CN114369438A

CN114369438A - Adhesive layer forming composition, method for producing laminate, and method for treating laminate

Info

Publication number: CN114369438A
Application number: CN202111195823.0A
Authority: CN
Inventors: 内田一幸; 吉村和明; 滑川崇平; 佐藤恵
Original assignee: Nippon Steel and Sumikin Chemical Co Ltd
Current assignee: Nippon Steel Chemical and Materials Co Ltd
Priority date: 2020-10-15
Filing date: 2021-10-14
Publication date: 2022-04-19
Also published as: JP2022065426A; TW202216831A; KR20220050788A

Abstract

The present invention relates to an adhesive layer forming composition having excellent laser processability, a method for producing a laminate comprising an adhesive layer of the adhesive layer forming composition, and a method for treating the laminate. The composition for forming an adhesive layer of the present invention is designed such that a support and an adherend can be separated from a laminate by irradiating the laminate with light from the support side, wherein the composition contains (A) an unsaturated group-containing alkali-soluble resin having an energy value of the lowest excited triplet state (T1) of 2.90eV or less. The method for producing a laminate of the present invention comprises: forming an adhesive layer on a surface of either or both of the support and the adherend; and a step of bonding the support to the adherend via the adhesive layer. The method for treating a laminate of the present invention comprises: a step of preparing the laminate, and a step of irradiating the laminate with light to separate the support from the adherend.

Description

Adhesive layer forming composition, method for producing laminate, and method for treating laminate

Technical Field

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

Background

In recent years, with the development of high functions of digital devices and the like, flexible displays, semiconductor chips (chips) and the like to be mounted thereon have been made thin, and it has been difficult to convey flexible displays, semiconductor chips (chips) and the like, which have been reduced in strength by thinning, by conventional automatic conveyance.

Therefore, a method for easily carrying a thinned flexible display, a semiconductor chip (chip), or the like is under study. For example, in a method of separating an adherend such as a semiconductor wafer from a support such as a glass substrate by irradiating the adhesive layer with light from the support side to the adhesive layer to modify or decompose the adhesive layer to reduce the adhesive force.

For example, patent document 1 describes a layer forming method for an electronic device, including: disposing an element on the substrate on which the resin layer is formed; and a step of separating the element disposed on the substrate from the substrate and disposing the element on another substrate by irradiating the resin layer with laser light. According to patent document 1, by using a resin having a difference between a glass transition temperature and a thermal decomposition temperature of 150 ℃ or less for the resin layer, softening of the resin at the time of laser ablation can be suppressed, and therefore, when separating the element from the substrate, chipping generated from the softened portion can be reduced.

Further, patent document 2 describes a method for processing an object, including: a step of forming a laminate having a support, a temporary fixing material (a release layer and an adhesive layer), and a treatment target; processing the object and moving the laminate; irradiating the separation layer with light; and separating the support from the object. According to patent document 2, the separation layer absorbs light rays to decompose or modify the light rays, and further, the object to be supported can be separated.

Patent document 3 describes a method of irradiating a separation layer with light to modify a polymer contained in the separation layer and separate a support from a substrate to be supported, in a laminate including the support, the substrate to be supported, an adhesive layer disposed on a surface of the substrate to be supported by the support, and the separation layer disposed between the support substrate and the substrate to be supported. According to patent document 3, since the release layer is modified by irradiation with light and loses its adhesiveness, the supporting substrate and the supported substrate can be easily separated from each other.

[ Prior art documents ]

[ patent document ]

[ patent document 1] International publication No. 2016/158264

[ patent document 2] International publication No. 2017/056662

[ patent document 3] Japanese patent No. 5580800.

Disclosure of Invention

[ problem to be solved by the invention ]

However, according to the findings of the present inventors, the laminated bodies described in patent documents 1 to 3 cannot obtain desired laser processability.

The present invention has been made in view of the above problems, and an object of the present invention is to provide an adhesive layer forming composition having excellent laser processability, and a method for producing and a method for treating a laminate having an adhesive layer containing the adhesive layer forming composition.

[ means for solving the problems ]

The present inventors have conducted studies to solve the above-described problems of the adhesive layer used for forming the laminate, and as a result, have found that an adhesive layer forming composition containing an alkali-soluble resin containing an unsaturated group is suitable as an adhesive layer, and have completed the present invention.

The composition for forming an adhesive layer of the present invention is a composition for forming an adhesive layer, which is capable of separating a support and an adherend from a laminate having an adhesive layer between the support and the adherend through which light passes by irradiating the laminate with light from the support side, wherein the composition for forming an adhesive layer contains (A) an unsaturated group-containing alkali-soluble resin as an essential component, and the energy value of the lowest excited triplet state (T1) calculated by quantum chemistry calculation of the (A) unsaturated group-containing alkali-soluble resin is 2.90eV or less.

The method for producing a laminate of the present invention comprises: forming an adhesive layer on a surface of either or both of a support and an adherend using the adhesive layer-forming composition; and a step of bonding the support to the adherend via the adhesive layer formed.

The method for treating a laminate of the present invention comprises: preparing a laminate having a support, an adhesive layer, and an adherend; and a step of irradiating light to separate the support from the attached body; wherein the support transmits light having a wavelength of 10nm to 400nm, and the adhesive layer of the laminate is irradiated with light to separate the support from the adherend.

[ Effect of the invention ]

According to the present invention, an adhesive layer-forming composition having excellent laser processability, and a method for producing and a method for treating a laminate having an adhesive layer containing the adhesive layer-forming composition can be provided.

Detailed Description

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. In the present invention, when the first digit after the decimal point is 0, the description below the decimal point may be omitted.

1. Composition for forming adhesive layer

The adhesive layer forming composition according to one embodiment of the present invention contains (a) an unsaturated group-containing alkali-soluble resin as an essential component.

[ (A) component ]

The unsaturated group-containing alkali-soluble resin which is the component (a) preferably has a polymerizable unsaturated group and an acid group for rendering alkali-soluble in 1 molecule, and more preferably has both a polymerizable unsaturated group and a carboxyl group. The resin is not particularly limited, and may be widely used. In the present invention, the component (a) is preferably an alkali-soluble resin containing an unsaturated group represented by the following general formula (1).

In the formula (1), Ar is each independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of the hydrogen atoms bonded may be substituted with a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl or aralkyl 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. R₁Each independently an alkylene group having 2 to 4 carbon atoms, and l each independently a number of 0 to 3. G is independently a (meth) acryloyl group, a substituent represented by the following general formula (2) or the following general formula (3), and Y is a 4-valent carboxylic acid residue. Each Z is independently a hydrogen atom or a substituent represented by the following general formula (4), and 1 or more substituents represented by the following general formula (4). N is a number having an average value of 1 to 20.

In the formulae (2) and (3), R₂Is a hydrogen atom or a methyl group, R₃Is C2-valent alkylene or alkylarylene of 2 to 10, R₄Is a 2-valent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number of 0 to 10.

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

Further, Y represented by the above general formula (1) preferably contains at least 1 aromatic hydrocarbon group. Examples of aromatic hydrocarbon groups include: phenyl, biphenyl, benzophenone, naphthyl, biphenyl ether, and the like. Among the above aromatic hydrocarbon groups, biphenyl, benzophenone or naphthyl are more preferable. When Y is an aromatic hydrocarbon group, the LUMO (lowest unoccupied molecular orbital) value of (a structural unit of) the resin becomes small. Accordingly, the HOMO (highest occupied molecular orbital) -LUMO energy gap is small, and the value of the lowest excited triplet state (T1) is also small.

Next, a method for producing the unsaturated group-containing alkali-soluble resin (a) represented by the general formula (1) will be described in detail.

First, an epoxide (a-1) having a bisarylfluorene skeleton (hereinafter also simply referred to as "epoxide (a-1)") which may have several oxyalkylene groups in 1 molecule represented by the following general formula (5) is reacted with either or both of (meth) acrylic acid and a (meth) acrylic acid derivative represented by the following general formula (6) or the following general formula (7) to obtain a diol compound which is an epoxy ester of (meth) acrylic acid.

Further, the bisarylfluorene skeleton is preferably a bisnaphthofluorene skeleton or a bisphenol fluorene skeleton.

