Primer layer forming composition, laminate, and method for decomposing the laminate

Abstract

A primer layer-forming composition for forming a primer layer having a cleavage structure in which chemical bonds are irreversibly cleaved in response to external stimuli, the composition containing a film-forming component and a solvent, and satisfying at least one among the following conditions (A) and (B).　Condition (A): The film-forming component has the cleavage structure.　Condition (B): The film-forming component has two types of partial structure capable of reacting with each other to form the cleavage structure.

Description

[Technical Field]

[0001] The present invention relates to a primer layer forming composition, a laminate, and a method for decomposing a laminate. [Background technology]

[0002] In recent years, there has been a growing demand for the reuse of electronic components and other materials. In the recycling of electronic components and other items, two components (adhered parts) bonded together via an adhesive layer are sometimes separated to allow them to be returned to their individual components. Each separated component can then be reused as is, or further broken down into raw materials for reuse (material recycling).

[0003] To enable easy separation of two components bonded together via an adhesive layer, photocatalytically disassemblable adhesives containing specific polymers have been proposed as adhesives for the adhesive layer (Patent Documents 1-3). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-172619 [Patent Document 2] Japanese Patent Publication No. 2020-172598 [Patent Document 3] Japanese Patent Publication No. 2020-056010 [Overview of the project] [Problems that the invention aims to solve]

[0005] The adhesive layer is required to have various properties such as adhesive strength, thermal properties, and durability, depending on the application of the substrate and the laminate containing the adhesive layer, as well as the type of substrate. However, if special additives are added to the adhesive layer to give it an easily disassembled function, other properties of the adhesive layer may be limited.

[0006] The present invention aims to provide a primer layer forming composition that allows for easy decomposition of a laminate including an adherend and an adhesive layer without adding an additive that imparts easy decomposition properties to the adhesive layer used to bond the adherend, a laminate using the same, and a method for decomposing the laminate. [Means for solving the problem]

[0007] The inventors of the present invention conducted diligent research to solve the above problems and, as a result, found that they could solve the above problems, and completed the present invention having the following gist. In other words, the present invention encompasses the following: [1] A primer layer forming composition for forming a primer layer having a cleavage structure in which chemical bonds irreversibly cleave in response to an external stimulus, It contains a film-forming component and a solvent, The following conditions (A) and (B) must be met: Composition for forming a primer layer. Condition (A): The film-forming component has the cracking structure. Condition (B): The film-forming component has two types of substructures that can react with each other to form the cleavage structure. [2] The external stimulus is an active energy ray, The aforementioned cleavage structure is a cleavage structure in which the chemical bond is irreversibly cleaved by absorbing the aforementioned active energy rays. [1] The primer layer forming composition described above. [3] The primer layer forming composition according to [2], wherein the active energy ray is not laser light. [4] A primer layer forming composition according to any one of [1] to [3], which is a composition for forming the primer layer adjacent to the adhesive layer. [5] A primer layer-forming composition according to any one of [1] to [4], wherein the cleavage structure comprises at least one of an oxime ester structure, an oxime ether structure, an o-nitrobenzyl structure, an acetophenone structure, an alkylphenone structure, a pyrenylmethyl structure, a coumarinylmethyl structure, an aminoalkylphenone structure, and a benzyl ketal structure. [6] The cleavage structure comprises at least one of the oxime ester structure, the oxime ether structure, the o-nitrobenzyl structure, and the acetophenone structure, The oxime ester structure or the oxime ether structure is a structure represented by the following formula (1): The o-nitrobenzyl structure is represented by the following formula (2): The acetophenone structure is represented by the following formula (3): [5] The primer layer forming composition described above. [ka] (In formula (1), R 1 This represents a hydrogen atom, halogen atom, nitro group, cyano group, hydrocarbon group having 1 to 30 carbon atoms, heterocyclic group having 2 to 30 carbon atoms, or a group in which one or more non-adjacent methylene groups in the hydrocarbon group or heterocyclic group are replaced by a divalent group selected from group I below. Group I consists of -O-, -C(=O)-, -C(=O)O-, and -N(-R 3 )-,-N(-R 3 )C(=O)-, -S-, -C(=S)-, -SO2-, -SC(=O)-, and -OC(=S)-, R 3 This represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. n1 represents 0 or 1, n2 represents either 0 or 1. In formula (2), R 11represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, or a group in which one or two or more non-adjacent methylene groups in the hydrocarbon group or the heterocyclic group are replaced by a divalent group selected from the following Group I, Group I is -O-, -C(=O)-, -C(=O)O-, -N(-R 3 )-, -N(-R 3 )C(=O)-, -S-, -C(=S)-, -SO2-, -SC(=O)-, and -OC(=S)-, and R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, R 12 represents a halogen atom, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms, n11 represents 0 or 1, n12 represents an integer of 0 to 3. When n12 is 2 or 3, R 12 may be the same or different. In formula (3), R 21 represents a halogen atom, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms, n21 represents an integer of 0 to 4. When n21 is 2 or more, R 21 may be the same or different, n22 represents 0 or 1. In formulas (1) to (3), * represents a bond. ) In formulas (1) to (3), * represents a bond. ) [7] Satisfying the above condition (A), the film-forming component contains a polymer, the polymer has the cleavage structure, The primer layer-forming composition according to any one of [1] to [6]. [8] Satisfying the above condition (A), the film-forming component contains a polymer and a crosslinking agent, at least one of the polymer and the crosslinking agent has the cleavage structure, A primer layer-forming composition according to any one of [1] to [6]. [9] The primer layer forming composition according to [8], wherein the polymer has reactive groups that can react with the crosslinking agent.

[10] The above condition (B) is met, The aforementioned film-forming component contains a polymer and a crosslinking agent, The polymer has one of two substructures that can react with each other to form the cleavage structure, The crosslinking agent has the other of the two types of substructures, A primer layer-forming composition according to any one of [1] to [6].

[11] The first object to be attached and The second adherend and, A primer layer located between the first adherend and the second adherend, A laminate comprising an adhesive layer located between the first adherend and the second adherend and in contact with the primer layer, The primer layer is formed from a primer layer forming composition containing a film-forming component and a solvent. The primer layer has a cleavage structure in which chemical bonds irreversibly cleave in response to external stimuli. Laminated structure.

[12] The external stimulus is an active energy ray, The aforementioned cleavage structure is a cleavage structure in which the chemical bond is irreversibly cleaved by absorbing the activation energy rays. At least one of the first adherend and the second adherend is permeable to the active energy rays.

[11] The laminate described above.

[13] The laminate according to

[12] , wherein the active energy ray is not laser light.

[14] A laminate according to any of

[11] to

[13] that satisfies at least one of the following conditions (A) and (B). Condition (A): The film-forming component has the cracking structure. Condition (B): The film-forming component has two types of substructures that can react with each other to form the cleavage structure.

[15] The laminate according to any one of

[11] to

[14] wherein the cleavage structure comprises at least one of an oxime ester structure, an oxime ether structure, an o-nitrobenzyl structure, an acetophenone structure, an alkylphenone structure, a pyrenylmethyl structure, a coumarinylmethyl structure, an aminoalkylphenone structure, and a benzyl ketal structure.

[16] The cleavage structure comprises at least one of the oxime ester structure, the oxime ether structure, the o-nitrobenzyl structure, and the acetophenone structure, The oxime ester structure or the oxime ether structure is a structure represented by the following formula (1): The o-nitrobenzyl structure is represented by the following formula (2): The acetophenone structure is represented by the following formula (3):

[15] The laminate described above. [ka] (In formula (1), R 1 This represents a hydrogen atom, halogen atom, nitro group, cyano group, hydrocarbon group having 1 to 30 carbon atoms, heterocyclic group having 2 to 30 carbon atoms, or a group in which one or more non-adjacent methylene groups in the hydrocarbon group or heterocyclic group are replaced by a divalent group selected from group I below. Group I consists of -O-, -C(=O)-, -C(=O)O-, and -N(-R 3 )-,-N(-R 3 )C(=O)-, -S-, -C(=S)-, -SO2-, -SC(=O)-, and -OC(=S)-, R 3 This represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. n1 represents 0 or 1, n2 represents either 0 or 1. In formula (2), R 11 This represents a hydrogen atom, halogen atom, nitro group, cyano group, hydrocarbon group having 1 to 30 carbon atoms, heterocyclic group having 2 to 30 carbon atoms, or a group in which one or more non-adjacent methylene groups in the hydrocarbon group or heterocyclic group are replaced by a divalent group selected from group I below. Group I consists of -O-, -C(=O)-, -C(=O)O-, and -N(-R 3 )-,-N(-R 3 )C(=O)-, -S-, -C(=S)-, -SO2-, -SC(=O)-, and -OC(=S)-, R 3 This represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. R 12 This represents a halogen atom, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms. n11 represents 0 or 1, n12 represents an integer from 0 to 3, and if n12 is 2 or 3, R 12 They may be the same or they may be different. In formula (3), R 21 This represents a halogen atom, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms. n21 represents an integer from 0 to 4, and if n21 is 2 or greater, R 21 They may be the same or they may be different. n22 represents either 0 or 1. In equations (1) to (3), * represents a bond.

[17] The above condition (A) is met, The aforementioned film-forming component contains a polymer, The polymer has the cracking structure, A laminate as described in any of

[14] to

[16] .

[18] The above condition (A) is met, The aforementioned film-forming component contains a polymer and a crosslinking agent, At least one of the polymer and the crosslinking agent has the cleavage structure. A laminate as described in any of

[14] to

[16] .

[19] The laminate according to

[18] , wherein the polymer has reactive groups that can react with the crosslinking agent.

[20] The above condition (B) is met, The aforementioned film-forming component contains a polymer and a crosslinking agent, The polymer has one of two substructures that can react with each other to form the cleavage structure, The crosslinking agent has the other of the two types of substructures, A laminate as described in any of

[14] to

[16] .

[21] A separation step of applying an external stimulus to the primer layer in the laminate described in any of

[11] to

[20] to separate the first adherend and the second adherend. A method for disassembling a laminate, including the following.

