CN118256177A

CN118256177A - Composition for forming adhesive layer, laminate, method for producing adhesive layer, method for producing laminate, and method for treating laminate

Info

Publication number: CN118256177A
Application number: CN202311818811.8A
Authority: CN
Inventors: 佐藤恵; 内田一幸; 滑川崇平; 高野正臣
Original assignee: Nippon Steel and Sumikin Chemical Co Ltd
Current assignee: Nippon Steel Chemical and Materials Co Ltd
Priority date: 2022-12-27
Filing date: 2023-12-27
Publication date: 2024-06-28

Abstract

The invention relates to a composition for forming an adhesive layer, a laminate, a method for producing an adhesive layer, a method for producing a laminate, and a method for processing the laminate, and aims to provide a composition for forming an adhesive layer, which can easily peel an adherend by irradiation with 355nm laser light and has good patterning properties before adhesion. The present invention relates to a composition for forming an adhesive layer, which is used for forming an adhesive layer by adhering a support and an adherend together and separating the support and the adherend by irradiation of light. The adhesive layer-forming composition contains (A) an alkali-soluble resin containing an unsaturated group having an ultraviolet-absorbing group, (B) a polymerizable compound containing an unsaturated group having no ultraviolet-absorbing group, and (C) a photopolymerization initiator.

Description

Composition for forming adhesive layer, laminate, method for producing adhesive layer, method for producing laminate, and method for treating laminate

Technical Field

The present invention relates to an adhesive layer forming composition, a laminate, a method for producing an adhesive layer, a method for producing a laminate, and a method for processing a laminate.

Background

In recent years, with the increasing functionality of digital devices and the like, the thickness of mounted flexible displays, semiconductor chips (chips) and the like has been reduced. However, flexible displays, such as semiconductor chips (chips), which are reduced in strength due to the reduction in thickness, are difficult to transport by conventional automated transportation.

Therefore, a method of safely and easily transporting a thinned flexible display, a semiconductor chip (chip), or the like has been studied. For example, a method of fixing a laminate of an adherend such as a flexible display and a semiconductor chip (chip) on a light-transmissive support such as a glass substrate via an adhesive layer and conveying the flexible display and the semiconductor chip (chip) together with the laminate has been studied. In this case, the adhesive layer may be formed of a composition which is degraded or decomposed by irradiation light and has a reduced adhesive strength. When the adhesive layer is used, light can be irradiated from the support side to the adhesive layer after the transfer, whereby the adherend can be separated (peeled) from the support and transferred to another substrate (laser peeling process, hereinafter simply referred to as "LLO process"), for example.

Patent document 1 describes a composition in which a curable resin having a9, 9' -diphenylfluorene (cardo) structure and an unsaturated group is dissolved in a solvent as an adhesive composition capable of performing an LLO process. Patent document 1 describes that the composition is applied to a glass support and heated, and the formed adhesive layer can be easily peeled from the adherend by irradiating the adherend with a laser beam having a wavelength of 308 nm. Patent document 1 describes that a composition obtained by dissolving a resin having a benzotriazole structure in a solvent is applied to a glass support and heated, and the formed adhesive layer can be easily peeled from the adherend by irradiating the adherend with a laser beam having a wavelength of 355 nm.

Patent document 2 describes a photosensitive composition as the adhesive composition, which includes a curable resin containing a carbo (cardo) structure and an unsaturated group, a photopolymerizable monomer, and a light absorber (carbon black). Patent document 2 describes that the photosensitive composition is applied to a glass support and the cured film formed by heating is excellent in adhesion to an adherend.

[ Prior Art literature ]

[ Patent literature ]

Patent document 1: japanese patent application laid-open No. 2012-106486

Patent document 2: japanese patent application laid-open No. 2018-001604.

Disclosure of Invention

[ Problem to be solved by the invention ]

Conventionally, development of an adhesive used in an LLO process has been studied centering on a composition capable of peeling off an adherend by a short wavelength laser (wavelength 248nm, 266nm, etc.) having high energy and excellent processability. However, in order to perform laser processing at these wavelengths, it is necessary to use a support made of an expensive material such as quartz glass or a sapphire substrate having high transmittance in the short wavelength region. Therefore, the conventional LLO process has a problem that the running cost is high. Therefore, in order to use a cheaper transparent glass, development of an adhesive layer capable of peeling an adherend by a laser light of a longer wavelength (for example, 355nm or the like) has been demanded.

Further, the present inventors have found that, by patterning an adhesive layer with an adhesive composition after forming the adhesive layer and before bonding, the adhesive layer formed of a curable composition can be formed only in the bonded portion of the support and the adherend, and peeling failure or displacement of the adherend when separating the support and the adherend can be suppressed.

However, conventionally known adhesive compositions have high transmittance at 355nm, and it is difficult to peel off an adherend by irradiation with laser light or patterning is not preferable. For example, the composition described in patent document 1 is expected to improve the absorption efficiency of 335nm laser light due to a resin having a benzotriazole structure. However, when an alkali-soluble resin is blended to impart alkali developability to the composition described in patent document 1, the amount of the resin blended needs to be increased to ensure alkali developability, and the relative amount of the resin having a benzotriazole structure is reduced, so that the absorption efficiency of 355nm laser light cannot be improved. On the other hand, if the amount of the above-mentioned resin blended is increased in order to improve the absorption efficiency of 355nm laser light, the amount of the alkali-soluble resin blended becomes small, and the patterning property is not good.

The present invention has been made in view of the above, and an object of the present invention is to provide an adhesive layer forming composition which can be easily peeled off an adherend by irradiation with 355nm laser light and has good patterning before adhesion, a laminate obtained by adhering a support and an adherend using the adhesive layer forming composition, a method for producing the adhesive layer and the laminate, and a method for processing the laminate.

[ Means for solving the problems ]

In order to solve the above problems, one aspect of the present invention relates to the adhesive layer forming composition described in the following [1] to [9 ].

[1] An adhesive layer forming composition for forming an adhesive layer which is formed by bonding a support and an adherend together and which is capable of separating the support and the adherend by irradiation with light, the adhesive layer forming composition comprising:

(A) An alkali-soluble resin containing an unsaturated group and having an ultraviolet absorbing group;

(B) An unsaturated group-containing polymerizable compound having no ultraviolet absorbing group; and

(C) A photopolymerization initiator is used as a raw material,

The content of the component (A) is 10 mass% or more relative to the total mass of the solid matters.

[2] The adhesive layer-forming composition according to [1], wherein the component (A) is an acrylic copolymer having a weight average molecular weight of 1000 to 100000 and an acid value of 20 to 200mg KOH/g.

[3] The composition for forming an adhesive layer according to any one of [1] to [2], wherein the molar absorption coefficient of the component (A) at a wavelength of 355nm is 3000 or more.

[4] The composition for forming an adhesive layer according to any one of [1] to [3], wherein the unsaturated group-containing polymerizable compound (B) contains an unsaturated group-containing polymerizable compound (B1) having no alkali-soluble group.

[5] The composition for forming an adhesive layer according to [4], wherein the component (B1) contains an alkylene oxide-modified or lactone-modified compound having a (meth) acryloyl group.

[6] The composition for forming an adhesive layer according to any one of [1] to [5], wherein the unsaturated group-containing polymerizable compound (B) contains (B2) an alkali-soluble resin,

The component (B2) is a resin having a weight average molecular weight of 1000 to 40000.

[7] The composition for forming an adhesive layer according to [6], wherein the alkali-soluble resin (B2) is a resin represented by the following general formula (B2-1).

( In the formula (B2-1), ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of hydrogen atoms constituting Ar may be substituted with a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group. R ₁ is independently an alkylene group having 2 to 4 carbon atoms. l is independently a number from 0 to 3. G is independently a (meth) acryloyl group, or a substituent represented by the following general formula (B2-2) or the following general formula (B2-3). Y is a 4-valent carboxylic acid residue. Z is independently a hydrogen atom or a substituent represented by the following general formula (B2-4), and at least one of Z is a substituent represented by the following general formula (B2-4). N is a number having an average value of 1 to 20 )

( In the formulae (B2-2) and (B2-3), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or an alkylarylene group having 2 to 10 carbon atoms, R ₄ is a saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number of 0 to 10. Indicating the bonding site )

( In the formula (B2-4), W is a 2-valent or 3-valent carboxylic acid residue, and m is a number of 1 or 2. Indicating the bonding site )

[8] The adhesive layer-forming composition according to any one of [1] to [7], which contains an oxime ester-based photopolymerization initiator as (C) a photopolymerization initiator.

[9] The composition for forming an adhesive layer according to any one of [1] to [8], wherein the ultraviolet absorbing group is a functional group having a benzotriazole structure or a triazine structure.

In order to solve the above problems, another aspect of the present invention relates to a laminate of the following [10 ].

[10] A laminate is provided with:

A support body;

an adherend; and

An adhesive layer comprising a cured product of the adhesive layer forming composition according to any one of [1] to [9] disposed between the support and the adherend.

In order to solve the above-described problems, still another aspect of the present invention relates to a method for producing an adhesive layer of the following [11 ].

[11] A method for manufacturing an adhesive layer comprises the following steps:

A step of applying the composition for forming an adhesive layer according to any one of [1] to [9] to at least one surface of a support and an adherend;

exposing the adhesive layer through a photomask; and

And developing the exposed adhesive layer.

In order to solve the above-described problems, still another aspect of the present invention relates to a method for producing a laminate of the following [12 ].

[12] A method for producing a laminate comprising the step of adhering the support to the adherend via the adhesive layer produced by the method for producing an adhesive layer described in [11 ].

In order to solve the above-described problems, still another aspect of the present invention relates to a method for treating an adhesive layer of the following [13 ].

[13] A method for processing a laminate, comprising the steps of:

A step of preparing the laminate as described in [10] or the laminate manufactured by the manufacturing method as described in [12 ]; and

And a step of separating the support and the adherend by irradiating the adhesive layer included in the laminate with light.

[ Efficacy of the invention ]

The present invention provides an adhesive layer forming composition which can be easily peeled off an adherend by irradiation with 355nm laser light and has good patterning properties before adhesion, a laminate formed by adhering a support and an adherend using the adhesive layer forming composition, a method for producing the adhesive layer and the laminate, and a method for treating the laminate.

Detailed Description

The following describes embodiments of the present invention, but the present invention is not limited to the following embodiments. In the present specification, the contents of the components are not described below in decimal places when the first decimal place is 0. In addition, the compounds, functional groups, or structures exemplified below may be used in combination of only 1 of the exemplified compounds, functional groups, or structures, unless otherwise specified.

In the present specification, "(meth) acrylic" means the sum of acrylic acid and methacrylic acid, and "(meth) acryl" means the sum of acryl and methacryl, and means one or both of these.

1. Composition for forming adhesive layer

The curable adhesive layer-forming composition (hereinafter referred to as "curable composition") according to one embodiment of the present invention comprises:

(C) A photopolymerization initiator.

The components that the curable composition may contain are described below.

1-1. (A) an alkali-soluble resin having an ultraviolet absorbing group and containing an unsaturated group

(A) An alkali-soluble resin containing an unsaturated group having an ultraviolet-absorbing group (hereinafter, also simply referred to as "component (a)") is a resin having an ultraviolet-absorbing group and a polymerizable unsaturated group and exhibiting alkali solubility.

(A) The component (A) has an ultraviolet absorbing group, so that the cured product is easily absorbed by ultraviolet rays, and the deterioration or decomposition of the cured product by irradiation with 355nm laser light can be promoted. Thus, the adherend can be peeled off more easily by irradiating with laser light. Further, since the component (a) is an alkali-soluble resin containing a polymerizable unsaturated group (more preferably, a (meth) acryl group) and an alkali-soluble group (carboxyl group or the like), patterning by photolithography can be performed before the application to the support or adherend with respect to the curable composition. Thus, the adhesive layer formed by the curable composition is formed only on the adhesive portion of the support and the adherend, and peeling failure or displacement of the adherend when separating the support and adherend can be suppressed.

(A) The content of the component (A) is 10% by mass or more relative to the total mass of the solid matters. (A) When the content of the component is 10% by mass or more, the adhesive layer is likely to absorb ultraviolet rays, and deterioration or decomposition of the cured product by irradiation with a 355nm laser beam can be more effectively promoted. (A) The content of the component is preferably 10 mass% or more and 90 mass% or less, more preferably 20 mass% or more and 80 mass% or less, still more preferably 25 mass% or more and 60 mass% or less, still more preferably 35 mass% or more and 60 mass% or less, and particularly preferably 45 mass% or more and 60 mass% or less, relative to the total mass of the solid matter. When the content of the component (a) is 90 mass% or less, the relative amount of other components in the curable composition becomes large, and the adhesive layer characteristics such as adhesive strength, pattern forming property, durability and the like can be improved.

(A) The component (a) may be, for example, a (meth) acrylic copolymer obtained by combining any or all of the following structural units (AA) to (AE) derived from different monomers. The (meth) acrylic copolymer contains at least the structural unit (AA), the structural unit (AB) and the structural unit (AC) of these, or contains at least the structural unit (AA) and the structural unit (AD).

(AA) structural unit having ultraviolet absorbing group

(AB) structural units having a polymerizable unsaturated group and having no carboxyl group

(AC) structural unit having carboxyl group and having no polymerizable unsaturated group

(AD) structural units having a polymerizable unsaturated group and a carboxyl group

(AE) structural unit not having ultraviolet absorbing group, polymerizable unsaturated group and carboxyl group

The structural unit (AA) is a structural unit having an ultraviolet absorbing group. The structural unit (AA) may have the above ultraviolet absorbing group in the main chain or side chain of the (meth) acrylic copolymer, but from the viewpoint of ease of production of the (meth) acrylic copolymer, it is more preferable to have the structural unit (AA) in the side chain.

In addition, from the viewpoint of improving the ultraviolet absorption energy of the (meth) acrylic copolymer, the structural unit (AA) is more preferably a structural unit derived from a monomer having a molar absorptivity of 3000 or more at a wavelength of 355 nm. From the same point of view, the structural unit (AA) is more preferably a structural unit derived from a monomer having a molar absorptivity of 3000 to 100000 at a wavelength of 355nm, still more preferably a structural unit derived from a monomer having 4000 to 90000, and particularly preferably a structural unit derived from a monomer having 5000 to 80000.

The ultraviolet absorbing group contains a functional group such as a benzotriazole structure, a diphenyl ketone structure (hereinafter, simply referred to as a "substituted diphenyl ketone structure") in which a part of a hydrogen atom contained in a benzene ring is substituted with a hydroxyl group, a triazine structure, a salicylic acid structure, a benzoate structure, a cinnamic acid derivative structure, a diphenyl sulfoxide structure, a diphenyl sulfone structure, a diphenyl structure, a diphenylamine structure, a naphthalene derivative structure, a structure based on anthracene or a derivative thereof, a structure having a dinaphthyl structure, or a structure having a phenanthroline structure. Among these, a functional group having a benzotriazole structure, a substituted benzophenone structure or a triazine structure is more preferable, a functional group having a benzotriazole structure or a triazine structure is more preferable, and a functional group having a benzotriazole structure (hydroxyphenyl benzotriazole structure) is still more preferable in terms of efficiently absorbing ultraviolet rays at 355 nm.

Examples of the functional group having a benzotriazole structure include: functional groups derived from compounds such as 2- (2 '-hydroxy-phenyl) benzotriazole, 2- (2' -hydroxy-5 '-methylphenyl) benzotriazole, 2- (2' -hydroxy-5 '-tert-butylphenyl) benzotriazole, 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) benzotriazole, 2- (2 '-hydroxy-3' -tert-butyl-5 '-methylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3', 5 '-di-tert-pentylphenyl) benzotriazole, 2- (2' -hydroxy-4 '-octyloxyphenyl) benzotriazole, 2- {2' -hydroxy-3 '- (3 ",4",5",6" -tetrahydrophthalimidomethyl) -5' -methylphenyl } benzotriazole, and C7-C9-alkyl-3- [3- (2H-benzotriazol-2-yl) -5- (1, 1-dimethylethyl) -4-hydroxyphenyl ] propyl ether.

Examples of the functional group having a substituted diphenyl ketone structure include: functional groups derived from the structures of compounds such as 4-dihydroxydiphenyl ketone, 2-hydroxy-4-methoxydiphenyl ketone, 2 '-dihydroxy-4-methoxydiphenyl ketone, 2-hydroxy-4-methoxy-2' -carboxydiphenyl ketone, 2-hydroxy-4-methoxy-5-sulfodiphenyl ketone trihydrate, 2 '-dihydroxy-4, 4' -dimethoxydiphenyl ketone, 2-hydroxy-4-octyloxydiphenyl ketone, 2-hydroxy-4-octadecyloxydiphenyl ketone, sodium 2,2 '-dihydroxy-4, 4' -dimethoxy-5-sulfodiphenyl ketone, 2', 4' -tetrahydroxydiphenyl ketone, 4-dodecyloxy-2-hydroxydiphenyl ketone, 5-chloro-2-hydroxydiphenyl ketone, and hydroxydodecyl diphenyl ketone.

Examples of the functional group having a triazine structure include: functional groups derived from the structure of 2, 4-bis (2, 4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl) -1,3, 5-triazine, 2- [4 ((2-hydroxy-3-dodecyloxypropyl) -oxy) -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- [4- ((2-hydroxy-3-tridecyloxypropyl) -oxy) -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, and the like.

The structural unit (AA) preferably does not have a polymerizable unsaturated group. In addition, the structural unit (AA) preferably has no carboxyl group.

The structural unit (AB) is a structural unit having a polymerizable unsaturated group. However, in the present specification, the structural unit having both a polymerizable unsaturated group and a carboxyl group is the structural unit (AD), and is not contained in the structural unit (AB).

Examples of the above-mentioned polymerizable unsaturated group include vinyl group, allyl group, and (meth) acryl group. Of these, (meth) acryl is more preferable.

The polymerizable unsaturated group is preferably a side chain grafted to the structural unit (AB). In other words, the polymerizable unsaturated group is more preferably a side chain bonded to the structural unit (AB) via a linking group or a linking structure generated at the time of grafting. Examples of the above-mentioned linking group or linking structure include an ester bond, a urethane bond, an epoxy acrylate residue and the like. Among these, the polymerizable unsaturated group is preferably grafted to a side chain via a urethane bond or an epoxy acrylate residue because of easy grafting. The polymerizable unsaturated group is preferably grafted to a side chain via a urethane bond in order to further improve the compatibility of the (meth) acrylic copolymer with other alkali-soluble resins (for example, alkali-soluble resins having a fluorene skeleton), and is preferably grafted to a side chain via an epoxy acrylate residue in order to further facilitate adjustment of the development rate.