In the formula (5), Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of the hydrogen atoms bonded may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl or aralkyl 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. R₁Each independently an alkylene group having 2 to 4 carbon atoms, and l each independently a number of 0 to 3.

In the formulae (6) and (7), R₂Is a hydrogen atom or a methyl group, R₃Is C2-valent alkylene or alkylarylene of 2 to 10, R₄Is a 2-valent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number of 0 to 10.

The reaction of the above-mentioned epoxide (a-1) with the above-mentioned (meth) acrylic acid or (meth) acrylic acid derivative can be carried out by a known method. For example, Japanese patent application laid-open No. 4-355450 discloses that a diol compound having a polymerizable unsaturated group is obtained by using about 2 moles of (meth) acrylic acid per 1 mole of an epoxide having 2 epoxy groups. In the present invention, the compound obtained by the above reaction is a diol (d) containing a polymerizable unsaturated group represented by formula (8) (hereinafter, also simply referred to as "diol (d) represented by general formula (8)").

(in the formula (8), Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of the hydrogen atoms bonded to the aromatic hydrocarbon group may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl or aralkyl 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 following general formula (2) or the following general formula (3), R is₁Each independently an alkylene group having 2 to 4 carbon atoms, and l each independently a number of 0 to 3).

In the synthesis of the diol (d) represented by the general formula (8) and the subsequent reaction with the polycarboxylic acid or its anhydride to produce the unsaturated group-containing alkali-soluble resin represented by the general formula (1), the reaction is usually carried out in a solvent using a catalyst as needed.

Examples of the solvent include: stachy solvents such as ethyl Stachys acetate and butyl Stachys acetate; high boiling point ether or ester solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; ketone solvents such as cyclohexanone and diisobutyl ketone. The reaction conditions of the solvent, catalyst, and the like used are not particularly limited, but it is preferable to use, for example, a solvent having no hydroxyl group and a boiling point higher than the reaction temperature as the reaction solvent.

In addition, in the reaction of epoxy group and carboxyl or hydroxyl group, preferably using a catalyst, Japanese patent laid-open No. 9-325494 describes tetraethylammonium bromide, triethyl benzyl ammonium chloride and other ammonium salt; phosphines such as triphenylphosphine and tris (2, 6-dimethoxyphenyl) phosphine.

Then, the diol (d) represented by the general formula (8) obtained by the reaction of the epoxide (a-1) with the (meth) acrylic acid derivative, the dicarboxylic acid or tricarboxylic acid or anhydride thereof (b), and the tetracarboxylic acid or acid dianhydride thereof (c) are reacted to obtain the alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in 1 molecule represented by the general formula (1).

In the formula (1), Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of the hydrogen atoms bonded may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl or aralkyl 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. R₁Each independently an alkylene group having 2 to 4 carbon atoms, and l each independently a number of 0 to 3. G is independently a (meth) acryloyl group, a substituent represented by the following general formula (2) or the following general formula (3), and Y is a 4-valent carboxylic acid residue. Each Z is independently a hydrogen atom or a substituent represented by the following general formula (4), and 1 or more substituents represented by the following general formula (4). n is a number having an average value of 1 to 20.

(in the formulae (2) and (3), R₂Is a hydrogen atom or a methyl group, R₃Is C2-valent alkylene or alkylarylene of 2 to 10, R₄Is a 2-valent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number of 0 to 10).

In the formula (4), W is a 2-valent or 3-valent carboxylic acid residue, and m is 1 or 2.

In order to synthesize the acid component used for the unsaturated group-containing alkali-soluble resin represented by the general formula (1), it is necessary to use a dicarboxylic acid or tricarboxylic acid or acid monoanhydride (b) thereof and a tetracarboxylic acid or acid dianhydride (c) thereof in combination as a polyvalent acid component which is reactive with the hydroxyl group in the molecule of the diol (d) represented by the general formula (8). The carboxylic acid residue of the acid component may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. These carboxylic acid residues may contain a bond containing a hetero element such as-O-, -S-, or a carbonyl group.

Examples of the above-mentioned dicarboxylic acid or tricarboxylic acid or acid monoanhydride (b) of these include: chain hydrocarbon dicarboxylic acid or tricarboxylic acid, alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid, aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid, or acid monoanhydride thereof.

Examples of the acid monoanhydrides of the above-mentioned chain hydrocarbon dicarboxylic acids or tricarboxylic acids: examples of the acid monoanhydrides include succinic acid, acetyl succinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid (citramalic acid), malonic acid, glutaric acid, citric acid, tartaric acid, lateral oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and 3-oxoglutaric acid (diglyclic acid), and acid monoanhydrides of dicarboxylic acids or tricarboxylic acids to which an optional substituent is introduced.

Examples of the acid monoanhydrides of the alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid include: and monoanhydrides of dicarboxylic acids or tricarboxylic acids having an optional substituent introduced thereto, such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and norbornanedicarboxylic acid.

Examples of the acid monoanhydride of the aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid include: acid monoanhydrides such as phthalic acid, isophthalic acid, trimellitic acid, 1, 8-naphthalenedicarboxylic acid, and 2, 3-naphthalenedicarboxylic acid, and acid monoanhydrides of dicarboxylic acids or tricarboxylic acids into which an arbitrary substituent is introduced.

Among the acid monoanhydrides of the above-mentioned dicarboxylic acid or tricarboxylic acid, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, trimellitic acid, 1, 8-naphthalenedicarboxylic acid, and 2, 3-naphthalenedicarboxylic acid are more preferable, and tetrahydrophthalic acid, 1, 8-naphthalenedicarboxylic acid, and 2, 3-naphthalenedicarboxylic acid are still more preferable.

Among the dicarboxylic acids and tricarboxylic acids, the use of the acid monoanhydrides is more preferable. The acid monoanhydrides of the above-mentioned dicarboxylic acids or tricarboxylic acids may be used alone in 1 kind, or 2 or more kinds may be used in combination.

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

Examples of the chain hydrocarbon tetracarboxylic acid include: butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and chain hydrocarbon tetracarboxylic acids into which a substituent such as an alicyclic hydrocarbon group or an unsaturated hydrocarbon group is introduced.

Examples of the alicyclic hydrocarbon tetracarboxylic acid include: cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornane-tetracarboxylic acid, and alicyclic tetracarboxylic acids having a substituent such as a chain hydrocarbon group or an unsaturated hydrocarbon group introduced thereinto.

In addition, examples of the aromatic hydrocarbon tetracarboxylic acid include: pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenylsulfone tetracarboxylic acid, naphthalene-1, 4,5, 8-tetracarboxylic acid, naphthalene-2, 3,6, 7-tetracarboxylic acid, and the like.

In addition, bis (trimellitic anhydride) aryl esters can also be used. The bis-trimellitic anhydride aryl ester is an acid dianhydride in the form of an ester bond formed by reacting 2 hydroxyl groups of an aromatic diol (naphthalene diol, biphenol, terphenyl diol, etc.) in structure with 2 molecules of carboxyl groups of trimellitic anhydride, which is a compound produced by the method described in, for example, international publication No. 2010/074065. These compounds are described below as bis-trimellitic anhydride esters of aromatic diols.

Among the above tetracarboxylic acids or acid dianhydrides thereof, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, diphenylethertetracarboxylic acid, naphthalene-1, 4,5, 8-tetracarboxylic acid and naphthalene-2, 3,6, 7-tetracarboxylic acid are more preferable, and biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, naphthalene-1, 4,5, 8-tetracarboxylic acid and naphthalene-2, 3,6, 7-tetracarboxylic acid are more preferable. Among the tetracarboxylic acids and acid dianhydrides thereof, the acid dianhydrides thereof are preferably used. Further, a ditrimellic anhydride ester of naphthalene diol can be used more preferably. Further, the above tetracarboxylic acid or its acid dianhydride and the trimellitic anhydride ester of an aromatic diol may be used alone in 1 kind or in combination of 2 or more kinds.

The reaction of the diol (d) represented by the general formula (8) with the acid components (b) and (c) is not particularly limited, and a well-known method can be employed. For example, Japanese patent application laid-open No. 9-325494 discloses a method of reacting an epoxy (meth) acrylate with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140 ℃.