[22] The external stimulus is an active energy ray, The aforementioned cleavage structure is a cleavage structure in which the chemical bond is irreversibly cleaved by absorbing the activation energy rays. At least one of the first adherend and the second adherend is permeable to the active energy rays.

[21] A method for disassembling a laminate as described above.

[23] The method for decomposing a laminate according to

[22] , wherein the active energy ray is not laser light. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a primer layer forming composition that allows for easy decomposition of a laminate including an adherend and an adhesive layer without adding an additive that imparts easy decomposition properties to the adhesive layer used to bond the adherend, a laminate using the same, and a method for decomposing the laminate. [Modes for carrying out the invention]

[0009] (Composition for forming primer layer) The primer layer-forming composition of the present invention contains a film-forming component and a solvent. A primer layer-forming composition is a composition for forming a primer layer having a cleavage structure. A cleavage structure is a structure in which chemical bonds irreversibly cleave in response to an external stimulus (stimulus from the outside). The primer layer-forming composition satisfies at least one of the following conditions (A) and (B). Condition (A): The film-forming component has a cleavage structure. Condition (B): The film-forming component has two types of substructures that can react with each other to form a cleavage structure.

[0010] A primer layer, sometimes also called an undercoat layer, is sometimes formed between the substrate and the adhesive layer to improve adhesion to the substrate.

[0011] Because the primer layer has a cleavage structure, when the primer layer is irradiated with active energy rays, the adhesion between the primer layer and the adhesive layer decreases due to the cleavage of the cleavage structure. As a result, the two adherends in a laminate, which is bonded together via the adhesive layer and the primer layer, can be easily separated.

[0012] The primer layer forming composition is preferably a composition for forming a primer layer adjacent to an adhesive layer. Primer layer forming compositions are used, for example, in packaging films, building materials, endoscopes, automobiles, and the like.

[0013] <cleavage structure> The cleavage structure is not particularly limited as long as it is a structure in which the chemical bond irreversibly cleaves in response to an external stimulus. Cracked structures include reversibly cracked structures and irreversibly cracked structures, but among these, irreversibly cracked structures are preferred. Irreversible cracking refers to cracking caused by an irreversible chemical reaction. If the cleavage is reversible, there is a risk that the chemical bonds may unintentionally recombine after being cleaved, which may result in a decrease in the ease of decomposition of the laminate. In this respect, it is preferable that the cleavage structure is irreversibly cleavable.

[0014] External stimuli are not particularly limited as long as they are external stimuli capable of cleaving the cleavage structure, and include, for example, active energy rays, heat, electricity, magnetism, and combinations of two or three of these.

[0015] When the external stimulus is an active energy ray, the cleavage structure is one in which the chemical bond is irreversibly cleaved by absorbing the active energy ray. Examples of active energy rays absorbed by the cleavage structure include ultraviolet light, electron beams, and X-rays, with ultraviolet light being particularly preferred. Examples of ultraviolet wavelengths include 300-380 nm. Examples of light sources used for ultraviolet irradiation include sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs. While laser light may be used as the active energy beam, it is preferable to use something other than laser light, as using laser light may damage the substrate.

[0016] In a cleavage structure, the chemical bonds that are cleaved are usually covalent bonds. Examples of covalent bonds that are cleaved include covalent bonds between two heteroatoms and covalent bonds between a heteroatom and a carbon atom. Examples of heteroatoms include oxygen atoms and nitrogen atoms.

[0017] The cleavage structure preferably includes at least one of the following: oxime ester structure, oxime ether structure, o-nitrobenzyl structure, acetophenone structure, alkylphenone structure, pyrenylmethyl structure, coumarinylmethyl structure, aminoalkylphenone structure, and benzyl ketal structure, and more preferably includes at least one of the following: oxime ester structure, oxime ether structure, o-nitrobenzyl structure, and acetophenone structure. These cleavage structures undergo irreversible cleavage upon low-energy external stimulation (e.g., active energy rays), thus enabling the separation of two adherends at low energy.

[0018] Here, an example of a crack in a cracked structure is shown below. The following is an example of cleavage of an oxime ester structure. [ka]

[0019] The following is an example of cleavage of the o-nitrobenzyl structure. [ka]

[0020] The following is an example of cleavage of the acetophenone structure. [ka]

[0021] The following is an example of pyrenylmethyl cleavage. [ka]

[0022] The following is an example of the cleavage of the coumarinyl methyl structure. [ka]

[0023] Examples of oxime ester structures or oxime ether structures include the structure represented by the following formula (1). An example of an o-nitrobenzyl structure is the structure represented by the following formula (2). An example of an acetophenone structure is the structure represented by the following formula (3).

[0024] [ka] (In formula (1), R 1 This represents a hydrogen atom, halogen atom, nitro group, cyano group, hydrocarbon group having 1 to 30 carbon atoms, heterocyclic group having 2 to 30 carbon atoms, or a group in which one or more non-adjacent methylene groups in the hydrocarbon group or heterocyclic group are replaced by a divalent group selected from group I below. Group I consists of -O-, -C(=O)-, -C(=O)O-, and -N(-R3 )-,-N(-R 3 )C(=O)-, -S-, -C(=S)-, -SO2-, -SC(=O)-, and -OC(=S)-, R 3 This represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. n1 represents 0 or 1, n2 represents either 0 or 1. In formula (2), R 11 This represents a hydrogen atom, halogen atom, nitro group, cyano group, hydrocarbon group having 1 to 30 carbon atoms, heterocyclic group having 2 to 30 carbon atoms, or a group in which one or more non-adjacent methylene groups in the hydrocarbon group or heterocyclic group are replaced by a divalent group selected from group I below. Group I consists of -O-, -C(=O)-, -C(=O)O-, and -N(-R 3 )-,-N(-R 3 )C(=O)-, -S-, -C(=S)-, -SO2-, -SC(=O)-, and -OC(=S)-, R 3 This represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. R 12 This represents a halogen atom, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms. n11 represents 0 or 1, n12 represents an integer from 0 to 3, and if n12 is 2 or 3, R 12 They may be the same or they may be different. In formula (3), R 21 This represents a halogen atom, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms. n21 represents an integer from 0 to 4, and if n21 is 2 or greater, R 21 They may be the same or they may be different. n22 represents either 0 or 1. In equations (1) to (3), * represents a bond.

[0025] -Hydroxide groups with 1 to 30 carbon atoms- The hydrocarbon groups having 1 to 30 carbon atoms are not particularly limited, but examples include alkyl groups having 1 to 30 carbon atoms, alkenyl groups having 2 to 30 carbon atoms, cycloalkyl groups having 3 to 30 carbon atoms, cycloalkylalkyl groups having 4 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, and arylalkyl groups having 7 to 30 carbon atoms. If the hydrocarbon group having 1 to 30 carbon atoms has substituents, the total number of carbon atoms is 1 to 30.

[0026] Alkyl alkyl groups having 1 to 30 carbon atoms may be linear or branched. Examples of linear alkyl groups include methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and eicosyl groups. Examples of branched alkyl groups include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, iso-amyl group, tert-amyl group, iso-octyl group, 2-ethylhexyl group, tert-octyl group, iso-nonyl group, and iso-decyl group. Among these, those with a straight chain are preferred. Furthermore, alkyl groups having 1 to 10 carbon atoms are preferred, and alkyl groups having 1 to 4 carbon atoms are more preferred, as they offer superior degradation of the primer layer due to external stimuli.

[0027] The alkenyl group having 2 to 30 carbon atoms may be linear or cyclic. If the alkenyl group is linear, it may be a terminal alkenyl group having an unsaturated bond at the end, or an internal alkenyl group having an unsaturated bond inside. Examples of terminal alkenyl groups having 2 to 30 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 4-pentenyl, and 5-hexenyl groups. Examples of internal alkenyl groups include 2-butenyl group, 3-pentenyl group, 2-hexenyl group, 3-hexenyl group, 2-heptenyl group, 3-heptenyl group, 4-heptenyl group, 3-octenyl group, 3-nonenyl group, 4-decenyl group, 3-undecenyl group, and 4-dodecenyl group. Examples of cyclic alkenyl groups include the 3-cyclohexenyl group, the 2,5-cyclohexadienyl-1-methyl group, and the 4,8,12-tetradecatrienylenylallyl group. Among these, alkenyl groups having 2 to 10 carbon atoms are preferred because they offer superior degradation of the primer layer due to external stimuli.

[0028] A cycloalkyl group with 3 to 30 carbon atoms refers to a saturated monocyclic or saturated polycyclic alkyl group having a total of 3 to 30 carbon atoms. Examples of saturated monocyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl groups. Examples of saturated polycyclic alkyl groups include adamantyl, decahydronaphthyl, octahydropentalene, bicyclo[1.1.1]pentanyl, and tetradecahydroanthracenyl groups. Among these, cycloalkyl groups having 3 to 10 carbon atoms are preferred because they exhibit superior degradation of the primer layer by external stimuli.