The structural unit (AB) is preferably not provided with an ultraviolet absorbing group.

The structural unit (AC) is a structural unit having a carboxyl group. However, in the present specification, the structural unit having both a carboxyl group and a polymerizable unsaturated group is the structural unit (AD), and is not included in the structural unit (AC).

The above carboxyl group may be a functional group derived from a monomer (e.g., (meth) acrylic acid or the like) which is a material belonging to the structural unit (AC), or may be grafted to a side chain in the structural unit (AC). In other words, the carboxyl group may be bonded to a side chain in the structural unit (AC) via a linking group or a linking structure generated at the time of grafting. The above-mentioned carboxyl group is more preferably a side chain grafted in the structural unit (AC) from the viewpoint of easier adjustment of the development speed. Examples of the above-mentioned linking group or linking structure include an ester bond, a urethane bond, an epoxy acrylate residue and the like. Among these, the carboxyl group is more preferably grafted to the side chain via a urethane bond or an epoxy acrylate residue in view of easy grafting, and the carboxyl group is more preferably grafted to the side chain via an ester bond in view of faster development.

In addition, the structural unit (AC) preferably has no ultraviolet absorbing group.

The structural unit (AD) is a structural unit having a polymerizable unsaturated group and a carboxyl group. The polymerizable unsaturated group is a functional group described as the structural unit (AB).

The polymerizable unsaturated group and the carboxyl group are preferably both grafted to a side chain in the structural unit (AD). In other words, the polymerizable unsaturated group is more preferably a side chain bonded to the structural unit (AD) via a linking group or a linking structure generated at the time of grafting. Examples of the above-mentioned linking group or linking structure include an ester bond, a urethane bond, an epoxy acrylate residue and the like. For example, after the skeleton of the structural unit (AD) is formed by copolymerization of a monomer having a glycidyl group or an alicyclic epoxy group, the skeleton is reacted with a monomer having a polymerizable unsaturated group and a carboxyl group, and the polymerizable unsaturated group is grafted by formation of an epoxy acrylate. In addition, a hydroxyl group generated by the formation of an epoxy acrylate may be reacted with a polycarboxylic acid or an anhydride thereof and joined to a carboxyl group, whereby a structural unit (AD) may be formed. In the structural unit (AD) formed as described above, the polymerizable unsaturated group and the carboxyl group are grafted to a side chain via an epoxy acrylate residue, and the carboxyl group is grafted to a side chain via an ester bond. Grafting of the ester bond and urethane bond can also be performed by publicly known methods.

The structural unit (AE) is a structural unit arbitrarily introduced for the purpose of adjusting the molecular weight, adjusting the amount of each functional group of an ultraviolet absorbing group, a polymerizable unsaturated group, and a carboxyl group, and the like.

The structural unit (AE) may be a structural unit derived from a monomer having no functional group. In order to adjust the physical properties of the (meth) acrylic copolymer, the functional group may be a structural unit to which a functional group different from the functional groups is grafted.

The structural units may be alkylene oxide-modified or lactone-modified.

The (meth) acrylic copolymer may be a copolymer containing the structural unit (AA), the structural unit (AB) and the structural unit (AC) as essential structural units and optionally containing the structural unit (AD) and the structural unit (AE), or a copolymer containing the structural unit (AA) and the structural unit (AD) as essential structural units and optionally containing the structural unit (AB), and optionally containing the structural unit (AC) and the structural unit (AE). The (meth) acrylic copolymer having the structural unit (AA), the structural unit (AB) and the structural unit (AC) as the essential structural units does not require a step for introducing the structural unit (AD), and thus the synthesis is easy. The amount of each functional group of the (meth) acrylic copolymer having the structural unit (AA) and the structural unit (AD) as essential structural units can be easily adjusted by the structural unit (AD), and thus the development speed can be easily adjusted.

The weight average molecular weight (Mw) of the (meth) acrylic copolymer is preferably 1000 to 100000, more preferably 5000 to 70000, still more preferably 10000 to 50000. When the weight average molecular weight (Mw) is 1000 or more, the adhesion when used as a composition for forming an adhesive layer can be improved. In addition, when the weight average molecular weight (Mw) is 100000 or less, the solution viscosity of the curable composition suitable for application can be easily adjusted, and the adhesion can be easily improved while the application is performed in a short time. The weight average molecular weight (Mw) of the (meth) acrylic acid copolymer may be a polystyrene equivalent measured by Gel Permeation Chromatography (GPC) (HLC-8220 GPC, manufactured by TOSOH Co., ltd.).

In the (meth) acrylic copolymer, the proportion of the structural unit (AA) is preferably 0.1 mol% or more and 90 mol% or less, more preferably 0.1 mol% or more and 89 mol% or less, still more preferably 1 mol% or more and 85 mol% or less, and particularly preferably 5 mol% or more and 80 mol% or less, based on 100 mol% of the total structural units. The proportion of the structural unit (AA) is 0.1 mol% or more, whereby the cured product is easily absorbed by ultraviolet rays, and the deterioration or decomposition of the cured product by irradiation with 355nm laser light can be more effectively promoted. By setting the proportion of the structural unit (a) to 90 mol% or less, the amount of functional groups other than the ultraviolet absorbing group contained in the (meth) acrylic copolymer can be increased, and the hardness, alkali solubility, and the like of the adhesive layer can be sufficiently improved.

The molar absorptivity of component (A) at a wavelength of 355nm is preferably 3000 or more and 90000 or less. More preferably 4000 or more and 80000 or less, still more preferably 5000 or more and 50000 or less. The absorbance of light having a wavelength of 355nm is preferably 0.10 or more, more preferably 0.10 or more and 1.5 or less, still more preferably 0.15 or more and 1.3 or less. When the molar absorptivity is 3000 or more, the adhesive layer is likely to absorb ultraviolet light, and deterioration or decomposition of the cured product by irradiation with 355nm laser light can be more effectively promoted. If the molar absorptivity is 90000 or less, the exposure sensitivity can be maintained, and thus a pattern can be formed. The molar absorptivity was calculated by measuring the absorbance of an acetonitrile solution having a concentration of 0.001% by weight in a 1cm quartz cell having an optical path using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by HITACHI HIGH-TECH SCIENCE Co., ltd.) and dividing the measured absorbance by the molar concentration. Not dissolved in acetonitrile can be measured in PGMEA solution.

The acid value of the (meth) acrylic copolymer is preferably 20 to 200mgKOH/g, more preferably 30 to 180mgKOH/g, still more preferably 50 to 150 mgKOH/g. When the acid value is at least 20mgKOH/g, residue is not liable to remain during alkali development. The acid value is set to 200mgKOH/g or less, whereby the penetration of the alkali developer in the composition can be appropriately controlled, and peeling and development due to rapid penetration of the alkali developer can be suppressed. The acid value can be obtained by titration with a 1/10N-KOH aqueous solution using a potential difference titration apparatus "COM-1600" (manufactured by Ping Zhu Shi Cheng Co., ltd.).

In the (meth) acrylic copolymer, the proportion of the structural unit having a carboxyl group (the proportion of the total amount of the structural units (AC) and the structural units (AD)) is preferably 3 to 50 mol%, more preferably 5 to 45 mol%, still more preferably 7 to 40 mol%, based on 100 mol% of the total structural units, from the same point of view.

The acrylic equivalent of the (meth) acrylic copolymer is preferably 300g/eq to 3000g/eq, more preferably 350g/eq to 2500g/eq, still more preferably 400g/eq to 2000 g/eq. The acrylic acid equivalent is 300g/eq or more, whereby the ultraviolet absorbing group and the carboxyl group can be easily incorporated into the same molecule. When the acrylic equivalent is 3000g/eq or less, sensitivity can be ensured even in a low exposure amount, and a good developed pattern can be formed.

In the (meth) acrylic copolymer, the proportion of the structural unit having a polymerizable unsaturated group (the proportion of the total amount of the structural units (AB) and the structural units (AD)) is preferably 3 to 90 mol%, more preferably 5 to 85 mol%, still more preferably 7 to 80 mol%, based on 100 mol% of the total structural units, from the same viewpoint.

The equivalent weight of the ultraviolet absorbing group, the acid value, the acrylic acid equivalent weight, and the ratio of each structural unit of the (meth) acrylic acid copolymer can be adjusted by copolymerizing the above monomers.

For example, the (meth) acrylic copolymer may be formed as a copolymer having the following structural units in the following proportions. The following ratio is the ratio (unit is mol%) of each structural unit to 100 mol% of all structural units of the (meth) acrylic copolymer.

0.1 To 80 mol% of a structural unit (AA),

5Mol% to 70 mol% of the structural unit (AB),

3 To 50 mol% of the structural unit (AC),

More preferably

6 Mol% to 70 mol% of the structural unit (AA),

0.1 To 60 mol% of a structural unit (AB),

The structural unit (AD) is 5-45 mol%,

More preferably

Specific examples of the (meth) acrylic copolymer include a copolymer in which the structural unit (AA) is a structural unit represented by the following general formula (A-1), the structural unit (AB) is a structural unit represented by the following general formula (A-2), the structural unit (AC) is a structural unit represented by the following general formula (A-3), and the structural unit (AE) is a structural unit represented by the following general formula (A-4).

In the general formulae (A-1) to (A-4), R ₁₁ to R ₁₄ and R ₁₉ represent a hydrogen atom or a methyl group. Of these, methyl is more preferable.

R ₁₅ to R ₁₈ and R ₂₀ to R ₂₁ each represent a hydrocarbon group having 1 to 10 carbon atoms which may have a cyclic structure or an aromatic ring, may have a substituent or may have an ether bond and may have an unsaturated bond.

Examples of the hydrocarbon group having 1 to 10 carbon atoms include: a linear or branched 2-valent alkylene group such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, etc.; a 2-valent hydrocarbon group having an alicyclic structure such as cyclohexylene, methylcyclohexylene, ethylcyclohexylene, dimethylcyclohexylene, diethylcyclohexylene, methylethylcyclohexylene, propylcyclohexylene, and methylpropylcyclohexylene; and 2-valent hydrocarbon groups having an aromatic group such as phenylene, methylphenylene, ethylphenylene, dimethylphenylene, methylethylphenylene, and naphthylene. Of these, methylene and ethylene are more preferable, ethylene is more preferable for R ₁₅ to R ₁₆, and methylene is more preferable for R ₁₇ to R ₁₈. Examples of the substituent include methyl and methoxy.

M1 and m2 are 0 or 1, and more preferably 0. m3 and m4 are 0, 1 or 2, and more preferably 0.

R ₂₂ represents a hydrocarbon group having 1 to 30 carbon atoms which may have a cyclic structure or an aromatic ring or may have a substituent and may be modified with an alkylene oxide and may have 1 or 2 hetero atoms. R ₂₂ is preferably an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, which may have a substituent, or an aryl group having 6 to 30 carbon atoms, which may have a substituent, which is linear or branched.

Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like. Examples of the cycloalkyl group having 3 to 30 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl groups. Examples of the aryl group having not less than 30 carbon atoms include phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-fused tetraphenyl group, 1-indenyl group, 2-azulenyl group, 9-fluorenyl group, biphenylyl group, o-, m-and p-tolyl groups, xylyl group (xylyl), o-, m-, and p-isopropylphenyl group, mesityl group, penta-cyclopentadienyl group, binaphthyl group, penta-enyl group, penta-cycloheptenyl group, biphenylene group, dicyclopentadiene-phenyl group, allene fluorenyl group, acenaphthenyl group, on-phenyl group, fluorenyl group, anthracenyl group, binaphthyl group, anthracenyl group, phenanthrenyl group, biphenylenyl group, pyrenyl group,A group, a fused tetraphenyl group, a obsidian alkenyl group, a picene group, a perylene group, a pentacenyl group, a fused pentacenyl group, a biphenylyl group, a fused hexaphenyl group, ru Ji, a coronenyl group, a binaphthyl group, an isoparaffin heptaphenyl group, a fused heptaphenyl group, a pyrene anthryl group, and the like. Among these, methyl and ethyl are more preferable, and methyl is more preferable. Examples of the substituent include methyl and methoxy.

X ₁ represents an epoxy acrylate residue having a secondary hydroxyl group, an ester bond, or a urethane bond. Of these, ester bonds and urethane bonds are more preferable, and ester bonds are more preferable.

X ₂ and X ₃ independently represent an epoxy acrylate residue having a secondary hydroxyl group, an ester bond or a urethane bond. Among these, a urethane bond is more preferable.

X ₁ to X ₃ are more preferably bonds or structures which are different from each other.

Z represents an ultraviolet absorbing group. The ultraviolet absorbing group may be a functional group having a structure as exemplified as the ultraviolet absorbing group of the structural unit (AA).

And represents a bonding site with other structural units.

(Molar ratio of structural units represented by the general formula (A-1): (molar ratio of structural units represented by the general formula (A-2): (molar ratio of structural units represented by the general formula (A-3): (molar ratio of structural units represented by the general formula (A-4)) of 0.1 to 89:5 to 89:5 to 50:0.1 to 89. But a: b: c: the preferable range of d may be the same as the preferable ranges of the above-mentioned structural unit (AA), structural unit (AB), structural unit (AC) and structural unit (AE).

Other specific examples of the (meth) acrylic copolymer include a copolymer in which the structural unit (AA) is a structural unit represented by the following general formula (A-5), the structural unit (AB) is a structural unit represented by the following general formula (A-6), the structural unit (AD) is a structural unit represented by the following general formula (A-7), and the structural unit (AE) is a structural unit represented by the following general formula (A-8).

In the general formulae (A-5) to (A-8), R ₃₁ to R ₃₄ and R ₃₉ independently represent a hydrogen atom or a methyl group. Of these, methyl is more preferable.

R ₃₅ to R ₃₈ independently represent a hydrocarbon group having 1 to 10 carbon atoms which may have a cyclic structure or an aromatic ring, may have a substituent or may have an ether bond and may have an unsaturated bond.

Examples of the hydrocarbon group having 1 to 10 carbon atoms include: a linear or branched 2-valent alkylene group such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, etc.; a 2-valent hydrocarbon group having an alicyclic structure such as cyclohexylene, methylcyclohexylene, ethylcyclohexylene, dimethylcyclohexylene, diethylcyclohexylene, methylethylcyclohexylene, propylcyclohexylene, and methylpropylcyclohexylene; and 2-valent hydrocarbon groups having an aromatic group such as phenylene, methylphenylene, ethylphenylene, dimethylphenylene, methylethylphenylene, and naphthylene. Of these, methylene and ethylene are more preferable, ethylene is more preferable for R ₃₅ to R ₃₆, and methylene is more preferable for R ₃₇ to R ₃₈. Examples of the substituent include methyl and methoxy.

M5 and m6 are 0 or 1, and more preferably 0.

R ₄₀ represents a hydrocarbon group having 1 to 10 carbon atoms which may have a cyclic structure or an aromatic ring, may have a substituent or may have an ether bond and may have an unsaturated bond. R ₄₀ is more preferably an alkylene group having 1 to 10 carbon atoms which may have a carboxyl group, a cycloalkylene group having 3 to 10 carbon atoms which may have a carboxyl group, a cycloalkenyl group having 3 to 10 carbon atoms which may have a carboxyl group, or an aryl group having 6 to 10 carbon atoms which may have a carboxyl group. Specific examples of R ₄₀ include hydrocarbon groups having 1 to 10 carbon atoms which R ₃₅ to R ₃₈ may have, and cyclic olefin groups having 3 to 10 carbon atoms such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, and cyclooctenyl. More preferably ethylene and propylene, and still more preferably ethylene.

R ₄₁ represents a hydrocarbon group having 1 to 30 carbon atoms which may have a cyclic structure or an aromatic ring or may have a substituent and may be modified with an alkylene oxide and may have 1 or 2 hetero atoms. R ₄₁ is preferably an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent.

X ₄ represents an epoxy acrylate residue having a secondary hydroxyl group, an ester bond, or a urethane bond. Of these, ester bonds are more preferable.

And represents a bonding site with other structural units.

(Molar ratio of structural units represented by the general formula (A-5): (molar ratio of structural units represented by the general formula (A-6): (molar ratio of structural units represented by the general formula (A-7): (molar ratio of structural units represented by the general formula (A-8)) of 0.1 to 90:0.001 to 50:5 to 50:0.1 to 94. But e: f: g: the preferable range of h may be the same as the preferable ranges of the above-mentioned structural unit (AA), structural unit (AB), structural unit (AD) and structural unit (AE).

The following monomers may be appropriately combined and copolymerized, and thereafter an ultraviolet absorbing group, a polymerizable unsaturated group, or a carboxyl group is grafted to the side chain possessed by the structural unit derived from the monomer (Ax 1) to the monomer (Ax 3) to synthesize the (meth) acrylic copolymer.

(Aa) a monomer having a (meth) acryloyl group and an ultraviolet absorbing group

(Ac) monomers having (meth) acryl and carboxyl groups

(Ae) a monomer having a (meth) acryloyl group and not having an ultraviolet absorbing group and a carboxyl group (Ax 1) a monomer having a (meth) acryloyl group and a hydroxyl group

(Ax 2) monomer having (meth) acryl and isocyanate group

(Ax 3) monomers having (meth) acryloyl groups and epoxypropyl or alicyclic epoxy groups

The monomer (Aa) is a monomer for introducing an ultraviolet absorbing group into the (meth) acrylic copolymer.

In addition, from the viewpoint of improving the ultraviolet absorption energy of the (meth) acrylic copolymer, the monomer (Aa) is preferably a monomer having a molar absorptivity of 3000 or more at a wavelength of 355 nm. From the same viewpoint, the monomer (Aa) is more preferably a monomer having a molar absorptivity of 3000 to 100000 at 355nm, still more preferably 4000 to 90000, and particularly preferably 5000 to 80000.

