TW202216831A - Adhesive layer forming composition, method of manufacturing and processing of laminate - Google Patents

Abstract

An object of the present invention is to provide a composition for forming an adhesive layer having excellent laser processability, and a method for manufacturing and processing a laminate having an adhesive layer containing the composition for forming the adhesive layer. The composition for forming an adhesive layer of the present invention makes it possible to separate a support and an adherend from the laminated body by irradiating light from the support side in the laminated body provided with the adhesive layer between the support that transmits light and the adherend, wherein the energy value of the lowest excited triplet state (T1) calculated by quantum chemistry calculation of the (A) unsaturated group-containing alkali-soluble resin contained in the above composition is 2.90 eV or less. The method for manufacturing the laminated body of the present invention contains: a step of forming an adhesive layer containing the above-mentioned adhesive layer forming composition on the surface of either one or both of the support and the adherend, and a step of adhering the support and the adherend through the formed adhesive layer. The method for processing the laminated body of the present invention contains: a step of preparing the laminated body and a step of irradiating light to separate the support and the adherend.

Description

Composition for forming adhesive layer, method for producing layered product, and method for processing

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

In recent years, with the high functionality of digital devices, etc., the flexible displays and semiconductor wafers mounted thereon have become thinner, and it is difficult to transport flexible displays and semiconductors whose strength is reduced due to thinning by conventional automatic transport. wafers etc.

Therefore, methods for easily transporting thinned flexible displays, semiconductor chips, and the like are under review. For example, in a laminate having an adherend such as a semiconductor wafer fixed on a support such as a glass substrate through an adhesive layer, the adhesive layer is modified or decomposed by irradiating light toward the adhesive layer from the support side. A method of lowering the adhesive force and separating the support body from the attached body.

For example, Patent Document 1 describes a method for producing a layer of an electronic device, which includes: a step of arranging elements on a substrate on which a resin layer is formed; The step of separating the components from the above-mentioned substrate and placing them on another substrate step. According to Patent Document 1, a resin having a difference between the glass transition temperature and the thermal decomposition temperature of 150° C. or less is used for the resin layer, whereby softening of the resin during laser ablation can be suppressed, so that when the element is separated from the substrate, it is possible to reduce the occurrence of Crumbs from softened parts.

In addition, Patent Document 2 describes a method for treating an object, which includes the steps of forming a layered body including a support, a temporary fixing material (a separation layer and an adhesive layer), and the object to be treated; The step of moving the layered body; the step of irradiating the separation layer with light; and the step of separating the support body from the object. According to Patent Document 2, the separation layer absorbs light to be decomposed or reformed, and further, the support object can be separated.

In addition, Patent Document 3 describes a method including a support body, a substrate to be supported, an adhesive layer arranged on the surface of the substrate to be supported on the side supported by the support body, and an adhesive layer arranged on the support substrate and the substrate to be supported. In the laminate of the separation layers between the support substrates, the separation layer is irradiated with light to modify the polymer contained in the separation layer, and the support body is separated from the substrate to be supported. According to Patent Document 3, the separation layer is modified by irradiating light to lose its adhesiveness, so that the supporting substrate and the substrate to be supported can be easily separated.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] International Publication No. 2016/158264

[Patent Document 2] International Publication No. 2017/056662

[Patent Document 3] Japanese Patent No. 5580800

However, according to the findings of the inventors of the present application, the laminates described in Patent Documents 1 to 3 cannot obtain desired laser processability.

The present invention has been made in view of this point, and an object of the present invention is to provide a composition for forming an adhesive layer excellent in laser processability, a method for producing a laminate having an adhesive layer including the composition for forming an adhesive layer, and processing method.

As a result of studies conducted by the present inventors to solve the problems of the adhesive layer used in the formation of the above-mentioned laminate, they found that a composition for forming an adhesive layer comprising an unsaturated group-containing alkali-soluble resin is suitable as an adhesive layer , and then complete the present invention.

The composition for forming an adhesive layer of the present invention is in a laminate having an adhesive layer between a support through which light penetrates and a to-be-attached body, and the support can be irradiated with light from the support side. The adhesive layer-forming composition separated from the adherend and the layered body, the adhesive layer-forming composition comprising (A) an unsaturated group-containing alkali-soluble resin as an essential component, and the (A) unsaturated group-containing The energy value of the lowest excited triplet state (T1) calculated by quantum chemical calculation of the alkali-soluble resin of the base is 2.90 eV or less.

The manufacturing method of the laminated body of the present invention includes the steps of forming an adhesive layer on the surface of either or both of the support and the adherend using the above-mentioned composition for forming an adhesive layer; A step of adhering the support body and the adherend to the agent layer.

The processing method of the layered body of the present invention includes: a step of preparing a layered body having a support, an adhesive layer and an adherend; and a step of irradiating light to separate the support and the adherend; wherein the support system Light having a wavelength of 10 nm or more and 400 nm or less is allowed to pass therethrough, and in the laminate, the support and the adherend can be separated by irradiating the adhesive layer with light.

ADVANTAGE OF THE INVENTION According to this invention, the composition for adhesive layer formation excellent in laser workability, the manufacturing method and the processing method of the laminated body which has an adhesive bond layer containing this composition for adhesive layer formation can be provided.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. In addition, in this invention, regarding the content of each component, when the 1st digit after a decimal point is 0, the description below a decimal point may be abbreviate|omitted.

1. Composition for forming an adhesive layer

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

[(A) Ingredient]

The unsaturated group-containing alkali-soluble resin belonging to the component (A) preferably has a polymerizable unsaturated group and an acid group for exhibiting alkali solubility in one molecule, and more preferably has both a polymerizable unsaturated group and a carboxyl group . As long as it is the said resin, it can be widely used without being specifically limited. In the present invention, the component (A) is preferably an unsaturated group-containing alkali-soluble resin represented by the following general formula (1).

In formula (1), Ar is each independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of the hydrogen atom to which it is bonded may be selected from an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms. Or substituted by a substituent in the group consisting of aralkyl, cycloalkyl or cycloalkylalkyl having 3 to 10 carbons, alkoxy having 1 to 5 carbons and halogen. R ₁ is each independently an alkylene group having 2 to 4 carbon atoms, and l is each independently a numerical value of 0 to 3. G is each independently a (meth)acryloyl group, a substituent represented by the following general formula (2) or the following general formula (3), and Y is a tetravalent carboxylic acid residue. Z is each independently a hydrogen atom or a substituent represented by the following general formula (4), and one or more of them are a substituent represented by the following general formula (4). The N-series average is a value from 1 to 20.

In formulas (2) and (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is a divalent alkylene group or an alkyl aryl group having 2 to 10 carbon atoms, and R ₄ is a divalent alkylene group having 2 to 20 carbon atoms Saturated or unsaturated hydrocarbyl, p is a number from 0 to 10.

In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is a numerical value of 1 or 2.

Moreover, it is preferable that Y represented by the said general formula (1) contains at least one aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a phenyl group, a biphenyl group, a benzophenone group, a naphthyl group, a biphenyl ether group, and the like. Among the above-mentioned aromatic hydrocarbon groups, a biphenyl group, a benzophenone group or a naphthyl group is preferable. When the above-mentioned Y is an aromatic hydrocarbon group, the value of the LUMO (lowest unoccupied molecular orbital) of (the structural unit of) the resin becomes small. Thereby, the HOMO (highest occupied molecular orbital)-LUMO energy gap becomes smaller, so the value of the lowest excited triplet state (T1) also becomes smaller.

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

First, an epoxide (a-1) having a bisaryl phenylene skeleton which may have several oxyalkylene groups in one molecule represented by the following general formula (5) (hereinafter also simply referred to as "epoxide (a-1)" -1)"), react with (meth)acrylic acid, either or both of the (meth)acrylic acid derivatives represented by the following general formula (6) or the following general formula (7) to obtain A diol compound of epoxy (meth)acrylate. In addition, the above-mentioned bisaryl fluoride skeleton is preferably a bis-naphthol fluoride skeleton or a bisphenol fluoride skeleton.

In formula (5), Ar is each independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of the bonded hydrogen atoms may also pass through an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl group. Alkyl, cycloalkyl or cycloalkylalkyl having 3 to 10 carbons, alkoxy or halogen having 1 to 5 carbons. R ₁ is each independently an alkylene group having 2 to 4 carbon atoms, and l is each independently a numerical value of 0 to 3.

In formulas (6) and (7), R ₂ is a hydrogen atom or a methyl group, R ₃ is a divalent alkylene group or an alkyl aryl group having 2 to 10 carbon atoms, and R ₄ is a divalent alkylene group having 2 to 20 carbon atoms Saturated or unsaturated hydrocarbyl, p is a number from 0 to 10.