[0029] A cycloalkylalkyl group with 4 to 30 carbon atoms refers to a group in which the hydrogen atoms of an alkyl group are replaced by cycloalkyl groups, and which has a total of 4 to 30 carbon atoms. The cycloalkyl group in the cycloalkylalkyl group may be monocyclic or polycyclic. Furthermore, the methylene group of the alkyl group in the cycloalkylalkyl group may be replaced with -CH=CH-. Examples of cycloalkylalkyl groups having 4 to 30 carbon atoms and being monocyclic include cycloalkylmethyl group, cycloalkylethyl group, cycloalkylpropyl group, and cycloalkylpropyl group. Examples of cycloalkylmethyl groups include cyclopropylmethyl group, cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, cycloheptylmethyl group, cyclooctylmethyl group, cyclononylmethyl group, and cyclodecylmethyl group. Examples of cycloalkylethyl groups include 2-cyclobutylethyl group, 2-cyclopentylethyl group, 2-cyclohexylethyl group, 2-cycloheptylethyl group, 2-cyclooctylethyl group, 2-cyclononylethyl group, and 2-cyclodecylethyl group. Examples of cycloalkylpropyl groups include 3-cyclobutylpropyl group, 3-cyclopentylpropyl group, 3-cyclohexylpropyl group, 3-cycloheptylpropyl group, 3-cyclooctylpropyl group, 3-cyclononylpropyl group, and 3-cyclodecylpropyl group. Examples of cycloalkylbutyl groups include 4-cyclobutylbutyl group, 4-cyclopentylbutyl group, 4-cyclohexylbutyl group, 4-cycloheptylbutyl group, 4-cyclooctylbutyl group, 4-cyclononylbutyl group, and 4-cyclodecylbutyl group. Examples of polycyclic cycloalkyl groups with 4 to 20 carbon atoms include bicyclo[1.1.0]butyl group, bicyclo[1.1.1]pentyl group, bicyclo[2.1.0]pentyl group, bicyclo[3.1.0]hexyl group, bicyclo[2.1.1]hexyl group, bicyclo[2.2.0]hexyl group, bicyclo[4.1.0]heptyl group, bicyclo[3.2.0]heptyl group, and bicyclo[4.1.0]heptyl group. Examples include chloro[3.1.1]heptyl group, bicyclo[2.2.1]heptyl group, bicyclo[5.1.0]octyl group, bicyclo[4.2.0]octyl group, bicyclo[4.1.1]octyl group, bicyclo[3.3.0]octyl group, bicyclo[3.2.1]octyl group, bicyclo[2.2.2]octyl group, spiro[4,4]nonanyl group, spiro[4,5]decanyl group, and tricyclodecanyl group. Among these, cycloalkylalkyl groups having 4 to 10 carbon atoms are preferred because they exhibit superior degradation of the primer layer by external stimuli.

[0030] The aryl group having 6 to 30 carbon atoms may have a monocyclic structure or a fused-ring structure. Furthermore, the aryl group may be formed by linking two monocyclic aryl groups, or by linking one monocyclic aryl group with a fused-ring aryl group, or by linking two fused-ring aryl groups. Examples of aryl groups having a monocyclic structure include phenyl groups and biphenylyl groups. Examples of aryl groups having a fused ring structure include naphthyl groups, anthuryl groups, and phenantrenyl groups. One or more hydrogen atoms of an aryl group having 6 to 30 carbon atoms may be substituted by substituents. Examples of substituents include the alkyl group, alkenyl group, carboxyl group, and halogen atom. Examples of substituted aryl groups having 6 to 30 carbon atoms include monocyclic substituted aryl groups such as tolyl group, xylyl group, ethylphenyl group, 4-chlorophenyl group, 4-carboxylphenyl group, 4-vinylphenyl group, 4-methylphenyl group, and 2,4,6-trimethylphenyl group. Among these, aryl groups having 6 to 10 carbon atoms are preferred because they offer superior degradation of the primer layer due to external stimuli.

[0031] An arylalkyl group having 7 to 30 carbon atoms refers to a group in which one or more hydrogen atoms of an alkyl group are substituted with the aforementioned aryl group. Examples of arylalkyl groups having 7 to 30 carbon atoms include phenylalkyl groups and naphthylalkyl groups. Examples of phenylalkyl groups include benzyl group, 2-methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group, α-dimethylbenzyl group, 2-phenylethyl group, 2-phenylpropyl group, 3-phenylpropyl group, diphenylmethyl group, triphenylmethyl group, and triphenylpropyl group. Examples of naphthylalkyl groups include naphthylpropyl groups. Among these, arylalkyl groups having 7 to 10 carbon atoms are preferred because they exhibit superior degradation of the primer layer due to external stimuli.

[0032] -Heterocyclic groups containing 2 to 30 carbon atoms (groups containing heterocyclic elements with 2 to 30 carbon atoms)- The heterocycle in the heterocycle-containing group having 2 to 30 carbon atoms may be monocyclic or fused. Furthermore, one or more hydrogen atoms of the heterocycle may be substituted with alkyl groups having 1 to 6 carbon atoms. Additionally, the heterocycle may form a fused heterocycle group by being bonded via alkylene groups having 1 to 6 carbon atoms. Examples of heterocyclic groups containing monocyclic heterocyclic groups include pyrrolyl group, pyridyl group, pyridylethyl group, pyrimidyl group, pyridazyl group, piperadyl group, piperidyl group, pyranyl group, pyranylethyl group, pyrazolyl group, triazyl group, triazylmethyl group, pyrrolidyl group, imidazolyl group, triazolyl group, furyl group, furanyl group, thienyl group, thiophenyl group, thiadiazolyl group, thiazolyl group, oxazolyl group, isothiazolyl group, isoxazolyl group, euroridyl group, morpholinyl group, thiomorpholinyl group, 2-pyrrolidinone-1-yl group, 2-piperidone-1-yl group, 2,4-dioxyimidazolidined-3-yl group, and 2,4-dioxyxazolidined-3-yl group. Examples of heterocyclic groups having a fused heterocyclic structure include quinolyl groups, isoquinolyl groups, benzimidazolyl groups, benzofuranyl groups, benzothiophenyl groups, benzothiazolyl groups, benzoxazolyl groups, and indolyl groups.

[0033] Examples of heterocyclic groups include the following groups: [ka] (In the above formula, R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Z independently represents a single bond or an alkylene group having 1 to 6 carbon atoms, and * represents a bond.) Examples of C1-C6 alkyl groups in R include those with C1-C6 from the C1-C30 alkyl groups exemplified above. Examples of alkylene groups with 1 to 6 carbon atoms in Z include methylene, ethylene, propylene, butylene, pentylene, and hexylene groups.

[0034] <Two types of substructures that can react with each other to form a cleavage structure> The two substructures that can react with each other to form a cleavage structure are not particularly limited. Examples of the cleavage structures that can be formed include oxime ester structures, o-nitrobenzyl structures, alkylphenone structures, pyrenylmethyl structures, coumarinylmethyl structures, aminoalkylphenone structures, and benzyl ketal structures.

[0035] An example of two substructures that can react with each other to form a cleavage structure is given below. The resulting cleavage structure is an o-nitrobenzyl structure. One of the two substructures is the o-nitrobenzyl alcohol structure, which is shown below as an example. [ka] (In the formula, * represents a bond.)

[0036] The other of the two substructures is, for example, an epoxy group, a methylol group, an alkoxymethyl group, an isocyanate group, or a blocked isocyanate group. One example of these is the structure shown below. [ka] (In the formula, * represents a bond.)

[0037] These two types of substructures react with each other to form the following cleavage structure (o-nitrobenzyl structure). [ka] (In the formula, * represents a bond.)

[0038] Such a reaction can be carried out, for example, by applying a primer layer-forming composition containing an acid catalyst onto the object to be coated, and then heating it. Examples of acid catalysts include the curing catalysts described later.

[0039] <Film-forming components> Film-forming components are the components that make up the primer layer when a primer layer is formed from a primer layer-forming composition. Examples of film-forming components include components that exist in the primer layer as is, components that exist in the primer layer as reaction products with other components, and components used as auxiliary agents to assist the reaction of other components (e.g., curing catalysts). In other words, film-forming components are a general term for all components of a primer layer-forming composition except for the solvent.

[0040] Examples of film-forming components include polymers and crosslinking agents.

[0041] If condition (A) is met, the film-forming component may contain a polymer. In this case, for example, the polymer may have a cleavage structure. In this case, for example, the film-forming component may contain two or more polymers, and at least one of the two or more polymers may have a cleavage structure.

[0042] If condition (A) is met, the film-forming component may contain a crosslinking agent. In this case, for example, the crosslinking agent may have a cleavage structure. In this case, the film-forming component may contain two or more crosslinking agents, and at least one of the two or more crosslinking agents may have a cleavage structure.

[0043] If condition (A) is met, the film-forming component may contain a polymer and a crosslinking agent. In this case, for example, at least one of the polymer and the crosslinking agent has a cleavage structure. In the combination of polymers and crosslinking agents in the film-forming component, only the polymer may have a cleaved structure, only the crosslinking agent may have a cleaved structure, or both the polymer and the crosslinking agent may have a cleaved structure. In that case, the film-forming component may contain two or more polymers, and at least one of the two or more polymers may have a cleaved structure. In that case, the film-forming component may also contain two or more crosslinking agents, and at least one of the two or more crosslinking agents may have a cleaved structure.

[0044] If condition (B) is met, the film-forming component may contain a polymer and a crosslinking agent. In this case, for example, the polymer may have one of two substructures that can react with each other to form a cleavage structure, and the crosslinking agent may have the other of the two substructures. In this case, the film-forming component may contain two or more polymers, and at least one of the two or more polymers may have one of the two substructures. In this case, the film-forming component may also contain two or more crosslinking agents, and at least one of the two or more crosslinking agents may have the other of the two substructures.

[0045] If condition (B) is met, the film-forming component may contain two or more polymers. In this case, for example, at least one of the two or more polymers has one of two substructures that can react with each other to form a cleavage structure, and at least one of the remaining polymers has the other of the two substructures.

[0046] If condition (B) is met, the film-forming component may contain two or more crosslinking agents. In this case, for example, at least one of the two or more crosslinking agents has one of two substructures that can react with each other to form a cleavage structure, and at least one of the remaining crosslinking agents has the other of the two substructures.

[0047] <<polymer>> The polymer may or may not have a cleavage structure.

[0048] <<<Polymers with a cleavage structure>>> When a polymer has a cleavage structure, the cleavage structure may be located in the main chain of the polymer or in the side chains of the polymer. Among these, polymers having a cleavage structure in the main chain are preferred because they allow for the introduction of more cleavage structures into the polymer.

[0049] In polymers having a cleavage structure in the main chain, the cleavage structure may be present in all repeating units of the polymer, or in some units. The molar ratio of repeating units having a cleavage structure to the total repeating units of the polymer is not particularly limited, but is preferably 10 mol% or more, more preferably 30 mol% or more, and particularly preferably 50 mol% or more. In polymers having cleavage structures in their side chains, the cleavage structure may be present in all repeating units of the polymer, or in some units. The molar ratio of repeating units with cleavage structures to the total repeating units of the polymer is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, and particularly preferably 10 mol% or more.