Examples of the monomer (Aa) include compounds described in Japanese patent application laid-open No. 2004-182924, japanese patent application laid-open No. 2007-286123, japanese patent application laid-open No. 2007-331359, japanese patent application laid-open No. 2013-204001, japanese patent application laid-open No. 2015-124254, japanese patent application laid-open No. 2019-137844, and Japanese patent application laid-open No. 2020-189906.

The monomer (Ac) is a monomer for introducing a carboxyl group into the (meth) acrylic copolymer. The monomer (Ac) is more preferably a monomer having no ultraviolet absorbing group as described above. The monomer (Ac) is more preferably a monomer having a molar absorptivity of less than 3000 at a wavelength of 355 nm.

Examples of the monomer (Ac) include (meth) acrylic acid, mono (2- (meth) acryloyloxyethyl) succinate, hexahydrophthalic acid (2- (meth) acryloyloxyethyl) ester, phthalic acid (2- (meth) acryloyloxyethyl) ester, maleic acid (2- (meth) acryloyloxyethyl) ester, fumaric acid (2-acryloyloxyethyl) (2- (meth) acryloyloxyethyl) ester, itaconic acid (2- (meth) acryloyloxyethyl) ester, citraconic acid (2- (meth) acryloyloxyethyl) ester, carboxyethyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, mono-n-butyl (2- (meth) acryloyloxyethyl) maleate, mono-n-butyl (2- (meth) acryloyloxyethyl) fumarate, and mono-n-butyl (2- (meth) acryloyloxyethyl) itaconate.

The monomer (Ae) is a monomer for adjusting the molecular weight or the amount of functional groups of the (meth) acrylic copolymer.

Examples of the monomer (Ae) include: (meth) acrylic esters having an alkyl chain of 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), such as ethyl (meth) acrylate, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate; (meth) acrylates having an alkylene oxide-modified alkyl chain of 1 to 10 carbon atoms, such as methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, and butoxydiglycol (meth) acrylate; (meth) acrylic esters of alicyclic hydrocarbons having 3 to 30 carbon atoms such as cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantane-1-yl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, 3, 5-trimethylcyclohexyl (meth) acrylate and the like; (meth) acrylic esters of aromatic hydrocarbons having 3 to 30 carbon atoms such as benzyl (meth) acrylate, phenylethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-biphenyl (meth) acrylate, and 2-naphthalene (meth) acrylate; (meth) acrylic acid esters of aromatic hydrocarbons having 3 to 30 carbon atoms modified with an alkylene oxide, such as neopentyl glycol-acrylic acid-benzoic acid ester, phenoxyethylene glycol methacrylate, and ethoxylated-O-phenylphenol (meth) acrylate; and (meth) acrylates containing a hydrocarbon group having 1 to 30 carbon atoms which may have 1 or 2 hetero atoms, such as phthalimide (meth) acrylate, maleimide (meth) acrylate, benzophenone (meth) acrylate, 2-hydroxy-4- (meth) acryloxybenzophenone, hydroxy-4- (2- (meth) acryloxy) ethoxybenzophenone, and the like.

Monomers (Ax 1) to (Ax 3) are monomers for introducing the above functional groups into the side chains of the (meth) acrylic copolymer by grafting.

The monomers (Ax 1) to (Ax 3) are more preferably monomers having no ultraviolet absorbing group as described above. Further, the monomers (Ax 1) to (Ax 3) are preferably monomers having a molar absorption coefficient of less than 3000 at a wavelength of 355 nm. The monomers (Ax 1) to (Ax 3) are more preferably monomers having no carboxyl group.

For example, the monomer (Ax 1) having a hydroxyl group may be used to react a compound having an isocyanate group and a polymerizable unsaturated group with the hydroxyl group after copolymerization with another monomer (Ay 1 a), and introduce the polymerizable unsaturated group into the (meth) acrylic copolymer via a urethane bond.

Alternatively, the monomer (Ax 1) having a hydroxyl group may be used to react the (Ay 1 b) dicarboxylic acid or its acid monoanhydride with the hydroxyl group after copolymerization with another monomer, and introduce the carboxyl group into the (meth) acrylic copolymer via an ester bond.

Examples of the monomer (Ax 1) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, and ethyl-. Alpha. -hydroxymethacrylate.

The compound having an isocyanate group and a polymerizable unsaturated group (Ay 1 a) used together with the monomer (Ax 1) may be exemplified by (2- (meth) acryloyloxyethyl) isocyanate and the like.

Examples of the (Ay 1 b) dicarboxylic acid or the acid monoanhydride used with the monomer (Ax 1) include chain hydrocarbon dicarboxylic acid, alicyclic hydrocarbon dicarboxylic acid, aromatic hydrocarbon dicarboxylic acid, and acid monoanhydride of these.

Examples of the chain hydrocarbon dicarboxylic acid include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, iconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and the like, and these dicarboxylic acids having any substituent introduced therein.

Examples of the alicyclic hydrocarbon dicarboxylic acid include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, chlorobridge acid, norbornane dicarboxylic acid, and the like, and these dicarboxylic acids having any substituent introduced therein.

Examples of the aromatic hydrocarbon dicarboxylic acid include phthalic acid, isophthalic acid, 1, 8-naphthalene dicarboxylic acid, 2, 3-naphthalene dicarboxylic acid, and the like, and these dicarboxylic acids having an optional substituent introduced therein.

Among the dicarboxylic acids, succinic acid, itaconic acid, tetrahydrophthalic acid, and phthalic acid are more preferable, and succinic acid, itaconic acid, and tetrahydrophthalic acid are more preferable.

The dicarboxylic acid is preferably an acid monoanhydride thereof.

Alternatively, a compound having an isocyanate group and an ultraviolet absorbing group or a compound having an isocyanate group and a carboxyl group may be used instead of the compound having an isocyanate group and a polymerizable unsaturated group (Ay 1 a), and the ultraviolet absorbing group or the carboxyl group may be introduced into a side chain of a structural unit derived from the monomer (Ax 1) through a urethane bond.

Alternatively, a compound having a carboxyl group and an ultraviolet absorbing group or a compound having a carboxyl group and a polymerizable unsaturated group may be used instead of the (Ay 1 b) dicarboxylic acid or the acid monoanhydride thereof, and the ultraviolet absorbing group or the polymerizable unsaturated group may be introduced into a side chain of a structural unit derived from the monomer (Ax 1) through a urethane bond.

The monomer (Ax 2) having an isocyanate group can be used to react a compound (Ay 2) having a hydroxyl group and a polymerizable unsaturated group with the isocyanate group after copolymerization with another monomer, and the polymerizable unsaturated group can be introduced into the (meth) acrylic copolymer via a urethane bond.

Examples of the monomer (Ax 2) include compounds exemplified by the above-mentioned compounds having an isocyanate group and a polymerizable unsaturated group.

The compound (y 2) having a hydroxyl group and a polymerizable unsaturated group used together with the monomer (Ax 2) may be exemplified by the respective compounds exemplified for the monomer (Ax 1).

In addition, a compound having a hydroxyl group and an ultraviolet absorbing group or a compound having a hydroxyl group and a carboxyl group may be used instead of the compound having a hydroxyl group and a polymerizable unsaturated group (Ay 2), and an ultraviolet absorbing group or a carboxyl group may be introduced into a side chain of a structural unit derived from the monomer (Ax 2) through a urethane bond.

The monomer (Ax 3) having a glycidyl group or an alicyclic epoxy group may be used to react a compound having a carboxyl group and a polymerizable unsaturated group in (Ay 3) with the glycidyl group or alicyclic epoxy group after copolymerization with another monomer, and the polymerizable unsaturated group may be introduced into the (meth) acrylic copolymer via an epoxyacrylate residue.

Examples of the monomer (Ax 3) include glycidyl (meth) acrylate, β -propyl glycidyl (meth) acrylate, β -methyl glycidyl- α -ethyl (meth) acrylate, 3-methyl-3, 4-epoxybutyl (meth) acrylate, 4-methyl-4, 5-epoxypentyl (meth) acrylate, 5-methyl-5, 6-epoxyhexyl (meth) acrylate, and 3, 4-epoxycyclohexylmethyl methacrylate.

The compound having a carboxyl group and a polymerizable unsaturated group (Ay 3) used together with the monomer (Ax 3) may be exemplified by the respective compounds exemplified by the monomer (Ac).

The epoxy acrylate residue formed from the monomer (Ax 3) may be further reacted with a (Az 3) polycarboxylic acid or an anhydride thereof, whereby a carboxyl group may be introduced into the (meth) acrylic copolymer through the epoxy acrylate residue.

Examples of the polycarboxylic acid to be reacted with the above-mentioned epoxy acrylate residue include dicarboxylic acid or its acid monoanhydride, and tricarboxylic acid or its acid monoanhydride and tetracarboxylic acid or its acid dianhydride as exemplified by the monomer (Ay 1 b).

Examples of the tricarboxylic acid include trimellitic acid and hexahydrotrimellitic acid.

Examples of the tetracarboxylic acid include chain hydrocarbon tetracarboxylic acid, alicyclic hydrocarbon tetracarboxylic acid, and aromatic tetracarboxylic acid.

Examples of the chain hydrocarbon tetracarboxylic acid include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and chain hydrocarbon tetracarboxylic acids obtained by introducing substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups.

Examples of the alicyclic hydrocarbon tetracarboxylic acid include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, and alicyclic tetracarboxylic acids having a substituent such as a chain hydrocarbon group or an unsaturated hydrocarbon group introduced therein.

Examples of the aromatic tetracarboxylic acid include Jiao Midan acid, diphenyl ketone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, naphthalene-1, 4,5, 8-tetracarboxylic acid, naphthalene-2, 3,6, 7-tetracarboxylic acid, and the like.

The tetracarboxylic acid is preferably an acid dianhydride thereof.

For example, a copolymer having the structural unit (AA) represented by the above general formula (A-1), the structural unit (AB) represented by the above general formula (A-2), the structural unit (AC) represented by the above general formula (A-3), and the structural unit (AE) represented by the above general formula (A-4) can be synthesized by the following steps.

[ Steps (1) -1]

Make the following steps

(Aa) a monomer having a (meth) acryloyl group and an ultraviolet absorbing group;

(Ac) a monomer having a (meth) acryloyl group and a carboxyl group;

(Ae) a monomer having a (meth) acryloyl group and neither an ultraviolet absorbing group nor a carboxyl group; and

(Ax 1) a monomer having a (meth) acryloyl group and a hydroxyl group;

And a step of copolymerizing to obtain a copolymer.

[ Steps (1) -2]

And (2) a step of reacting the copolymer obtained in the step (1) -1 with a compound having an isocyanate group and a polymerizable unsaturated group (Ay 1 a), forming a urethane bond between a hydroxyl group derived from the monomer (Ax 1) and the isocyanate group of the compound (Ay 1 a), and grafting the polymerizable unsaturated group to the copolymer.

The copolymerization of step (1) -1 may be performed by mixing and reacting the monomers to be copolymerized with a thermal polymerization initiator in a solvent. The reaction temperature depends on the kind of the thermal polymerization initiator used, but for example, it is more preferable to react in a solvent at a temperature range of 60 to 100℃for 2 to 12 hours.

The thermal polymerization initiator may be a general thermal radical polymerization initiator, and is more preferably an azo compound or a peroxide, and from the viewpoint of producing a linear polymer, an azo compound is more preferred.

Azo compounds include 2,2' -azobisisobutyronitrile, 2' -azobis (2-methylbutyronitrile), 2' -azobis (2, 4-dimethylvaleronitrile), 1' -azobis (cyclohexane-1-carbonitrile), dimethyl 2,2' -azobis (isobutyric acid), and the like. Among them, 2' -azobis (2, 4-dimethylvaleronitrile) is more preferable from the viewpoint of reaction temperature.

The solvent may be appropriately selected from solvents used for the resin composition. Examples of the solvent that can be used include alcohols, glycols, aliphatic cyclic ketones, and acetates. Among these, solvents other than alcohols are more preferably used.

Examples of the glycols include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether.

Examples of the aliphatic cyclic ketone include cyclohexanone, o-methylcyclohexanone, m-methylcyclohexanone, and p-methylcyclohexanone.

Examples of the acetate esters include ethyl acetate, n-propyl acetate, and n-butyl acetate.

In addition to these, solvent naphtha, methyl ethyl ketone, methyl isobutyl ketone, saturated hydrocarbon solvents such as n-octane and isooctane, and ethyl proxirsu, butyl proxirsu, and the like can be used.

In this case, a solvent containing a hydroxyl group such as isopropyl alcohol (IPA) or Propylene Glycol Monomethyl Ether (PGME) is preferably not used. Accordingly, the reaction between the isocyanate group of the compound having an isocyanate group and a polymerizable unsaturated group in the following step (Ay 1 a) and the hydroxyl group of the solvent can be avoided, and the reaction for forming the urethane bond can be performed reliably and sufficiently.

The amount of the solvent is preferably 10 to 2000 parts by weight, more preferably 50 to 500 parts by weight, based on 100 parts by weight of the total of the monomers mixed and copolymerized in the above-described range.

The reaction in step (1) -2 is more preferably carried out by mixing the compound having an isocyanate group and a polymerizable unsaturated group with the monomer (Ay 1 a) in the reaction solution obtained in step (1) -1, and then reacting the mixture in a solvent at a temperature ranging from 40℃to 100℃for 2 to 12 hours.

The solvent may be appropriately selected and used from the above. In addition, the reaction may optionally be carried out with the addition of a catalyst. Examples of the catalyst include tin compounds, titanium compounds, and amine compounds. Specific examples of the catalyst include dibutyltin laurate, titanium tetra-n-butoxide, triethylamine and the like. Among these, tin compounds are more preferable in view of easy control of the reaction. The amount of the catalyst to be added is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the total of the compounds having an isocyanate group and a polymerizable unsaturated group in the monomer (Ay 1 a). In this case, it is preferable that the (meth) acryl group of the compound having an isocyanate group and a polymerizable unsaturated group of the monomer (Ay 1 a) is not polymerized, and a polymerization inhibitor or the like may be added for this purpose.

The compound having an isocyanate group and a polymerizable unsaturated group in the monomer (Ay 1 a) is more preferably reacted under the condition that the number of moles of the isocyanate group is smaller than the number of moles of the hydroxyl group derived from the monomer (Ax 1). Specifically, the mole number of isocyanate groups derived from the monomer (Ay 1 a) is 95 to 99% of the mole number of hydroxyl groups derived from the monomer (Ax 1).

The materials used may be appropriately changed in accordance with the constitution of each structural unit of the obtained polymer.

The copolymer having the structural unit (AA) represented by the above general formula (A-5), the structural unit (AB) represented by the above general formula (A-6), the structural unit (AD) represented by the above general formula (A-7), and the structural unit (AE) represented by the above general formula (A-8) can be synthesized by the following steps.

[ Step (2) -1]

Make the following steps

(Ax 3) a monomer having a (meth) acryloyl group, a glycidoxypropyl group, or an alicyclic epoxy group;

copolymerization to obtain a copolymer

[ Steps (2) -2]

A step of reacting the copolymer obtained in the step (2) -1 with a compound having a carboxyl group and a polymerizable unsaturated group (Ay 3), forming an epoxyacrylate residue by a reaction of an epoxypropyl group or alicyclic epoxy group derived from the monomer (Ax 3) and the carboxyl group of the compound (Ay 3), and grafting the polymerizable unsaturated group to the copolymer

[ Steps (2) -3]

A step of reacting the copolymer having the graft polymerizable unsaturated group in the step (2) -2 with (Az 3) a polycarboxylic acid or an anhydride thereof, and further grafting a carboxyl group to the copolymer by reacting an epoxy acrylate residue obtained by the reaction of the hydroxyl group of the monomer (Ax 1) or the monomer (Ax 3) with the monomer (Ay 3) with a carboxyl group or a carboxylic acid anhydride group of the compound (Az 3)

The copolymerization of step (2) -1 can be carried out in the same manner as the copolymerization of step (1) -1 described above. The reaction temperature depends on the kind of the thermal polymerization initiator used, but for example, it is more preferable to react in a solvent at a temperature range of 60 to 100℃for 2 to 12 hours.

The solvent may be appropriately selected and used by the user of the resin composition. Examples of the solvent that can be used include alcohols, glycols, aliphatic cyclic ketones, and acetates. Among these, solvents other than alcohols are more preferably used.

In this case, the reaction of the acid anhydride group of the (Az 3) polycarboxylic acid or the anhydride thereof in the following step with the hydroxyl group of the solvent is avoided by not using a solvent containing a hydroxyl group such as isopropyl alcohol (IPA) or Propylene Glycol Monomethyl Ether (PGME), and the reaction to form an ester bond can be performed reliably and sufficiently.

The amount of the solvent is preferably 10 to 2000 parts by weight, more preferably 50 to 500 parts by weight, based on 100 parts by weight of the total of the copolymerized monomers mixed in the above range.

The reaction of step (2) -2 may be formed by reacting in a solvent at a temperature ranging from 80 to 130 ℃ for 5 to 18 hours. In addition, the reaction can be efficiently performed by adding a base catalyst. Examples of the base catalyst include ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, phosphines such as triphenylphosphine and tris (2, 6-dimethoxyphenyl) phosphine.

The reaction of step (2) -3 may be formed by reacting in a solvent at a temperature ranging from 80 to 130 ℃ for 5 to 48 hours.

In addition, the (Ax 1) monomer having a (meth) acryloyl group and a hydroxyl group may be copolymerized in step (2) -1, and an ester bond may be formed between the hydroxyl group derived from the monomer (Ax 1) and the carboxyl group or carboxylic anhydride group of the compound (Az 3) in step (2) -3, and the carboxyl group may be grafted to the copolymer. The reaction conditions at this time may be the same as those of steps (2) -3.

The monomers and compounds exemplified by the above synthetic methods are only examples, and it is needless to say that monomers and compounds other than those having the same functional groups may be used.

1-2 (B) unsaturated group-containing polymerizable Compound having no ultraviolet absorbing group

(B) The unsaturated group-containing polymerizable compound having no ultraviolet absorbing group (hereinafter referred to as "component (B)") is a compound having a polymerizable unsaturated group and causing the polymerizable unsaturated group to undergo polymerization reaction and harden by stimulation with heat, light, or the like. (B) The component (A) has no ultraviolet absorbing group as described in the description of the component (A) in the molecule.

(B) The component (A) can improve the adhesion and solvent resistance of the adhesive layer formed by curing the curable composition to an adherend.