A known method can be used for the reaction of the said epoxide (a-1) and the said (meth)acrylic acid or (meth)acrylic acid derivative. For example, Japanese Patent Laid-Open No. 4-355450 describes that a polymerizable unsaturated group is obtained by using about 2 moles of (meth)acrylic acid with respect to 1 mole of an epoxide having two epoxy groups. of glycol compounds. In the present invention, the compound obtained by the above reaction is a diol (d) containing a polymerizable unsaturated group represented by the formula (8) (hereinafter also simply referred to as "diol (d) represented by the general formula (8)"). ).

(In formula (8), Ar is each independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of the bonded hydrogen atoms may be an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or substituted by aralkyl, cycloalkyl or cycloalkylalkyl with 3 to 10 carbon atoms, alkoxy with 1 to 5 carbon or halogen group; G is independently (meth)acryloyl, the following In the substituent represented by the general formula (2) or the following general formula (3), R ₁ is each independently an alkylene group having 2 to 4 carbon atoms, and l is each independently a numerical value of 0 to 3).

In formulas (2) and (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is a divalent alkyl group or an alkyl aryl group with 2 to 10 carbon atoms, and R ₄ is 2 with 2 to 20 carbon atoms. A saturated or unsaturated hydrocarbon group with a valence, p is a number from 0 to 10.

In the synthesis of the diol (d) represented by the general formula (8) and the production of the unsaturated group-containing alkali-soluble resin represented by the general formula (1), which is subsequently reacted with a polycarboxylic acid or its anhydride, the The reaction is carried out in a solvent using a catalyst as required.

Examples of the solvent include: ethyl celuside, butyl celuside and other celusol-based solvents; diglyme, ethyl carbitol acetate, butyl carbitol ethyl High-boiling ether-based or ester-based solvents such as acid esters and propylene glycol monomethyl ether acetate; ketone-based solvents such as cyclohexanone and diisobutyl ketone, etc. In addition, the reaction conditions of the solvent, catalyst, etc. to be 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.

In addition, in the reaction of an epoxy group with a carboxyl group or a hydroxyl group, it is preferable to use a catalyst, and Japanese Patent Laid-Open No. 9-325494 describes ammonium bromide, triethylbenzylammonium chloride, etc. salts; phosphines such as triphenylphosphine, ginseng (2,6-dimethoxyphenyl)phosphine, etc.

Next, the diol (d) represented by the general formula (8), the dicarboxylic acid or tricarboxylic acid or its anhydride obtained by the reaction of the above epoxide (a-1) and the above (meth)acrylic acid derivative is made (b) and tetracarboxylic acid or its acid dianhydride (c) are reacted, and the alkali-soluble resin which has a carboxyl group and a polymerizable unsaturated group in 1 molecule represented by following General formula (1) can be obtained.

In formula (1), Ar is each independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of the bonded hydrogen atoms may also pass through an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl group. Alkyl, cycloalkyl or cycloalkylalkyl having 3 to 10 carbons, alkoxy or halogen having 1 to 5 carbons. R ₁ is each independently an alkylene group having 2 to 4 carbon atoms, and l is each independently a numerical value of 0 to 3. G is each independently a (meth)acryloyl group, a substituent represented by the following general formula (2) or the following general formula (3), and Y is a tetravalent carboxylic acid residue. Z is each independently a hydrogen atom or a substituent represented by the following general formula (4), and one or more of them are a substituent represented by the following general formula (4). The n-series average is a numerical value from 1 to 20.

(In formulas (2) and (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is a divalent alkylene group or an alkyl aryl group having 2 to 10 carbon atoms, and R ₄ is a carbon number 2 to 20 A divalent saturated or unsaturated hydrocarbon group, p is a value from 0 to 10).

In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.

The acid component used for synthesizing the unsaturated group-containing alkali-soluble resin represented by the general formula (1) is a polyvalent acid component that can react with the hydroxyl group in the molecule of the diol (d) represented by the general formula (8). , it is necessary to use dicarboxylic acid or tricarboxylic acid or these acid monoanhydrides (b) and tetracarboxylic acid or its acid dianhydride (c). The carboxylic acid residue of the said acid component may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. In addition, these carboxylic acid residues may contain bonds containing hetero elements such as -O-, -S-, and carbonyl groups.

Examples of the above-mentioned dicarboxylic acid or tricarboxylic acid or these acid monoanhydrides (b) include: chain hydrocarbon dicarboxylic acid or tricarboxylic acid, alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid, aromatic hydrocarbon dicarboxylic acid Acids or tricarboxylic acids, or their acid monoanhydrides, etc.

Examples of the acid monoanhydrides of the above-mentioned chain hydrocarbon dicarboxylic acids or tricarboxylic acids include: succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid , malonic acid, glutaric acid, citric acid, tartaric acid, side oxyglutaric acid, pimelic acid, sebacic acid, suberic acid, 3-oxoglutaric acid (diglycollic acid) and other acid monoanhydrides and any Substituents of dicarboxylic acid or tricarboxylic acid monoanhydride, etc.

Further, examples of the acid monoanhydride of the above-mentioned alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, and the like Acid monoanhydrides and acid monoanhydrides of dicarboxylic or tricarboxylic acids into which arbitrary substituents are introduced, etc.

In addition, examples of the acid monoanhydride of the above-mentioned aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid include phthalic acid, isophthalic acid, trimellitic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid Acid monoanhydrides such as carboxylic acids and acid monoanhydrides of dicarboxylic acids or tricarboxylic acids into which optional substituents are introduced.

Among the acid monoanhydrides of the above-mentioned dicarboxylic acids or tricarboxylic acids, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydromellitic acid, phthalic acid, trimellitic acid, 1,8-naphthalene are preferred Dicarboxylic acid and 2,3-naphthalenedicarboxylic acid, more preferably tetrahydrophthalic acid, 1,8-naphthalenedicarboxylic acid, and 2,3-naphthalenedicarboxylic acid.

Moreover, it is preferable to use these acid monoanhydrides among dicarboxylic acids and tricarboxylic acids. As for the acid monoanhydride of the above-mentioned dicarboxylic acid or tricarboxylic acid, only one of them may be used alone, or two or more of them may be used in combination.

Moreover, the example of the said tetracarboxylic acid or its acid dianhydride (c) contains a chain hydrocarbon tetracarboxylic acid, an alicyclic hydrocarbon tetracarboxylic acid, an aromatic hydrocarbon tetracarboxylic acid, or these acid dianhydrides, etc..

Examples of the above-mentioned chain hydrocarbon tetracarboxylic acid include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and chain hydrocarbon tetracarboxylic acid into which substituents such as alicyclic hydrocarbon group and unsaturated hydrocarbon group are introduced.

In addition, examples of the above-mentioned alicyclic hydrocarbon tetracarboxylic acid include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, and a chain hydrocarbon group introduced therein, Alicyclic tetracarboxylic acids of substituents such as unsaturated hydrocarbon groups, etc.

In addition, examples of the aromatic hydrocarbon tetracarboxylic acid include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl tetracarboxylic acid, and naphthalene-1,4 , 5,8-tetracarboxylic acid, naphthalene-2,3,6,7-tetracarboxylic acid, etc.

In addition, bismellitic anhydride aryl esters can also be used. Dimellitic anhydride aryl esters are compounds produced by the method described in, for example, International Publication No. 2010/074065, and are structurally aromatic diols (naphthalene diol, biphenol, triphenyl diol, etc.) ) is an acid dianhydride in the form of an ester bond by reacting two hydroxyl groups of the trimellitic acid anhydride with two molecules of the carboxyl group. These compounds are hereinafter described as trimellitic anhydride esters of aromatic diols.

Among the above-mentioned tetracarboxylic acids or their acid dianhydrides, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, diphenyl ether tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, Naphthalene-2,3,6,7-tetracarboxylic acid, more preferably biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, naphthalene-2,3 ,6,7-tetracarboxylic acid. Moreover, among the said tetracarboxylic acid or its acid dianhydride, it is preferable to use its acid dianhydride. Furthermore, the trimellitic anhydride ester of naphthalene glycol can be preferably used. In addition, the above-mentioned tetracarboxylic acid or its acid dianhydride, and the trimellitic acid anhydride ester of an aromatic diol may be used individually by 1 type, and may use 2 or more types together.

The reaction between the diol (d) represented by the general formula (8) and the acid components (b) and (c) is not particularly limited, and a known method can be employed. For example, Japanese Patent Application Laid-Open No. 9-325494 describes a method of reacting epoxy (meth)acrylate and tetracarboxylic dianhydride at a reaction temperature of 90 to 140°C.

Here, it is preferable to make epoxy (meth)acrylate (d), dicarboxylic acid or tricarboxylic acid, or these acid monoanhydrides (b), tetracarboxylic acid such that the terminal of the compound is a carboxyl group. The molar ratio of the dianhydride (c) becomes (d):(b):(c)=1.0:0.01 to 1.0:0.2 to 1.0 to react.

