agent layer, the film for protective film formation, and the 2nd release film were laminated in this order in the thickness direction of these film layers, and the composite sheet for protective film formation which has the structure shown in FIG.

<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)) For the energy ray-curable component (a0)-1 and the non-energy ray-curable polymer (b)-1 which are components contained in the protective film forming film, and the acrylic polymer which is a component contained in the adhesive layer (X)-1, get HSP. More specifically, as described below. Acetone, cyclohexanone, toluene, 2-propanol, propylene glycol, dimethylformamide, quinoline, benzyl alcohol, ethyl benzoate, and hexane are used as solvents for confirming the solubility of the target component. , tetrachloroethylene, diethylene glycol, acetonitrile, cyclohexanol, nitrobenzene, 1-butanol, ethanol, ethyl acetate, methyl ethyl ketone, tetraethyl orthosilicate and γ-butyrolactone. The above-mentioned solvents were added to the container one at a time, and the target component (15 mg) was added to the solvent (2 mL) at a temperature stabilized at 23° C., and the container was capped and sealed. The contents were mixed by inverting the sealed container 50 times, then the container (in other words, the aforementioned intermediate mixture) was left to stand for 4 hours, and then the container was inverted 50 times in the same manner as above to mix the contents (in other words, the aforementioned intermediate mixture), then the container (in other words, the resulting final mixture) was allowed to stand for 1 day. During the above period, these steps of mixing and standing were carried out at a temperature of 23°C. Next, it was immediately visually confirmed whether or not the target component in the aforementioned final mixture was dissolved. Furthermore, even when only a small amount of insoluble matter (undissolved residue) of the target component was observed in the aforementioned final mixture, the target component was still judged as "insoluble", whereas none was observed at all in the aforementioned final mixture When the target component is insoluble, the target component is judged as "dissolved".

Next, using the analysis software "HSPiP (version 4.1)", input the HSP of all solvents and the above judgment results to obtain the HSP of the target component.

(Obtaining R _23A and R _13A ) From the obtained HSP, R _23A and R _13A were further obtained. The results are shown in Table 1.

(Obtain the change rate of the adhesive force between the protective film and the support sheet) The composite sheet for protective film formation obtained by the above-mentioned method was cut into the strip shape whose width of all layers is 25 mm. Then, the second peeling film was removed from the film for forming a protective film in the composite sheet for forming a protective film after cutting, and the exposed surface of the film for forming a protective film was attached to a 6-inch silicon wafer ( thickness of 300μm) on a #2000 grinding surface. At this time, the film for protective film formation was heated at 70 degreeC, and it stuck.

After that, by using an ultraviolet irradiation device ("RAD 2000m/8" manufactured by Lintec Corporation), under the conditions of an illumination intensity of 200mW/cm ² and a light intensity of 200mJ/cm ² , through the above-mentioned substrate and the adhesive The agent layer irradiated ultraviolet rays three times to the film for protective film formation to harden the film for protective film formation into a protective film, and a test piece with a protective film was obtained.

One hour after the production of the protective film-forming composite sheet, the time-lapsed adhesive force between the protective film and the support sheet (adhesive layer) was measured for this test piece. The time-lapse adhesive force between the protective film and the support sheet (adhesive layer) was measured by the following method. That is, under the condition of 23°C, using a precision universal testing machine (manufactured by Shimadzu Corporation "Autograph AG-IS"), at a peeling speed of 300mm/min, the support sheet was peeled off from the protective film attached to the aforementioned silicon wafer. The peeling is pulled apart in such a way that the surfaces of the protective film and the support sheet (in other words, the adhesive layer) that were in contact with each other form an angle of 180° to each other, that is, a so-called 180° peeling is performed. Also, the peeling force (N/25 mm) at this time was measured, and this measured value was defined as the pre-adhesion force over time between the protective film and the support sheet.

Furthermore, a test piece was separately produced by the same method as above, and after 48 hours after the composite sheet for forming a protective film was produced, the protective film and the support sheet were measured in the same manner as in the case of the above-mentioned adhesive force over time ( Adhesive force between adhesive layers) after time. In addition, the produced test piece was left still and stored at 21 to 25° C. and a relative humidity of 45 to 65% until the time-lapse adhesive force was measured.

Next, the rate of change (%) of the adhesive force between the protective film and the support sheet (adhesive layer) was obtained from the following formula. The results are shown in Table 1. [Change rate of adhesive force (%)]={[(adhesion force before time-lapse N/25mm)]-[(adhesion force after time-lapse N/25mm)]}/[(adhesion force before time-lapse N/25mm) ]x100

<Manufacture and evaluation of composite sheet for protective film formation> [Examples 2-3, Comparative Examples 1-2] Except that either or both of the types of ingredients required for the preparation of the protective film-forming composition (IV-1) and the types of the adhesive composition are changed as shown in Table 1, the rest are as follows: In the same manner as in Example 1, a composite sheet for forming a protective film was manufactured and evaluated. The results are shown in Table 1.

In addition, in Table 1, "adhesive composition (I-4)-2" means containing acrylic polymer (X)-2 (100 parts by mass, solid content), and isocyanate crosslinking agent (To "Coronate L" manufactured by Cao Co., trimethylolpropane toluene diisocyanate trimer adduct) (5 parts by mass, solid content), and also contains methyl ethyl ketone as a solvent, the solid content concentration is 30% by mass of non-energy ray curable adhesive composition. The acrylic polymer (X)-2 is a polymer obtained by copolymerizing 2 EHMA (70 parts by mass) and HEA (30 parts by mass), and has a weight average molecular weight of 600,000. Furthermore, the term "adhesive composition (I-4)-4" means an acrylic polymer (X)-4 (100 parts by mass, solid content) and an isocyanate crosslinking agent (manufactured by Tosoh Corporation) "Coronate L", trimethylolpropane toluene diisocyanate trimer adduct) (5 parts by mass, solid content), and also contains methyl ethyl ketone as a solvent, the solid content concentration is 30 mass% or less Non-energy ray hardening adhesive composition. The aforementioned acrylic polymer (X)-4 is obtained by copolymerizing 2 EHA (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 of polymers.