Here, it is more preferable that the molar ratio of the epoxy (meth) acrylate (d), the dicarboxylic acid or tricarboxylic acid or the acid monoanhydride (b) thereof, and the tetracarboxylic dianhydride (c) is (d): (b) the method comprises the following steps (c) 1.0: 0.01 to 1.0: 0.2 to 1.0.

For example, in the case of using the acid monoanhydride (b) and the acid dianhydride (c), it is preferable to carry out the reaction so that the molar ratio of the amount of the acid component [ (b)/2+ (c) ] to the polymerizable unsaturated group-containing diol (d) [ [ (b)/2+ (c) ]/(d) ] is 0.5 to 1.0. Here, when the molar ratio is 0.5 or more, the content of unreacted diol having a polymerizable unsaturated group is not increased, and the stability of the alkali-soluble resin composition with time can be improved. On the other hand, when the molar ratio is 1.0 or less, the terminal of the alkali-soluble resin represented by the general formula (2) 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 alkali-soluble resin composition over time can be improved. The molar ratio of each component (b), (c) and (d) can be arbitrarily changed within the above range for the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin represented by the general formula (2).

The content of the unsaturated group-containing alkali-soluble resin (a) represented by the general formula (1) in the adhesive layer-forming composition of the present invention is preferably 10 mass% or more and 90 mass% or less, and more preferably 30 mass% or more and 80 mass% or less, based on the total mass of the solid content. When the content of the component (a) is 10% by mass or more based on the total mass of the solid components, the component (a) is easily modified by absorbing irradiated light (for example, ultraviolet rays), and thus the support and the adherend can be easily separated. When the content is 90% by mass or less, the crosslinking density of the adhesive layer after curing is not so high, and thus the adhesive layer is likely to be degraded by irradiation with light and is less likely to generate residue.

(A) The energy of the lowest excited triplet state (T1) of the unsaturated group-containing alkali-soluble resin calculated by quantum chemistry calculation is 2.90eV or less, and more preferably 2.0eV or more and 2.90eV or less. By using the component (A) having the lowest excited triplet state (T1) of 2.0eV or more, the activation energy of the decomposition reaction of the resin can be reduced, and the decomposition reaction can be accelerated. Further, by using the component (a) having the lowest excited triplet state (T1) of 2.9eV or less, the decomposition of the resin and the vaporization of the decomposition product can be easily performed by the energy of the laser beam, and the adhesive layer can be efficiently peeled off by the pressure of the generated gas.

In the present invention, when the unsaturated group-containing alkali-soluble resin (a) represented by the general formula (1) is used, a resin in which Y represented by the general formula (1) contains at least 1 aromatic hydrocarbon group and in which the energy of the lowest excited triplet state (T1) is 2.9eV or less. In addition, in order to make Y at least containing 1 aromatic hydrocarbon, preferably using the aromatic hydrocarbon four carboxylic acid or its acid dianhydride.

By using biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, naphthalene-1, 4,5, 8-tetracarboxylic acid, naphthalene-2, 3,6, 7-tetracarboxylic acid, or the like as the above aromatic hydrocarbon tetracarboxylic acid or its acid dianhydride, the above Y has a structure containing an aromatic hydrocarbon group. Then, the resin having the lowest excited triplet state (T1) of the unsaturated group-containing alkali-soluble resin (a) represented by the general formula (1) has an energy of 2.9eV or less. Further, by using a naphthalene compound such as naphthalene-1, 4,5, 8-tetracarboxylic acid or naphthalene-2, 3,6, 7-tetracarboxylic acid as the above aromatic hydrocarbon tetracarboxylic acid or its acid dianhydride, a resin having a minimum excited triplet state (T1) energy of 2.0eV or more and 2.9eV or less can be obtained.

Further, by using the biphenyltetracarboxylic acid or the benzophenonetetracarboxylic acid as the aromatic hydrocarbon tetracarboxylic acid or the acid dianhydride thereof and using a naphthalene compound such as 1, 8-naphthalenedicarboxylic acid or 2, 3-naphthalenedicarboxylic acid as the acid monoanhydride of the aromatic dicarboxylic acid or tricarboxylic acid, a resin having a minimum excited triplet state (T1) energy of 2.0eV or more and 2.9eV or less can be obtained.

The energy of the lowest excited triplet state (T1) calculated by quantum chemical calculation of the unsaturated group-containing alkali-soluble resin (a) represented by the general formula (1) can be calculated, for example, using the software set "Gaussian 16, revision b.01" (Gaussian Inc.). As for the calculation method, structure optimization calculation of the ground state was performed using the density functional method (DFT) using B3LYP as a functional function and 6-31G (d) as a basis function with respect to the molecular structure (molecular coordinates) of the constituent unit (terminal substituted with hydrogen) of component (A) by using the charge 0 and multiplicity 1 (Gaussian input column "# B3LYP/6-31G (d) OPT"). Next, in the molecular structure subjected to the structure optimization, the lowest excited triplet energy (T1) was calculated using charge 0 and multiplicity 1, using time-dependent density function theory (TDDFT), B3LYP for the global function, and 6-31g (d) for the basis function (Gaussian input column "# B3LYP/6-31g (d) × (50-50, nstates ═ 4)"). In this way, the energy value of the lowest excited triplet state (T1) of component (a) can be obtained. In addition, computational chemistry software having the same function may be used instead in the calculation of DFT and TDDFT.

The acid value of the unsaturated group-containing alkali-soluble resin (A) represented by the general formula (1) is preferably 50mgKOH/g or more and 200mgKOH/g or less, and more preferably 60mgKOH/g or more and 150mgKOH/g or less. When the acid value is 50mgKOH/g or more, residue is not likely to remain during alkali development, and when the acid value is 200mgKOH/g or less, the alkali developing solution does not permeate too quickly, so that peeling development can be suppressed. The acid value can be determined by titration with 1/10N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Pongan industries, Ltd.).

The weight average molecular weight (Mw) of the unsaturated group-containing alkali-soluble resin (A) represented by the general formula (1) in terms of polystyrene, as measured by Gel Permeation Chromatography (GPC) (HLC-8220GPC, manufactured by Tosoh Corporation), is preferably 1000 to 100000 inclusive, more preferably 1500 to 30000 inclusive, and still more preferably 2000 to 15000 inclusive. When the weight average molecular weight (Mw) is 1000 or more, the adhesion between the support and the adherend can be improved. When the weight average molecular weight (Mw) is less than 100000, the solution viscosity of the photosensitive resin composition suitable for application can be easily adjusted, and the application to the surface of the support or the adherend is not excessively time-consuming.

In addition, the adhesive layer forming composition according to an embodiment of the present invention includes: (B) a photopolymerizable monomer having at least 1 or more ethylenically unsaturated bond; and (C) a photopolymerization initiator and/or (D) a photosensitizer. The components are described below.

[ (B) component ]

(B) Examples of the photopolymerizable monomer having at least 1 or more ethylenically unsaturated bond include: (meth) acrylates such as trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate or dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, alkylene oxide-modified hexa (meth) acrylate of phosphazene, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and dendrimer-type polyfunctional acrylates. These photopolymerizable monomers may be used alone in 1 kind, or 2 or more kinds may be used in combination.

The content of the component (B) is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the component (a). When the content of the component (B) is 5 parts by mass or more per 100 parts by mass of the component (a), the photoreactive functional group in the resin is sufficient, and therefore a sufficient crosslinked structure can be formed, and chemical resistance is improved. When the amount is 200 parts by mass or less, the crosslinking density of the adhesive layer after curing is suppressed from becoming too high, so that the adhesive layer is likely to be degraded when irradiated with light, and is less likely to generate residue.