(B) The component (b) may be an alkali-soluble resin, an acrylic resin, or other publicly known polymerizable compound having an unsaturated group, as long as the adhesiveness to the adherend and solvent resistance are ensured.

(B) The component (c) is roughly classified into a component (B1) of a polymerizable compound having an unsaturated group and not having an alkali-soluble group, and a component (B2) of a polymerizable alkali-soluble resin having an unsaturated group. The curable composition may contain only the component (B1), may contain only the component (B2), and may contain both the component (B1) and the component (B2).

1-2-1. (B1) component (B) having no alkali-soluble group

(B1) The component (A) is a compound having an alkali-soluble group which has a polymerizable unsaturated group and causes polymerization by stimulation with heat, light or the like. (B1) The component (c) preferably has 2 or more polymerizable unsaturated groups in the molecule.

(B1) The component (A) can improve the adhesive strength and solvent resistance of the adhesive layer formed by curing the curable composition to the adherend. (B1) The component (B2) is preferably a polymer having at least 2 or more polymerizable unsaturated groups capable of reacting (polymerizing) with the polymerizable unsaturated groups of the component (a) or the polymerizable unsaturated groups of the component (B2). When the polymerizable unsaturated group is used in combination with the component (B2), the functional group is preferably the same as the polymerizable unsaturated group of the component (B2). Specifically, the polymerizable unsaturated group is more preferably a (meth) acryloyl group. The component (B1) may be a monomer, oligomer, or polymer. When the component (B2) is used in combination, the component (B1) is preferably a monomer or an oligomer.

(B1) Examples of the component include:

(meth) acrylic esters having a hydroxyl group, such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate;

Urethane acrylate monomers such as pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate hexamethylene isocyanate urethane prepolymer, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, and dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer;

Epoxy (meth) acrylates such as bisphenol a epoxy (meth) acrylate, bisphenol F epoxy (meth) acrylate, bisphenol fluorene epoxy (meth) acrylate, diphenylfluorene epoxy (meth) acrylate, phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, phenol aralkyl epoxy (meth) acrylate, and the like; and

Dendritic polymers having (meth) acryloyl groups as compounds having ethylenic double bonds, and the like.

(B1) The component (a) preferably has 2 or more (meth) acryloyl groups, and more preferably has 3 or more (meth) acryloyl groups. (B1) If the component has 2 or more (meth) acryloyl groups, the crosslinking density is increased, and the solvent resistance of the adhesive layer is improved.

The component (B1) is preferably an alkylene oxide-modified or lactone-modified compound in order to further improve the adhesion of the adhesive layer to the adherend. These modified substances can increase the contact area (adhesion area) by increasing the fluidity of the curable composition at the interface of the adherend and filling up the minute gap between the adherend and the curable composition, thereby further improving the adhesion of the adhesive layer to the adherend. In particular, when the component (B) is a high molecular weight compound, the component (B1) of the modified product compensates for the decrease in fluidity of the curable composition caused by the component (B), thereby making the effect of improving the adhesion more remarkable.

The alkylene oxide modifier is preferably a compound having an alkylene oxide group having 2 to 6 carbon atoms, more preferably a compound having an alkylene oxide group having 2 to 4 carbon atoms, and still more preferably a compound having an alkylene oxide group having 2 to 3 carbon atoms.

The lactone modified substance is more preferably a compound having a structure in which a lactone having 2 or more and 6 or less carbon atoms is ring-opened (-C (=o) - (CH ₂)_k -O-, k is a number smaller than 1 of the lactone carbon atoms), still more preferably a compound having a structure in which a lactone having 4 or more and 6 or less carbon atoms is ring-opened, still more preferably a compound having a structure in which a lactone having 6 carbon atoms is ring-opened.

The ring-opened structure of the alkylene oxide and lactone may exist in a molecule alone or may exist in succession with 2 or more and 6 or less of the alkylene oxide or lactone, but it is more preferable that 2 of the alkylene oxide or lactone exist alone or in succession.

The modified substance may be, for example, a compound represented by the following general formula (B1-1).

In the formula (B1-1), V is independently a group having a ring-opened structure of an alkylene oxide group or a lactone. a to e are independently integers from 0 to 6, but at least one of a to e is an integer from 1 to 6. a to e are more preferably 1 or 2. More preferably, R ₅ to R ₉ are independently (meth) acryloyl groups or hydroxyl groups, but at least 2 of R ₅ to R ₉ are (meth) acryloyl groups. R ₅ to R ₉ are preferably (meth) acryl groups. T is a group selected from the group consisting of substituted or unsubstituted 1-4 valent hydrocarbon groups, -O-and-S-, more preferably substituted or unsubstituted 2 valent hydrocarbon groups, -O-and-S-, and still more preferably-O-. q is independently 0 or 1, more preferably 0.r is the same as the valence of Z and is an integer from 1 to 4, more preferably 2.

Examples of the modified substance represented by the general formula (B1-1) include ethylene oxide modified dipentaerythritol hexaacrylate, dipentaerythritol dicyclohectone hexaacrylate, dipentaerythritol tricaprolactone hexaacrylate, dipentaerythritol polycaprolactone hexaacrylate (all manufactured by Nippon chemical Co., ltd.), trimethylolpropane propylene oxide modified triacrylate, and trimethylolpropane ethylene oxide modified triacrylate (all manufactured by Toyama Co., ltd.).

Examples of the modified substances other than the compounds represented by the general formula (B1-1) include bisphenol F ethylene oxide modified diacrylate, bisphenol A ethylene oxide modified diacrylate, isocyanatoethylene oxide modified di-and triacrylates, diglycerol ethylene oxide modified acrylate (all manufactured by Tokyo Co., ltd.), and phosphazene alkylene oxide modified hexa (meth) acrylate.

(B1) The content of the component is preferably 10 mass% or more and 60 mass% or less, more preferably 10 mass% or more and 50 mass% or less, still more preferably 10 mass% or more and 40 mass% or less, relative to the total mass of the solid matter. (B1) When the content of the component is 10% by mass or more, crosslinking is sufficiently formed, and thus the developed pattern is formed well, and the chemical resistance of the cured film is also improved. (B1) When the content of the component (A) is 50% by mass or less, the crosslinking density of the adhesive layer after curing is sufficient, and therefore the adhesive layer is easily degraded when irradiated with light, and residues are not easily generated.

1-2-2. (B2) component (B) having an alkali-soluble group

(B2) The component (B1) preferably has a polymerizable unsaturated group (more preferably a (meth) acryloyl group) and an acid group (an alkali-soluble group) for exhibiting alkali solubility in the molecule, and more preferably contains a polymerizable unsaturated group of the component (a) or both a polymerizable unsaturated group and a carboxyl group of the component (B1). The resin is not particularly limited and may be widely used. Since the alkali-soluble resin has both a polymerizable unsaturated group and a carboxyl group, it is necessary to impart excellent photo-hardening properties, good developability and patterning properties to the composition for forming an adhesive layer, and further, to improve the adhesion of a cured film to a substrate.

The alkali-soluble resin belonging to the component (B2) of the present embodiment is more preferably an alkali-soluble resin containing a polymerizable unsaturated group obtained by further reacting a reactant of an epoxy compound having 2 or more epoxy groups and (meth) acrylic acid with a polycarboxylic acid or an anhydride thereof. In the production of the alkali-soluble resin, the polyester is produced by the reaction of the hydroxyl group with the polycarboxylic acid, but the average degree of polymerization is preferably low molecular weight of about 2 to 500.

The epoxy compound is more preferably an epoxy compound having 2 or more epoxy groups. Examples of the epoxy compound include bisphenol a type epoxy compound, bisphenol F type epoxy compound, bisphenol fluorene type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound (for example, EPPN to 501H: available from Mitsubishi chemical Co., ltd.), phenol aralkyl type epoxy compound, phenol novolac compound containing naphthalene skeleton (e.g., NC-7000L: available from Japan chemical Co., ltd.), biphenyl type epoxy compound (e.g., jorYX 4000: available from Mitsubishi chemical Co., ltd.), naphthol aralkyl type epoxy compound, triphenolmethane type epoxy compound, tetraphenolethane type epoxy compound, epoxypropyl ether of polyhydric alcohol, epoxypropyl ester of polybasic carboxylic acid, copolymer of monomer having (meth) acryloyl group as a unit represented by copolymer of methacrylic acid and epoxypropyl methacrylate, 3',4' -epoxycyclohexylmethyl 3, 4-epoxycyclohexane carboxylate (e.g., celloxide2021P: available from Mitsubishi chemical Co., ltd.), butanetetracarboxylic acid tetrakis (3, 4-epoxycyclohexylmethyl) ester modified epsilon-caprolactone (e.g., EPOLEAD GT: available from Daicel Co., ltd.), epoxycyclohexane compound having (e.g., available from GmbH-HiREM) as a functional epoxy group represented by the four-state chemical industry Co., ltd., HP-3 ',4' -epoxycyclohexylmethyl 3, 4-epoxycyclohexane carboxylate (e.g., available from Cellux 2021P: daicel Co., ltd.) having a functional group represented by epoxy group as a functional group (HP-7200), 1, 2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol (for example, EHPE3150: manufactured by Daicel Co., ltd.), epoxidized polybutadiene (for example, NISSO-PB. JP-100: manufactured by Nippon Caesada Co., ltd.), an epoxy compound having a polysilicone skeleton, and the like.

The alkali-soluble resin belonging to the component (B2) is also preferably an acrylic copolymer.

Examples of the acrylic copolymer include (meth) acrylic acid, (meth) acrylic acid ester and other copolymers, and resins having a (meth) acryloyl group and a carboxyl group. Examples of the resin include alkali-soluble resins containing a polymerizable unsaturated group obtained by reacting a copolymer obtained by copolymerizing a (meth) acrylic acid ester containing glycidyl (meth) acrylate in a solvent with (meth) acrylic acid and finally reacting the copolymer with an anhydride of a dicarboxylic acid or a tricarboxylic acid. The above copolymer can be constituted by referring to a copolymer having a number average molecular weight (Mn) of 2000 to 20000 and an acid value of 35 to 120mgKOH/g, which is shown in JP-A2014-111722, wherein the copolymer is composed of 20 to 90 mol% of a repeating unit derived from a diglyceride having both end hydroxyl groups (meth) acrylated and 10 to 80 mol% of a repeating unit derived from 1 or more polymerizable unsaturated compounds copolymerizable therewith; and an alkali-soluble resin containing a polymerizable unsaturated group, which is a polymer having a weight average molecular weight (Mw) of 3000 to 50000 and an acid value of 30 to 200mg/KOH, and which contains a unit derived from a (meth) acrylate compound and a unit having a (meth) acryloyl group and a di-or tricarboxylic acid residue, as shown in JP-A-2018-141968.

The component (B2) is preferably an alkali-soluble resin having a plurality of aromatic rings, more preferably a repeating unit having a fluorene structure, and still more preferably an alkali-soluble resin having a repeating unit having a bisaryl fluorene skeleton, from the viewpoint of further improving the heat resistance and solvent resistance of the adhesive layer and further improving the adhesion of the cured film to the substrate. For example, the component (B2) is more preferably a resin represented by the following general formula (B2-1).

In the formula (B2-1), ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of hydrogen atoms constituting Ar may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. R ₁ is independently an alkylene group having 2 to 4 carbon atoms. l is independently a number from 0 to 3. G is independently a (meth) acryloyl group, or a substituent represented by the following general formula (B2-2) or the following general formula (B2-3). Y is a 4-valent carboxylic acid residue. Z is independently a hydrogen atom or a substituent represented by the following general formula (B2-4), and at least one of Z is a substituent represented by the following general formula (B2-4). n is a number of 1 to 20 on average.

In the formulae (B2-2) and (B2-3), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or an alkylarylene group having 2 to 10 carbon atoms, R ₄ is a saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number of 0 to 10. * Indicating the bonding site.

In the formula (B2-4), W is a 2-valent or 3-valent carboxylic acid residue, and m is a number of 1 or 2. And represents a bonding site.

The resin represented by the general formula (B2-1) can be synthesized by the following method.

First, an epoxy (meth) acrylate diol compound is obtained by reacting an epoxy compound (a-1) having a bisaryl fluorene skeleton (hereinafter referred to as "epoxy compound (a-1)") which may have a plurality of alkylene oxide-modified groups in the molecule represented by the following general formula (B2-5), with at least one of (meth) acrylic acid, a (meth) acrylic acid derivative represented by the following general formula (B2-6), and a (meth) acrylic acid derivative represented by the following general formula (B2-7). The bisaryl fluorene skeleton is more preferably a binaphthol fluorene skeleton or a bisphenol fluorene skeleton.

In the formula (B2-5), ar is an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of hydrogen atoms constituting Ar may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. R ₁ is independently an alkylene group having 2 to 4 carbon atoms. l is independently a number from 0 to 3.

In the formulae (B2-6) and (B2-7), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or an alkylarylene group having 2 to 10 carbon atoms, R ₄ is a saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number of 0 to 10.

The reaction of the epoxy compound (a-1) with (meth) acrylic acid or a derivative thereof can be carried out by publicly known methods. For example, JP-A-4-355450 discloses that a diol compound containing a polymerizable unsaturated group is obtained by using about 2 moles of (meth) acrylic acid per 1 mole of an epoxy compound having 2 epoxy groups. In this embodiment, the compound obtained by the above reaction is a diol (d) having a polymerizable unsaturated group (hereinafter referred to as "diol (d)") represented by the following general formula (B2-8).

In the formula (B2-8), ar is an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of hydrogen atoms constituting Ar may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. G is independently a (meth) acryloyl group, a substituent represented by the general formula (B2-2) or the general formula (B2-3), and R ₁ is independently an alkylene group having 2 to 4 carbon atoms. l is independently a number from 0 to 3.

In the formulae (B2-2) and (B2-3), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or an alkylarylene group having 2 to 10 carbon atoms, R ₄ is a saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number of 0 to 10.

Then, the diol (d), the dicarboxylic acid or the tricarboxylic acid or the acid monoanhydride thereof (B), the tetracarboxylic acid or the acid dianhydride thereof (c) obtained above is reacted to obtain the unsaturated group-containing curable resin having a carboxyl group and a polymerizable unsaturated group in the 1 molecule represented by the general formula (B2-1).

The acid component is a polyvalent acid component which can react with hydroxyl groups in the molecule of the diol (d). In order to obtain the resin represented by the general formula (B2-1), it is necessary to use a dicarboxylic acid or tricarboxylic acid or an acid monoanhydride (B) of these and a tetracarboxylic acid or an acid dianhydride (c) thereof in combination. The carboxylic acid residue of the acid component may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. These carboxylic acid residues may contain bonds containing hetero elements such as-O-, -S-, and carbonyl groups.

Examples of the acid monoanhydride (b) of the dicarboxylic acid, the tricarboxylic acid, or the acid mono-anhydride thereof include chain hydrocarbon dicarboxylic acid, tricarboxylic acid, alicyclic hydrocarbon dicarboxylic acid, tricarboxylic acid, aromatic hydrocarbon dicarboxylic acid, and the acid mono-anhydride thereof.

Examples of the chain hydrocarbon dicarboxylic acid or tricarboxylic acid include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, iconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, pendant oxyglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and the like, and dicarboxylic acids or tricarboxylic acids in which any substituent is introduced.

Examples of the alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, chlorobridge acid, hexahydrotrimellitic acid, norbornane dicarboxylic acid, and the like, and dicarboxylic acids or tricarboxylic acids in which any substituent is introduced.

Examples of the aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid include phthalic acid, isophthalic acid, 1, 8-naphthalene dicarboxylic acid, 2, 3-naphthalene dicarboxylic acid, and the like, and dicarboxylic acid or tricarboxylic acid having any substituent introduced therein.

Among these, the dicarboxylic acid or tricarboxylic acid is more preferably succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid, and more preferably succinic acid, itaconic acid, and tetrahydrophthalic acid.

The dicarboxylic acid or tricarboxylic acid is preferably an acid monoanhydride thereof.

Examples of the tetracarboxylic acid or its acid dianhydride (c) include chain hydrocarbon tetracarboxylic acid, alicyclic hydrocarbon tetracarboxylic acid, aromatic hydrocarbon tetracarboxylic acid, and acid dianhydride thereof.

Examples of the aromatic hydrocarbon tetracarboxylic acid include Jiao Midan acid, diphenyl ketone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, naphthalene-1, 4,5, 8-tetracarboxylic acid, and naphthalene-2, 3,6, 7-tetracarboxylic acid.

Among these, the tetracarboxylic acids are more preferably biphenyl tetracarboxylic acid, diphenyl ketone tetracarboxylic acid, and diphenyl ether tetracarboxylic acid, and further preferably biphenyl tetracarboxylic acid and diphenyl ether tetracarboxylic acid.

The tetracarboxylic acid is preferably an acid dianhydride thereof.

In addition, the above tetracarboxylic acid or its acid dianhydride (c) may be replaced with a trimellitic anhydride aryl ester. The arylbistrimellitic anhydride ester is, for example, a compound produced by the method described in international publication No. 2010/074065, and is an acid dianhydride in which 2 hydroxyl groups of an aromatic diol (naphthalene diol, biphenyl diol, or the like) in the structure react with carboxyl groups of 2 molecules of trimellitic anhydride to form ester bonds.

The method for reacting the diol (d) with the acid components (b) and (c) is not particularly limited, and publicly known methods can be employed. For example, JP-A-9-325494 discloses a method in which an epoxy (meth) acrylate is reacted with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140 ℃.

In this case, it is more preferable that the molar ratio of the epoxy group (meth) acrylate (diol (d)), the dicarboxylic acid or the tricarboxylic acid or the acid monoanhydride (b) of these, and the tetracarboxylic dianhydride (c) is (d): (b): (c) =1.0: 0.01 to 1.0:0.2 to 1.0.

For example, when the acid monoanhydride (b) or the acid dianhydride (c) is used, it is preferable that the molar ratio of the acid component [ (b)/2+ (c) ] to the diol (d) [ (b)/2+ (c) ]/(d) ] is more than 0.5 and 1.0 or less. When the molar ratio is 1.0 or less, the terminal of the unsaturated group-containing curable resin represented by the general formula (B2-1) does not become an acid anhydride, so that the increase in the content of unreacted acid dianhydride can be suppressed and the stability of the curable composition with time can be improved. If the molar ratio is more than 0.5, the remaining amount of unreacted components in the polymerizable unsaturated group-containing diol (d) can be suppressed from increasing, and the stability of the curable composition with time can be improved. The molar ratio of the components (B), (c) and (d) may be arbitrarily changed within the above-mentioned range for the purpose of adjusting the acid value and molecular weight of the unsaturated group-containing curable resin represented by the general formula (B2-1).