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

The content of the (A) unsaturated group-containing alkali-soluble resin represented by the general formula (1) in the composition for forming an adhesive layer of the present invention is preferably 10% by mass or more and 90% with respect to the total mass of the solid content. The mass % or less is more preferably 30 mass % or more and 80 mass % or less. When the content of the component (A) is 10 mass % or more relative to the total mass of the solid content, it is easy to absorb and modify the irradiated light (eg, ultraviolet rays), so that the support and the adherend can be easily separated. Moreover, if it is 90 mass % or less, since the crosslinking density of the adhesive layer after hardening will not become too high, it will be easy to peel off when it irradiates a light, and it will become difficult to generate|occur|produce a residue.

(A) The energy of the lowest excited triplet state (T1) of the alkali-soluble resin containing unsaturated group calculated by quantum chemical calculation is 2.90eV or less, preferably 2.0eV or more and 2.90eV or less Down. By using the component (A) whose lowest excited triplet state (T1) is 2.0 eV or more, the activation energy of the decomposition reaction of the resin can be lowered, and the decomposition reaction can be accelerated. In addition, by using the component (A) whose lowest excited triplet state (T1) is 2.9 eV or less, the decomposition of the resin and the vaporization of the decomposition products can be easily performed by using the energy of the laser, and the pressure of the generated gas can be used efficiently. The adhesive layer is peeled off.

In the present invention, when the (A) unsaturated group-containing alkali-soluble resin represented by the general formula (1) is used, the energy of the lowest excited triplet state (T1) is 2.9 eV or less, which is represented by the general formula (1). Resin in which Y contains at least one aromatic hydrocarbon group. Moreover, in order to make Y contain at least one aromatic hydrocarbon group, it is preferable to use the above-mentioned aromatic hydrocarbon tetracarboxylic 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, etc. as the above-mentioned aromatic hydrocarbon A tetracarboxylic acid or its acid dianhydride, the said Y becomes a structure containing an aromatic hydrocarbon group. Then, the (A) unsaturated group-containing alkali-soluble resin represented by the general formula (1) can be obtained as a resin in which the energy of the lowest excited triplet state (T1) is 2.9 eV or less. Furthermore, by using a naphthalene compound such as naphthalene-1,4,5,8-tetracarboxylic acid and naphthalene-2,3,6,7-tetracarboxylic acid as the above-mentioned aromatic hydrocarbon tetracarboxylic acid or its acid dianhydride, it is possible to A resin in which the energy of the lowest excited triplet state (T1) is 2.0 eV or more and 2.9 eV or less is obtained.

Moreover, by using the above-mentioned biphenyltetracarboxylic acid and benzophenone tetracarboxylic acid as the aromatic hydrocarbon tetracarboxylic acid or its acid dianhydride, and using 1,8-naphthalenedicarboxylic acid and 2,3-naphthalenedicarboxylic acid A naphthalene compound such as an acid can also be used as an acid monoanhydride of an aromatic dicarboxylic acid or a tricarboxylic acid to obtain a resin in which the energy of the lowest excited triplet state (T1) is 2.0 eV or more and 2.9 eV or less.

The energy of the lowest excited triplet state (T1) of the (A) unsaturated group-containing alkali-soluble resin represented by the general formula (1) is calculated by quantum chemical calculation. For example, the "Gaussian16, RevisionB.01" package software ( Gaussian Inc.) calculated. In terms of the calculation method, with respect to the molecular structure (molecular coordinates) of the constituent unit (terminal substituted with hydrogen) of the component (A), the density functional method (DFT) is used with a charge of 0 and a multiplicity of 1, and the functional function is used. B3LYP, the basis function uses 6-31G(d), The structure optimization calculation of the ground state is performed (Gaussian input column "#B3LYP/6-31G(d)OPT"). Next, in the structure-optimized molecular structure, using charge 0 and multiplicity 1, using time-dependent density function theory (TDDFT), using B3LYP for the functional function, and using 6-31G(d) for the basis function, the minimum excitation is calculated. Triplet energy (T1) (Gaussian input column "#B3LYP/6-31G(d)td=(50-50, nstates=4)"). In this way, the energy value of the lowest excited triplet state (T1) of the (A) component can be obtained. In addition, in the calculation of DFT and TDDFT, computational chemistry software with the same function can also be used as an alternative.

Moreover, the acid value of the (A) unsaturated group-containing alkali-soluble resin represented by the general formula (1) is preferably 50 mgKOH/g or more and 200 mgKOH/g, more preferably 60 mgKOH/g or more and 150 mgKOH/g or less. When the acid value is 50 mgKOH/g or more, residues are less likely to remain during alkali development, and when the acid value is 200 mgKOH/g or less, the penetration of the alkali developer will not be too fast, so peeling development can be suppressed. In addition, the acid value can be obtained by titration with a 1/10 N-KOH aqueous solution using a potentiometric titration apparatus "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

Moreover, the polystyrene conversion obtained by gel permeation chromatography (GPC) measurement (HLC-8220GPC, manufactured by Tosoh Corporation) of the (A) unsaturated group-containing alkali-soluble resin represented by the general formula (1) The weight average molecular weight (Mw) is usually preferably 1,000 or more and 100,000 or less, more preferably 1,500 or more and 30,000 or less, and even more preferably 2,000 or more and 15,000 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 less than 100,000, it is easy to adjust the solution viscosity of the photosensitive resin composition suitable for coating, and the coating on the surface of the support or the adherend does not take too much time.

Furthermore, the composition for forming an adhesive layer according to an embodiment of the present invention comprises: (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond; and (C) a photopolymerization initiator and /or (D) a photosensitizer. Each component will be described below.

[(B) Ingredient]

(B) Examples of the photopolymerizable monomer having at least one or more ethylenically unsaturated bonds include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, Neotaerythritol tri(meth)acrylate, neotaerythritol tetra(meth)acrylate, dipeoerythritol tetra(meth)acrylate, sorbitol penta(meth)acrylate, two new Pentaerythritol penta(meth)acrylate or dipivalerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene modified with alkylene oxide hexa(meth)acrylic acid Esters, (meth)acrylates such as caprolactone-modified dipovaerythritol hexa(meth)acrylate, dendrimer-type multifunctional acrylates, and the like. Only one of these photopolymerizable monomers may be used alone, or two or more of them may be used in combination.

It is preferable that content of (B) component is 5 mass parts or more and 200 mass parts or less with respect to 100 mass parts of (A) components. If the content of the (B) component is 5 parts by mass or more relative to 100 parts by mass of the (A) component, the photoreactive functional groups occupied in the resin are sufficient, and a sufficient cross-linked structure can be formed, thereby improving the chemical resistance. Moreover, when it is 200 mass parts or less, since the crosslinking density of the adhesive layer after hardening is suppressed from becoming too high, it is easy to peel off when it irradiates a light, and it becomes difficult to generate|occur|produce a residue.

[(C) Ingredient]

啉基)丙烷、2-(鄰氯苯)-4,5-苯基聯咪唑、2-(鄰氯苯)-4,5-二(間甲氧苯基)聯咪唑、2-(鄰氟苯基)-4,5-二苯基聯咪唑、2-(鄰甲氧苯基)-4,5-二苯基聯咪唑、2、4,5-三芳基聯咪唑等聯咪唑系化合物類；2-三氯甲基-5-苯乙烯基-1,3,4-

二唑、2-三氯甲基-5-(對氰基苯乙烯基)-1,3,4-

二唑、2-三氯甲基-5-(對甲氧基苯乙烯基)-1,3,4-

二唑等鹵甲基二唑化合物類；2,4,6-參(三氯甲基)-1,3,5-三嗪、2-甲基-4,6-雙(三氯甲基)-1,3,5-三嗪、2-苯基-4、6-雙(三氯甲基)-1,3,5-三嗪、2-(4-氯苯基)-4,6-雙(三氯甲基)-1,3,5-三嗪、2-(4-甲氧苯基)-4,6-雙(三氯甲基)-1,3,5-三嗪、2-(4-甲氧基萘基)-4,6-雙(三氯甲基)-1,3,5-三嗪、2-(4-甲氧基苯乙烯基)-4,6-雙(三氯甲基)-1,3,5-三嗪、2-(3,4,5- 三甲氧基苯乙烯基)-4,6-雙(三氯甲基)-1,3,5-三嗪、2-(4-甲硫基苯乙烯基)-4,6-雙(三氯甲基)-1,3,5-三嗪等鹵甲基對稱三嗪系化合物類；1,2-辛二酮，1-[4-(苯基硫基)苯基]-，2-(鄰苯甲醯肟)、1-(4-苯基磺醯基苯基)丁烷-1,2-二酮-2-肟-O-苯甲酸酯、1-(4-甲基磺醯基苯基)丁烷-1,2-二酮-2-肟-O-乙酸酯、1-(4-甲基磺醯基苯基)丁烷-1-酮肟-O-乙酸酯等O-醯基肟系化合物類；苄基二甲基縮酮、噻噸酮、2-氯噻噸酮、2,4-二乙基噻噸酮、2-甲基噻噸酮、2-異丙基噻噸酮等硫化合物；2-乙基蒽醌、八甲基蒽醌、1,2-苯並蒽醌(1,2-Benzanthraquinone)、2,3-二苯基蒽醌等蒽醌類、偶氮雙異丁腈、過氧化苯甲醯、過氧化異丙苯等有機過氧化物；2-巰基苯并咪唑、2-巰基苯并