[0050] When a polymer has one of two substructures that can react with each other to form a cleavage structure, that substructure is usually located in the side chain of the polymer. In a polymer having one of two substructures in its side chains that can react with each other to form a cleavage structure, the substructure may be present in all repeating units of the polymer, or in some of them. The molar ratio of repeating units containing the substructure to the total repeating units of the polymer is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, and particularly preferably 10 mol% or more.

[0051] Examples of these polymers include condensed polymers such as polyester, polyamide, polyimide, and polyamic acid, as well as polyurethane and vinyl polymers.

[0052] Examples of polymers having a cleavage structure in the main chain include polymers having repeating units represented by the following formulas (11) or (12). [ka] (In formula (11), R 1 , and n1 are R in equation (1), respectively. 1 , and is the same as n1. R101 R represents a divalent organic group. 102 This represents a divalent organic group. In formula (12), R 11 , R 12 , and n12 are R in equation (2), respectively. 11 , R 12 , and is the same as n12. R 111 R represents a divalent organic group. 112 (where m1 represents a divalent organic group; m1 represents 0 or 1.)

[0053] R 101 Examples of divalent organic groups include those having 1 to 30 carbon atoms. Examples of divalent organic groups having 1 to 30 carbon atoms include divalent aromatic hydrocarbon groups which may have substituents. Examples of divalent aromatic hydrocarbon groups include phenylene groups and naphthylene groups. Examples of substituents include hydrogen atoms, halogen atoms, nitro groups, cyano groups, and hydrocarbon groups having 1 to 10 carbon atoms.

[0054] R 102 Examples include divalent organic groups having 1 to 30 carbon atoms. Examples of divalent organic groups having 1 to 30 carbon atoms include divalent organic groups represented by any of the following formulas (K-1) to (K-13). [ka] (In formula (K-5), R2 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms. In formula (K-13), R3 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms. * represents a bond.) The number of carbon atoms in the aliphatic hydrocarbon group in R2 and R3 may be 1 to 8, 1 to 6, or 1 to 4, respectively.

[0055] R 111 For example, a divalent organic group represented by the following formula (12-1) can be cited. [ka] (In formula (12-1), R 11 R in equation (12) 11 It is the same as (* represents a bonding operation).

[0056] R 112 Examples include divalent organic groups having 1 to 30 carbon atoms. In equation (12), when m1 is 1, R 112 Examples include divalent organic groups represented by any of the above formulas (K-1) to (K-13). In equation (12), when m is 0, R 112 Examples of divalent organic groups include those having 1 to 30 carbon atoms. Examples of divalent organic groups having 1 to 30 carbon atoms include divalent aromatic hydrocarbon groups which may have substituents. Examples of divalent aromatic hydrocarbon groups include phenylene groups and naphthylene groups. Examples of substituents include hydrogen atoms, halogen atoms, nitro groups, cyano groups, and hydrocarbon groups having 1 to 30 carbon atoms.

[0057] Here, an example of a polymer having a cleavage structure in its main chain is shown below. [ka] (In the formula, n represents an integer greater than or equal to 1.) This polymer is a polymer in which the o-nitrobenzyl structure is located in the main chain. In this polymer, the o-nitrobenzyl structure is present in all repeating units of the polymer. This polymer can be obtained, for example, by condensation polymerization of 2-nitro-m-xylylene glycol and isophthaloyl chloride. The resulting polymer is a type of polyester. Furthermore, by reacting (2-nitro-1,3-phenylene)dimethanol with diisocyanate, a polyurethane having an o-nitrobenzyl structure in its main chain can be obtained.

[0058] Furthermore, by reacting a compound having two oxime groups (>C=N-OH) with the structure shown below with a diisocyanate compound, a polyurethane having an oxime ester structure in its main chain can be obtained. [ka]

[0059] Here, an example of a polymer having a cleavage structure in its side chains is shown below. [ka] This polymer is one in which the acetophenone structure is located in the side chain. In this polymer, n mole% (n+m=50) of the total repeating units are repeating units having an acetophenone structure. This polymer is a type of vinyl polymer. This polymer can be obtained, for example, by radical polymerization of monomers having polymerizable unsaturated double bonds corresponding to each repeating unit.

[0060] Here, we show an example in which a polymer side chain has one of two substructures that can react with each other to form a cleavage structure. [ka] This polymer is one in which substructures capable of forming an o-nitrobenzyl structure are located in the side chains. In this polymer, 20 mol% of the total repeating units are repeating units having the aforementioned substructure. This polymer is a type of vinyl polymer. This polymer can be obtained, for example, by radical polymerization of monomers having polymerizable unsaturated double bonds corresponding to each repeating unit.

[0061] <<<Polymers that do not have a cleavage structure>>> The polymer that does not have a cleavage structure is not particularly limited, and for example, known polymers can be used. Examples of known polymers include polyesters, polyamides, polyimides, polyamic acids, polyurethanes, and vinyl polymers.

[0062] -Polyurethane- Examples of polyurethanes that do not have a cleavage structure include reaction products of diols and diisocyanates. The diol is not particularly limited, and examples include diols having 1 to 30 carbon atoms. The diol may or may not have an aromatic hydrocarbon group, but it is preferable that it has an aromatic hydrocarbon group. Examples of aromatic rings in the aromatic hydrocarbon group include benzene rings and naphthalene rings. The diisocyanate is not particularly limited, and examples include diisocyanates having 3 to 30 carbon atoms. A preferred diisocyanate is one represented by the following formula. [ka] (In the formula, R2 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms. In the formula, R3 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms.) The number of carbon atoms in the aliphatic hydrocarbon group in R2 and R3 may be 1 to 8, 1 to 6, or 1 to 4, respectively.

[0063] -Condensed polymer- Examples of polymers that do not have a cleavage structure include condensation polymers having repeating units represented by the following formula (A1). [ka] (In formula (A1), A 1 , A 2 , A 3 , A 4 , A 5 and A 6 These are, independently, a hydrogen atom, a methyl group, or an ethyl group. X 1This is a group represented by the following formulas (A1-1), (A1-2), (A1-3), or (A1-4), Q 1 This is a group represented by the following formula (A1-5) or (A1-6). [ka] (In formulas (A1-1) to (A1-4), R 1 and R 2 Each of these is independently a hydrogen atom, a C1-C6 alkyl group, a C3-C6 alkenyl group, a benzyl group, or a phenyl group. The phenyl group may be substituted with at least one group selected from the group consisting of a C1-C6 alkyl group, a halogen atom, a C1-C6 alkoxy group, a nitro group, a cyano group, a hydroxyl group, and a C1-C6 alkylthio group. Also, R 1 and R 2 These atoms may bond to each other, forming a ring with 3 to 6 carbon atoms together with the carbon atoms to which they are bonded. R 3 This is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group. The phenyl group may be substituted with at least one group selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups having 1 to 6 carbon atoms. * represents a bonding bond. *1 represents a bonding bond with a carbon atom. *2 represents a bonding bond with a nitrogen atom. [ka] (In formulas (A1-5) and (A1-6), X 2 This is a group represented by formula (A1-1), formula (A1-2), or formula (A1-4). Q 2This is an alkylene group, phenylene group, naphthylene group, or anthrylene group having 1 to 10 carbon atoms. The phenylene group, naphthylene group, and anthrylene group may be substituted with at least one group selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups having 1 to 6 carbon atoms. n 1 and n 2 Each of these is independently either 0 or 1. *1 is A 3 This represents the bond between the carbon atom and the bonded carbon atom. *2 is A 4 (This represents the bonding bond between a carbon atom and another carbon atom.)

[0064] A 1 ~A 6 Preferably, all of them are hydrogen atoms.

[0065] In equation (A1-5), for example, X 2 If the group is represented by formula (A1-2), its structure is given by the following formula (A1-5-1). [ka] (In formula (A1-5-1), R 1 and R 2 This is R in equation (A1-2). 1 and R 2 These are the same as above.

[0066] In formula (A1-6), Q 2 When the group is a phenylene group, naphthylene group, or anthrylene group, the positions of their bonds are not particularly limited. That is, for example, the phenylene group may be bonded at positions 1 and 2, 1 and 3, or 1 and 4; the naphthylene group may be bonded at positions 1 and 2, 1 and 4, 1 and 5, or 2 and 3; and the anthrylene group may be bonded at positions 1 and 2, 1 and 4, or 9 and 10, and any of these may be acceptable.

[0067] The alkyl group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and examples include methyl, ethyl, isopropyl, n-butyl, and cyclohexyl groups. The alkenyl group having 3 to 6 carbon atoms can be linear, branched, or cyclic, and examples include the 2-propenyl group and the 3-butenyl group. The alkoxy group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and examples include methoxy, ethoxy, isopropoxy, n-pentyloxy, and cyclohexyloxy groups. The alkylthio group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and examples include methylthio group, ethylthio group, isopropylthio group, n-pentylthio group, and cyclohexylthio group. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Also, R 1 and R 2 Examples of rings with 3 to 6 carbon atoms formed by the bonding of these atoms include cyclobutane rings, cyclopentane rings, and cyclohexane rings.

[0068] The alkylene group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and examples include methylene, ethylene, propylene, pentamethylene, cyclohexylene, and 2-methylpropylene.

[0069] Note that in equation (A1), X 1 If the group is represented by formula (A1-2), its structure will be represented by the following formula (A2), and X 1 If the group is represented by formula (A1-3), its structure will be represented by the following formula (A3). Also, in formula (A3), R 3 However, a 2-propenyl group is preferred. [ka] (In formulas (A2) and (A3), A1 ~A 6 、 and Q 1 is A in formula (A1) 1 ~A 6 、 and Q 1 are the same as those respectively. R 1 and R 2 is R in formula (A1-2) 1 and R 2 are the same as those respectively. R 3 is R in formula (A1-3) 3 is the same as that. )

[0070] In formula (A1), Q 1 preferably contains a cyclic structure from the viewpoint of the heat resistance of the condensed polymer. That is, Q 1 is a group represented by formula (A1-5) or a group represented by formula (A1-6), and Q 2 is preferably a cyclic alkylene group, a phenylene group, a naphthylene group or an anthrylene group, and Q 1 is more preferably a group represented by formula (A1-5).