In addition, the synthesis of the diol (d) and the subsequent reaction of the polycarboxylic acid or anhydride thereof are generally carried out in a solvent, optionally with the use of a catalyst.

Examples of the solvent include a celluloid-based solvent such as ethyl celluloid Su Yisuan ester and butyl celluloid Su Yisuan ester, a high boiling point ether-based or ester-based solvent such as diethylene glycol dimethyl ether, ethyl carbitol acetate, butyl carbitol acetate and propylene glycol monomethyl ether acetate, and a ketone-based solvent such as cyclohexanone and diisobutanone. The reaction conditions of the solvent, catalyst, etc. used are not particularly limited, but, for example, a solvent having no hydroxyl group and a boiling point higher than the reaction temperature is preferably used as the reaction solvent.

The reaction of the epoxy group with the carboxyl group or the hydroxyl group is preferably performed using a catalyst. The above-mentioned catalyst is described in JP-A-9-325494 as being composed of ammonium salts such as tetraethylammonium bromide and triethylbenzyl ammonium chloride, phosphines such as triphenylphosphine and tris (2, 6-dimethoxyphenyl) phosphine.

(B2) The acid value of the component is preferably 50 to 200mgKOH/g, more preferably 60 to 150 mgKOH/g. When the acid value is 50mgKOH/g or more, residue is less likely to remain during alkali development, and when the acid value is 200mgKOH/g or less, penetration of the alkali developer is not too fast, so that peeling development can be suppressed. The acid value can be obtained by titration with a 1/10N-KOH aqueous solution using a potential difference titration apparatus "COM-1600" (manufactured by Ping Zhu Shi Zhi Shi Co., ltd.).

(B2) The weight average molecular weight (Mw) in terms of polystyrene as measured by Gel Permeation Chromatography (GPC) of the components (HLC-8220 GPC, manufactured by TOSOH Co., ltd.) is preferably 1000 or more and 40000 or less, more preferably 1500 or more and 30000 or less, still more preferably 2000 or more and 15000 or less. When the weight average molecular weight (Mw) is 1000 or more, the adhesion between the support and the adherend can be improved. In addition, when the weight average molecular weight (Mw) is 40000 or less, the solution viscosity of the curable composition suitable for application can be easily adjusted, the application to the surface of a support or adherend is not excessively time-consuming, and the adhesion to the adherend can be easily further improved. When importance is attached to the adhesive strength, the weight average molecular weight (Mw) is more preferably 1000 to 4500.

(B2) The content of the component is preferably 5 mass% or more and 60 mass% or less, more preferably 10 mass% or more and 50 mass% or less, still more preferably 10 mass% or more and 40 mass% or less, relative to the total mass of the solid matters. When the component (B2) is contained, the adhesiveness of the cured film to the adherend can be improved, and the cured film is easily absorbed by the irradiated laser light (for example, ultraviolet light) and is degraded or decomposed, so that the support and the adherend can be separated more easily. (B2) If the content of the component is 60 mass% or less, the hardness of the adhesive layer after curing is not excessively high, so that the adhesive layer is easily eroded when irradiated with light, and residues are not easily generated.

When the component (B1) and the component (B2) are used in combination, the content of the component (B2) in the curable composition is preferably 5 to 1000 parts by mass, more preferably 10 to 600 parts by mass, still more preferably 20 to 300 parts by mass, based on 100 parts by mass of the total mass of the component (B1). (B2) When the content of the component (A) is 5 parts by mass or more, the polymerizable unsaturated group contained in the resin is sufficient to form a sufficiently crosslinked structure, and thus the chemical resistance is improved. In addition, if the amount is 1000 parts by mass or less, the crosslinking density of the adhesive layer after curing is sufficient, so that the adhesive layer is easily degraded when irradiated with light, and residues are not easily generated.

(B) The content of the component is preferably 5 to 89.9 mass%, more preferably 10 to 80 mass%, and even more preferably 15 to 70 mass% when the adhesive strength is important, based on the total mass of the solid components. (B) When the content of the component is 5% by mass or more, the adhesion of the adhesive layer to the adherend can be improved, and the adhesive layer is likely to absorb the irradiated laser light (e.g., ultraviolet light) and deteriorate or decompose, so that the support and the adherend are more likely to separate. In addition, if the content is 89.9 mass% or less, the hardness (crosslinking density) of the adhesive layer after curing is not excessively high, so that the adhesive layer is easily eroded when irradiated with light, and residues are not easily generated.

1-3. (C) photopolymerization initiator

(C) The component (c) is not particularly limited as long as it is a compound capable of initiating polymerization of an additively polymerizable compound having a polymerizable unsaturated bond. (C) Examples of the component (c) include photopolymerization initiators such as acetophenone compounds, triazine compounds, benzoin compounds, diphenyl ketone compounds, thioxanthone compounds, imidazole compounds, and oxime ester compounds. In addition, in the present specification, the photopolymerization initiator includes a sensitizer.

As acetophenone compounds, there may be exemplified acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, diphenylethanedione dimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-N-morpholino-1- (4-methylthiophenyl) propane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butane-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propane-1-one, and the like. Commercial products of acetophenone compounds include, for example, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone (trade name: omnirad 379EG, manufactured by Omnirad series IGM RESINS B.V. Co., ltd.), 2-methyl-1- (4-methylthiophenyl) -2-N-morpholinopropan-1-one (trade name: omnirad 907), and APi-307 (1- (biphenyl-4-yl) -2-methyl-2-N-morpholinopropan-1-one, shenzhen UV-ChemTech Ltd.).

Examples of the triazine compound include 2,4, 6-tris (trichloromethyl) -1,3, 5-triazine, 2-methyl-4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-chlorophenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (3, 4, 5-trimethoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methylthiostyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, and 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine.

Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin-t-butyl ether and the like.

Examples of the diphenyl ketone compound include diphenyl ketone, methyl o-benzoyl benzoate, 4-phenyldiphenyl ketone, 4-benzoyl-4 '-methyldiphenyl sulfide, 3',4 '-tetrakis (t-butylperoxycarbonyl) diphenyl ketone, 2,4, 6-trimethyldiphenyl ketone, 4' -bis (N, N-diethylamino) diphenyl ketone, and the like.

Examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

The imidazole compound may be exemplified by 2- (o-chlorophenyl) -4, 5-phenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, 2,4, 5-triarylimidazole dimer, etc.

Examples of the oxime ester compound include 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -bicycloheptyl-1-ketoxime-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -adamantylmethane-1-ketoxime-O-benzoate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -adamantylmethane-1-ketoxime-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -tetrahydrofuranylmethane-1-ketoxime-O-benzoate, and, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -tetrahydrofuranylmethan-1-one oxime-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -thiophenylmethane-1-one oxime-O-benzoate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -thiophenylmethane-1-one oxime-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -morpholinomethane-1-one oxime-O-benzoate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -morpholinomethane-1-one oxime-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethane-1-ketoxime-O-bicycloheptane carboxylate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethane-1-ketoxime-O-tricyclodecane carboxylate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethane-1-ketoxime-O-adamantanecarboxylate, 1- [4- (phenylmercapto) phenyl ] octane-1, 2-dione-2-O-benzoyl oxime, 1- [ 9-ethyl-6- (2-methylbenzoyl) carbazol-3-yl ] ethanone-O-acetyl oxime, (2-methylphenyl) (7-nitro-9, 9-dipropyl-9H-fluoren-2-yl) -acetyl oxime, ethanone, 1- [7- (2-methylbenzoyl) -9, 9-dipropyl-9H-fluoren-2-yl ] -1- (O-acetyl oxime), ethanone, 1- (9, 9-dibutyl-7-nitro-9H-fluoren-2-yl) -1-O-acetyl oxime, ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyl oxime), 1, 2-octadiene, 1- [4- (phenylthio) -,2- (O-benzoyl oxime) ] Ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyl oxime), 1- (4-phenylmercaptophenyl) butane-1, 2-dione-2-oxime-O-benzoate, 1- (4-methylthiophenyl) butane-1, 2-dione-2-oxime-O-acetate, 1- (4-methylthiophenyl) butane-1-ketoxime-O-acetate, 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-carbazolo-3-yl-O-acetyl oxime, 5- (4-isopropylphenylthio) -1, 2-indene dione, 2- (O-acetyl oxime) and the like. The photopolymerization initiator may be used alone in an amount of 1 or in an amount of 2 or more.

Examples of commercial products of oxime ester-based initiators include 1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyl oxime) ] (trade name: IRGACURE OXE-01, IRGACURE series, manufactured by BASF corporation), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (0-acetyl oxime) (trade name: IRGACURE OXE-02, manufactured by BASF corporation), [8- [5- (2, 4, 6-trimethylphenyl) -11- (2-ethylhexyl) -11H-benzo [ a ] hydrazono ] [2- (2, 3-tetrafluoropropoxy) phenyl ] methanone- (O-acetyl oxime) (manufactured by BASF corporation), [ 1- [4- [4- (2-benzofuranylcarbonyl) phenyl ] thio ] phenyl ] -4-methylpentanone-1- (O-acetyl oxime) (manufactured by IRGACURE XE-04, manufactured by BASF corporation, manufactured by Lunar 6, DKSH JAPAN corporation), 1- [4- (phenylthio) phenyl ] -3-cyclopentylpropane-1, 2-dione-2- (O-benzoyl oxime) (manufactured by TR-PBG-305, manufactured by Heteropoly new materials), 1, 2-propanedione, 3-cyclohexyl-1- [ 9-ethyl-6- (2-furylcarbonyl) -9H-carbazol-3-yl ] -,2- (O-acetyl oxime) (trade name: TR-PBG-326, manufactured by new materials for powerful electronics, usa), 3-cyclohexyl-1- (6- (2- (benzoyloxy) hexanoyl) -9-ethyl-9H-carbazol-3-yl) -propane-1, 2-dione-2- (O-benzoyl oxime) (trade name: TR-PBG-391, TR-PBG-345 (manufactured by the company of the new materials for powerful front-end electronics, all state), TR-PBG-B (manufactured by the company of the front-end electronics, all state), nikkacureYJ-04 (T) (manufactured by the company of the chemical industry, japan), nikkacureIW-15 (manufactured by the company of the chemical industry, japan), ADEKA ARKLS NCI-831E (manufactured by the company of the ADEKA), omnirad 1312 (manufactured by the company IGM RESINS b.v.), DFI-020 (manufactured by the company Daito Chemix), and the like.

Of these, the component (C) is more preferably an oxime ester-based (including ketoxime) photopolymerization initiator. Since the sensitivity of the oxime ester photopolymerization initiator is high, the photosensitivity of the curable resin composition can be sufficiently improved, and the developability (resolution) of the adhesive layer can be sufficiently improved.

Examples of the oxime ester-based photopolymerization initiator include O-oxime ester-based photopolymerization initiators represented by the general formula (C-1) or the general formula (C-2).

In the formula (C-1), R ₅₁、R₅₂ independently represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic group having 4 to 12 carbon atoms, and R ₅₃ represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. The alkyl group and the aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, or a halogen, and the alkylene moiety may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond. In addition, the alkyl group may be any of a linear, branched, or cyclic alkyl group.

( In the formula (C-2), R ₅₄ and R ₅₅ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a cycloalkylalkyl group or an alkylcycloalkyl group, or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms. R ₅₆ is each independently a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, a part of the-CH ₂ -group in the alkyl or alkenyl group being optionally substituted by an-O-group. In addition, a part of hydrogen atoms in the radicals R ₅₄ to R ₅₆ may be substituted by halogen atoms )

The molar absorptivity of component (C) at 365nm is more preferably 10000L/mol cm or more. Since the photopolymerization initiator has high sensitivity, the photosensitivity of the curable composition can be further improved, and the developability (resolution) of the curable resin composition can be sufficiently improved. Examples of the photopolymerization initiator include Omnirad 1312 (IGM RESINS b.v., manufactured by Omnirad "is a registered trademark of the same company), ADEKA ARKLS NCI-831 (manufactured by ADEKA corporation," ADEKA ARKLS "is a registered trademark of the same company), and the like.

In the present specification, the molar absorptivity of the photopolymerization initiator is determined by measuring the absorbance of an acetonitrile solution having a concentration of 0.001% by weight in a 1cm quartz cell having an optical path, using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by HITACHI HIGH-TECH SCIENCE Co., ltd.).

In addition, a thermal polymerization initiator may be used as the component (C). As examples of the thermal polymerization initiator, benzoyl peroxide, lauroyl peroxide, di-t-butylperoxy hexahydroterephthalate, t-butylperoxy-2-ethylhexyl ester, organic peroxides such as 1, 1-t-butylperoxy-3, 5-trimethylcyclohexane, azobisisobutyronitrile, azobis-4-methoxy-2, 4-dimethylvaleronitrile, azobicyclohexanone-1-carbonitrile, azodibenzoyl, azo compounds such as 1,1 '-azobis (1-acetoxy-1-phenylethane), 2' -azobis (methyl isobutyrate), water-soluble catalysts such as potassium persulfate and ammonium persulfate, and redox catalysts formed by a combination of peroxides or persulfates and reducing agents may be used for general radical polymerization. The thermal polymerization initiator may be selected in consideration of the storage stability of the thermosetting resin composition of the present invention and the conditions for forming a cured product.

In addition, the component (C) may use a reactive radical generator or an acid generator.

Examples of the active radical generator include 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, 2 '-bis (o-chlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, diphenyldione (benzil), 9, 10-phenanthrenequinone, camphorquinone, phenylglyoxylic acid methyl ester, and titanocene compounds.

Examples of the acid generator include onium salts such as 4-hydroxyphenyldimethyl sulfonium p-toluenesulfonate, 4-hydroxyphenyldimethyl sulfonium hexafluoroantimonate, 4-acetoxyphenyl dimethyl sulfonium p-toluenesulfonate, 4-acetoxyphenyl/methyl/benzyl sulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl toluene sulfonates, benzoin toluene sulfonates, and the like.

(C) The content of the component is preferably 0.01 mass% or more and 20 mass% or less, more preferably 0.1 mass% or more and 10 mass% or less, relative to the total mass of the solid matters. When the content of the photopolymerization initiator is 0.01 mass% or more, photopolymerization can be promoted and the photopolymerization rate can be increased. When the content of the photopolymerization initiator is 20 mass% or less, excessive improvement in sensitivity can be suppressed, and scorching, peeling residue, and the like are less likely to occur at the time of irradiation photodegradation.

The curable composition may contain a photosensitizer in addition to the component (C).

Examples of the photosensitizer include acetophenones such as triethanolamine, triisopropanolamine, diphenyl ketone, 4' -bis-dimethylaminodiphenyl ketone (mizolone), 4-phenyldiphenyl ketone, 4' -dichlorodiphenyl ketone, hydroxydiphenyl ketone, 4' -diethylaminodiphenyl ketone, acetophenone, 2-diethoxyacetophenone, p-dimethylacetamide, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-t-butylacetophenone; benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; diphenyl ketone systems such as 2-dimethylaminoethyl benzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate (n-butoxy) ethyl ester, 4-dimethylaminobenzoate isoamyl, 4-dimethylaminobenzoate 2-ethylhexyl ester, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, 4-benzoyl-4 '-methyl-diphenyl sulfide, acrylated diphenyl ketone, 3',4 '-tetra (t-butylperoxycarbonyl) diphenyl ketone, and 3,3' -dimethyl-4-methoxydiphenyl ketone, thioxanthone systems such as 2-isopropylthioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, and 2, 4-dichlorothioxanthone; amino diphenyl ketone systems such as 4,4' -bis-diethylaminodiphenyl ketone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9, 10-phenanthrenequinone, and camphorquinone.

The content of the photosensitizer is preferably 0.5 parts by mass or more and 400 parts by mass or less, more preferably 1 part by mass or more and 300 parts by mass or less, based on 100 parts by mass of the total mass of the component (C). When the content of the photosensitizer is 0.5 parts by mass or more, the sensitivity of the photopolymerization initiator can be improved and the photopolymerization rate can be increased. When the content of the photosensitizer is 400 parts by mass or less, excessive improvement in sensitivity can be suppressed, and scorching, peeling residue, and the like are less likely to occur at the time of irradiation photodegradation.

1-4. (D) epoxy compound

The curable composition may contain a (D) epoxy compound (hereinafter also referred to simply as a (D) component). (D) The composition can improve crosslinking density after hardening, and improve chemical resistance or heat resistance.

(D) Examples of the component (B2) include compounds mentioned as raw materials of the component (B).

Of these, bisphenol a type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, and biphenyl type epoxy compounds are more preferable. The biphenyl-based epoxy compound is excellent in balance between light absorption energy required for separation by light irradiation and patterning property of the photosensitive resin composition at the time of light curing, and can increase the degree of freedom of design of the curable composition.

(D) The epoxy group equivalent of the component (A) is preferably 100g/eq to 300g/eq, more preferably 100g/eq to 250 g/eq. The number average molecular weight (Mn) of the component (E) is preferably 100 to 5000. The epoxy equivalent is 100g/eq to 300g/eq, and the number average molecular weight (Mn) is 100 to 5000, the solvent resistance of the adhesive layer can be further improved. In addition, when the epoxy equivalent is 300g/eq or less, sufficient alkali resistance can be maintained even when an alkali chemical is used in the subsequent step.

(D) The content of the component is preferably 5 mass% or more and 60 mass% or less, more preferably 10 mass% or more and 50 mass% or less, relative to the total mass of the solid components. When the content of the epoxy compound is 5% by mass or more, a sufficiently crosslinked structure can be formed and the chemical resistance can be further improved. When the content of the epoxy compound is 60 mass% or less, the crosslinking density of the adhesive layer after curing is not excessively high, so that the adhesive layer is easily degraded when irradiated with light, and residues are hardly generated.

In addition, when the component (D) is used, a hardener may be used in combination. Examples of the curing agent include amine compounds, polycarboxylic acid compounds, phenol resins, amine resins, dicyandiamide, and lewis acid complexes.