唑基、2-巰基苯并噻唑等硫醇化合物等。此外，此等光聚合起始劑可僅單獨使用其中1種，亦可併用2種以上。 (C) Examples of photopolymerization initiators include: 2-[4-(methylthio)benzyl]-2-(4-

Lino) propane, 2-(o-chlorobenzene)-4,5-phenylbiimidazole, 2-(o-chlorobenzene)-4,5-bis(m-methoxyphenyl)biimidazole, 2-(o-fluoro) Phenyl)-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole and other biimidazole compounds ; 2-Trichloromethyl-5-styryl-1,3,4-

oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-

oxadiazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-

Halomethyloxadiazole compounds such as oxadiazole; 2,4,6-para(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 other halomethyl symmetric triazine compounds; 1, 2-Octanedione, 1-[4-(Phenylthio)phenyl]-, 2-(o-benzoyl oxime), 1-(4-phenylsulfonylphenyl)butane-1, 2-Diketo-2-oxime-O-benzoate, 1-(4-Methylsulfonylphenyl)butane-1,2-dione-2-oxime-O-acetate, 1 -(4-Methylsulfonylphenyl)butane-1-ketooxime-O-acetate and other O-acyl oxime compounds; benzyl dimethyl ketal, thioxanthone, 2-chloro Sulfur compounds such as thioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone; 2-ethylanthraquinone, octamethylanthraquinone, 1, 2-Benzanthraquinone (1,2-Benzanthraquinone), 2,3-diphenylanthraquinone and other anthraquinones, azobisisobutyronitrile, benzyl peroxide, cumene peroxide and other organic peroxides compounds; 2-mercaptobenzimidazole, 2-mercaptobenzo

azoles, thiol compounds such as 2-mercaptobenzothiazole, etc. In addition, these photoinitiators may be used individually by 1 type, and may use 2 or more types together.

The content of the (C) component is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 20 parts by mass, relative to 100 parts by mass of the total of the (A) component and (B) component. If content of the said (C)component is 0.1 mass part or more, since it has an appropriate photopolymerization rate, it can suppress the fall of sensitivity. Moreover, when it is 30 mass parts or less, the suppression sensitivity becomes too high, and it becomes difficult to generate|occur|produce the scorch, peeling residue, etc. which generate|occur|produce when a light is irradiated and ablation is performed. In addition, when the composition for forming an adhesive layer is patterned by photolithography, the component (C) may be contained, and when the pattern is not formed or when the pattern is formed by a method other than photolithography, the component (C) may not be contained. Element.

[(D) Ingredient]

(D) Examples of photosensitizers include: triethanolamine, triisopropanolamine, benzophenone, 4,4'-bis-dimethylaminobenzophenone (Micheler's ketone), 4-phenyldiphenone Benzophenone, 4,4'-Dichlorobenzophenone, Hydroxybenzophenone, 4,4'-Diethylaminobenzophenone, Acetophenone, 2,2-diethoxybenzene Acetophenones such as ethyl ketone, p-dimethylacetophenone, p-dimethylaminopropyl benzene, dichloroacetophenone, trichloroacetophenone, p-tertiary butylacetophenone, benzoin, Benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether Isobenzoin ethers; 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid (n-butoxy)ethyl ester, 4-dimethylaminobenzoic acid Isoamyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 4-benzyl Acrylo-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetrakis(tertiary butylperoxycarbonyl)benzophenone, 3,3 '-Dimethyl-4-methoxybenzophenone and other benzophenone series, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone Thioxanthone series such as xanthone and 2,4-dichlorothioxanthone; 4,4'-bisdiethylaminobenzophenone and other aminobenzophenone series, 10-butyl-2-chloro Acridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, etc. Moreover, these photosensitizers may be used individually by 1 type, and may use 2 or more types together.

The content of the component (D) is preferably 0.5 part 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, with respect to 100 parts by mass of the total amount of the component (C). When content of (D)component is 0.5 mass part or more, the sensitivity of a photopolymerization initiator can be improved, and the speed|rate of photopolymerization can be accelerated|stimulated. Moreover, if it is 400 mass parts or less, it will suppress that reaction is accelerated|promoted excessively, and it will become difficult to generate|occur|produce the scorch, peeling residue, etc. which generate|occur|produce when a light is irradiated and ablation is performed.

[(E) Ingredient]

Moreover, the composition for adhesive layer formation of this invention may contain the epoxide which has two or more epoxy groups as (E) component.

(E) Examples of epoxides having two or more epoxy groups include bisphenol A-type epoxides, bisphenol F-type epoxides, bisphenol phenylephrine-type epoxides, and phenol novolac-type epoxides , cresol novolak type epoxies (eg, EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), phenol aralkyl type epoxies, phenol novolak compounds containing a naphthalene skeleton (eg, NC-7000L: Japan Kayaku Co., Ltd.), biphenyl-type epoxide (for example, jERYX4000: manufactured by Mitsubishi Chemical Co., Ltd.), naphthol aralkyl-type epoxide, samphenolmethane-type epoxide, tetraphenolethane-type Epoxides, glycidyl ethers of polyols, polycarboxylic acids The glycidyl ester, the copolymer of methacrylic acid and glycidyl methacrylate represented by the copolymer containing glycidyl (meth)acrylate as a unit of a monomer having a (meth)acrylic acid group, 3', 4'-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (for example, CELLOXIDE 2021P: manufactured by Daicel Co., Ltd.), butanetetracarboxylic acid tetrakis(3,4-epoxycyclohexylmethyl) ) modified ε-caprolactone (eg, Epolead GT401: manufactured by Daicel Co., Ltd.), epoxide having an epoxycyclohexyl group represented by HiREM-1 manufactured by Shikoku Chemical Co., Ltd., having a dicyclopentadiene skeleton Polyfunctional epoxides (for example, HP7200 series: manufactured by DIC CORPORATION), 1,2-epoxy-4-(2-oxiranyl group of 2,2-bis(hydroxymethyl)-1-butanol ) cyclohexane adduct (eg, EHPE3150: manufactured by Daicel Co., Ltd.), epoxidized polybutadiene (eg, NISSO-PB. JP-100: manufactured by Nippon Soda Co., Ltd.), Epoxide etc.

(E) Among epoxides having two or more epoxy groups, bisphenol A-type epoxides, bisphenol F-type epoxides, bisphenol phenylephrine-type epoxides, and phenol novolac-type epoxies are preferred compound, cresol novolac type epoxide, biphenyl type epoxide, more preferably biphenyl type epoxide. By using the biphenyl type epoxy, the light absorption ability required for separation by light irradiation and the patterning ability of the photosensitive resin composition during photocuring can be combined, and the design of the photosensitive resin composition can be improved. degrees of freedom.

The epoxy equivalent of the epoxide of the component (E) is preferably 100 g/eq or more and 300 g/eq or less, more preferably 100 g/eq or more and 250 g/eq or less. Moreover, it is preferable that the number average molecular weight (Mn) of the epoxide of (E) component is 100-5000. When the said epoxy equivalent is 100 g/eq or more and 300 g/eq or less, and the number average molecular weight (Mn) of the said epoxide is 100-5000, it can become a cured film which has favorable solvent resistance. In addition, when the epoxy equivalent is 300 g/eq or less, sufficient alkali resistance can be maintained even when an alkaline chemical solution is used in the subsequent step. Moreover, these compounds may use only 1 type of these compounds, and may use 2 or more types together.

The content of the component (E) is preferably 0 parts by mass or more and 60 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, with respect to the total mass of the solid content. When content of (E) component is 5 mass parts or more with respect to the total mass of solid content, since a sufficient crosslinked structure can be formed, chemical resistance improves. Moreover, when it is 60 mass parts or less, since the crosslinking density of the adhesive agent layer after hardening is suppressed from becoming too high, it becomes easy to peel off when it irradiates a light, and it becomes difficult to generate|occur|produce a residue. Moreover, by combining with (A) component or (B) component, even if content of (E) component is 0 mass part, required chemical resistance etc. can be ensured.

[(F) Ingredient]

Moreover, the composition for adhesive layer formation of one Embodiment of this invention may contain a solvent as a (F) component.