[Table 1]

It is clear from the above results that in Examples 1 to 3, R _23A is 5.8 or less (5.5 to 5.8), and R _13A is 2.5 or more (2.5 to 4.0). Furthermore, the rate of change in the adhesive force between the protective film and the support sheet (adhesive layer) is as low as 23% or less (14 to 23%), suppressing the aforementioned change in the adhesive force over time.

In comparison, in Comparative Example 1, R _13A was 2.1, and in Comparative Example 2, R _23A was 6.7. In these comparative examples, the rate of change in the adhesive force between the protective film and the support sheet (adhesive layer) was as high as 34% or more (34 to 47%), so the aforementioned change in adhesive force over time was not suppressed. The reason for obtaining such a result in Comparative Example 1 is considered to be that the combination of the energy ray-curable component (a0)-1 and the acrylic polymer (X)-4 in the composite sheet for forming a protective film does not For proper sake. On the other hand, the reason for obtaining such a result in Comparative Example 2 is considered to be that, in the composite sheet for forming a protective film, the energy ray-curable component (a0)-1 and the non-energy ray-curable polymer (b) The combination of -3 is not appropriate for the sake.

From the results of these examples and comparative examples, it can be clearly confirmed that the change of the adhesive force between the protective film and the support sheet over time is affected by R _23A and R _13A . [industrial availability]

The present invention can be applied to the manufacture of semiconductor devices.

1A, 1A', 1B, 1C‧‧‧Composite sheet for protective film formation 9‧‧‧semiconductor wafer 9b‧‧‧The back surface of the semiconductor wafer 9'‧‧‧semiconductor chip 10‧‧‧Support piece 10a‧‧‧The surface of the support sheet (1st surface) 11‧‧‧Substrate 11a‧‧‧The surface of the substrate (1st surface) 12‧‧‧adhesive layer 12a‧‧‧The surface of the adhesive layer (1st surface) 13.23‧‧‧Film for protective film formation 13a, 23a‧‧‧The surface of the protective film forming film (1st surface) 13b‧‧‧The surface of the protective film forming film (second surface) 13'‧‧‧Protective film 130‧‧‧cut protective film forming film 130'‧‧‧cut protective film 15‧‧‧Peeling film 16‧‧‧adhesive layer for jig 16a‧‧‧The surface of the adhesive layer for jigs

[ Fig. 1] Fig. 1 is a schematic cross-sectional view of a composite sheet for forming a protective film according to an embodiment of the present invention. [ Fig. 2] Fig. 2 is a schematic cross-sectional view of a composite sheet for forming a protective film according to an embodiment of the present invention. [ Fig. 3 ] is a schematic cross-sectional view of a composite sheet for forming a protective film according to an embodiment of the present invention. [ Fig. 4] Fig. 4 is a schematic cross-sectional view of a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [ Fig. 5] Fig. 5 is a schematic cross-sectional view of a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [ Fig. 6] Fig. 6 is a schematic cross-sectional view of a method of manufacturing a semiconductor wafer according to an embodiment of the present invention.

1A‧‧‧Composite sheet for protective film formation

10‧‧‧Support piece

10a‧‧‧The surface of the supporting sheet (the first surface)

11‧‧‧Substrate

11a‧‧‧The surface of the substrate (the first surface)

12‧‧‧adhesive layer

12a‧‧‧The surface of the adhesive layer (the first surface)

13‧‧‧Film for protective film formation

13a‧‧‧The surface of the film for protective film formation (1st surface)

15‧‧‧Peeling film

16‧‧‧adhesive layer for jig

16a‧‧‧The surface of the adhesive layer for jigs

Claims (3)

A composite sheet for forming a protective film, which is a composite sheet for forming a protective film comprising a support sheet and an energy ray curable protective film forming film provided on the support sheet, wherein the protective film forming film contains an energy ray curable film. The active component (a0) and the non-energy ray curable polymer (b), the layer of the support sheet in contact with the protective film forming film contains a resin component (X), the energy ray curable component (a0) and the aforementioned The HSP distance R _23A between the non-energy ray-curable polymers (b) is greater than 0 and 6.5 or less, and the HSP distance R _13A between the energy ray-curable component (a0) and the aforementioned resin component (X) is 2.2 Above, HSP is expressed as Hansen solubility parameter. The composite sheet for forming a protective film according to Claim 1 of the patent application, wherein the support sheet includes a base material and an adhesive layer provided on the base material, and the adhesive layer is the same as the film for forming a protective film contact layer. A method for manufacturing a semiconductor wafer, comprising: attaching the film for forming a protective film in the composite sheet for forming a protective film as described in item 1 or 2 of the scope of the patent application to a semiconductor wafer; The film for forming a protective film after being rounded is irradiated with energy rays to form a protective film; the semiconductor wafer is divided, and the protective film or the film for forming a protective film is cut to obtain a protective film or a dicing film after cutting. A plurality of semiconductor wafers comprising the cut protective film forming film; and separating and picking up the semiconductor wafer having the cut protective film or the cut protective film forming film from the support sheet.

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