[0071] As the repeating unit represented by formula (A1), those represented by the following formula (A4) to formula (A22) are preferable. In the following formula, Me is a methyl group and Et is an ethyl group.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0072] -Vinyl polymer- Vinyl polymers are polymers obtained by polymerizing monomers having polymerizable unsaturated double bonds, such as acrylic acid esters, methacrylic acid esters, and styrene. Vinyl polymers without cleavage structures can be obtained, for example, by polymerizing monomers having polymerizable unsaturated double bonds that do not have cleavage structures.

[0073] Examples of monomers having polymerizable unsaturated double bonds include monomers with carboxyl groups, monomers with epoxy groups, acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

[0074] Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl) phthalate, mono-(2-(methacryloyloxy)ethyl) phthalate, mono-(2-(acryloyloxy)ethyl) hexahydrophthalate, mono-(2-(methacryloyloxy)ethyl) hexahydrophthalate, mono-(2-(acryloyloxy)ethyl) succinate, mono-(2-(methacryloyloxy)ethyl) succinate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide, and ω-carboxy-polycaprolactone mono(meth)acrylate. Examples of these monomers that can be used are those commercially available as "Light Ester HO-MS", "Light Acrylate HOA-MS(N)", "Light Acrylate HOA-HH(N)", and "Light Acrylate HOA-MPL(N)" (all manufactured by Kyoeisha Chemical Co., Ltd., trade names), Arronix® M-5300, Arronix® M-5400 (both manufactured by Toagosei Co., Ltd., trade names), A-SA, and SA (both manufactured by Shin Nakamura Chemical Industry Co., Ltd., trade names).

[0075] Examples of monomers having an epoxy group include glycidyl methacrylate, glycidyl acrylate, 4-hydroxybutyl methacrylate glycidyl ether, allyl glycidyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.

[0076] Examples of acrylic acid ester compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthyl acrylate, anthyl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

[0077] Examples of methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthyl methacrylate, anthyl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.

[0078] Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0079] Examples of styrene compounds include styrene, methylstyrene, chlorostyrene, and bromostyrene.

[0080] Examples of vinyl compounds include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, and vinyl carbazole.

[0081] Vinyl polymers can be obtained by known methods, for example, by radical polymerization of monomers having one or more polymerizable unsaturated double bonds.

[0082] The polymer preferably has reactive groups that can react with the crosslinking agent. For example, if the crosslinking agent has an epoxy group, the reactive group may include epoxy groups, amino groups, carboxyl groups, phenolic hydroxyl groups, and the like. For example, if the crosslinking agent has an alkoxymethyl group or a methylol group, the reactive group could be an alkoxymethyl group, a methylol group, or the like. For example, if the crosslinking agent has an isocyanate group, the reactive group could be, for instance, a carboxyl group or a hydroxyl group.

[0083] The molecular weight of the polymer (polymer having a cleavage structure, polymer not having a cleavage structure) is not particularly limited, but the weight-average molecular weight determined by GPC (gel permeation chromatography) is preferably 2,000 to 100,000, and more preferably 2,500 to 50,000.

[0084] The polymer content in the primer layer-forming composition is not particularly limited, but is preferably 10% to 99.5% by mass, more preferably 30% to 95% by mass, and particularly preferably 50% to 90% by mass, relative to the film-forming component. These contents may consist only of polymers having a cleavage structure, only of polymers not having a cleavage structure, or as a total of polymers having a cleavage structure and polymers not having a cleavage structure.

[0085] <<Crosslinking agent>> The crosslinking agent may or may not have a cleavage structure. If the crosslinking agent has a cleavage structure, the number of cleavage structures contained in the crosslinking agent may be one or two or more. If the crosslinking agent has one or the other of two substructures that can react with each other to form a cleavage structure, the number of such substructures contained in the crosslinking agent may be one or two or more.

[0086] Examples of crosslinking agents include epoxy compounds, methylol compounds, and isocyanate compounds. Epoxy compounds are compounds that have two or more epoxy groups. A methylol compound is a compound having at least one of a methylol group and an alkoxymethyl group, with a total of two or more methylol and alkoxymethyl groups. An isocyanate compound is a compound having at least one of an isocyanate group and a blocked isocyanate group, with a total of two or more isocyanate groups and blocked isocyanate groups.

[0087] <<<Crosslinking agent with a cleavage structure>>> Examples of crosslinking agents having a cleavage structure include epoxy compounds, methylol compounds, and isocyanate compounds. The crosslinking agent having a cleavage structure may contain one or more cleavage structures. A crosslinking agent having a cleavage structure is represented, for example, by the following formula (B1) or formula (B2).

[0088] [ka] (In equation (B1), X represents a cleavage structure. L 1 and L 2 Each of these independently represents a single bond or a linking group. 1 and Y 2 Each of these independently represents an epoxy group, an alkoxyalkyl group, a methylol group, or an isocyanate group. In formula (B2), n represents an integer between 3 and 6. Z represents an n-valent group. X independently represents a cleavage structure. L independently represents a single bond or a linking group. Y independently represents an epoxy group, an alkoxyalkyl group, a methylol group, or an isocyanate group.

[0089] In equations (B1) and (B2), X (the cracked structure) is, for example, a structure represented by any of equations (1) to (3). The linking group in formulas (B1) and (B2) is not particularly limited as long as it is a divalent group. Examples of linking groups include divalent groups with 1 to 20 atoms. In formula (B2), Z is not particularly limited as long as it is an n-valent group. Examples of Z include n-valent groups with 5 to 30 atoms.

[0090] Specific examples of crosslinking agents having a cleavage structure include the following compounds, for example. [ka]

[0091] <<<Crosslinking agent without a cleavage structure>>> Examples of epoxy compounds that do not have a cleavage structure as crosslinking agents include 1,2,7,8-diepoxyoctane, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,6-dimethylol perfluorohexane diglycidyl ether, (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol triglycidyl ether, diglycerol polyglycidyl ether, and trimethylol ethane. Liglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, resorcinol diglycidyl ether, bis(2,7-diglycidyloxynaphthalen-1-yl)methane, 1,1,2,2-tetrakis(4-glycidyloxyphenyl)ethane, 1,1,3-tris(4-glycidyl) Xyphenyl)propane, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, tetrabromobisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol hexafluoroacetone diglycidyl ether, bis(2,3-epoxycyclopentyl) ether, 1,2-bis(3,4-epoxycyclohexylmethoxy)ethane, ethylene glycol bis(3,4-epoxycyclohexanecarboxylate), 3,4-epoxy (3,4-epoxycyclohexyl)methyl chlorohexanecarboxylic acid, (4,5-epoxy-2-methylcyclohexyl)methyl 4,5-epoxy-2-methylcyclohexyl)methyl 4,5-epoxy-2-methylcyclohexyl 4,5-epoxy-2-methylcyclohexyl 4,5-epoxy-2-methyl 4,5-epoxycyclohexane-1,5'-[1,3]dioxane]-2'-yl 4,5-epoxycyclohexane, diglycidyl adipate, diglycidyl phthalate, diglycidyl tetrahydrophthalate, 1,2-Cyclohexanedicarboxylate diglycidyl, triglycidyl isocyanurate, tris(3,4-epoxybutyl) isocyanurate, tris(4,5-epoxypentyl) isocyanurate, tris(5,6-epoxyhexyl) isocyanurate, tris(6,7-epoxyheptyl) isocyanurate, tris(7,8-epoxyoctyl) isocyanurate, tris(8,9-epoxynonyl) isocyanurate, tris( 2-Glycidyloxyethyl) isocyanurate, monoallyl diglycidyl isocyanurate, N,N'-diglycidyl N''-(2,3-dipropionyloxypropyl) isocyanurate, 1,3,5-Tris(2-(2,2-bis(glycidyloxymethyl)butoxycarbonyl)ethyl) isocyanurate, Tris(2,2-bis(glycidyloxymethyl)butyl)3,3',3''-(2,4,6-trioxo-1,3,5 Examples include triazine-1,3,5-triyl) tripropanoate, N,N-diglycidyl-4-glycidyloxyaniline, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 4,4'-methylenebis(N,N-diglycidylaniline), 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctanoate 2,2-bis(glycidyloxymethyl)butyl, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthalene novolac type epoxy resin, anthracene novolac type epoxy resin, biphenylene novolac type epoxy resin, xylylene novolac type epoxy resin, triphenolmethane novolac type epoxy resin, tetrakisphenol novolac type epoxy resin, and dicyclopentadiene novolac type epoxy resin. Examples of commercially available epoxy compounds include TEPIC(registered trademark)-G, TEPIC(registered trademark)-S, TEPIC(registered trademark)-SS, TEPIC(registered trademark)-SP, TEPIC(registered trademark)-L, TEPIC(registered trademark)-HP, TEPIC(registered trademark)-VL, TEPIC(registered trademark)-FL, TEPIC(registered trademark)-PAS B22, TEPIC(registered trademark)-PAS B26, TEPIC(registered trademark)-PAS B26L, TEPIC(registered trademark)-UC, FOLDI(registered trademark)-E201 [all manufactured by Nissan Chemical Corporation], jER(registered trademark)-828, jER(registered trademark)-807, jER(registered trademark)-YX8000, jER(registered trademark)-157S70 [all manufactured by Mitsubishi Chemical Corporation], Rikaresin(registered trademark)-DME100 [manufactured by Shin Nippon Rika Co., Ltd.], Celoxide 2021P [manufactured by Daicel Corporation], EPICLON(registered trademark)-HP-4700, jER(registered trademark)-HP-4710, jER(registered trademark)-HP-7200L [all manufactured by DIC Corporation], AV Light(registered trademark)-TEP-G [manufactured by Asahi Organic Chemicals Co., Ltd.], and others.