(F) Examples of the solvent contained in the adhesive layer-forming composition include methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, and ethylene glycol Alcohols such as monobutyl ether, 3-hydroxy-2-butanone, and diacetone alcohol; terpenes such as α- or β-terpineol; acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidine Ketones such as ketones; Aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene; Selus, methyl Sel, ethyl Sel, carbitol, methyl carbitol, ethyl carbitol Alcohol, 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, triethylene glycol Glycol ethers such as monoethyl ether; ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl acetate 1-Butyl-1-Butyl, Cyruxyl Acetate, Ethyl-xeloxetle Acetate, Butyl-1-Butyl Acetate, Carbitol Acetate, Ethyl Carbitol Acetate, Butyl Carbitol Acetate, Propylene Glycol Esters such as monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. By dissolving and mixing these solvents, a uniform solution composition can be formed. Among these solvents, in order to obtain necessary properties such as coatability, these may be used alone or in combination of two or more. solvent The amount varies depending on the target viscosity, but is preferably 60 to 90% by mass in the photosensitive resin composition solution.

A hardener, a hardening accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, a Defoamers, surfactants, coupling agents and other additives.

、受阻酚系化合物等。塑化劑的例子包含：鄰苯二甲酸二丁酯、鄰苯二甲酸二辛酯、磷酸三甲苯酯等。填充劑的例子包含：玻璃纖維、二氧化矽、雲母、氧化鋁等。消泡劑或調平劑的例子包含：聚矽氧系、氟系、丙烯酸系化合物。界面活性劑的例子包含：氟系界面活性劑、聚矽氧系界面活性劑等。偶合劑的例子包含：3-(環氧丙氧基)丙基三甲氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-異氰酸丙基三乙氧基矽烷、3-脲基丙基三乙氧基矽烷等。 Examples of the hardener include amine-based compounds, polycarboxylic acid-based compounds, phenolic resins, amine-based resins, dicyandiamide, Lewis acid zirconium compounds, etc., which contribute to the hardening of epoxy resins. Examples of hardening accelerators include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, borate esters, Lewis acids, organometallic compounds, imidazoles, and the like, which help to promote the hardening of epoxy resins. Examples of thermal polymerization inhibitors and antioxidants include: hydroquinone, hydroquinone monomethyl ether, pyrogallicol, tertiary butylcatechol, phenthiophene

, hindered phenolic compounds, etc. Examples of the plasticizer include: dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of fillers include: fiberglass, silica, mica, alumina, and the like. Examples of the defoaming agent or leveling agent include polysiloxane-based, fluorine-based, and acrylic-based compounds. Examples of the surfactant include fluorine-based surfactants, polysiloxane-based surfactants, and the like. Examples of coupling agents include: 3-(glycidoxy)propyltrimethoxysilane, 3-propenyloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3- Ureidopropyl triethoxysilane, etc.

The composition for forming an adhesive layer of the present invention can be applied to a necessary part and used, or can be used through a process of forming a necessary pattern by photolithography.

2. Manufacturing method of laminated body

The method for producing a layered product according to an embodiment of the present invention includes: (1) forming an adhesive layer including the composition for forming an adhesive layer on the surface of either or both of the support and the adherend. step; and (2) the step of adhering the support body and the adherend through the formed adhesive layer. Each step is explained below.

[Step of Forming Adhesive Layer]

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

(support body)

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

In the present invention, the support body preferably has laser transparency. In particular, it is more preferable that the above-mentioned support transmits light (laser) having a wavelength of 10 nm or more and 400 nm or less, and even more preferably transmits light (laser) having a wavelength of 100 nm or more and 400 nm or less. Examples of the support body having the above-mentioned laser transparency include glass substrates, acrylic substrates, sapphire substrates, quartz substrates, and the like. However, regarding a glass substrate and an acrylic substrate, it is necessary to use a substrate whose composition is sufficient for the wavelength-based transmittance of the light to be used. Among the above-mentioned supports, a glass substrate is preferred.

(attached body)

Examples of the adherend include semiconductor wafers, semiconductor wafers, light-emitting elements, optical glass wafers, metal foils, polishing pads, resin coating films, wiring layers, and the like.

(adhesive layer)

The adhesive layer can be formed by applying an adhesive to the surface of either or both of the support and the adherend. It is preferable that the said adhesive agent is the composition for adhesive agent layer formation containing the said (A) unsaturated-group containing alkali-soluble resin. The above-mentioned unsaturated group-containing alkali-soluble resin system has a low crosslinking density after curing, so that it is easy to be peeled off when irradiated with a laser, and thus it is excellent in laser processability.

Examples of the method of applying the above-mentioned adhesive include conventional solution dipping method, spin coating method, ink jet method, spray method, method using a roll coater, die coater, slit coater, or spin coater, and the like.

After applying the adhesive by the above-mentioned applying method, the solvent is dried (pre-baking) to form an adhesive layer. Further, prebaking is performed by heating with an oven, a hot plate, or the like. pre-bake The heating temperature and heating time in baking are appropriately selected according to the solvent used, for example, the temperature is 60 to 110° C. for 1 to 3 minutes.

The thickness of the adhesive layer can be arbitrarily selected. In the present invention, the thickness of the adhesive layer is preferably 0.1 μm or more and 50 μm or less, and more preferably 0.5 μm or more and 30 μm or less. If the thickness of the adhesive agent layer is 0.1 μm or more, the adhesive agent layer can have sufficient holding power for bonding the adherend. Moreover, if it is 50 micrometers or less, the adhesive layer can be hardened sufficiently by light or heat hardening.

Moreover, in this process, after giving an adhesive agent to the surface of either or both of the said support body and the said to-be-adhered body, you may have an exposure process and a development process for patterning an adhesive agent layer. By patterning the adhesive layer, the adhesive layer can be formed only in the part where the adherend is bonded, and the peeling of the adherend can be suppressed in the step of separating the support and the adherend (described below) bad or misplaced.

Examples of the light used in the exposure step include visible rays, ultraviolet rays, extreme ultraviolet rays, electron rays, X-rays, and the like. Among the above-mentioned light, ultraviolet rays (wavelength 250 to 400 nm) are preferable. In addition, a developer suitable for alkali development is used in the development step. Examples of the above-mentioned developer include aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylamine hydroxide, and the like. These developers can be appropriately selected according to the characteristics of the resin layer, and a surfactant can also be added as required. The developing temperature is preferably 20 to 35° C., and a fine image can be precisely formed using a commercially available developing machine, an ultrasonic cleaner, or the like. In addition, water washing is usually performed after alkali development. The development treatment method can be applied to a shower development method, a spray development method, a dip development method, a slurry development method, and the like.

[Steps for adhering the support body and the attached body]

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

As a method of bonding the support and the adherend, for example, the adherend (a surface adhesive to which the adhesive layer has been applied) is brought into contact with the surface of the adhesive layer formed on the surface of the support, and pressure is applied while heating. Methods. Moreover, as for the bonding conditions of the support body and the adherend, the temperature at the time of pressurization is preferably room temperature or higher and 200°C or lower, more preferably 30°C or higher and 150°C or lower. The pressure at the subsequent time is preferably 0.01 MPa or more and 20 MPa or less, more preferably 0.03 MPa or more and 15 MPa or less. Moreover, you may make it thermosetting at the temperature of 120 degreeC - 250 degreeC after completion|finish of pressurization thermocompression as needed. By bonding the support and the adherend under the above conditions, the adherend is more firmly fixed to the surface of the support through the adhesive layer.

Moreover, in the above-mentioned following step, a support body and a to-be-adhered body may be bonded by photohardening. An example of the method of photohardening the adhesive layer is a method of irradiating light using a high-pressure mercury lamp. Moreover, as for the bonding conditions of a support body and a to-be-adhered body, the wavelength of the light irradiated is preferably 200 to 500 nm. The exposure amount of the irradiated light is preferably 25 mJ/cm ² or more and 3000 mJ/cm ² or less, more preferably 50 mJ/cm ² or more and 2000 mJ/cm ² or less.

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

Moreover, the said laminated body can isolate|separate a support body and a to-be-adhered body by irradiating the laser (described below) with a wavelength of 10 nm or more and 400 nm or less with respect to an adhesive bond layer from a support body side.

3. Processing method of laminated body

The processing method of the layered body according to one embodiment of the present invention includes: (1) a step of preparing the layered body; and (2) a step of irradiating the layered body with light to separate the support body and the adherend. Each step is explained below.