[ (C) ingredient ]

(C) Examples of the photopolymerization initiator include: biimidazole compounds such as 2- [4- (methylthio) benzoyl ] -2- (4-morpholinyl) propane, 2- (o-chlorobenzene) -4, 5-phenylbiimidazole, 2- (o-chlorobenzene) -4, 5-bis (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4, 5-diphenylbiimidazole, 2- (o-methoxyphenyl) -4, 5-diphenylbiimidazole, and 2,4, 5-triarylbiimidazole; halomethyl oxadiazole compounds such as 2-trichloromethyl-5-styryl-1, 3, 4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3, 4-oxadiazole, and 2-trichloromethyl-5- (p-methoxystyryl) -1,3, 4-oxadiazole; 2,4, 6-Ginseng (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, halomethyl symmetric triazine compounds such as 3, 5-triazine, 2- (3,4, 5-trimethoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, and 2- (4-methylthiostyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine; o-acyloxime-based compounds such as 1, 2-octanedione, 1- [4- (phenylsulfanyl) phenyl ] -, 2- (O-benzoyloxime), 1- (4-phenylsulfonylphenyl) butane-1, 2-dione-2-oxime-O-benzoate, 1- (4-methylsulfonylphenyl) butane-1, 2-dione-2-oxime-O-acetate and 1- (4-methylsulfonylphenyl) butane-1-ketoxime-O-acetate; sulfur compounds such as benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2, 4-diethylthioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1, 2-benzoanthraquinone (1,2-Benzanthraquinone) and 2, 3-diphenylanthraquinone, and organic peroxides such as azobisisobutyronitrile, benzoyl peroxide and cumene peroxide; and thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazolyl and 2-mercaptobenzothiazole. Further, only 1 kind of these photopolymerization initiators may be used alone, or 2 or more kinds may be used in combination.

The content of the component (C) is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 20 parts by mass, based on 100 parts by mass of the total amount of the components (a) and (B). When the content of the component (C) is 0.1 parts by mass or more, the photopolymerization rate is appropriate, and the sensitivity can be suppressed from being lowered. When the amount is 30 parts by mass or less, the sensitivity is suppressed from being excessively high, and scorching, peeling residue, and the like generated when the irradiation light is ablated are unlikely to occur. The component (C) may be contained in the case where the adhesive layer forming composition is patterned by photolithography, or may not be contained in the case where the composition is not patterned or is patterned by a method other than photolithography.

[ (D) component ]

(D) Examples of the photosensitizing agent include: acetophenones such as triethanolamine, triisopropanolamine, benzophenone, 4 ' -bisdimethylaminobenzophenone (mikolerone), 4-phenylbenzophenone, 4 ' -dichlorobenzophenone, hydroxybenzophenone, 4 ' -diethylaminobenzophenone, acetophenone, 2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropionylbenzene, dichloroacetophenone, trichloroacetophenone and p-tert-butylacetophenone, and benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether; 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, ethyl (n-butoxy) 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, 4-benzoyl-4 '-methyl-diphenyl sulfide, acrylated benzophenone, 3', benzophenone-based ones such as 4,4 '-tetrakis (t-butylperoxycarbonyl) benzophenone and 3, 3' -dimethyl-4-methoxybenzophenone, and thioxanthone-based ones such as 2-isopropylthioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone and 2, 4-dichlorothioxanthone; aminobenzophenones such as 4, 4' -bisdiethylaminobenzophenone, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9, 10-phenanthrenequinone, camphorquinone, etc. Further, these photosensitizers may be used alone in 1 kind, or in combination of 2 or more kinds.

The content of the component (D) is preferably 0.5 to 400 parts by mass, more preferably 1 to 300 parts by mass, relative to 100 parts by mass of the total amount of the component (C). When the content of the component (D) is 0.5 parts by mass or more, the sensitivity of the photopolymerization initiator can be improved to increase the photopolymerization rate. When the amount is 400 parts by mass or less, excessive acceleration of the reaction is suppressed, and scorching, peeling residue, and the like generated when the irradiation light is ablated are unlikely to occur.

[ (E) ingredient ]

The adhesive layer-forming composition of the present invention may contain an epoxy compound having 2 or more epoxy groups as the component (E).

(E) Examples of the epoxy compound having 2 or more epoxy groups include: bisphenol A type epoxy, bisphenol F type epoxy, bisphenol fluorene type epoxy, phenol novolac type epoxy, cresol novolac type epoxy (e.g., EPPN-501H, manufactured by Nippon chemical Co., Ltd.), phenol aralkyl type epoxy, phenol novolac compound containing a naphthalene skeleton (e.g., NC-7000L, manufactured by Nippon chemical Co., Ltd.), biphenyl type epoxy (e.g., jERYX4000, manufactured by Mitsubishi chemical Co., Ltd.), naphthol aralkyl type epoxy, phenol methane type epoxy, tetraphenol ethane type epoxy, glycidyl ether of polyhydric alcohol, glycidyl ester of polycarboxylic acid, copolymer containing a monomer having a (meth) acrylic group as a unit, represented by a copolymer of methacrylic acid and glycidyl methacrylate, copolymer of a monomer having a (meth) acrylic group, and the like, 3 ', 4' -epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate (for example, CELLOXIDE 2021P: manufactured by Daicel Co., Ltd.), butane tetracarboxylic acid tetra (3, 4-epoxycyclohexylmethyl) -modified epsilon-caprolactone (for example, EpoleadGT 401: manufactured by Daicel Co., Ltd.), epoxide having epoxycyclohexyl group represented by HiREM-1 manufactured by Shikoku Co., Ltd., four countries, polyfunctional epoxide having dicyclopentadiene skeleton (for example, HP7200 series: DIC CORPORATION), 1, 2-epoxy-4- (2-epoxyethyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol (for example, EHPE 3150: manufactured by Daicel Co., Ltd.), epoxidized polybutadiene (for example, NISSO-PB. JP-100: manufactured by Nissada Co., Ltd.), Epoxy compounds having a silicone skeleton, and the like.

(E) Among the epoxides having 2 or more epoxy groups, bisphenol a type epoxides, bisphenol F type epoxides, bisphenol fluorene type epoxides, phenol novolac type epoxides, cresol novolac type epoxides, biphenyl type epoxides are more preferable, and biphenyl type epoxides are more preferable. By using the biphenyl type epoxy, the light absorbing ability required for separation by light irradiation and the patterning ability of the photosensitive resin composition at the time of light curing can be combined, and the degree of freedom in designing the photosensitive resin composition can be improved.

(E) The epoxy equivalent of the component (A) is preferably 100 to 300g/eq, more preferably 100 to 250 g/eq. Further, the number average molecular weight (Mn) of the epoxide of the (E) component is more preferably 100 to 5000. When the epoxy equivalent is 100g/eq to 300g/eq and the number average molecular weight (Mn) of the epoxy compound is 100 to 5000, a cured film having good solvent resistance can be obtained. In addition, when the epoxy equivalent is 300g/eq or less, sufficient alkali resistance can be maintained even when an alkali chemical liquid is used in the subsequent step. Further, only 1 kind of the compound may be used, or 2 or more kinds may be used in combination.

The content of the component (E) is preferably 0 to 60 parts by mass, more preferably 5 to 50 parts by mass, relative to the total mass of the solid components. When the content of the component (E) is 5 parts by mass or more based on the total mass of the solid components, a sufficient crosslinked structure can be formed, and chemical resistance is improved. When the amount is 60 parts by mass or less, the crosslinking density of the adhesive layer after curing is suppressed from becoming too high, so that the adhesive layer is likely to be degraded when irradiated with light, and thus the residue is unlikely to be generated. In addition, by combining with the component (a) or the component (B), even if the content of the component (E) is 0 part by mass, chemical resistance and the like necessary can be secured.

[ (F) ingredient ]

The adhesive layer forming composition according to an embodiment of the present invention may further include a solvent as the component (F).

(F) Examples of the solvent contained in the adhesive layer forming composition 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, diacetone alcohol, etc.; terpenes such as α -and β -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 cerosu, methyl cerosu, ethyl cerosu, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol methyl ethyl 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; esters such as ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, celiosu acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. By dissolving and mixing these solvents, a uniform solution composition can be formed. Among these solvents, these may be used alone or in combination of 2 or more in order to obtain the required properties such as coatability. The amount of the solvent varies depending on the target viscosity, but is preferably 60 to 90% by mass in the photosensitive resin composition solution.

Additives such as a curing agent, a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a surfactant, and a coupling agent may be blended in the adhesive layer forming composition according to one embodiment of the present invention.