1-5. (E) solvent

(E) The solvent (hereinafter, also simply referred to as "component (E)") is a solvent that dissolves or disperses each component contained in the curable composition and improves the coatability of the curable composition on the support.

(E) Examples of the component include: alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, and diacetone alcohol; terpenes such as alpha-or beta-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone (Methyl pyrrolidone); aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as juju, methyl juju, ethyl juju, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, celluloid Su Yisuan ester, ethylcyclooid Su Yisuan ester, butylcelluloid Su Yisuan ester, carbitol acetate, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and the like. These are used and dissolved and mixed, whereby the curable composition can be formed into a uniform solution.

(E) The content of the component (a) varies depending on the target viscosity of the curable composition, but is preferably 50 mass% or more and 90 mass% or less relative to the total mass of the curable composition.

1-6 Other ingredients

The curable composition may optionally contain a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a surfactant, a coupling agent, and the like.

Examples of the curing accelerator include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, lewis acids, organometallic compounds, imidazoles, and the like which are useful for accelerating the curing of the epoxy resin. Examples of the thermal polymerization inhibitor and the antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, phenothiazine, and hindered phenol compounds. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of the filler include glass fiber, silica, mica, and alumina. Examples of the defoaming agent and the leveling agent include silicone-based, fluorine-based, and acrylic-based compounds. Examples of the surfactant include fluorine-based surfactants and silicone-based surfactants. Examples of the coupling agent include 3- (epoxypropyloxy) propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane.

2. Method for producing laminated body

The method for producing a laminate according to another embodiment of the present invention comprises (1) a step of applying the curable composition (adhesive layer-forming composition) to at least one surface of a support and an adherend to form an adhesive layer; and (2) bonding the support and the adherend via the formed adhesive layer. The steps are described below.

[ Step of Forming adhesive layer ]

The adhesive layer is formed by forming an adhesive layer containing the curable composition on at least one surface of the support and the adherend.

(Support)

The type of the support is not limited as long as the adhesive layer can be formed on the surface thereof.

In the present embodiment, the support is preferably provided with laser transmissivity. The support preferably transmits light (laser light) having a wavelength of 10nm to 450nm, more preferably transmits light (laser light) having a wavelength of 100nm to 450nm, and particularly preferably transmits light (laser light) having a wavelength of 350nm to 450 nm. Examples of the support having the above-mentioned laser transmissivity include a glass substrate, an acryl substrate, a sapphire substrate, and a quartz glass substrate. However, a glass substrate or an acryl substrate needs to be a substrate having a composition with sufficient transmittance at the wavelength of light to be used. Among the above-mentioned supports, a glass substrate is preferable because it is inexpensive.

The support preferably has a transmittance of light having a wavelength of 350nm to 450nm, and a transmittance of 70% or more in the entire wavelength range. The support having the above transmittance can sufficiently transmit the laser light (for example, 355nm or the like) of a long wavelength irradiated from the support side and reach the adhesive layer.

The transmittance is measured using an ultraviolet-visible-infrared spectrophotometer "UH4150" (hitachi-hightech, inc.) as a value based on the transmittance of the atmosphere.

(Adherend)

Examples of the adherend include a semiconductor wafer, a semiconductor chip (chip), a light emitting element, an optical glass wafer, a metal foil, a polishing pad, a resin coating film, and a wiring layer.

(Adhesive layer)

The adhesive layer is formed by applying a curable composition to at least one surface of the support and the adherend, pre-baking the composition, and patterning the composition. The adhesive layer after curing the curable composition can sufficiently absorb laser light having a long wavelength (for example, 355 nm). Therefore, by irradiating a laser beam with a long wavelength, the adherend can be sufficiently ablated and easily peeled (excellent laser processability).

Examples of the method for applying the adhesive include publicly known solution dipping methods, spin coating methods, inkjet methods, spray methods, and methods using roll coaters, knife coaters, slot coaters, and rotary machines.

After the adhesive is applied by the above-described application method, the solvent is dried (prebaked). In addition, the pre-baking may be performed by heating with an oven, a hot plate, or the like. The heating temperature and heating time in the pre-baking may be appropriately selected depending on the solvent used, and may be, for example, 1 to 10 minutes at a temperature of 60 to 110 ℃.

The thickness after the pre-baking (the thickness of the adhesive layer) can be arbitrarily selected. In this embodiment, the thickness of the adhesive layer is preferably 0.1 μm to 50 μm, more preferably 0.5 μm to 30 μm. If the thickness of the adhesive layer is 0.1 μm or more, the adhesive layer may have sufficient holding power for adhering to the adherend. If the thickness is 50 μm or less, the adhesive layer can be sufficiently cured by curing with light or heat.

In this step, the curable composition may be applied to the surface of either or both of the support and the adherend, and after prebaking, the adhesive layer may be patterned by an exposure step and a development step. By patterning, an adhesive layer can be formed only in the adherend-adhering portion, and peeling failure and displacement of the adherend in the step of separating the support and adherend (described later) can be suppressed.

In the exposure step, the pre-baked curable composition is exposed to light through a photomask. Examples of the light used for exposure include visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. The light is preferably ultraviolet (wavelength 250 to 400 nm).

In the development step, a developer suitable for alkali development is applied and the portion where light is not irradiated is removed. Examples of the developer include aqueous solutions of sodium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, and the like. These developing solutions may be appropriately selected in accordance with the characteristics of the resin layer, but a surfactant may be optionally added. The development temperature is preferably 20 ℃ to 35 ℃ inclusive, and a fine image can be precisely formed using a commercially available developing machine, an ultrasonic washing machine, or the like. Further, after alkali development, washing with water is usually performed. The development treatment method may be applied to a shower development method, a spray development method, an immersion development method, a paddle (liquid filling) development method, or the like.

[ Step of adhering support and adherend ]

The step of adhering the support and the adherend is a step of adhering the support and the adherend via the adhesive layer.

Examples of the method for bonding the support and the adherend include a method in which the surface of an adhesive layer formed on the surface of the support is brought into contact with the adherend (an adhesive is applied to the surface in contact with the adhesive layer) and heated and pressurized. The pressure-sensitive adhesive conditions between the support and the adherend are preferably room temperature to 200℃and more preferably 30℃to 150 ℃. The pressure at the time of the subsequent step is preferably 0.01MPa to 20MPa, more preferably 0.03MPa to 15 MPa. After the completion of the compression thermocompression bonding, the adhesive layer may be thermally cured at a temperature of 120 ℃ to 250 ℃. The adhesive layer is formed on the surface of the support body, and the adhesive layer is formed on the surface of the support body.

In the following step, the adhesive support and the adherend may be photo-cured. Examples of the method for photo-curing the adhesive layer include a method of irradiating light using a high-pressure mercury lamp. Further, as conditions for adhering the support and the adherend, the wavelength of the irradiated light is preferably 200nm to 500 nm. The exposure amount of the irradiated light is preferably 25mJ/cm ² to 3000mJ/cm ², more preferably 50mJ/cm ² to 2000mJ/cm ².

In the above-described manner, a laminate is formed, which has a support, an adherend, and an adhesive layer containing a cured product of the adhesive layer forming composition disposed between the support and the adherend.

3. Method for processing laminate

The method for processing a laminate according to an embodiment of the present invention includes (1) a step of preparing the laminate, and (2) a step of irradiating the laminate with light to separate the support and the adherend. The steps are described below.

[ Step of preparing laminate ]

The step of preparing the laminate is a step of forming the laminate in the above manner or a step of preparing the already formed laminate.

[ Separation step of support and adherend ]

The step of separating the support and the adherend is a step of separating the support and the adherend by irradiating light to the adhesive layer.

The irradiated light is not particularly limited as long as the support and the adherend can be separated. In the present embodiment, the light is preferably ultraviolet light. The wavelength of the light is more preferably 10nm to 450nm, still more preferably 100nm to 450nm, particularly preferably 350nm to 450 nm. When the wavelength of the light is 10nm or more, the polymer which is a component of the adhesive layer is degraded or decomposed by light absorption, and the strength and adhesion are reduced, so that the support and the adherend can be easily separated. In addition, if the wavelength of light is 450nm or less, the adhesive layer of the processing portion absorbs light, so that generation of residues of the adhesive layer can be suppressed. In addition, if the wavelength of the ultraviolet light is 350nm or more, inexpensive glass substrates and acryl substrates, particularly glass substrates, can be used, and thus running costs can be suppressed.

Examples of the light source include a low-mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a far ultraviolet lamp, and a laser light source. The light source is preferably a laser light source for irradiating laser light.

Examples of the laser include a solid laser, a liquid laser, and a gas laser. The solid-state laser may be, for example, a semiconductor excitation laser. Examples of the liquid laser include pigment lasers. The gas laser may be, for example, an excimer laser or the like. Among these, the laser light is more preferably a semiconductor excitation laser light.

Examples of the semiconductor excitation laser include Nd: YAG laser, nd: YLF laser, nd: glass laser, nd: YVO ₄ laser, yb: YAG laser, yb doped fiber laser, er: YAG laser, tm: YAG laser, and the like. Examples of the excimer laser include KrF laser, xeCl laser, arF laser, F2 laser, and the like. Of these, the laser light is more preferably Nd: YAG laser.

The output and the cumulative light amount of the light irradiated to the adhesive layer vary depending on the type of the light source or the like, but when the irradiated light is a laser beam, the output may be 0.1mW or more and 200W or less. The cumulative light amount is more preferably 1mJ/cm ² to 50J/cm ². When the cumulative light amount is 0.1mJ/cm ² or more, scorching, peeling residue and the like generated during ablation are less likely to occur. If the ratio is 50J/cm ² or less, the etching rate can be appropriately controlled and the processing can be appropriately performed.

When the adhesive layer is irradiated with light (laser light), it is preferable to irradiate the entire surface of the adhesive layer with laser light from the support side. The method of irradiating the laser is not particularly limited, and may be performed by publicly known methods.

The present embodiment may also include a step of processing the prepared laminate before the step of separating the support and the adherend.

Methods for processing the laminate include thinning of an adherend such as dicing and inner surface grinding, photofabrication, lamination of semiconductor chips (chips), mounting of various elements, resin sealing, and the like.

In addition, the present embodiment may include a step of moving the laminate subjected to the processing described above from one apparatus to another apparatus. The method of moving the laminate includes a method of moving by a robot arm, and the like.

The above-described operation is performed to process the laminate of the present embodiment.

Example (example)

Embodiments of the present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these.

First, examples of synthesis of the unsaturated group-containing alkali-soluble resin as the component (A) will be described, and the evaluation of the resin in these examples was performed in the following manner unless otherwise specified.

In addition, when the same model is used for various measuring machines, the machine manufacturer name is omitted from the second appearance. In the examples, the same treatment was performed on all glass substrates used for producing the substrates with the cured films for measurement. The contents of the components are not described below in the decimal point when the first decimal point is 0.

[ Solid concentration ]

From the resin solution obtained in the synthesis example, 1g was immersed in a glass filter [ weight: the weight [ W ₁ (g) ] after W ₀ (g) ] and the weight [ W ₂ (g) ] after heating at 130℃and 160℃for 2 hours of the component (A) were obtained as follows.

Solid concentration (wt%) =100× (W ₂-W₀)/(W₁-W₀)

[ Acid value ]

The resin solution was dissolved in dioxane and was obtained by titration with a 1/10N-KOH aqueous solution using a potential difference titration apparatus "COM-1600" (manufactured by Ping Zhu Shi Zhi Shi Co., ltd.).

[ Molecular weight ]

The weight average molecular weight (Mw) was determined as a standard polystyrene (PS-Oligomer Kit, manufactured by TOSOH Co., ltd.) conversion value by Gel Permeation Chromatography (GPC) "HLC-8220GPC" (manufactured by TOSOH Co., ltd., solvent: tetrahydrofuran, column: TSKgelSuper H-2000 (2 branches) + TSKgelSuperH-3000 (1 branch) + TSKgelSuper H-4000 (1 branch) + TSKgelSuper H-5000 (1 branch) (manufactured by TOSOH Co., ltd.), temperature: 40 ℃ C., speed: 0.6 ml/min).

Abbreviations reported in the synthesis examples are as follows.

MMA: methyl methacrylate

MA: methacrylic acid

AA: acrylic acid

GMA: glycidyl methacrylate

HPMA: 2-hydroxy propyl methacrylate

HEMA: methacrylic acid 2-hydroxy ethyl ester

MOI: methacrylic acid 2-isocyanatoethyl ester

AOI: acrylic acid 2-isocyanatoethyl ester

SA: succinic anhydride

RUVA-93:2- (2 '-hydroxy-5' -methacryloyloxyethylphenyl) -2-H-benzotriazole (molecular weight: 323.35, absorbance at 355nm, wavelength: 0.25, manufactured by tsukamurelca chemical Co., ltd.)

Tinuvin400: hydroxyphenyl triazine ultraviolet absorbent (manufactured by BASF corporation, molecular weight 583.8, absorbance of light with wavelength of 355nm of 0.12)

ADVN:2,2' -azobis (2, 4-dimethylvaleronitrile)

TPP: triphenylphosphine and process for preparing same

BPFE: bisphenol fluorene type epoxy resin (epoxy equivalent 256 g/eq)

BPDA:3,3', 4' -biphenyltetracarboxylic dianhydride

THPA:1,2,3, 6-tetrahydrophthalic anhydride

PGME: propylene glycol monomethyl ether

PGMEA: propylene glycol monomethyl ether acetate

The absorbance is a value obtained by measuring the absorbance of an acetonitrile solution having a concentration of 0.001% by weight in a 1cm quartz cell having an optical path using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by HITACHI HIGH-TECH SCIENCE Co., ltd.).

Synthesis example A-1

233 Parts by weight of PGME, 59 parts by weight (0.18 mol) of RUVA-93, 0.047 parts by weight (0.047 mmol) of MMA and 28 parts by weight (0.32 mol) of MA, which are unsaturated monomers having an ultraviolet ray absorbing group, were added to a reactor equipped with a temperature regulator, a stirrer, a reflux cooler, and a nitrogen inlet tube, and the mixture was heated to 80℃and then replaced with nitrogen. The reaction was allowed to proceed for 1 hour by adding 4 parts by weight of ADVN as a polymerization initiator. Thereafter, 0.5 parts by weight of ADVN was added thereto and the mixture was heated to 90 ℃ to age it for 3 hours to synthesize an ultraviolet-absorbing copolymer. Cooled to 70 ℃, 31 parts by weight (0.22 mol) of GMA, 2 parts by weight of a quaternary ammonium salt of a catalyst, and 0.03 parts by weight of hydroquinone monomethyl ether of a polymerization inhibitor were added, and the addition reaction of GMA to the ultraviolet-absorbing polymer was carried out at 90 ℃ for 24 hours. The end point of the reaction is the epoxide equivalent when the titration procedure is used and the epoxide reaction is 90% converted. PGME was added thereto and adjusted so that the solid content became 30% by weight, to obtain the inventive product (A-1). The acid value (in terms of solids) of the obtained resin solution was 65mgKOH/g, the Mw by GPC analysis was 18000, the structural unit (AA) containing an ultraviolet absorbing group as calculated from the addition ratio was 36.0 mol%, and the acrylic acid equivalent as calculated from the addition ratio was 539.5.

Synthesis example A-2

233 Parts by weight of PGME, 58 parts by weight (0.18 mol) of RUVA-93, 23 parts by weight (0.23 mol) of MMA and 19 parts by weight (0.22 mol) of MA, which are unsaturated monomers having an ultraviolet light absorbing group, were added to a reactor equipped with a temperature regulator, a stirrer, a reflux cooler and a nitrogen introduction tube, and the mixture was heated to 80℃and then replaced with nitrogen. The reaction was allowed to proceed for 1 hour by adding 4 parts by weight of ADVN as a polymerization initiator. Thereafter, 0.5 parts by weight of ADVN was added thereto and the mixture was heated to 90 ℃ to age it for 3 hours to synthesize an ultraviolet-absorbing copolymer. After cooling to 70℃16 parts by weight (0.12 mol) of GMA, 2 parts by weight of a quaternary ammonium salt of a catalyst and 0.03 parts by weight of hydroquinone monomethyl ether of a polymerization inhibitor were added, and the addition reaction of GMA to an ultraviolet-absorbing polymer was carried out at 90℃for 24 hours. The end point of the reaction is the epoxide equivalent when the titration procedure is used and the epoxide reaction is 90% converted. PGME was added thereto and adjusted so that the solid content became 30% by weight, to obtain the inventive product (A-2). The acid value (in terms of solid matter) of the obtained resin solution was 59mgKOH/g, mw by GPC analysis was 16000, the structural unit (AA) containing an ultraviolet absorbing group calculated from the addition ratio was 28.7 mol%, and the acrylic acid equivalent calculated from the addition ratio was 1001.1.

Synthesis example A-3

233 Parts by weight of PGMEA, 64 parts by weight (0.20 mol) of RUVA-93, 5.6 parts by weight (0.06 mol) of MMA, and 24 parts by weight (0.17 mol) of HPMA were added to a reactor equipped with a temperature regulator, a stirrer, a reflux cooler, and a nitrogen inlet tube, and the mixture was heated to 80℃and then replaced with nitrogen. The reaction was allowed to proceed for 1 hour by adding 4 parts by weight of ADVN as a polymerization initiator. Thereafter, 0.5 parts by weight of ADVN was added thereto and the mixture was heated to 90 ℃ to age it for 3 hours to synthesize an ultraviolet-absorbing copolymer. To this, 27 parts by weight (0.17 mol) of MOI, 0.01 part by weight of a tin compound as a catalyst and 0.04 part by weight of hydroquinone monomethyl ether as a polymerization inhibitor were added, and the addition reaction of MOI to the ultraviolet-absorbing copolymer was carried out at 60℃for about 6 hours. The end point of the reaction was the disappearance of the isocyanate peak confirmed by FT-IR. After the completion of the reaction, PGMEA was added thereto and the mixture was adjusted so that the solid content became 30% by weight, to obtain the inventive product (A-3). The acid value (in terms of solids) of the obtained resin solution was 59mgKOH/g, the Mw by GPC analysis was 17000, the structural unit (AA) containing an ultraviolet absorbing group as calculated from the addition ratio was 37.1 mol%, and the acrylic acid equivalent as calculated from the addition ratio was 761.2.