[0092] Examples of methylol compounds that do not have a cleavage structure and can be used as crosslinking agents include alkoxymethylated glycoluryl, alkoxymethylated benzoguanamine, alkoxymethylated melamine, tetra(alkoxymethyl)bisphenol, and tetra(hydroxymethyl)bisphenol. Examples of alkoxymethylated glycoluryls include 1,3,4,6-tetrakis(methoxymethyl) glycoluryl, 1,3,4,6-tetrakis(butoxymethyl) glycoluryl, 1,3,4,6-tetrakis(hydroxymethyl) glycoluryl, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone. Examples of commercially available products include glycoluryl compounds manufactured by Mitsui Cytec Co., Ltd. (product names: Cymel® 1170, Powderlink® 1174), methylated urea resins (product name: UFR® 65), butylated urea resins (product names: UFR® 300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea / formaldehyde resins manufactured by DIC Corporation (high condensation type, product names: Beccamine® J-300S, P-955, N). Examples of alkoxymethylated benzoguanamines include tetramethoxymethylbenzoguanamine. Commercially available products include those manufactured by Mitsui Cytec Co., Ltd. (product name: Cymel® 1123) and Sanwa Chemical Co., Ltd. (product names: Nikalac® BX-4000, BX-37, BL-60, BX-55H). Examples of alkoxymethylated melamines include hexamethoxymethylmelamine. Commercially available products include methoxymethyl type melamine compounds (product names: Cymel® 300, 301, 303, 350) and butoxymethyl type melamine compounds (product names: Mycoat® 506, 508) manufactured by Mitsui Cytec Co., Ltd., methoxymethyl type melamine compounds (product names: Nikalac® MW-30, MW-22, MW-11, MW-100LM, MS-001, MX-002, MX-730, MX-750, MX-035) and butoxymethyl type melamine compounds (product names: Nikalac® MX-45, MX-410, MX-302) manufactured by Sanwa Chemical Co., Ltd. Examples of tetra(alkoxymethyl)bisphenol and tetra(hydroxymethyl)bisphenol include tetra(alkoxymethyl)bisphenol A and tetra(hydroxymethyl)bisphenol A.

[0093] If condition (B) is met, a crosslinking agent that does not have a cleavage structure may be a crosslinking agent having one or the other of two substructures that can react with each other to form a cleavage structure. For example, epoxy groups, alkoxymethyl groups, methylol groups, isocyanate groups, etc., may react with the other of two substructures that can form a cleavage structure to form one.

[0094] The molecular weight of the crosslinking agent (crosslinking agent having a cleavage structure, crosslinking agent not having a cleavage structure) is not particularly limited, but is preferably 2,000 or less, and more preferably 1,500 or less.

[0095] The content of the crosslinking agent in the primer layer forming composition is not particularly limited, but is preferably 1% to 100% by mass, more preferably 3% to 80% by mass, and particularly preferably 5% to 50% by mass relative to the polymer. These contents may consist only of crosslinking agents having a cleavage structure, only of crosslinking agents not having a cleavage structure, or as a total of crosslinking agents having a cleavage structure and crosslinking agents not having a cleavage structure.

[0096] <<Other ingredients>> The primer layer-forming composition may contain components other than polymers and crosslinking agents as film-forming components. Examples of other components include curing catalysts, surfactants, and silane coupling agents.

[0097] <<<Curing catalyst>>> The curing catalyst is effective in accelerating the thermosetting reaction during the formation of a primer layer using a primer layer-forming composition. Examples of curing catalysts include acids and thermal acid generators. As a thermal acid generator, a compound that decomposes at a temperature of 80°C to 250°C to generate acid is preferred.

[0098] Examples of acids include sulfonic acids such as hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphosulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H,1H,2H,2H-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, or their hydrates or salts.

[0099] Furthermore, examples of compounds that generate acid upon heating (thermal acid generators) include bis(tosyloxy)ethane, bis(tosyloxy)propane, bis(tosyloxy)butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3-phenylentris(methylsulfonate), pyridinium salt of p-toluenesulfonate, morpholinium salt of p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, isobutyl p-toluenesulfonate, methyl p-toluenesulfonate, phenethyl p-toluenesulfonate, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-tosylate, N-ethyl-4-toluenesulfonamide, and compounds represented by the following formulas [TAG-1] to [TAG-41]. [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0100] Furthermore, examples of onium salts such as iodonium salts, sulfonium salts, phosphonium salts, and selenium salts can be used as thermal acid generators.

[0101] Examples of iodonium in iodonium salts include diphenyliodonium, 4,4'-dichlorodiphenyliodonium, 4,4'-dimethoxydiphenyliodonium, 4,4'-di-tert-butyldiphenyliodonium, 4-methylphenyl(4-(2-methylpropyl)phenyl)iodonium, 3,3'-dinitrophenyliodonium, 4-(1-ethoxycarbonylethoxy)phenyl(2,4,6-trimethylphenyl)iodonium, and 4-methoxyphenyl(phenyl)iodonium. Examples of iodonium salts include diaryliodonium salts such as chloride, bromide, mesylate, tosylate, trifluoromethanesulfonate, tetrafluoroborate, tetrakis(pentafluorophenyl)borate, hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate.

[0102] Examples of sulfonium in sulfonium salts include triphenylsulfonium, diphenyl(4-tert-butylphenyl)sulfonium, tris(4-tert-butylphenyl)sulfonium, diphenyl(4-methoxyphenyl)sulfonium, tris(4-methylphenyl)sulfonium, tris(4-methoxyphenyl)sulfonium, tris(4-ethoxyphenyl)sulfonium, diphenyl(4-(phenylthio)phenyl)sulfonium, tris(4-(phenylthio)phenyl)sulfonium, and benzyl(4-acetoxyphenyl)(methyl)sulfonium. Examples of sulfonium salts include aryl sulfonium salts of the above-mentioned sulfonium, such as chloride, bromide, trifluoromethanesulfonate, tetrafluoroborate, hexafluorophosphate, hexafluoroarcenate, tetrakis(pentafluorophenyl)borate, and hexafluoroantimonate.

[0103] Examples of phosphoniums used in phosphonium salts include tetraphenylphosphonium, ethyltriphenylphosphonium, tetra(p-methoxyphenyl)phosphonium, ethyltri(p-methoxyphenyl)phosphonium, and benzyltriphenylphosphonium. Examples of phosphonium salts include arylphosphonium salts such as phosphonium chloride, bromide, tetrafluoroborate, hexafluorophosphate, and hexafluoroantimonate.

[0104] Examples of selenium salts include triarylselenium salts such as triphenylselenium hexafluorophosphate.

[0105] The content of the acid or hot acid generator in the primer layer-forming composition is preferably 0.01% to 15% by mass, and more preferably 0.1% to 10% by mass, relative to the polymer.

[0106] <<<Surfactants>>> By adding a surfactant to the primer layer-forming composition, the applicability of the primer layer-forming composition can be improved. Examples of surfactants include well-known surfactants such as nonionic surfactants, fluorinated surfactants, and silicone surfactants. Surfactants can be used individually or in combination of two or more types.

[0107] Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate.

[0108] Examples of fluorine-based surfactants include F-Top® EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac® F171, F173, F554, F559, F563, R-30, R-40, R-40-LM, DS-21 (manufactured by DIC Corporation), FLUORAD® FC430, FC431 (manufactured by 3M Company), Asahiguard® AG710, Surflon® S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Inc.), and others.

[0109] Examples of silicone-based surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0110] If the primer layer-forming composition contains a surfactant, its content is preferably 0.0001% to 1% by mass, and more preferably 0.001% to 0.5% by mass, relative to the polymer.

[0111] <<<Silane coupling agent>>> By adding a silane coupling agent to the composition for forming a primer layer, the adhesion of the composition for forming a primer layer to the object to be coated can be improved.

[0112] Examples of silane coupling agents include vinyl-based silane coupling agents such as trimethoxy(vinyl)silane, triethoxy(vinyl)silane, trimethoxy(4-vinylphenyl)silane, and triethoxy(4-vinylphenyl)silane; 3-(meth)acryloyloxypropyltrimethoxysilane, triethoxy(3-(meth)acryloyloxypropyl)silane, 3-(meth)acryloyloxypropyl(dimethoxy)(methyl)silane, diethoxy(3-(meth)acryloyloxypropyl (Meth)acrylic silane coupling agents such as (methyl)silane; epoxy silane coupling agents such as 3-glycidyloxypropyltrimethoxysilane, triethoxy(3-glycidyloxypropyl)silane, 3-glycidyloxypropyl(dimethoxy)(methyl)silane, diethoxy(3-glycidyloxypropyl)(methyl)silane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyl(dimethoxy)(methyl)silane, N-(2-aminoethyl)-3-aminopropyl(diethoxy)(methyl)silane, N-(1-methylpentylidene)-3-trimethoxysilylpropylamine, 3-triethoxysilyl Amine-based silane coupling agents such as -N-(1-methylpentylidene)propylamine, N-(1,3-dimethylbutylidene)-3-trimethoxysilylpropylamine, N-(1,3-dimethylbutylidene)-3-triethoxysilylpropylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane; ureido-based silane coupling agents such as 3-ureidopropyltrimethoxysilane and triethoxy(3-ureidopropyl)silane;Mercapto-based silane coupling agents such as 3-mercaptopropyltrimethoxysilane, triethoxy(3-mercaptopropyl)silane, (3-mercaptopropyl)(dimethoxy)(methyl)silane, diethoxy(3-mercaptopropyl)(methyl)silane; Sulfide-based silane coupling agents such as bis(3-trimethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)tetrasulfide; Isocyanate-based silane coupling agents such as 3-isocyanatopropyltrimethoxysilane, triethoxy(3-isocyanatopropyl)silane, etc. are included. Among these, silane coupling agents having the same reactive groups as the crosslinking agent are preferred. For example, when the crosslinking agent has an epoxy group, an epoxy-based silane coupling agent is preferred as the silane coupling agent.

[0113] When the primer layer-forming composition contains a silane coupling agent, its content is preferably 0.1% by mass to 5% by mass, more preferably 0.3% by mass to 3% by mass, based on the polymer. <(Solvent)>

[0114] Examples of the solvent include glycol ether solvents having 3 to 20 carbon atoms, ester solvents having 3 to 20 carbon atoms, ketone solvents having 3 to 20 carbon atoms, cyclic compound solvents having 3 to 20 carbon atoms, and the like.