Examples of the curing agent include amine-based compounds, polycarboxylic acid-based compounds, phenol resins, amino resins, dicyandiamide, lewis acid complex compounds, and the like, which contribute to curing of the epoxy resin. Examples of the hardening accelerator include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, lewis acids, organometallic compounds, imidazoles, and the like, which contribute to accelerating hardening of the epoxy resin. Examples of the thermal polymerization inhibitor and the antioxidant include: hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenol compounds, and the like. Examples of plasticizers include: dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of fillers include: glass fibers, silica, mica, alumina, and the like. Examples of defoaming or leveling agents include: silicone, fluorine, and acrylic compounds. Examples of the surfactant include: fluorine-based surfactants, silicone-based surfactants, and the like. Examples of coupling agents include: 3- (glycidoxy) propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, etc.

The adhesive layer-forming composition of the present invention can be used by applying it to a necessary portion, or by a process of forming a necessary pattern by photolithography.

2. Method for producing laminate

A method for manufacturing a laminate according to an embodiment of the present invention includes: (1) forming an adhesive layer containing the adhesive layer-forming composition on the surface of either or both of a support and an adherend; and (2) a step of bonding the support to the adherend via the adhesive layer formed. The respective steps are explained below.

[ procedure for Forming adhesive layer ]

The adhesive layer forming step is a step of forming an adhesive layer containing the adhesive layer forming composition on the surface of either or both of the support and the adherend.

(support)

The support is not limited in its kind as long as an adhesive layer can be formed on the surface thereof.

In the present invention, the support is preferably laser-transmissive. In particular, the support is preferably transparent to light (laser light) having a wavelength of 10nm to 400nm, and more preferably transparent to light (laser light) having a wavelength of 100nm to 400 nm. Examples of the support having the above laser light permeability include: glass substrates, acrylic substrates, sapphire substrates, quartz substrates, and the like. However, as for the glass substrate and the acrylic substrate, it is necessary to use a substrate having a sufficient wavelength transmittance of light to be used. Among the above supports, a glass substrate is more preferable.

(adherend)

Examples of the adherend include: semiconductor wafers, semiconductor chips (chips), light emitting elements, optical glass wafers, metal foils, polishing pads, resin coatings, wiring layers, and the like.

(adhesive layer)

The adhesive layer may be formed by applying an adhesive to the surface of either or both of the support and the adherend. The adhesive is preferably an adhesive layer-forming composition containing the unsaturated group-containing alkali-soluble resin (a). The unsaturated group-containing alkali-soluble resin has a low crosslinking density after curing, and therefore is easily degraded when irradiated with a laser beam, and therefore has excellent laser processability.

Examples of the method for applying the adhesive include a well-known solution dipping method, a spin coating method, an ink jet method, a spray coating method, a method using a roll coater, a die coater, a slot coater, a spin coater, and the like.

After the adhesive is applied by the above-described application method, the solvent is dried (prebaked), thereby forming an adhesive layer. Further, prebaking is performed by heating with an oven, a hot plate, or the like. The heating temperature and the heating time in the prebaking are appropriately selected depending on the solvent used, and are, for example, performed at a temperature of 60 to 110 ℃ for 1 to 3 minutes.

The thickness of the adhesive layer can be selected arbitrarily. In the present invention, 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 can have a sufficient holding force for attaching an adherend. When the thickness is 50 μm or less, the adhesive layer can be sufficiently cured by light or heat curing.

In this step, after an adhesive is applied to the surface of either or both of the support and the adherend, an exposure step and a development step for patterning the adhesive layer may be provided. By patterning the adhesive layer, the adhesive layer can be formed only in the portion to be adhered to the adherend, and peeling defects and misalignment of the adherend can be suppressed in the step of separating the support from the adherend (described below).

Examples of light used for the exposure step include: visible rays, ultraviolet rays, far ultraviolet rays, electron rays, X-rays, and the like. Among the above lights, ultraviolet rays (wavelength 250 to 400nm) are more preferable. In addition, a developer suitable for alkali development is used in the development step. Examples of the developing solution include: sodium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, and the like. These developing solutions may be appropriately selected according to the characteristics of the resin layer, and a surfactant may be added as needed. The developing temperature is preferably 20 to 35 ℃, and a fine image can be formed precisely by using a commercially available developing machine, an ultrasonic cleaning machine, or the like. Further, alkali development is usually followed by water washing. The developing treatment method may be applied: a shower developing method, a spray developing method, a dip (dip) developing method, a slurry (coating) developing method, and the like.

[ procedure for bringing the support and the adherend into contact ]

The step of bonding the support and the adherend to each other is a step of bonding the support and the adherend to each other through the adhesive layer.

As a method for bonding the support to the adherend, for example, a method in which the adherend (surface adhesive provided in contact with the adhesive layer) is brought into contact with the surface of the adhesive layer formed on the surface of the support, and heated and pressurized may be used. The temperature under pressure is preferably from room temperature to 200 ℃ inclusive, more preferably from 30 ℃ to 150 ℃ inclusive. The pressure at the time of bonding is preferably 0.01MPa or more and 20MPa or less, and more preferably 0.03MPa or more and 15MPa or less. In addition, it is also possible to thermally cure the steel sheet at a temperature of 120 ℃ to 250 ℃ after the press and hot press are completed. By bonding the support and the adherend under the above conditions, the adherend is more firmly fixed to the surface of the support by the adhesive layer.

In the above-mentioned subsequent step, the support and the adherend may be bonded to each other by photo-curing. An example of a method of photo-curing the adhesive layer is a method of irradiating light using a high-pressure mercury lamp. In additionIn the condition for bonding the support and the adherend, the wavelength of the light to be irradiated is preferably 200 to 500 nm. The exposure amount of the irradiated light is more preferably 25mJ/cm²Above 3000mJ/cm²Hereinafter, more preferably 50mJ/cm²Above 2000mJ/cm²The following.

In this manner, the laminate of the present invention is formed.

The laminate can be separated from the support and the adherend by irradiating the adhesive layer with a laser beam having a wavelength of 10nm to 400nm (described below) from the support side.

3. Method for treating laminate

A method for processing a laminate according to an embodiment of the present invention includes: (1) preparing the laminate; and (2) irradiating the laminate with light to separate the support from the adherend. The respective steps are explained below.

[ procedure for preparing a laminate ]

The step of preparing the laminated body is a step of forming the laminated body or preparing an already formed laminated body in the above-described manner.

[ step of separating the support from the adherend ]

The step of separating the support from the adherend is a step of irradiating the adhesive layer with light to separate the support from the adherend.

The light to be irradiated is not particularly limited as long as the support and the adherend can be separated from each other. In the present invention, the light is preferably ultraviolet light, and the wavelength of the ultraviolet light is more preferably 10nm to 400nm, and still more preferably 100nm to 400 nm. When the wavelength of the ultraviolet ray is 10nm or more, the polymer as a component of the adhesive layer is modified by absorption of light, and the strength and the adhesive strength are lowered, so that the support and the adherend can be easily separated. In addition, when the wavelength is 400nm or less, the adhesive layer of the processing portion absorbs light, and thus the generation of a residue of a cured film can be suppressed.

Examples of the light source of the ultraviolet ray include: low-pressure mercury lamp, high-pressure mercury lamp, ultrahigh-pressure mercury lamp, metal halogen lamp, and far ultraviolet lamp. Among the light sources, laser light is more preferable.

Examples of the laser include: solid laser, liquid laser, gas laser. Examples of the solid-state laser include a semiconductor excitation laser and the like. Examples of the liquid laser include a dye laser and the like. Examples of the gas laser include an excimer laser and the like. Among the above lasers, a semiconductor excitation laser is more preferable.

Examples of the semiconductor excitation laser include Nd: YAG laser, Nd: YLF laser, Nd: glass laser, Nd: YVO4 laser, Yb: YAG laser, ytterbium-doped fiber laser, Er: YAG laser, Tm: YAG laser, and the like. Examples of excimer lasers include KrF lasers, XeCl lasers, ArF lasers, F2 lasers, and the like. Among the above lasers, Nd: YAG laser.