Synthesis example A-4

233 Parts by weight of PGMEA, 59 parts by weight (0.18 mol) of RUVA-93, which is an ultraviolet-absorbing group-containing unsaturated monomer, 16 parts by weight (0.16 mol) of MMA, 9.0 parts by weight (0.10 mol) of MA, and 15 parts by weight (0.12 mol) of HEMA were added to a reactor equipped with a temperature regulator, a stirrer, a reflux cooler, and a nitrogen inlet tube, and the mixture was heated to 80℃and then replaced with nitrogen. The reaction was allowed to proceed for 1 hour by adding 4 parts by weight of ADVN as a polymerization initiator. Thereafter, 0.5 parts by weight of ADVN was added thereto and the mixture was heated to 90 ℃ to age it for 3 hours to synthesize an ultraviolet-absorbing copolymer. To this, 18 parts by weight (0.12 mol) of MOI, 0.01 part by weight of a tin compound as a catalyst and 0.04 part by weight of hydroquinone monomethyl ether as a polymerization inhibitor were added, and the addition reaction of MOI to the ultraviolet-absorbing copolymer was carried out at 60℃for about 6 hours. The end point of the reaction was the disappearance of the isocyanate peak confirmed by FT-IR. After the completion of the reaction, PGMEA was added thereto and the mixture was adjusted so that the solid content became 30% by weight, to obtain the inventive product (A-4). The acid value (in terms of solid matter) of the obtained resin solution was 52mgKOH/g, the Mw by GPC analysis was 16000, the structural unit (AA) containing an ultraviolet absorbing group as calculated from the addition ratio was 32.1 mol%, and the acrylic acid equivalent as calculated from the addition ratio was 1001.0.

Synthesis example A-5

233 Parts by weight of PGMEA, 59 parts by weight (0.18 mol) of RUVA-93, which is an ultraviolet-absorbing group-containing unsaturated monomer, 16 parts by weight (0.16 mol) of MMA, 9.0 parts by weight (0.10 mol) of MA, and 15 parts by weight (0.12 mol) of HEMA were added to a reactor equipped with a temperature regulator, a stirrer, a reflux cooler, and a nitrogen inlet tube, and the mixture was heated to 80℃and then replaced with nitrogen. The reaction was allowed to proceed for 1 hour by adding 2 parts by weight of ADVN as a polymerization initiator. Thereafter, 0.5 parts by weight of ADVN was added thereto and the mixture was heated to 90 ℃ to age it for 3 hours to synthesize an ultraviolet-absorbing copolymer. To this, 18 parts by weight (0.12 mol) of MOI, 0.01 part by weight of a tin compound as a catalyst and 0.04 part by weight of hydroquinone monomethyl ether as a polymerization inhibitor were added, and the addition reaction of MOI to the ultraviolet-absorbing copolymer was carried out at 60℃for about 6 hours. The end point of the reaction was the disappearance of the isocyanate peak confirmed by FT-IR. After the completion of the reaction, PGMEA was added thereto and the mixture was adjusted so that the solid content became 30% by weight, to obtain the inventive product (A-5). The acid value (in terms of solids) of the obtained resin solution was 55mgKOH/g, the Mw by GPC analysis was 30000, the structural unit (AA) containing an ultraviolet absorbing group as calculated from the addition ratio was 32.1 mol%, and the acrylic acid equivalent as calculated from the addition ratio was 1001.0.

Synthesis example A-6

233 Parts by weight of PGMEA, 59 parts by weight (0.18 mol) of RUVA-93, which is an ultraviolet-absorbing group-containing unsaturated monomer, 16 parts by weight (0.16 mol) of MMA, 9.0 parts by weight (0.10 mol) of MA, and 15 parts by weight (0.12 mol) of HEMA were added to a reactor equipped with a temperature regulator, a stirrer, a reflux cooler, and a nitrogen inlet tube, and the mixture was heated to 80℃and then replaced with nitrogen. The reaction was allowed to proceed for 1 hour by adding 1 part by weight of ADVN as a polymerization initiator. Thereafter, 0.5 parts by weight of ADVN was added thereto and the mixture was heated to 90 ℃ to age it for 3 hours to synthesize an ultraviolet-absorbing copolymer. To this, 18 parts by weight (0.12 mol) of MOI, 0.01 part by weight of a tin compound as a catalyst and 0.04 part by weight of hydroquinone monomethyl ether as a polymerization inhibitor were added, and the addition reaction of MOI to the ultraviolet-absorbing copolymer was carried out at 60℃for about 6 hours. The end point of the reaction was the disappearance of the isocyanate peak confirmed by FT-IR. After the completion of the reaction, PGMEA was added thereto and the mixture was adjusted so that the solid content became 30% by weight, to obtain the inventive product (A-6). The acid value (in terms of solids) of the obtained resin solution was 63mgKOH/g, the Mw by GPC analysis was 48000, the structural unit (AA) containing an ultraviolet absorbing group as calculated from the addition ratio was 32.1 mol%, and the acrylic acid equivalent as calculated from the addition ratio was 1001.0.

Synthesis example A-7

233 Parts by weight of PGMEA, 59 parts by weight (0.18 mol) of RUVA-93, which is an ultraviolet-absorbing group-containing unsaturated monomer, 16 parts by weight (0.16 mol) of MMA, 9 parts by weight (0.10 mol) of MA, and 15 parts by weight (0.12 mol) of HEMA were added to a reactor equipped with a temperature regulator, a stirrer, a reflux cooler, and a nitrogen inlet tube, and the mixture was heated to 80℃and then replaced with nitrogen. The reaction was allowed to proceed for 1 hour by adding 4 parts by weight of ADVN as a polymerization initiator. Thereafter, 0.5 parts by weight of ADVN was added thereto and the mixture was heated to 90 ℃ to age it for 3 hours to synthesize an ultraviolet-absorbing copolymer. 17 parts by weight (0.12 mol) of AOI, 0.01 part by weight of a tin compound as a catalyst, and 0.04 part by weight of hydroquinone monomethyl ether as a polymerization inhibitor were added thereto, and the addition reaction of AOI to the ultraviolet-absorbing copolymer was carried out at 60℃for about 6 hours. The end point of the reaction was the disappearance of the isocyanate peak confirmed by FT-IR. After the completion of the reaction, PGMEA was added thereto and the mixture was adjusted so that the solid content became 30% by weight, to obtain the inventive product (A-7). The acid value (in terms of solids) of the obtained resin solution was 58mgKOH/g, the Mw by GPC analysis was 17000, the structural unit (AA) containing an ultraviolet absorbing group as calculated from the addition ratio was 32.1 mol%, and the acrylic acid equivalent as calculated from the addition ratio was 986.1.

Synthesis example A-8

233 Parts by weight of PGMEA as a solvent, 67 parts by weight (0.21 mol) of RUVA-93 as an ultraviolet-absorptive-group-containing unsaturated monomer, and 34 parts by weight (0.24 mol) of GMA as another unsaturated monomer were charged into a reactor equipped with a temperature regulator, a stirrer, a reflux cooler, and a nitrogen introduction tube, and the mixture was heated to 80℃and then replaced with nitrogen. The reaction was allowed to proceed for 1 hour by adding 4 parts by weight of ADVN as a polymerization initiator. Thereafter, 0.5 parts by weight of ADVN was added thereto and the mixture was heated to 90 ℃ to age it for 3 hours to synthesize an ultraviolet-absorbing copolymer. Cooled to 70 ℃, 21 parts by weight (0.24 mol) of MA, 2 parts by weight of a quaternary ammonium salt of a catalyst, and 0.03 parts by weight of hydroquinone monomethyl ether of a polymerization inhibitor were added, and the addition reaction of MA to the ultraviolet-absorbing copolymer was carried out at 90℃for about 10 hours. The reaction end point was the end point of using the equivalent amount of epoxy groups calculated by the titration method and taking the equivalent amount of epoxy groups at the time of conversion of 90% by the epoxy group reaction. Thereafter, 12 parts by weight (0.12 mol) of succinic anhydride of a polybasic acid anhydride was added to impart a carboxyl group, and the reaction was carried out at 90℃for about 28 hours. The end point of the reaction is the use of an acid value or the disappearance of the peak of the anhydride can be confirmed by IR measurement. The reaction end point is determined here by the acid number. If neither of them is added, the reaction is ended at a point in time when the acid valence difference in the ring-opening of the polybasic acid anhydride to water is within 2 mmgKOH/g. PGMEA was added thereto and adjusted so that the solid content became 30 wt%, to obtain the present invention (a-8). The acid value (in terms of solids) of the obtained resin solution was 60mgKOH/g, the Mw by GPC analysis was 32000, the structural unit (AA) containing an ultraviolet absorbing group as calculated from the addition ratio was 46.2 mol%, and the acrylic acid equivalent as calculated from the addition ratio was 555.4.

Synthesis example A-9

233 Parts by weight of PGMEA, 61 parts by weight (0.19 mol) of RUVA-93, 8 parts by weight (80 mmol) of MMA, 14 parts by weight (0.11 mol) of HEMA, 17 parts by weight (0.12 mol) of GMA, and the mixture were heated to 80℃and then replaced with nitrogen. The reaction was allowed to proceed for 1 hour by adding 4 parts by weight of ADVN as a polymerization initiator. Thereafter, 0.5 parts by weight of ADVN was added thereto and the mixture was heated to 90 ℃ to age it for 3 hours to synthesize an ultraviolet-absorbing copolymer. The reaction mixture was cooled to 70℃and then added with 11 parts by weight (0.12 mol) of MA, 2 parts by weight of a quaternary ammonium salt of a catalyst and 0.03 part by weight of hydroquinone monomethyl ether as a polymerization inhibitor, whereby the addition reaction of methacrylic acid to the ultraviolet-absorbing copolymer was carried out at 90℃for about 10 hours. The reaction end point was the end point of using the equivalent amount of epoxy groups calculated by the titration method and taking the equivalent amount of epoxy groups at the time of conversion of 90% by the epoxy group reaction. 11 parts by weight (0.11 mol) of succinic anhydride of a polybasic acid anhydride was then added to impart a carboxyl group, and the reaction was carried out at 90℃for about 28 hours. If neither of them is added, the reaction is ended at a point in time when the acid valence difference in the ring-opening of the polybasic acid anhydride to water is within 2 mmgKOH/g. PGMEA was added thereto and adjusted so that the solid content became 30 wt%, to obtain the present invention (a-9). The acid value (in terms of solids) of the obtained resin solution was 65mgKOH/g, the Mw by GPC analysis was 25000, the structural unit (AA) containing an ultraviolet absorbing group as calculated from the addition ratio was 37.7 mol%, and the acrylic acid equivalent as calculated from the addition ratio was 1000.9.

Synthesis example A-10

233 Parts by weight of PGMEA, 59 parts by weight (0.18 mol) of RUVA-93, which is an ultraviolet-absorbing group-containing unsaturated monomer, 16 parts by weight (0.16 mol) of MMA, 9 parts by weight (0.10 mol) of MA, and 18 parts by weight (0.12 mol) of MOI were added to a reactor equipped with a temperature regulator, a stirrer, a reflux cooler, and a nitrogen inlet tube, and the mixture was heated to 80℃and then replaced with nitrogen. The reaction was allowed to proceed for 1 hour by adding 4 parts by weight of ADVN as a polymerization initiator. Thereafter, 0.5 parts by weight of ADVN was added thereto and the mixture was heated to 90 ℃ to age it for 3 hours to synthesize an ultraviolet-absorbing copolymer. 15 parts by weight (0.12 mol) of HEMA, 0.01 part by weight of a tin compound as a catalyst and 0.04 part by weight of hydroquinone monomethyl ether as a polymerization inhibitor were added thereto, and the addition reaction of HEMA to the ultraviolet-absorbing copolymer was carried out at 60℃for about 6 hours. The end point of the reaction was the disappearance of the isocyanate peak confirmed by FT-IR. After the completion of the reaction, PGMEA was added thereto and the mixture was adjusted so that the solid content became 30% by weight, to obtain the inventive product (A-10). The acid value (in terms of solids) of the obtained resin solution was 63mgKOH/g, the Mw by GPC analysis was 19000, the structural unit (AA) containing an ultraviolet absorbing group as calculated from the addition ratio was 32.1 mol%, and the acrylic acid equivalent as calculated from the addition ratio was 1001.0.

Synthesis example A-11

A reactor equipped with a thermometer and a stirrer was charged with 500g of tetrahydrofuran as a solvent and 91 parts by weight (0.14 mol) of Tinuvin400 as an ultraviolet-absorbing monomer, followed by stirring at room temperature, followed by dropwise addition reaction with 22 parts by weight (0.21 mol) of methacryloyl chloride. Thereafter, 28 parts by weight of triethylamine was added dropwise thereto, and the mixture was stirred at room temperature for 1 hour. Then, 1.0kg of water was added to the reaction vessel, and the reaction mixture was dropped into the vessel, followed by stirring at room temperature. The resulting reaction solution was distilled off under reduced pressure to remove tetrahydrofuran until a reaction product was precipitated, and then filtered. Thereafter, further washing with 500g of water was carried out. The precipitate obtained by filtration was poured into a beaker containing 500g of water, stirred at room temperature for 30 minutes, and then filtered again. This operation was repeated 2 times, and then vacuum-dried at 40℃to obtain the intended ultraviolet-absorptive-group-containing unsaturated monomer 1.

Then, 233 parts by weight of PGMEA, 59 parts by weight (0.08 mol) of the ultraviolet-absorbing-group-containing unsaturated monomer 1, 16 parts by weight (0.16 mol) of MMA of other unsaturated monomers, 9 parts by weight (0.10 mol) of MA, and 15 parts by weight (0.12 mol) of HEMA were added to a reactor equipped with a temperature regulator, a stirrer, a reflux cooler, and a nitrogen inlet tube, and the mixture was heated to 80℃and then replaced with nitrogen. The reaction was allowed to proceed for 1 hour by adding 4 parts by weight of ADVN as a polymerization initiator. Thereafter, 0.5 parts by weight of ADVN was added thereto and the mixture was heated to 90 ℃ to age it for 3 hours to synthesize an ultraviolet-absorbing copolymer. To this, 18 parts by weight (0.12 mol) of MOI, 0.01 part by weight of a tin compound as a catalyst and 0.04 part by weight of hydroquinone monomethyl ether as a polymerization inhibitor were added, and the addition reaction of MOI to the ultraviolet-absorbing copolymer was carried out at 60℃for about 6 hours. The end point of the reaction was the disappearance of the isocyanate peak confirmed by FT-IR. After the completion of the reaction, PGMEA was added thereto and the mixture was adjusted so that the solid content became 30% by weight, to obtain the inventive product (A-11). The acid value (in terms of solids) of the obtained resin solution was 58mgKOH/g, the Mw by GPC analysis was 14000, the structural unit (AA) containing an ultraviolet absorbing group as calculated from the addition ratio was 17.8 mol%, and the acrylic acid equivalent as calculated from the addition ratio was 1001.0.

Synthesis example A-12

233 Parts by weight of PGMEA, 82 parts by weight (0.25 mol) of RUVA-93, which is an ultraviolet-absorbing group-containing unsaturated monomer, 0.1 part by weight (1 mmol) of MMA, 4 parts by weight (0.04 mol) of MA, and 14 parts by weight (0.11 mol) of HEMA were added to a reactor equipped with a temperature regulator, a stirrer, a reflux cooler, and a nitrogen inlet tube, and the mixture was heated to 80℃and then replaced with nitrogen. The reaction was allowed to proceed for 1 hour by adding 4 parts by weight of ADVN as a polymerization initiator. Thereafter, 0.5 parts by weight of ADVN was added thereto and the mixture was heated to 90 ℃ to age it for 3 hours to synthesize an ultraviolet-absorbing copolymer. To this, 17 parts by weight (0.11 mol) of MOI, 0.01 part by weight of a tin compound as a catalyst and 0.04 part by weight of hydroquinone monomethyl ether as a polymerization inhibitor were added, and the addition reaction of MOI to the ultraviolet-absorbing copolymer was carried out at 60℃for about 6 hours. The end point of the reaction was the disappearance of the isocyanate peak confirmed by FT-IR. After the completion of the reaction, PGMEA was added thereto and the mixture was adjusted so that the solid content became 30% by weight, to obtain the inventive product (A-12). The acid value (in terms of solids) of the obtained resin solution was 25mgKOH/g, the Mw by GPC analysis was 17000, the structural unit (AA) containing an ultraviolet absorbing group as calculated from the addition ratio was 62.4 mol%, and the acrylic acid equivalent as calculated from the addition ratio was 1062.7.

Synthesis example A-13

A reactor equipped with a temperature regulator, a stirrer, a reflux condenser, and a nitrogen inlet tube was charged with 233 parts by weight of PGMEA, 30 parts by weight (0.09 mol) of RUVA-93, 30 parts by weight (0.04 mol) of unsaturated monomer containing an ultraviolet-absorbing group 1, 17 parts by weight (0.17 mol) of MMA, 9 parts by weight (0.11 mol) of MA, and 16 parts by weight (0.12 mol) of HEMA, and the mixture was heated to 80℃and then replaced with nitrogen. The reaction was allowed to proceed for 1 hour by adding 4 parts by weight of ADVN as a polymerization initiator. Thereafter, 0.5 parts by weight of ADVN was added thereto and the mixture was heated to 90 ℃ to age it for 3 hours to synthesize an ultraviolet-absorbing copolymer. To this, MOI19 parts by weight (0.12 mol), 0.01 part by weight of a tin compound as a catalyst, and 0.04 part by weight of hydroquinone monomethyl ether as a polymerization inhibitor were added, and the addition reaction of MOI to the ultraviolet-absorbing copolymer was carried out at 60℃for about 6 hours. The end point of the reaction was the disappearance of the isocyanate peak confirmed by FT-IR. After the completion of the reaction, PGMEA was added thereto and the mixture was adjusted so that the solid content became 30% by weight, to obtain the inventive product (A-13). The acid value (in terms of solids) of the obtained resin solution was 60mgKOH/g, the Mw by GPC analysis was 15000, the structural unit (AA) containing an ultraviolet absorbing group as calculated from the addition ratio was 25.6 mol%, and the acrylic acid equivalent as calculated from the addition ratio was 1001.0.