[Procedures for preparing the laminate]

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

[Step of separating the support body from the attached body]

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

The light to be irradiated is not particularly limited as long as the support and the adherend can be separated. In the present invention, the light rays are preferably ultraviolet rays, and the wavelength of the ultraviolet rays is more preferably 10 nm or more and 400 nm or less, and even more preferably 100 nm or more and 400 nm or less. When the wavelength of the above-mentioned ultraviolet rays is 10 nm or more, the polymer as a component of the adhesive layer is modified by absorbing light, and the strength and the adhesive force are reduced, so that the support and the adherend can be easily separated. Moreover, since the adhesive layer of a processed part absorbs light as a wavelength is 400 nm or less, generation|occurrence|production of the residue of a cured film can be suppressed.

Examples of the above-mentioned ultraviolet light source include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, and a far-ultraviolet lamp laser. Among the above-mentioned light sources, lasers are preferred.

Examples of the above lasers include: solid lasers, liquid lasers, and gas lasers. In addition, examples of the above-mentioned solid-state lasers include semiconductor excitation lasers and the like. Examples of liquid lasers include pigmented lasers and the like. Examples of gas lasers include excimer lasers and the like. Among the above lasers, semiconductor excitation lasers are preferred.

Examples of the above semiconductor excitation lasers 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, etc. Examples of excimer lasers include KrF lasers, XeCl lasers, ArF lasers, F2 lasers, and the like. Among the above lasers, Nd:YAG lasers are preferred.

In addition, the output and the accumulated light amount of the light irradiated to the adhesive layer vary depending on the type of light source, etc., but when the irradiated light is a laser, the above-mentioned output of 0.1 mW or more and 200 W or less can be used. In addition, the above-mentioned cumulative light amount is preferably 1 mJ/cm ² or more and 50 J/cm ² or less. When the accumulated light amount is 0.1 mJ/cm ² or more, scorch, peeling residue, etc., which are generated during the peeling, are less likely to occur. If it is 50 J/cm ² or less, the rate of erosion can be appropriately controlled to perform appropriate processing.

As a method of irradiating the adhesive layer with light (laser), it is preferable to irradiate the entire surface of the adhesive layer with a laser from the support side. The method of irradiating the laser is not particularly limited, and a known method can be used.

In the said laminated body, by irradiating light (laser) to the said adhesive bond layer, the said support body and the said to-be-adhered body can be isolate|separated.

In the processing method of the laminated body which concerns on one embodiment of this invention, the process of processing the prepared laminated body may be included before the process of separating a support body and a to-be-adhered body.

The method of processing the above-mentioned laminate includes thinning of the adherend such as dicing and back surface grinding, photoetching, lamination of semiconductor wafers, mounting of various elements, resin sealing, and the like.

Moreover, in the processing method of the laminated body which concerns on one Embodiment of this invention, the process of moving the laminated body processed by the said process from one apparatus to another apparatus may be included. A method of moving the above-mentioned laminated body includes a robot arm or the like.

The laminate of the present invention is processed in this way.

[Example]

Embodiments of the present invention will be specifically described below based on Examples and Comparative Examples, but the present invention is not limited to these.

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

In addition, when using the same type of measurement equipment, the equipment manufacturer name is omitted from the second point. Moreover, in the Example, the manufacturing method of the board|substrate with a cured film for measurement was used. The glass substrates used are all subjected to the same treatment and used. In addition, regarding the content of each component, when the first digit below the decimal point is 0, the description below the decimal point may be omitted.

[Solid content concentration]

1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: W0(g)], weighed [W1(g)], and the weight [W2(g)] after heating at 160° C. for 2 hours was obtained by using obtained by the following formula.

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

[acid value]

烷，使用電位滴定裝置「COM-1600」(平沼產業股份有限公司製)以1/10N-KOH水溶液進行滴定而求得。 Dissolve the resin solution in two

The alkane was obtained by titration with a 1/10 N-KOH aqueous solution using a potentiometric titration apparatus "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[Molecular weight]

Gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuper H-2000 (2 pieces) + TSKgelSuper H-3000 (1 piece) + TSKgelSuper H-4000 ( 1 piece) + TSKgelSuper H-5000 (1 piece) (manufactured by Tosoh Corporation), temperature: 40° C., speed: 0.6 ml/min) for measurement, using standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer set) ) conversion value to obtain the weight average molecular weight (Mw).

The abbreviations described in the synthesis examples are as follows.

BPFE: Bisphenol-based epoxy resin (the epoxy resin in which Ar is a benzene ring and 1 is 0 in the general formula (1), epoxy equivalent 256g/eq)

BNFE: bisnaphthol-type epoxy resin (in general formula (1), Ar is a naphthalene ring and 1 is an epoxy resin, epoxy equivalent 281g/eq)

YD-7011R: Bisphenol A epoxy resin (EPOTOHTOYD-7011R, manufactured by NIPPON STEEL Chemical & Material Co., Ltd., "EPOTOHTO" is a registered trademark of the same company)

YX8000: Hydrogenated epoxy resin (“jER YX8000”, epoxy equivalent 205 g/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-cyclohexanetetracarboxylic dianhydride

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

TPP: Triphenylphosphine

AA: Acrylic

PGMEA: Propylene Glycol Monomethyl Ether Acetate

[Synthesis Example 1]

Put BPFE (50.00g, 0.10mol), AA (14.07g, 0.20mol), TPP (0.26g) and PGMEA (40.00g) into a 250mL four-necked flask with a reflux cooler, at 100 to 105°C After stirring for 12 hours, a reaction product was obtained. Then, PGMEA (25.00g) was put in, and it adjusted so that a solid content might become 50 mass %.

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

[Synthesis Example 2]

Put BPFE (50.00g, 0.10mol), AA (14.07g, 0.20mol), TPP (0.26g) and PGMEA (40.00g) into a 250mL four-necked flask with a reflux cooler, at 100 to 105°C After stirring for 12 hours, a reaction product was obtained. Then, PGMEA (25.00g) was put in, and it adjusted so that a solid content might become 50 mass %.

Next, BTDA (15.73 g, 0.05 mol) and THPA (7.43 g, 0.05 mol) were placed in the obtained reaction product, and the mixture was stirred at 115 to 120° C. for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A) -2. The solid content concentration of the obtained resin solution was 57.4 mass %, the acid value (solid content conversion) was 105 mgKOH/g, and the Mw obtained by GPC analysis was 3200.

[Synthesis Example 3]

Put BPFE (50.00g, 0.10mol), AA (14.07g, 0.20mol), TPP (0.26g) and PGMEA (40.00g) into a 250mL four-necked flask with a reflux cooler, at 100 to 105°C After stirring for 12 hours, a reaction product was obtained. Then, PGMEA (25.00g) was put in, and it adjusted so that a solid content might become 50 mass %.

Next, naphthalene-1,4,5,8-tetracarboxylic dianhydride (13.09 g, 0.05 mol) and THPA (7.43 g, 0.05 mol) were placed in the obtained reaction product, and stirred at 115 to 120° C. for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A)-3. The solid content concentration of the obtained resin solution was 56.6 mass %, the acid value (solid content conversion) was 101 mgKOH/g, and the Mw obtained by GPC analysis was 3300.

[Synthesis Example 4]

Put BPFE (50.00g, 0.10mol), AA (14.07g, 0.20mol), TPP (0.26g) and PGMEA (40.00g) into a 250mL four-necked flask with a reflux cooler, at 100 to 105°C After stirring for 12 hours, a reaction product was obtained. Then, PGMEA (25.00g) was put in, and it adjusted so that a solid content might become 50 mass %.

Next, naphthalene-2,3,6,7-tetracarboxylic dianhydride (13.09 g, 0.05 mol) and THPA (7.43 g, 0.05 mol) were placed in the obtained reaction product, and stirred at 115 to 120° C. for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A)-4. The solid content concentration of the obtained resin solution was 56.6 mass %, the acid value (solid content conversion) was 99 mgKOH/g, and the Mw obtained by GPC analysis was 3400.

[Synthesis Example 5]

Put BPFE (50.00g, 0.10mol), AA (14.07g, 0.20mol), TPP (0.26g) and PGMEA (40.00g) into a 250mL four-necked flask with a reflux cooler, at 100 to 105°C After stirring for 12 hours, a reaction product was obtained. Then, PGMEA (25.00g) was put in, and it adjusted so that a solid content might become 50 mass %.

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

[Synthesis Example 6]

Put BPFE (50.00g, 0.10mol), AA (14.07g, 0.20mol), TPP (0.26g) and PGMEA (40.00g) into a 250mL four-necked flask with a reflux cooler, at 100 to 105°C After stirring for 12 hours, a reaction product was obtained. Then, PGMEA (25.00g) was put in, and it adjusted so that a solid content might become 50 mass %.

Next, BPDA (14.37 g, 0.05 mol) and 2,3-naphthalene dicarboxylic anhydride (9.68 g, 0.05 mol) were placed in the obtained reaction product, and the mixture was stirred at 115 to 120° C. for 6 hours to obtain an unsaturated group-containing material. The alkali-soluble resin (A)-6. The solid content concentration of the obtained resin solution was 57.6 mass %, the acid value (solid content conversion) was 95 mgKOH/g, and the Mw obtained by GPC analysis was 3600.