The output and the cumulative light amount of light irradiated to the adhesive layer vary depending on the type of the light source, and when the light to be irradiated is a laser light, a laser light having an output of 0.1mW or more and 200W or less as described above can be used. In addition, the accumulated light amount is more preferably 1mJ/cm²Above 50J/cm²The following. If the cumulative light amount is 0.1mJ/cm²As described above, scorching, peeling residue, and the like generated during the ablation are less likely to occur. If it is 50J/cm²Hereinafter, the speed of the ablation can be appropriately controlled to perform appropriate processing.

The method of irradiating the adhesive layer with light (laser light) is more preferably a method of irradiating the entire surface of the adhesive layer with laser light from the support side. The method of irradiating the laser beam is not particularly limited, and may be performed by a known method.

In the laminate, the support and the adherend can be separated from each other by irradiating the adhesive layer with light (laser light).

The method of processing a laminate according to an embodiment of the present invention may include a step of processing the prepared laminate before the step of separating the support from the adherend.

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

The method of processing a laminate according to an embodiment of the present invention may further include a step of moving the processed laminate from one apparatus to another apparatus. The method of moving the laminated body includes a robot arm and the like.

The laminate of the present invention is treated in this manner.

[ examples ]

The following specifically describes embodiments of the present invention with reference to examples and comparative examples, but the present invention is not limited to these examples.

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

When the same model is used for each measurement device, the device manufacturer name is omitted from the second place. In the examples, the glass substrates used for producing the substrates with the cured films for measurement were all subjected to the same treatment. In addition, when the first digit of the decimal point is 0, the following description of the decimal point may be omitted.

[ solid concentration ]

1g of the resin solution obtained in the synthesis example was immersed in a glass filter [ weight: w0(g) ] was weighed and the weight of the resultant mixture [ W1(g) ] was determined from the weight [ W2(g) ] of the mixture after heating at 160 ℃ for 2 hours according to the following formula.

Solid concentration (wt%) < 100 × (W2-W0)/(W1-W0)

[ acid value ]

The resin solution was dissolved in dioxane, and the solution was titrated with 1/10N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Pongan industries, Ltd.).

[ molecular weight ]

The weight average molecular weight (Mw) was determined as a value converted from standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit) by measuring with a Gel Permeation Chromatograph (GPC) "HLC-8220 GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuper H-2000(2 pieces) + TSKgelSuper H-3000(1 pieces) + TSKgelSuper H-4000(1 pieces) + TSKgelSuper H-5000(1 pieces) (manufactured by Tosoh Corporation), temperature: 40 ℃ and speed: 0.6 ml/min).

The abbreviations described in the synthesis examples are as follows.

BPFE: bisphenol fluorene type epoxy resin (epoxy resin of general formula (1) wherein Ar is a benzene ring and l is 0, epoxy equivalent 256g/eq)

BNFE: binaphthofluorene type epoxy resin (epoxy resin in which Ar is naphthalene ring and l is 0 in the general formula (1); epoxy equivalent 281g/eq)

YD-7011R: bisphenol A type epoxy resin (EPOTHTOYD-7011R, NIPPON STEEL Chemical & Material Co., Ltd., "EPOTHTO" is a registered trademark of the same company)

YX 8000: hydrogenated epoxy resin ("jER YX 8000", epoxy equivalent 205g/eq, manufactured by Mitsubishi chemical corporation, "jER" is a registered trademark of the same company)

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

BTDA: 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride

HPMDA: 1,2,4, 5-cyclohexane tetracarboxylic dianhydride

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

TPP: triphenylphosphine

AA: acrylic acid

PGMEA: propylene glycol monomethyl ether acetate

[ Synthesis example 1]

BPFE (50.00g, 0.10mol), AA (14.07g, 0.20mol), TPP (0.26g) and PGMEA (40.00g) were placed in a 250mL four-necked flask equipped with a reflux condenser, and stirred at 100 to 105 ℃ for 12 hours to obtain a reaction product. Thereafter, PGMEA (25.00g) was placed therein, and the solid content was adjusted to 50 mass%.

Next, BPDA (14.37g, 0.05mol) and THPA (7.43g, 0.05mol) were put into the obtained reaction product, and the mixture was stirred at 115 to 120 ℃ for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A) -1. The resin solution thus obtained had a solid content of 57.0% by mass, an acid value (in terms of solid content) of 96mgKOH/g, and Mw of 3600 as determined by GPC analysis.

[ Synthesis example 2]

Next, BTDA (15.73g, 0.05mol) and THPA (7.43g, 0.05mol) were put into the obtained reaction product, and stirred at 115 to 120 ℃ for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A) -2. The resin solution thus obtained had a solid content of 57.4% by mass, an acid value (in terms of solid content) of 105mgKOH/g, and Mw of 3200 as determined by GPC analysis.

[ Synthesis example 3]

Then, naphthalene-1, 4,5, 8-tetracarboxylic dianhydride (13.09g, 0.05mol) and THPA (7.43g, 0.05mol) 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 alkali-soluble resin (A) -3. The resin solution thus obtained had a solid content of 56.6% by mass, an acid value (in terms of solid content) of 101mgKOH/g, and Mw according to GPC analysis was 3300.

[ Synthesis example 4]

Then, naphthalene-2, 3,6, 7-tetracarboxylic dianhydride (13.09g, 0.05mol) and THPA (7.43g, 0.05mol) 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 alkali-soluble resin (A) -4. The resin solution thus obtained had a solid content of 56.6% by mass, an acid value (in terms of solid content) of 99mgKOH/g, and Mw of 3400 as determined by GPC analysis.

[ Synthesis example 5]

Next, BPDA (14.37g, 0.05mol) and 1, 8-naphthalenedicarboxylic anhydride (9.68g, 0.05mol) were put into the obtained reaction product, and the mixture was stirred at 115 to 120 ℃ for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A) -5. The resin solution thus obtained had a solid content of 57.6% by mass, an acid value (in terms of solid content) of 97mgKOH/g, and Mw of 3700 as determined by GPC analysis.

[ Synthesis example 6]

Next, BPDA (14.37g, 0.05mol) and 2, 3-naphthalenedicarboxylic anhydride (9.68g, 0.05mol) were put into the obtained reaction product, and the mixture was stirred at 115 to 120 ℃ for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A) -6. The resin solution thus obtained had a solid content of 57.6% by mass, an acid value (in terms of solid content) of 95mgKOH/g, and Mw of 3600 as determined by GPC analysis.

[ Synthesis example 7]

Next, BPDA (10.06g, 0.03mol) and THPA (11.89g, 0.08mol) were put into the obtained reaction product, and the mixture was stirred at 115 to 120 ℃ for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A) -7. The resin solution thus obtained had a solid content of 57.0% by mass, an acid value (in terms of solid content) of 98mgKOH/g, and an Mw of 2300 as determined by GPC analysis.

[ Synthesis example 8]

Next, BPDA (19.25g, 0.07mol) and THPA (0.30g, 0.002mol) were put into the obtained reaction product, and stirred at 115 to 120 ℃ for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A) -8. The resin solution thus obtained had a solid content of 56.3% by mass, an acid value (in terms of solid content) of 97mgKOH/g, and Mw of 4700 as determined by GPC analysis.

[ Synthesis example 9]

A250 mL four-necked flask equipped with a reflux condenser was charged with BNFE (50.00g, 0.09mol), AA (12.82g, 0.20mol), TPP (0.23g) and PGMEA (40.00g), and stirred at 100 to 105 ℃ for 12 hours to obtain a reaction product. Thereafter, PGMEA (25.00g) was placed therein, and the solid content was adjusted to 50 mass%.

Next, BPDA (13.09g, 0.04mol) and THPA (6.77g, 0.04mol) were put into the obtained reaction product, and the mixture was stirred at 115 to 120 ℃ for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A) -9. The resin solution thus obtained had a solid content of 56.1% by mass, an acid value (in terms of solid content) of 91mgKOH/g, and an Mw of 3500 by GPC analysis.

[ Synthesis example 10]

Next, BTDA (14.33g, 0.04mol) and THPA (6.77g, 0.04mol) were put into the obtained reaction product, and stirred at 115 to 120 ℃ for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A) -10. The resin solution thus obtained had a solid content of 56.5% by mass, an acid value (in terms of solid content) of 90mgKOH/g, and Mw of 2700 as determined by GPC analysis.