[0115] Examples of the glycol ether solvent include ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether, propylene glycol monopropyl ether, and the like. Examples of the ester solvent include ethyl lactate, γ-butyrolactone, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, and the like. Examples of the ketone solvent include methyl ethyl ketone, cyclohexanone, cyclopentanone, benzophenone, and the like. Examples of cyclic compound solvents include N-methylpyrrolidone and γ-butyrolactone. These can be used individually or in combination of two or more types.

[0116] The solvent content in the primer layer forming composition is preferably such that the concentration of the film-forming component of the primer layer forming composition is 0.1% to 40% by mass, more preferably 0.5% to 20% by mass, and particularly preferably 0.5% to 10% by mass.

[0117] The method for preparing the primer layer-forming composition is not particularly limited, and known methods that allow for uniform mixing of each component can be used.

[0118] (Laminated structure) The laminate of the present invention comprises a first adherend, a second adherend, a primer layer, and an adhesive layer. The primer layer is located between the first adherend and the second adherend. The adhesive layer is located between the first adherend and the second adherend. The adhesive layer is in contact with the primer layer. The primer layer is formed from a primer layer-forming composition. The primer layer-forming composition contains a film-forming component and a solvent. The primer layer has a cleavage structure in which chemical bonds irreversibly break in response to external stimuli.

[0119] The laminate preferably satisfies at least one of the following conditions (A) and (B). Condition (A): The film-forming component has a cleavage structure. Condition (B): The film-forming component has two types of substructures that can react with each other to form a cleavage structure.

[0120] <Primer layer> The primer layer is formed, for example, from the primer layer forming composition of the present invention. The primer layer can be obtained, for example, by applying a primer layer-forming composition and heating it.

[0121] The coating method is not particularly limited and includes, for example, cast coating, spin coating, blade coating, dip coating, roll coating, bar coating, die coating, inkjet, and printing methods (relief printing, intaglio printing, planographic printing, screen printing, etc.).

[0122] The heating temperature is not particularly limited, as long as it is a temperature that can evaporate the solvent contained in the primer layer-forming composition, in the case where the primer layer-forming composition does not contain a crosslinking agent. For example, temperatures of 40°C to 100°C are possible. If the primer layer-forming composition contains a crosslinking agent, the heating temperature is not particularly limited as long as it is a temperature at which the crosslinking agent can react, for example, 120°C to 200°C. If the film-forming component contained in the primer layer-forming composition satisfies condition (B), the heating temperature is not particularly limited, as long as it is a temperature at which the two types of substructures can react with each other to form a cleavage structure. There are no particular restrictions on the heating time; for example, it can range from 1 minute to 1 hour. Examples of heating devices include hot plates and ovens. The heating atmosphere may be air or an inert gas, and may be at normal pressure or under reduced pressure.

[0123] The thickness of the primer layer is not particularly limited, but is preferably 0.01 μm to 10 μm, more preferably 0.03 μm to 5 μm, and particularly preferably 0.05 μm to 1 μm.

[0124] The thickness of the primer layer is usually thinner than the thickness of the adhesive layer. The thickness of the primer layer is preferably 1 / 1000 to 1 / 10 times the thickness of the adhesive layer, and more preferably 1 / 750 to 1 / 50 times.

[0125] <The first adherend and the second adherend> The first adherend and the second adherend are not particularly limited as long as at least one of the first adherend and the second adherend can provide an external stimulus to the primer layer without blocking the external stimulus. For example, when the external stimulus is an active energy ray, at least one of the first adherend and the second adherend has permeability to the active energy ray. As the permeability of the first adherend and the second adherend to the active energy ray, for example, the transmittance of light with a wavelength of 365 nm is preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more.

[0126] The main materials of the first adherend and the second adherend are not particularly limited, and examples include resins, glass, metals, and the like.

[0127] The first adherend and the second adherend may each be processed, or they may themselves be laminates. Examples of the processing include circuit formation processing and element formation processing. Examples of the element include a light-emitting element.

[0128] <Adhesive layer> The adhesive layer is obtained from an adhesive composition. The adhesive composition is not particularly limited, and examples include polysiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide-based adhesives, and phenol resin-based adhesives. The adhesive composition may contain a solvent or may not contain a solvent. The adhesive composition may be a thermosetting adhesive composition or a non-thermosetting adhesive composition. Generally, once a thermosetting adhesive composition is adhered, it is difficult to separate the adherends. Therefore, in order to obtain the effects of the present invention more, a thermosetting adhesive composition is preferred.

[0129] The adhesive layer can be obtained, for example, by applying an adhesive composition and heating it.

[0130] The coating method is not particularly limited and includes, for example, cast coating, spin coating, blade coating, dip coating, roll coating, bar coating, die coating, inkjet, and printing methods (relief printing, intaglio printing, planographic printing, screen printing, etc.).

[0131] The heating temperature is not particularly limited; for example, it could be between 80°C and 200°C. There are no particular restrictions on the heating time; for example, it could range from 1 minute to 2 hours.

[0132] The thickness of the adhesive layer is not particularly limited, but is preferably 0.5 μm to 500 μm, more preferably 1 μm to 200 μm, and especially preferably 2 μm to 100 μm.

[0133] In a laminate, for example, the first adherend and the primer layer are in contact. In a laminate, for example, the second adherend and the adhesive layer are in contact. In a laminate, for example, the second adherend is permeable to active energy rays.

[0134] The method for manufacturing the laminate is not particularly limited. An example of a manufacturing method for a laminate in which the first adherend, primer layer, adhesive layer, and second adherend are arranged in this order will be described. A primer layer is formed on the first adherend. The primer layer is formed by applying a primer layer-forming composition to the surface of the first adherend and heating it. If the primer layer-forming composition contains a crosslinking agent, the heating is preferably at a temperature at which the crosslinking agent reacts. Furthermore, if the primer layer-forming composition satisfies condition (B), the heating is preferably at a temperature at which two types of substructures that can react with each other to form a cleavage structure react to form a cleavage structure. Next, the adhesive composition is applied onto the primer layer. The second adherend is placed on top of the applied adhesive composition. Then, it is heated. If the adhesive composition is a thermosetting type, the heating is preferably at the temperature at which the adhesive composition will heat-cur.

[0135] (Method for disassembling laminates) The present invention's method for decomposing a laminate includes at least a separation step, and may further include other steps as needed.

[0136] <Separation process> The separation step is not particularly limited as long as it is a step of applying an external stimulus to the primer layer in the laminate of the present invention to separate the first adherend and the second adherend.

[0137] When the external stimulus is an active energy ray, and the first adherend of the laminate faces the irradiation source of the active energy ray, the first adherend is permeable to the active energy ray. When the external stimulus is an active energy ray, and the second adherend of the laminate faces the irradiation source of the active energy ray, the second adherend is permeable to the active energy ray.

[0138] Examples of active energy rays (active energy rays absorbed by the cleavage structure) include ultraviolet rays, electron beams, and X-rays, with ultraviolet rays being particularly preferred. Examples of ultraviolet wavelengths include 300 to 380 nm. Examples of light sources used for ultraviolet irradiation include sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs. While laser light may be used as the active energy beam, it is preferable to use something other than laser light, as using laser light may damage the substrate.

[0139] The irradiation dose of the active energy beam is not particularly limited as long as it is an irradiation dose that can perform the separation process, but for example, 100 mJ / cm² 2 ~10,000 mJ / cm2 These are some examples.

[0140] When an external stimulus is applied to the primer layer (for example, by irradiating the primer layer with active energy rays), the cleavage structure responds to the external stimulus (for example, by absorbing the active energy rays), causing the chemical bonds of the cleavage structure to break. This cleavage reduces the adhesion between the primer layer and the adhesive layer, making it easy to separate the first adherend and the second adherend.

[0141] The separated first or second adherend can be reused as is after, for example, washing as necessary. Alternatively, the separated first or second adherend can be further broken down into raw materials and reused as raw materials. [Examples]

[0142] The present invention will be described in more detail below with reference to synthesis examples, preparation examples, examples, and comparative examples, but the present invention is not limited to the following examples.

[0143] The compounds used in the following synthesis examples, preparation examples, and examples are as follows. [solvent] PGME: Propylene glycol monomethyl ether NMP: N-methylpyrrolidone BCS: Ethylene glycol monobutyl ether CPN: Cyclopentanone THF: Tetrahydrofuran DMF: N,N-dimethylformamide DMAc: N,N-dimethylacetamide DMSO: Dimethyl sulfoxide [Crosslinking agent] PL: 1,3,4,6-Tetrakis(methoxyethyl)glycoluryl (Ornex Corporation, trade name: POWDERLINK 1174) TP: 1,3,5-Triglycidyl isocyanurate (Nissan Chemical Corporation, trade name: TEPIC®-L) [Curing catalyst] PPTS: Pyridinium p-toluenesulfonate SI: (4-acetoxyphenyl)methyl(2-methylbenzyl)sulfonium tetrakis(pentafluorophenyl)borate (Sanshin Chemical Industry Co., Ltd., product name: SI-B2A) [Silane coupling agent] TGS: Triethoxy(3-glycidyloxypropyl)silane

[0144] Furthermore, the weight-average molecular weight (Mw) of the polymers was measured using a GPC instrument manufactured by Shimadzu Corporation (columns: Shodex® KF803L and KF804L (manufactured by Showa Denko K.K.), eluent: THF, flow rate: 1.0 mL / min, column temperature: 40°C, Mw: standard polystyrene equivalent) for synthesis examples 1-3 and 6-7, and a GPC instrument manufactured by JASCO Corporation (columns: Shodex® columns KF803L and KF805L (manufactured by Showa Denko K.K.), eluent: DMF, flow rate: 1.0 mL / min, column temperature: 50°C, Mw: standard polystyrene equivalent) for synthesis examples 4 and 5.