[Synthesis Example 7]

In a 250mL four-neck flask with a reflux cooler, put BPFE (50.00g, 0.10mol), AA (14.07g, 0.20mol), TPP (0.26g) and PGMEA (40.00g) at 100 It stirred at 105 degreeC for 12 hours, and obtained the reaction product. Then, PGMEA (25.00g) was put in, and it adjusted so that a solid content might become 50 mass %.

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

[Synthesis Example 8]

Put BPFE (50.00g, 0.10mol), AA (14.07g, 0.20mol), TPP (0.26g) and PGMEA (40.00g) into a 250mL four-necked flask with a reflux cooler, at 100 to 105°C After stirring for 12 hours, a reaction product was obtained. Then, PGMEA (25.00g) was put in, and it adjusted so that a solid content might become 50 mass %.

Next, BPDA (19.25 g, 0.07 mol) and THPA (0.30 g, 0.002 mol) were placed in the obtained reaction product, and the mixture was stirred at 115 to 120° C. for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A) -8. The solid content concentration of the obtained resin solution was 56.3 mass %, the acid value (solid content conversion) was 97 mgKOH/g, and the Mw obtained by GPC analysis was 4700.

[Synthesis Example 9]

Put BNFE (50.00g, 0.09mol), AA (12.82g, 0.20mol), TPP (0.23g) and PGMEA (40.00g) into a 250mL four-necked flask with a reflux cooler, at 100 to 105°C After stirring for 12 hours, a reaction product was obtained. Then, PGMEA (25.00g) was put in, and it adjusted so that a solid content might become 50 mass %.

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

[Synthesis Example 10]

Put BNFE (50.00g, 0.09mol), AA (12.82g, 0.20mol), TPP (0.23g) and PGMEA (40.00g) into a 250mL four-necked flask with a reflux cooler, at 100 to 105°C After stirring for 12 hours, a reaction product was obtained. Then, PGMEA (25.00g) was put in, and it adjusted so that a solid content might become 50 mass %.

Next, BTDA (14.33 g, 0.04 mol) and THPA (6.77 g, 0.04 mol) were placed in the obtained reaction product, and the mixture was stirred at 115 to 120° C. for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A) -10. The solid content concentration of the obtained resin solution was 56.5 mass %, the acid value (solid content conversion) was 90 mgKOH/g, and the Mw obtained by GPC analysis was 2700.

[Synthesis Example 11]

Put BPFE (50.00g, 0.10mol), AA (14.07g, 0.20mol), TPP (0.26g) and PGMEA (40.00g) into a 250mL four-necked flask with a reflux cooler, at 100 to 105°C After stirring for 12 hours, a reaction product was obtained. Then, PGMEA (25.00g) was put in, and it adjusted so that a solid content might become 50 mass %.

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

[Synthesis Example 12]

In a 250mL four-necked flask with a reflux cooler, put YD-7011R (50.00g, 0.05mol), AA (7.59g, 0.11mol), TPP (0.14g) and PGMEA (40.00g) at 100 to The mixture was stirred at 105°C for 12 hours to obtain a reaction product. Then, PGMEA (20.00g) was put in, and it adjusted so that a solid content might become 50 mass %.

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

[Synthesis Example 13]

In a 250mL four-neck flask with a reflux cooler, put 3',4'-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate (25.00g, 0.10mol), AA (14.28 g, 0.20 mol), TEAB (0.63 g) and PGMEA (40.00 g), and stirred at 100 to 105° C. for 20 hours to obtain a reaction product. Then, PGMEA (20.00g) was put in, and it adjusted so that a solid content might become 50 mass %.

Next, BPDA (10.29 g, 0.03 mol) and THPA (11.97 g, 0.08 mol) were put into the obtained reaction product, and the mixture was stirred at 120 to 125° C. for 8 hours. GMA (11.60 g, 0.08 mol) was added, and the mixture was stirred at 105 to 110° C. for 8 hours to obtain an unsaturated group-containing alkali-soluble resin (A)-13. The solid content concentration of the obtained resin solution was 64.8 mass %, the acid value (solid content conversion) was 55 mgKOH/g, and the Mw obtained by GPC analysis was 4200.

[Synthesis Example 14]

In a 250mL four-neck flask with a reflux cooler, put YX8000 (50.00g, 0.12mol), AA (17.58g, 0.24mol), TPP (0.32g) and PGMEA (40.00g) at 100 to 105°C After stirring for 20 hours, a reaction product was obtained. Then, PGMEA (20.00g) was put in, and it adjusted so that a solid content might become 50 mass %.

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

The adhesive layer forming compositions of Examples 1 to 12 and Comparative Examples 1 to 4 were prepared in the compounding amounts (unit: mass %) described in Table 1. The formulation ingredients used in Table 1 are as follows.

(Alkali-soluble resin containing unsaturated group)

(A)-1: Resin solution obtained in Synthesis Example 1 (solid content concentration 57.0% by mass)

(A)-2: Resin solution obtained in Synthesis Example 2 (solid content concentration 57.4% by mass)

(A)-3: Resin solution obtained in Synthesis Example 3 (solid content concentration 56.6% by mass)

(A)-4: Resin solution obtained in Synthesis Example 4 (solid content concentration 56.6% by mass)

(A)-5: Resin solution obtained in Synthesis Example 5 (solid content concentration 57.6% by mass)

(A)-6: Resin solution obtained in Synthesis Example 6 (solid content concentration 57.6 mass %)

(A)-7: Resin solution obtained in Synthesis Example 7 (solid content concentration 57.0% by mass)

(A)-8: Resin solution obtained in Synthesis Example 8 (solid content concentration 56.3% by mass)

(A)-9: Resin solution obtained in Synthesis Example 9 (solid content concentration 56.1% by mass)

(A)-10: Resin solution obtained in Synthesis Example 10 (solid content concentration 56.5% by mass)

(A)-11: Resin solution obtained in Synthesis Example 11 (solid content concentration 56.0% by mass)

(A)-12: Resin solution obtained in Synthesis Example 12 (solid content concentration 53.7% by mass)

(A)-13: Resin solution obtained in Synthesis Example 13 (solid content concentration 64.8% by mass)

(A)-14: Resin solution obtained in Synthesis Example 14 (solid content concentration 58.3% by mass)

(photopolymerizable monomer)

(B): Mixture of dipivalerythritol pentaacrylate and hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.)

(photopolymerization initiator)

啉基)丙烷(「Omnirad907」IGMResins B.V.公司製，「Omnirad」為同公司的註冊商標) (C): 2-[4-(methylthio)benzyl]-2-(4-

Lino) propane ("Omnirad907", manufactured by IGMResins BV, "Omnirad" is a registered trademark of the same company)

(photosensitizer)

(D): Michler's ketone

(epoxide)

(E): Biphenyl type epoxy resin (jER YX4000, manufactured by Mitsubishi Chemical Corporation)

(solvent)

(F): Propylene Glycol Monomethyl Ether Acetate (PGMEA)

[Table 1]

[Evaluate]

(A) Calculate the energy of the lowest excited triplet state (T1) of the unsaturated group-containing alkali-soluble resin, and use the hardening obtained by hardening the adhesive layer forming compositions of Examples 1 to 12 and Comparative Examples 1 to 4 The films were evaluated as follows.

[Calculation method of the energy of the 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) is based on the structural unit of the component (A) represented by the following general formula (9), by means of obtained by quantum chemical calculations. In order to obtain the energy of the lowest excited triplet state (T1), the "Gaussian16, RevisionB.01" software package (Gaussian Inc.) was used. Specifically, the lowest excited triplet energy (T1) was obtained by the following calculation method. First, for the molecular structure (molecular coordinates) of the constituent unit (the terminal is substituted with hydrogen) of the component (A) represented by the general formula (9), with a charge of 0 and a multiplicity of 1, the density functional method (DFT) is used to calculate the general B3LYP is used for the function and 6-31G(d) is used for the basis function, and the structure optimization calculation of the ground state is performed (Gaussian input column "#B3LYP/6-31G(d)OPT"). Next, in the structure-optimized molecular structure, using charge 0 and multiplicity 1, using time-dependent density function theory (TDDFT), using B3LYP for the functional function, and using 6-31G(d) for the basis function, the minimum excitation is calculated. Triplet energy (T1) (Gaussian input column "#B3LYP/6-31G(d)td=(50-50, nstates=4)"). In addition, in the calculation of DFT and TDDFT, computational chemistry software with the same function can also be used as an alternative.

In addition, the energy of the lowest excited triplet state (T1) of the unsaturated group-containing alkali-soluble resin ((A)-12, 13, 14) is represented by the following general formula (10), general formula (11) and general formula, respectively The constituent unit of the component (A) shown in (12) is based on the above-mentioned quantum chemical calculation.