[ Synthesis example 11]

Next, HPMDA (10.95g, 0.05mol) and THPA (7.43g, 0.05mol) were put into the obtained reaction product, and the mixture was stirred at 115 to 120 ℃ for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A) -11. The resin solution thus obtained had a solid content of 56.0% by mass, an acid value (in terms of solid content) of 105mgKOH/g, and Mw of 4000 as determined by GPC analysis.

[ Synthesis example 12]

YD-7011R (50.00g, 0.05mol), AA (7.59g, 0.11mol), TPP (0.14g) and PGMEA (40.00g) were placed in a 250mL four-necked flask equipped with a reflux condenser, and stirred at 100 to 105 ℃ for 12 hours to obtain a reaction product. Thereafter, PGMEA (20.00g) was placed therein, and the solid content was adjusted to 50 mass%.

Next, BPDA (5.42g, 0.02mol) and THPA (6.41g, 0.04mol) were put into the obtained reaction product, and the mixture was stirred at 115 to 120 ℃ for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A) -12. The resin solution thus obtained had a solid content of 53.7% by mass, an acid value (in terms of solid content) of 68mgKOH/g, and Mw according to GPC analysis was 7300.

[ Synthesis example 13]

In a 250mL four-necked flask equipped with a reflux condenser, 3 ', 4' -epoxycyclohexylmethyl 3 ', 4' -epoxycyclohexanecarboxylate (25.00g, 0.10mol), AA (14.28g, 0.20mol), TEAB (0.63g) and PGMEA (40.00g) were placed, and the mixture was stirred at 100 to 105 ℃ for 20 hours to obtain a reaction product. Thereafter, PGMEA (20.00g) was placed therein, and the solid content was adjusted to 50 mass%.

Then, BPDA (10.29g, 0.03mol) and THPA (11.97g, 0.08mol) were put into the obtained reaction product, and stirred at 120 to 125 ℃ for 8 hours. GMA (11.60g, 0.08mol) was further charged and stirred at 105 to 110 ℃ for 8 hours to obtain an alkali-soluble resin (A) -13 containing an unsaturated group. The resin solution thus obtained had a solid content of 64.8% by mass, an acid value (in terms of solid content) of 55mgKOH/g, and Mw of 4200 as determined by GPC analysis.

[ Synthesis example 14]

A250 mL four-necked flask equipped with a reflux condenser was charged with YX8000(50.00g, 0.12mol), AA (17.58g, 0.24mol), TPP (0.32g) and PGMEA (40.00g), and stirred at 100 to 105 ℃ for 20 hours to obtain a reaction product. Thereafter, PGMEA (20.00g) was placed therein, and the solid content was adjusted to 50 mass%.

Next, HPMDA (13.67g, 0.06mol) and THPA (9.28g, 0.06mol) were put into the obtained reaction product, and the mixture was stirred at 115 to 120 ℃ for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A) -14. The resin solution thus obtained had a solid content of 58.3% by mass, an acid value (in terms of solid content) of 115mgKOH/g, and Mw of 4000 as determined by GPC analysis.

Adhesive layer-forming compositions of examples 1 to 12 and comparative examples 1 to 4 were prepared in the formulation amounts (unit is mass%) shown in table 1. The formulation ingredients used in table 1 are as follows.

(unsaturated group-containing alkali-soluble resin)

(A) -1: synthesis example 1 obtained resin solution (solid concentration 57.0 mass%)

(A) -2: synthesis example 2 the obtained resin solution (solid content concentration: 57.4% by mass)

(A) -3: synthesis example 3 the obtained resin solution (solid content concentration 56.6 mass%)

(A) -4: synthesis example 4 the obtained resin solution (solid content concentration 56.6 mass%)

(A) -5: synthesis example 5 the obtained resin solution (solid content concentration 57.6 mass%)

(A) -6: synthesis example 6 the obtained resin solution (solid content concentration: 57.6% by mass)

(A) -7: synthesis example 7 the obtained resin solution (solid content concentration 57.0 mass%)

(A) -8: synthesis example 8 the obtained resin solution (solid content concentration 56.3% by mass)

(A) -9: synthesis example 9 the obtained resin solution (solid content concentration 56.1% by mass)

(A) -10: synthesis example 10 obtained resin solution (solid content concentration 56.5 mass%)

(A) -11: synthesis example 11 the obtained resin solution (solid content concentration 56.0 mass%)

(A) -12: synthesis example 12 the obtained resin solution (solid content concentration 53.7% by mass)

(A) -13: synthesis example 13 the obtained resin solution (solid content concentration: 64.8% by mass)

(A) -14: synthesis example 14 obtained resin solution (solid content concentration 58.3 mass%)

(photopolymerizable monomer)

(B) The method comprises the following steps Mixture of dipentaerythritol pentaacrylate and hexaacrylate (DPHA, manufactured by Nippon chemical Co., Ltd.)

(photopolymerization initiator)

(C) The method comprises the following steps 2- [4- (methylthio) benzoyl ] -2- (4-morpholinyl) propane ("Omnirad 907", IGMResins B.V. Co., "Omnirad" is a registered trademark of the same company)

(photosensitizing agent)

(D) The method comprises the following steps Mueller Ketone of Michelle

(epoxide)

(E) The method comprises the following steps Biphenyl type epoxy resin (jER YX4000, manufactured by Mitsubishi chemical Co., Ltd.)

(solvent)

(F) The method comprises the following steps Propylene Glycol Monomethyl Ether Acetate (PGMEA)

[ Table 1]

[ evaluation ]

The energy of the lowest excited triplet state (T1) of the unsaturated group-containing alkali-soluble resin (a) was calculated, and the following evaluation was performed using a cured film obtained by curing the adhesive layer-forming composition of examples 1 to 12 and comparative examples 1 to 4.

[ method for calculating energy of lowest excited triplet state (T1) ]

The energy of the lowest excited triplet state (T1) of the unsaturated group-containing alkali-soluble resins ((a) -1 to 11) was determined by quantum chemical calculation based on the constituent unit of the component (a) represented by the following general formula (9). To determine the energy of the lowest excited triplet state (T1) "Gaussian 16, revision b.01" suite of software (Gaussian Inc.). Specifically, the lowest excited triplet energy (T1) was obtained by the following calculation method. First, the molecular structure (molecular coordinates) of the constituent unit (end substituted with hydrogen) of the component (a) represented by the general formula (9) was calculated by density functional method (DFT) using B3LYP as a functional function and 6 to 31g (d) as a basis function, using charge 0 and multiplicity 1, and performing structure optimization of the ground state (Gaussian input column "# B3LYP/6 to 31g (d) OPT"). Next, in the molecular structure subjected to the structure optimization, the lowest excited triplet energy (T1) was calculated using charge 0 and multiplicity 1, using time-dependent density function theory (TDDFT), B3LYP for the global function, and 6-31g (d) for the basis function (Gaussian input column "# B3LYP/6-31g (d) × (50-50, nstates ═ 4)"). In addition, computational chemistry software having the same function may be used instead in the calculation of DFT and TDDFT.

The energy of the lowest excited triplet state (T1) of the unsaturated group-containing alkali-soluble resins ((a) -12, 13, 14) was determined by the quantum chemical calculation described above based on the constituent units of the component (a) represented by the following general formula (10), general formula (11) and general formula (12), respectively.

(preparation of substrate with hardened film for evaluation of laser processability)

The photosensitive resin compositions shown in Table 1 were applied to a substrate using a spin coater so that the film thickness after heat curing treatment became 1.0. mu.m, and the substrate was irradiated with a low-pressure mercury lamp at an illuminance of 1000mJ/cm at a wavelength of 254nm²A synthetic quartz glass substrate (hereinafter referred to as "quartz glass substrate") having a size of 125mm × 125mm and having a surface cleaned with ultraviolet rays of (b), and pre-baked at 90 ℃ for 1 minute by using a hot plate to prepare a dry film. Subsequently, the substrate was subjected to main curing (post-baking) at 250 ℃ for 30 minutes using a hot air dryer, to obtain substrates with a cured film of examples 1 to 12 and comparative examples 1 to 4.