Synthesis example B2-1

BPFE50 parts by weight (0.10 mol), AA14 parts by weight (0.20 mol), TPP0.26 parts by weight, and PGMEA40 parts by weight were charged into a reactor equipped with a temperature regulator, a stirrer, and a reflux condenser, and stirred at 100 to 105℃for 12 hours to obtain a reaction product. Thereafter, 25 parts by weight of PGMEA was added thereto, and the mixture was adjusted so that the solid content became 50 mass%.

Then, 14 parts by weight (0.05 mol) of BPDA and 7 parts by weight (0.05 mol) of THPA were added to the obtained reaction product, and the mixture was stirred at 115 to 120℃for 6 hours to obtain an unsaturated group-containing curable resin (B2) -1. The solid concentration of the obtained resin solution was 57% by mass, the acid value (in terms of solid matter) was 96mgKOH/g, and the Mw by GPC analysis was 3600.

Synthesis example B2-2

Next, 10 parts by weight (0.03 mol) of BPDA and 12 parts by weight (0.08 mol) of THPA were added to the obtained reaction product, and the mixture was stirred at 115 to 120℃for 6 hours to obtain an unsaturated group-containing curable resin (B2) -2. The solid concentration of the obtained resin solution was 57 mass%, the acid value (in terms of solid matter) was 98mgKOH/g, and the Mw by GPC analysis was 2300.

Synthesis examples B2-3

Then, 19 parts by weight (0.07 mol) of BPDA and 0.30 parts by weight (0.002 mol) of THPA were added to the obtained reaction product, and the mixture was stirred at 115 to 120℃for 6 hours to obtain an unsaturated group-containing curable resin (B2) -3. The solid concentration of the obtained resin solution was 56% by mass, the acid value (in terms of solid content) was 97mgKOH/g, and the Mw by GPC analysis was 4700.

The adhesive layer-forming compositions were prepared in the amounts (in parts by mass) shown in tables 1 to 5. The blending components used in tables 1 to 5 are as follows.

(Unsaturated group-containing alkali-soluble resin having ultraviolet absorbing group)

(A) -1: the resin solution obtained in Synthesis example A-1 (solid content: 30% by mass)

(A) -2: the resin solution obtained in Synthesis example A-2 (solid content: 30% by mass)

(A) -3: the resin solution obtained in Synthesis example A-3 (solid content: 30% by mass)

(A) -4: the resin solution obtained in Synthesis example A-4 (solid content: 30% by mass)

(A) -5: the resin solution obtained in Synthesis example A-5 (solid content: 30% by mass)

(A) -6: the resin solution obtained in Synthesis example A-6 (solid content: 30% by mass)

(A) -7: the resin solution obtained in Synthesis example A-7 (solid content: 30% by mass)

(A) -8: the resin solution obtained in Synthesis example A-8 (solid content: 30% by mass)

(A) -9: the resin solution obtained in Synthesis example A-9 (solid content: 30% by mass)

(A) -10: the resin solution obtained in Synthesis example A-10 (solid content: 30% by mass)

(A) -11: the resin solution obtained in Synthesis example A-11 (solid content: 30% by mass)

(A) -12: the resin solution obtained in Synthesis example A-12 (solid content: 30% by mass)

(A) -13: the resin solution obtained in Synthesis example A-13 (solid content: 30% by mass)

(Polymerizable Compound having no ultraviolet absorbing group)

(B1) -1: mixtures of dipentaerythritol pentaacrylate and hexaacrylate (DPHA, manufactured by Japanese chemical Co., ltd.)

(B1) -2: ethylene oxide 6 mole adduct of trimethylolpropane triacrylate (Aronix M-360, manufactured by Toyama Synthesis Co., ltd.)

(B1) -3: ethylene oxide 12 mole adduct of dipentaerythritol hexaacrylate (KAYARAD DPEA-12, manufactured by Japanese chemical Co., ltd.)

(B1) -4: epsilon-caprolactone 6 mole adduct of dipentaerythritol hexaacrylate (KAYARAD DPCA-60, manufactured by Japanese chemical Co., ltd.)

(B2) -1: synthesis example B2-1 gave a resin solution (solid content: 57% by mass)

(B2) -2: synthesis example B2-2 gave a resin solution (solid content: 57% by mass)

(B2) -3: the resin solution (solid content: 56% by mass) obtained in Synthesis example B2-3

(Photopolymerization initiator)

(C) -1: ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (0-acetyl oxime) (Irgacure OXE-02, manufactured by BASF JAPAN Co., ltd., "Irgacure" is a registered trademark of the same company)

(C) -2: oxime ester photopolymerization initiator (ADEKA ARKLS NCI-8231E, manufactured by ADEKA Co., ltd.)

(C) -3:2- [4- (methylthio) benzoyl ] -2- (4-morpholinyl) propane ("Omnirad 907"IGM Resins B.V. Co., ltd., "Omnirad" is a registered trademark of the same company)

(C) -4: oxime ester photopolymerization initiator (TR-PBG-345, manufactured by Hemsl front end electronics Co., ltd.)

(C) -5: oxime ester photopolymerization initiator (TR-PBG-B, manufactured by Changzhou Strong front-end electronics Co., ltd.)

(C) -6: oxime ester photopolymerization initiator (NikkacureYJ-04 (T), japanese chemical industry Co., ltd.)

(C) -7: oxime ester-series photopolymerization initiator (NikkacureIW-15, japanese chemical industry Co., ltd.)

(Epoxy resin)

(D) : tetramethyl biphenyl diphenol type solid epoxy resin (jER YX4000HK, mitsubishi chemical Co., ltd., epoxy equivalent weight 180 g/eq)

(Solvent)

(E) : propylene Glycol Monomethyl Ether Acetate (PGMEA)

(Sensitizer)

(F) :2, 4-Diethylthioxanthone (KAYACURE DETX-S, manufactured by Japanese chemical Co., ltd.)

(Ultraviolet absorbent containing no alkali-soluble group and unsaturated group)

(X): polymer ultraviolet absorbing resin (UVA-5080, new Zhongcun chemical Co., ltd.)

TABLE 1

TABLE 2

TABLE 3

TABLE 4

TABLE 5

[ Evaluation ]

The cured film obtained by curing the adhesive layer-forming composition was evaluated as follows.

[ Preparation of a substrate with a cured film for evaluation of transmittance and laser processability ]

Each adhesive layer-forming composition was applied to a synthetic quartz glass substrate (hereinafter referred to as "quartz glass substrate") having a surface of 125mm×125mm, which was previously irradiated with ultraviolet light having an illuminance of 1000mJ/cm ² at a wavelength of 254nm by a low-pressure mercury lamp, so that the film thickness after the heat-hardening treatment became 1.0 μm, using a spin coater, and was pre-baked at 90 ℃ for 3 minutes by using a heating plate to prepare a dry film. Then, the cured film (coated film) was obtained by actual curing (post-baking) at 250℃for 30 minutes using a hot air dryer. The transmittance of light at a wavelength of 350nm to 450nm of the synthetic quartz glass substrate is 90% or more over the entire wavelength range.

The transmittance was measured using an ultraviolet-visible-infrared spectrophotometer "UH4150" (HITACHI HIGH-TECH SCIENCE, inc.) with the transmittance of the quartz glass single body as a baseline.

[ Transmittance evaluation ]

The transmittance of the substrate with the cured film after the actual curing was measured at 355nm and 400nm wavelengths using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by HITACHI HIGH-TECH SCIENCE Co., ltd.).

[ Evaluation of laser processability (peelability) ]

(Evaluation method)

The Nd was excited with a flash lamp with respect to the hardened film after the actual hardening: YAG Q-SW laser oscillator "Calisto" (manufactured by V-Technology Co., ltd.) irradiates laser light (laser wavelength: 355 nm) from the quartz glass substrate side. The cured film was processed (coating film was removed) with a laser energy of 100 to 600mJ/cm ², and the processed cured film was observed with an optical microscope. Further, Δ or more is a pass.

(Evaluation criterion)

The following is true: no film residue at the laser irradiation part below 400mJ/cm ²

O: no coating residue at the laser irradiation part of more than 400mJ/cm ² and less than 500mJ/cm ²

Delta: no coating residue at the laser irradiation part of more than 500mJ/cm ² and less than 600mJ/cm ²

X: coating film residue at laser irradiation part exceeding 600mJ/cm ²

[ Production of a substrate with a cured film for evaluation of adhesive Strength ]

Each adhesive layer-forming composition was applied to a glass substrate "#1737" using a spin coater so that the film thickness after the heat-hardening treatment became 5.0 μm, and was pre-baked at 90℃for 3 minutes using a heating plate to prepare a dry film. Subsequently, a glass substrate "#1737" cut to 2mm×2mm was placed on the dried film, heated on a heating plate at 110℃for 1 minute and temporarily attached. Thereafter, the resultant was subjected to actual curing (post-baking) at 230℃for 30 minutes using a hot air dryer, thereby obtaining a cured film-attached substrate.

[ Evaluation of adhesive Strength (shear Strength) ]

(Evaluation method)

The adhesion strength of a 2mm×2mm glass substrate "#1737" adhered to a cured film was tested by a bare die shear tester (Arctec). Further, Δ or more is a pass.

(Evaluation criterion)

And (3) the following materials: the adhesive strength is 20MPa or more

O: the adhesive strength is 10MPa or more and less than 20MPa

Delta: the adhesive strength is 5MPa or more and less than 10MPa

X: the adhesive strength is less than 5MPa

[ Production of cured film-attached substrate for evaluation of developability ]

Each adhesive layer-forming composition was applied to a glass substrate "#1737" with a spin coater so that the film thickness after the heat-hardening treatment was 5.0 μm, and was pre-baked at 90℃for 3 minutes with a heating plate to prepare a dry film. Then, a negative mask of 10 to 50 μm (5 μm scale) was covered on the dried film, and a light curing reaction was performed by irradiating 500mJ/cm ² of ultraviolet light with a high-pressure mercury lamp having an i-line illuminance of 30mW/cm ².

Subsequently, the exposed cured film was subjected to Dip development with a 0.8% aqueous tetramethylammonium hydroxide solution at 25 ℃, and after a development time (film breaking time=bt) from which the development treatment was performed until the pattern was started to be displayed was 20 seconds, the exposed portion of the cured film was removed by washing with water, and a cured film pattern was formed on a glass substrate, and the cured film was actually cured (post-baked) at 230 ℃ for 30 minutes using a hot air dryer, thereby obtaining a substrate with a cured film for development evaluation.

The following evaluation was performed using the cured film-attached substrate for development property evaluation.

[ Evaluation of developability ]

(Pattern Forming Property)

(Evaluation method)

The actual cured (post-baked) 20 μm mask pattern was observed with an optical microscope. Further, Δ or more is a pass.

(Evaluation criterion)

And (2) the following steps: patterning

Delta: a part is not patterned

X: unpatterned

[ Production of cured film for evaluation of Heat resistance, chemical resistance and washing Property ]

Each adhesive layer-forming composition was applied to a glass substrate "#1737" using a spin coater so that the film thickness after the heat-hardening treatment became 5.0 μm, and was pre-baked at 90℃for 3 minutes using a heating plate to prepare a dry film. Thereafter, the cured film was actually cured (post-baked) at 230℃for 30 minutes using a hot air dryer to obtain a substrate with a cured film. In addition, the resulting cured film was cut out at the time of heat resistance evaluation and used for measurement of TG-DTA.

[ Evaluation of Heat resistance ]

(Evaluation method)

The powder of the obtained cured film was heated from 30℃to 400℃in air at a heating rate of 5℃per minute by using a TG-DTA apparatus "TG/DTA6200" (manufactured by Seiko Instruments Co., ltd.) to measure a temperature at which the weight of the specimen was reduced by 5%. Further, Δ or more is a pass.

(Evaluation criterion)

O: 5% weight reduction temperature of 280 ℃ or higher

Delta: a weight reduction temperature of 5% of more than 250 ℃ and less than 280 DEG C

X: 5% weight reduction temperature of less than 250 DEG C

[ Evaluation of solvent resistance ]

(Evaluation method)

The cured film (coating film) of the substrate with the cured film was immersed in N-methylpyrrolidone (Methyl pyrrolidone) for 10 minutes, and then washed and dried. Thereafter, the film thickness of the cured film (coating film) after the test was measured by using a stylus type height difference shape measuring device "P-17" (manufactured by KLA-Tencor Co., ltd.). Further, Δ or more is a pass.

The residual film ratio in the drug resistance evaluation was calculated by the following formula, with the film thickness before the test being L1 and the film thickness after the test being L2.

Residual film ratio (%) =l2/l1×100

(Evaluation criterion)

O: the residual film rate is more than 90 percent

Delta: the residual film rate is more than 80% and less than 90%

X: the residual film rate is less than 80 percent

[ Evaluation of detergency ]

(Evaluation method)

The cured film (coating film) of the substrate with the cured film was immersed in a washing liquid "NK poleve 480" (manufactured by japan chemical Co., ltd.) at room temperature for 10 minutes, and the cured film (coating film) was washed. Thereafter, the glass substrate after the test was washed and dried, and the presence or absence of residues on the glass substrate was confirmed by an optical microscope. Further, Δ or more is a pass.

(Evaluation criterion)

O: no residue was confirmed on the glass substrate

Delta: a part of the residue on the glass substrate was confirmed

X: the residue was completely confirmed on the glass substrate

The evaluation results are shown in tables 6 to 10.

TABLE 6

TABLE 7

TABLE 8

TABLE 9

TABLE 10

As shown in tables 6 to 10, it was found that the laminate using the adhesive layer-forming composition for adhesive layers had a low transmittance at 355nm and excellent processability (releasability) of laser light at 355 nm. The reason for this is considered to be that the adhesive layer absorbs light of the wavelength efficiently by adding the component (a) and the adhesive layer is degraded and decomposed.

It was found that by setting the amount of component (a) to 10 mass% or more relative to the total mass of the solid matter, a cured film excellent in patterning properties can be obtained while ensuring good laser processability (releasability). The reason for this is considered that the unsaturated group of the component (a) can improve the sensitivity of the coating film after drying, and the alkali-soluble group can improve the solubility of the developer, so that the development characteristics can be ensured even when the amount of the additive is high.

It has been found that by setting the amount of component (a) to be 10 mass% or more and 80 mass% or less relative to the total mass of the solid components, good laser processability (releasability) can be ensured, and a cured film excellent in patterning properties, adhesive strength and chemical resistance can be obtained. The reason for this is considered to be that the unsaturated groups of the component (B1) or the component (B2) are polymerized and thermally cured, and the strength of the cured film can be improved and the dissolution into the solvent can be suppressed.

Further, it is known that the adhesive layer forming composition containing the (meth) acrylate-containing alkylene oxide modified body or lactone modified body as the component (B1) is excellent in adhesive strength. The reason for this is considered that the component (B1) contains a compound having a high fluidity when heated, and this can improve the fluidity of the dried film when heated and then adhered.

(Industrial applicability)

The present invention can provide a laminate having an adhesive agent usable in the production of various products. In particular, a laminate suitable for a step of temporarily fixing and processing a support such as a semiconductor wafer can be provided.

Claims

1. A composition for forming an adhesive layer by bonding a support and an adherend together and separating the support and the adherend by irradiation of light,

The adhesive layer forming composition comprises:

(C) A photopolymerization initiator is used as a raw material,

2. The composition for forming an adhesive layer according to claim 1, wherein the component (A) is an acrylic copolymer having a weight average molecular weight of 1000 to 100000 and an acid value of 20 to 200mgKOH/g.

3. The composition for forming an adhesive layer according to claim 1 or 2, wherein the molar absorptivity of the component (A) at a wavelength of 355nm is 3000 or more.

4. The composition for forming an adhesive layer according to claim 1 or 2, wherein the unsaturated group-containing polymerizable compound (B) contains an unsaturated group-containing polymerizable compound (B1) having no alkali-soluble group.

5. The composition for forming an adhesive layer according to claim 4, wherein the component (B1) contains an alkylene oxide-modified or lactone-modified compound having a (meth) acryloyl group.

6. The composition for forming an adhesive layer according to claim 1 or 2, wherein the unsaturated group-containing polymerizable compound (B) contains (B2) an alkali-soluble resin,

7. The composition for forming an adhesive layer according to claim 6, wherein the alkali-soluble resin (B2) is a resin represented by the following general formula (B2-1),

In the formula (B2-1), ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, a part of hydrogen atoms constituting Ar may be substituted with a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group, R ₁ is independently an alkylene group having 2 to 4 carbon atoms, l is independently a number of 0 to 3, G is independently a (meth) acryloyl group, or a substituent represented by the following general formula (B2-2) or the following general formula (B2-3), Y is a 4-valent carboxylic acid residue, Z is independently a hydrogen atom or a substituent represented by the following general formula (B2-4), at least one of Z is a substituent represented by the following general formula (B2-4), and n is a number of 1 to 20 on average

In the formulae (B2-2) and (B2-3), R ₂ is a hydrogen atom or methyl group, R ₃ is an alkylene group or an alkylarylene group having 2 to 10 carbon atoms, R ₄ is a saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, p is a number of 0 to 10 carbon atoms, and p represents a bonding site

In the formula (B2-4), W is a 2-valent or 3-valent carboxylic acid residue, m is a number of 1 or 2, and X represents a bond site.

8. The composition for forming an adhesive layer according to claim 1 or 2, which contains an oxime ester-based photopolymerization initiator as (C) a photopolymerization initiator.

9. The composition for forming an adhesive layer according to claim 1 or 2, wherein the ultraviolet absorbing group is a functional group having a benzotriazole structure or a triazine structure.

10. A laminate is provided with:

A support body;

an adherend; and

An adhesive layer comprising a cured product of the adhesive layer forming composition according to any one of claims 1 to 9, disposed between the support and the adherend.

11. A method for manufacturing an adhesive layer comprises the following steps:

A step of applying the adhesive layer forming composition according to any one of claims 1 to 9 to at least one surface of a support and an adherend;

exposing the adhesive layer through a photomask; and

And developing the exposed adhesive layer.

12. A method for producing a laminate comprising the step of adhering the support to the adherend via the adhesive layer produced by the method for producing an adhesive layer according to claim 11.

13. A method for processing a laminate, comprising the steps of:

a step of preparing the laminate according to claim 10; and