(Production of substrate with cured film for evaluation of laser processability)

Using a spin coater, the photosensitive resin compositions shown in Table 1 were previously irradiated with ultraviolet rays with a wavelength of 254 nm and an illuminance of 1000 mJ/cm ² so that the film thickness after the heat curing treatment was 1.0 μm. On the synthetic quartz glass substrate (hereinafter referred to as "quartz glass substrate") of 125 mm x 125 mm, the surface of which was cleaned, pre-baked at 90° C. for 1 minute using a hot plate to prepare a dry film. Next, main hardening (post-baking) was performed at 250 degreeC for 30 minutes using a hot-air dryer, and the board|substrates with the cured film of Examples 1-12 and Comparative Examples 1-4 were obtained.

[Laser Processability Evaluation]

(assessment method)

For the cured film (coating film) after the main curing (post-baking), the Nd:YAGQ-SW laser oscillator "Callisto" (manufactured by V Technology Co., Ltd.) was excited using a flash lamp, and the laser was irradiated from the quartz glass substrate side. radiation (laser wavelength: 266nm). The cured film (coating film) is processed (coating film removal) with a laser energy of 3 to 550 mJ/cm ² , and the processed cured film (coating film) is observed with an optical microscope. In addition, ○ or more is regarded as a pass.

(assessment benchmark)

○: Less than 20mJ/ ^cm2 , no coating residue on the laser-irradiated part

△: Over 20 mJ/cm ² and 50 mJ/cm ² or less, there is no coating residue on the laser-irradiated part

×: Over 50 mJ/cm ² , there is coating residue in the laser-irradiated part

(Preparation of substrate with cured film for evaluation of development residue)

Using a spin coater, the composition for forming an adhesive layer shown in Table 1 was applied to a glass substrate "#1737" (manufactured by Corning Incorporated) of 125 mm x 125 mm so that the film thickness after the heat curing treatment was 3.0 μm. (Hereinafter referred to as a "glass substrate"), a hard film (coating film) was produced by prebaking at 90° C. for 1 minute using a hot plate. Next, ultraviolet rays of 300 mJ/cm ² were irradiated with an ultra-high pressure mercury lamp having an illuminance of 30 mW/cm ² at a wavelength of 365 nm to perform a photohardening reaction of the photosensitive portion.

Next, with 0.8% TMAH (tetramethylammonium hydroxide) developer at 23°C, the exposed film was developed with a shower pressure of 1kgf/cm ² (break time from the beginning of pattern appearance). =BT)) 10 seconds later, 5kgf/cm ² of water spray cleaning was performed to remove the unexposed part of the exposed film to form a dot pattern with a diameter of 30 μm on the glass substrate, and the main curing was performed at 250°C using a hot air dryer. (Post-baking) for 30 minutes, the substrates with cured films of Examples 1 to 12 and Comparative Examples 1 to 4 were obtained.

[Development Residue Evaluation]

(assessment method)

The 30 μm diameter dot pattern of the cured film (coating film) of the obtained cured film-attached substrate was observed using an optical microscope and a scanning electron microscope (SEM). Residues of the composition for forming the agent layer. In addition, ○ or more is regarded as a pass.

(assessment benchmark)

○: No residue was found on the edge of the pattern and the substrate

△: Residues were found on the pattern edge and part of the substrate

×: The residue on the edge of the pattern and on the substrate is conspicuous

-: No pattern formed

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

The photosensitive resin composition shown in Table 1 was applied on the glass substrate "#1737" using a spin coater so that the film thickness after the heat curing treatment was 3.0 μm, and preliminarily performed at 90° C. using a hot plate. A dry film was produced by baking for 3 minutes. Next, ultraviolet rays of 100 mJ/cm ² were irradiated with an ultra-high pressure mercury lamp having an illuminance of 30 mW/cm ² at a wavelength of 365 nm to perform a photohardening reaction. Then, using a hot-air dryer, main hardening (post-baking) was performed for 30 minutes at 230 degreeC, and the board|substrates with the cured film of Examples 1-12 and Comparative Examples 1-4 were obtained.

[Chemical Resistance Evaluation]

(assessment method)

The cured film (coating film) of the obtained board|substrate with a cured film was immersed in acetone, 5 wt % sodium hydroxide aqueous solution, and 5 wt % hydrochloric acid for 30 minutes, respectively, and it wash|cleaned and dried. After that, the test will be hard The film thickness of the chemical film (coating film) was measured using a stylus-type level difference shape measuring apparatus "P-17" (manufactured by KLA-Tencor Co., Ltd.). In addition, △ or more was regarded as a pass.

The residual film ratio in the chemical 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 rate (%)=L2/L1×100

(assessment benchmark)

○: The residual film rate is 90% or more

△: The residual film rate is more than 80% and less than 90%

×: The residual film rate is less than 80%

The above evaluation results are shown in Table 2.

[Table 2]

It turned out that the laminated body which used the adhesive layer formation composition which has the alkali-soluble resin containing an unsaturated group of this invention for an adhesive bond layer is excellent in laser processability. It is considered that this is because the alkali-soluble resin containing an unsaturated group has a low crosslinking density after curing, so that it is easily eroded by irradiation with a laser.

In addition, it was found that if 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 2.90 eV or less, and the Excellent shot processability. It is considered that this is because when Y is an aromatic hydrocarbon group, the value of the LUMO (lowest unoccupied molecular orbital) of (the structural unit of) the resin becomes small. As a result, the HOMO (highest occupied molecular orbital)-LUMO energy gap becomes smaller, so the value of the lowest excited triplet state (T1) also becomes smaller.

Moreover, it turns out that the composition for adhesive layer formation containing the epoxy which has 2 or more epoxy groups as a component (E) is excellent in chemical resistance. It is considered that this is because a sufficient cross-linked structure can be formed by including the (E) component.

[Industrial Availability]

The present invention can provide a laminate having an adhesive that can be used in the manufacture of various products. In particular, it is possible to provide a laminated body suitable for a step of temporarily bonding and processing on a support body such as a semiconductor wafer.

Claims (8)

A composition for forming an adhesive layer, which is designed so that in a laminate having an adhesive layer between a support through which light penetrates and an adherend, the support can be irradiated with light from the support side. Separated from the above-mentioned layered body from the above-mentioned adherend, wherein, The aforementioned composition for forming an adhesive layer 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 (A) unsaturated group-containing alkali-soluble resin calculated by quantum chemical calculation is 2.90 eV or less. The composition for forming an adhesive layer according to claim 1, wherein the (A) unsaturated group-containing alkali-soluble resin is a resin represented by the following general formula (1),

In formula (1), Ar is each independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of the hydrogen atom to which it is bonded may be selected from an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms. or substituted by a substituent in the group consisting of aralkyl, cycloalkyl or cycloalkylalkyl with 3 to 10 carbons, alkoxy with 1 to 5 carbons and halogen; R ₁ are independently is an alkylene group having 2 to 4 carbon atoms, and l is independently a number from 0 to 3; G is independently a (meth)acryloyl group, the following general formula (2) or the following general formula (3) In the substituents shown, 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 one or more of them are represented by the following general formula (4) Substituents; n is a numerical value with an average value of 1 to 20;

In formulas (2) and (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is a divalent alkyl group or an alkyl aryl group with 2 to 10 carbon atoms, and R ₄ is 2 with 2 to 20 carbon atoms. valence saturated or unsaturated hydrocarbon group, p is a value from 0 to 10;

In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is a numerical value of 1 or 2. The composition for forming an adhesive layer according to claim 2, wherein the Y contains at least one aromatic hydrocarbon group. The composition for forming an adhesive layer according to any one of claims 1 to 3, comprising: (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond; and (C) photopolymerizable Initiator and/or (D) photosensitizer. The composition for forming an adhesive layer according to any one of Claims 1 to 4, which contains (E) an epoxide having two or more epoxy groups. The composition for forming an adhesive layer according to any one of claims 1 to 5, wherein the (A) unsaturated group-containing alkali-soluble resin has a weight average molecular weight of 1,000 or more and 100,000 or less, and an acid value of 50 mgKOH/ g or more and 200 mgKOH/g or less. A method of manufacturing a laminate, comprising the following steps: A step of forming an adhesive layer on the surface of either or both of the support and the adherend using the composition for forming an adhesive layer according to any one of claims 1 to 6; and The step of adhering the support body and the adherend through the formed adhesive layer. A method for processing a laminated body, comprising the following steps: a step of preparing a laminate having a support, an adhesive layer, and an adherend; and The step of irradiating light to separate the support body from the attached body; wherein, The aforementioned support system allows light with a wavelength of 10 nm to 400 nm to penetrate, In the lamination system, the support body and the adherend can be separated by irradiating the adhesive layer with light.