[ evaluation of laser processability ]

(evaluation method)

For the cured film (coating film) after the main curing (post-baking), a flash lamp was used to excite Nd: a YAGQ-SW laser oscillator "Callisto" (V Technology Co., Ltd.) irradiated with a laser beam (laser wavelength: 266nm) from the quartz glass substrate side. At a rate of 3 to 550mJ/cm²The laser energy of (2) is used to process (remove) the cured film (coating film), and the processed cured film (coating film) is observed with an optical microscope. Further, O or more was regarded as acceptable.

(evaluation Standard)

O: at 20mJ/cm²Hereinafter, the laser irradiation part was free from coating film residue

And (delta): at more than 20mJ/cm²And 50mJ/cm²Hereinafter, the laser irradiation part was free from coating film residue

X: at more than 50mJ/cm²Coating film residue on the laser irradiation part

(production of substrate with hardened film for evaluation of development residue)

The adhesive layer-forming composition shown in table 1 was applied to a 125mm × 125mm glass substrate "# 1737" (manufactured by corning corporation) (hereinafter referred to as "glass substrate") using a spin coater so that the film thickness after the heat curing treatment became 3.0 μm, and prebaked at 90 ℃ for 1 minute using a hot plate to prepare a hard film (coating film). Then, the illuminance at a wavelength of 365nm was 30mW/cm²The ultra-high pressure mercury lamp irradiates 300mJ/cm²Ultraviolet rays of (4), light of the photosensitive partAnd (5) hardening reaction.

Then, the resultant was passed through a developing solution of 0.8% TMAH (tetramethylammonium hydroxide) at 23 ℃ in a pressure of 1kgf/cm²The exposed film was subjected to a developing treatment (from the development time (BT) at which the pattern appeared) for 10 seconds, and then subjected to a pressure of 5kgf/cm²The unexposed portion of the exposed film was removed to form a dot pattern having a diameter of 30 μm on the glass substrate, and the resultant was subjected to main curing (post-baking) at 250 ℃ for 30 minutes using a hot air dryer to obtain substrates with a cured film of examples 1 to 12 and comparative examples 1 to 4.

[ evaluation of development residue ]

(evaluation method)

The cured film (coating film) of the obtained substrate with the cured film was observed for a 30 μm-diameter dot pattern, by using an optical microscope and a Scanning Electron Microscope (SEM), for the jaggy of the edge of the pattern and the residue derived from the adhesive layer-forming composition on the substrate. Further, O or more was regarded as acceptable.

(evaluation Standard)

O: no residue was found on the edge of the pattern and the substrate

And (delta): residue is found at the edge of the pattern and a part of the substrate

X: the residue on the edge of the pattern and the substrate is obvious

-: without forming a pattern

(preparation of substrate with cured film for evaluation of chemical resistance)

The photosensitive resin composition shown in Table 1 was applied to a glass substrate "# 1737" by using a spin coater so that the film thickness after the heat curing treatment was 3.0. mu.m, and prebaked at 90 ℃ for 3 minutes by using a hot plate to prepare a dried film. Then, the illuminance at a wavelength of 365nm was 30mW/cm²The ultra-high pressure mercury lamp irradiates 100mJ/cm²The ultraviolet ray of (2) to perform a photo-curing reaction. Thereafter, the substrate was subjected to main curing (post-baking) at 230 ℃ for 30 minutes using a hot air dryer, to obtain substrates with a cured film of examples 1 to 12 and comparative examples 1 to 4.

[ evaluation of chemical resistance ]

(evaluation method)

The cured film (coating film) of the obtained substrate with the cured film was immersed in acetone, a 5 wt% aqueous solution of sodium hydroxide, and 5 wt% hydrochloric acid for 30 minutes, and then washed and dried. Then, the thickness of the cured film (coating film) after the test was measured by using a stylus type step shape measuring apparatus "P-17" (manufactured by KLA-Tencor Co., Ltd.). Moreover, Δ or more is regarded as acceptable.

The residual film ratio in the chemical resistance evaluation was calculated from the following equation, assuming that the film thickness before the test was L1 and the film thickness after the test was L2.

Residual film ratio (%) (% L2/L1X 100)

(evaluation Standard)

O: the residual film rate is more than 90 percent

And (delta): the residual film rate is more than 80 percent and less than 90 percent

X: the residual film rate is less than 80 percent

The above evaluation results are shown in table 2.

[ Table 2]

It is found that a laminate using the adhesive layer-forming composition having an unsaturated group-containing alkali-soluble resin of the present invention for an adhesive layer is excellent in laser processability. This is considered because the alkali-soluble resin containing an unsaturated group has a low crosslinking density after hardening, and is likely to be degraded by laser irradiation.

In addition, it is found that when Y of the unsaturated group-containing alkali-soluble resin represented by the general formula (1) of the present invention is an aromatic hydrocarbon group, the energy value of the lowest excited triplet state (T1) can be made 2.90eV or less, and laser processability is excellent. This is considered to be because when Y is an aromatic hydrocarbon group, the LUMO (lowest unoccupied molecular orbital) value of (a structural unit of) the resin becomes small. Accordingly, the HOMO (highest occupied molecular orbital) -LUMO energy gap is small, and the value of the lowest excited triplet state (T1) is also small.

Further, it is found that an adhesive layer forming composition containing an epoxy compound having 2 or more epoxy groups as the component (E) is excellent in chemical resistance. This is considered to be because a sufficient crosslinked structure can be formed by including the component (E).

[ industrial applicability ]

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

Claims

1. An adhesive layer-forming composition designed so that, in a laminate having an adhesive layer between a support and an adherend which are light-transmissive, the support and the adherend can be separated from the laminate by irradiation with light from the support side,

the adhesive layer forming composition contains (A) an unsaturated group-containing alkali-soluble resin as an essential component,

the energy value of the lowest excited triplet state (T1) of the unsaturated group-containing alkali-soluble resin (a) calculated by quantum chemistry calculation is 2.90eV or less.

2. The composition for forming an adhesive layer according to claim 1, wherein the unsaturated group-containing alkali-soluble resin (A) is a resin represented by the following general formula (1),

in the formula (1), Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of the bonded hydrogen atoms may be substituted by a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl or aralkyl 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; r₁Each independently an alkylene group having 2 to 4 carbon atoms, and l each independently a number of 0 to 3; g is independently (meth) acryloyl group, the following general formula (2) orA substituent represented by the general formula (3), wherein Y is a 4-valent carboxylic acid residue; z is each independently a hydrogen atom or a substituent represented by the following general formula (4), and 1 or more substituents represented by the following general formula (4); n is a number having an average value of 1 to 20;

in the formulae (2) and (3), R₂Is a hydrogen atom or a methyl group, R₃Is C2-valent alkylene or alkylarylene of 2 to 10, R₄Is a 2-valent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number of 0 to 10;

3. The composition for forming an adhesive layer according to claim 2, wherein Y contains at least 1 aromatic hydrocarbon group.

4. The adhesive layer forming composition according to any one of claims 1 to 3, comprising: (B) a photopolymerizable monomer having at least 1 or more ethylenically unsaturated bond; and (C) a photopolymerization initiator and/or (D) a photosensitizer.

5. The adhesive layer forming composition according to any one of claims 1 to 4, comprising (E) an epoxy compound having 2 or more epoxy groups.

6. The composition for forming an adhesive layer according to any one of claims 1 to 5, wherein the unsaturated group-containing alkali-soluble resin (A) has a weight average molecular weight of 1000 or more and 100000 or less and an acid value of 50 or more and 200mgKOH/g or less.

7. A method of manufacturing a laminate comprising the steps of:

a step of forming an adhesive layer on the surface of either or both of a support and an adherend using the adhesive layer forming composition according to any one of claims 1 to 6; and

and a step of bonding the support to the adherend via the adhesive layer.

8. A method of treating a laminate comprising the steps of:

preparing a laminate having a support, an adhesive layer, and an adherend; and

irradiating light to separate the support from the attached body; wherein the content of the first and second substances,

the support is transparent to light having a wavelength of 10nm to 400nm,

the laminate is capable of separating the support from the adherend by irradiating the adhesive layer with light.