[0145] Also, 1 ¹H-NMR measurements were performed using a Bruker AVANCE III HD, with a measurement frequency of 500 MHz, and the measurement solvent being deuterated chloroform (CDCl3) or deuterated DMSO (DMSO-d6) manufactured by Kanto Chemical Co., Ltd., with tetramethylsilane (δ=0.00 ppm) as the internal standard.

[0146] [1] Polymer synthesis [Synthesis Example 1] A polymer solution was obtained by dissolving 2.40 g (13.10 mmol) of 2-nitro-p-xylylene glycol (Tokyo Chemical Industries, Ltd.), 2.24 g (112.84 mmol) of triylene-2,4-diisocyanate, and 0.01 g of dibutyltin dilaurate as a polymerization catalyst in 41.8 g of THF and reacting under reflux for 20 hours. The obtained polymer solution was gradually added dropwise to 300 g of methanol to precipitate a solid. The precipitated solid was filtered off and dried under reduced pressure to obtain polymer (PA-1) containing a cleavage structure. The Mw of polymer (PA-1) was 19,000. [ka]

[0147] [Synthesis Example 2] 3.58 g of 2-nitroisophthalic acid was dissolved in 40 mL of anhydrous THF, and 102 mL of borane-tetrahydrofuran complex (8.5% tetrahydrofuran solution) was slowly added dropwise under ice cooling. The reaction was carried out under ice cooling until the foaming subsided, and then allowed to continue overnight at room temperature. After the reaction was complete, the mixture was cooled on ice and quenched with ice water. Ethyl acetate was added, and the mixture was separated by liquid-liquid extraction and washed with saturated saline. 2.8 g of the resulting crude product was purified by column chromatography to obtain 2.40 g of 2-nitro-m-xylylene glycol. 1 The results of the 1H-NMR spectrum are shown below. 1 H-NMR (500MHz, CDCl3): δ 7.58(s,3H),4.74(d,4H,J=6.0Hz),2.18(t,2H,J=6.0Hz)

[0148] 2.40 g (13.10 mmol) of the obtained 2-nitro-m-xylylene glycol, 2.24 g (12.84 mmol) of triylene-2,4-diisocyanate, and 0.01 g of dibutyltin dilaurate as a polymerization catalyst were dissolved in 41.8 g of THF and reacted under reflux for 20 hours to obtain a polymer solution. The obtained polymer solution was gradually added dropwise to 300 g of methanol to precipitate a solid. The precipitated solid was filtered off and dried under reduced pressure to obtain polymer (PA-2) containing a cleavage structure. The Mw of polymer (PA-2) was 18,000. [ka]

[0149] [Synthesis Example 3] 2.40 g of 2-nitro-m-xylylene glycol was obtained by the same method as in Synthesis Example 2. 2.31 g (12.61 mmol) of the obtained 2-nitro-m-xylylene glycol, 2.51 g (12.36 mmol) of isophthaloyl chloride, and 2.00 g (25.22 mmol) of pyridine were dissolved in 15.9 g of NMP and reacted at 60°C for 20 hours to obtain a polymer solution. The obtained polymer solution was gradually added dropwise to 300 g of methanol to precipitate a solid. The precipitated solid was filtered off and dried under reduced pressure to obtain polymer (PA-3) containing a cleavage structure. The Mw of polymer (PA-3) was 3,100. [ka]

[0150] [Synthesis Example 4] 12.05 g of 1,4-diacetylbenzene and 12.46 g of hydroxylamine hydrochloride were added to 60 mL of DMF and reacted at 80°C for 3 hours. After the reaction was complete, 200 mL of water was added, the solid was filtered off, washed three times with water, and dried to obtain 14.07 g of a compound having two oxime groups (>C=N-OH). 1 The results of the 1H-NMR spectrum are shown below. 1H-NMR (500MHz, DMSO-d6): δ 11.26(s,2H),7.67(s,4H),2.17(s,6H)

[0151] 1.70 g (8.84 mmol) of the obtained compound, 2.17 g (8.67 mmol) of methylenediphenyl 4,4'-diisocyanate, and 0.01 g of dibutyltin dilaurate as a polymerization catalyst were dissolved in 34.9 g of NMP and reacted at 60°C for 20 hours to obtain a polymer solution. The obtained polymer solution was gradually added dropwise to 300 g of methanol to precipitate a solid. The precipitated solid was filtered off and dried under reduced pressure to obtain polymer (PA-4) containing a cleavage structure. The Mw of polymer (PA-4) was 14,000. [ka]

[0152] [Synthesis Example 5] 5.02 g of 1,3-diacetylbenzene and 5.44 g of hydroxylamine hydrochloride were added to 40 mL of DMF and reacted at 80°C for 3 hours. After the reaction was complete, 100 mL of water was added, the solid was filtered off, washed three times with water, and dried to obtain 5.29 g of a compound having two oxime groups (>C=N-OH). 1 The results of the 1H-NMR spectrum are shown below. 1 H-NMR (500MHz, DMSO-d6): δ 7.93(dd,2H,J=2.0Hz,2.0Hz),7.64(dd,4H,J=7.5Hz,2.0Hz),7.40(dd,2H,J=7.5Hz,7.5Hz),2.16(s,6H)

[0153] 1.70 g (8.84 mmol) of the obtained compound, 2.17 g (8.67 mmol) of methylenediphenyl 4,4'-diisocyanate, and 0.01 g of dibutyltin dilaurate as a polymerization catalyst were dissolved in 34.9 g of NMP and reacted at 60°C for 20 hours to obtain a polymer solution. The obtained polymer solution was gradually added dropwise to 300 g of methanol to precipitate a solid. The precipitated solid was filtered off and dried under reduced pressure to obtain a polymer (PA-5) containing a cleavage structure. The Mw of polymer (PA-5) was 6,800. [ka]

[0154] [Synthesis Example 6] A polymer solution was obtained by dissolving 4.00 g (39.95 mmol) of methyl methacrylate, 1.42 g (9.99 mmol) of glycidyl methacrylate, and 0.25 g of azobisisobutyronitrile as a polymerization catalyst in 50.0 g of PGME and reacting at 80°C for 20 hours. The obtained polymer solution was added dropwise to 400 g of hexane to precipitate a solid. The precipitated solid was filtered off and dried under reduced pressure to obtain a polymer (PA-6) that did not contain cleavage structures. The Mw of polymer (PA-6) was 22,000. [ka]

[0155] [Synthesis Example 7] A polymer solution was obtained by dissolving 4.00 g (28.97 mmol) of p-xylylene glycol, 4.54 g (26.08 mmol) of triylene-2,4-diisocyanate, and 0.02 g of dibutyltin dilaurate as a polymerization catalyst in 34.2 g of THF and reacting under reflux for 20 hours. The obtained polymer solution was gradually added dropwise to 300 g of methanol to precipitate a solid. The precipitated solid was filtered off and dried under reduced pressure to obtain a polymer (PA-7) that did not contain cleavage structures. The Mw of polymer (PA-7) was 21,000. [ka]

[0156] [2] Synthesis of crosslinking agents [Synthesis Example 8] 2.52 g of 2-nitro-1,4-dibenzyl alcohol and 3.9 g of 2-allyloxypropionic acid were mixed with 100 mL of THF and stirred. Then, 6.88 g of 1-(dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 0.35 g of dimethylaminopyridine were added and the mixture was reacted overnight at room temperature. After the reaction was complete, the mixture was extracted using ethyl acetate, washed with 100 mL of dilute hydrochloric acid, concentrated and dried to obtain 5.64 g of crude product. The crude product was purified by column chromatography to obtain 3.39 g of 2-nitro-1,4-dibenzyl alcohol 2-allyloxypropionic acid ester. 3.99 g of the obtained 2-nitro-1,4-dibenzyl alcohol 2-allyloxypropionic acid ester was mixed with 40 mL of chloroform under ice cooling and stirred. Then, 4.92 g of m-chloroperbenzoic acid was added and the mixture was reacted overnight. After the reaction was complete, the solution was extracted using chloroform, washed three times with sodium bicarbonate solution, and then concentrated and dried to obtain 4.68 g of crude product. The obtained crude product was purified by column chromatography to obtain 2.6 g of crosslinking agent (B-1) containing cleavage structures. 1 The results of the 1H-NMR spectrum are shown below. 1 H-NMR (500MHz, CDCl3):δ 8.11(s,1H),7.61(s,2H),5.55(s,2H),5.22(s,2H),3.88-3.76(m,6H),3.42-3.35 (m,2H),3.17-3.11(m,2H),2.81-2.77(m,2H),2.74-2.66(m,4H),2.62-2.57(m,2H) [ka]

[0157] [Synthesis Example 9] 10.11 g of 1,3,5-triacetylbenzene and 12.45 g of hydroxylamine hydrochloride were added to 60 mL of DMAc and reacted at 80°C for 5 hours. After the reaction was complete, 200 mL of water was added, the solid was filtered off, washed three times with water, and dried to obtain 11.96 g of 1,3,5-triacetylbenzene oxime. 1.81 g of the obtained 1,3,5-triacetylbenzene oxime and 2.93 g of 2-allyloxypropionic acid were added to 40 mL of THF and stirred. Then, 5.43 g of 1-(dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 4.46 g of 1-hydroxybenzotriazole were added and the mixture was reacted overnight at room temperature. After the reaction was complete, liquid-liquid extraction was performed with ethyl acetate, washed with sodium bicarbonate solution, concentrated and dried to obtain 4.12 g of crude product. The obtained crude product was column purified to obtain 3.78 g of 1,3,5-triacetylbenzene oxime 2-allyloxypropionic acid ester. 3.78 g of the obtained 1,3,5-triacetylbenzene oxime 2-allyloxypropionic acid ester was mixed with 60 mL of chloroform and stirred under ice cooling. Then, 6.28 g of m-chloroperbenzoic acid was added and the reaction was allowed to continue overnight. After the reaction was complete, the mixture was extracted using chloroform, washed three times with sodium bicarbonate solution, concentrated and dried to obtain 5.8 g of crude product. The obtained crude product was purified by column to obtain 2.0 g of a crosslinking agent (B-2) containing a cleavage structure. 1 The results of the 1H-NMR spectrum are shown below. 1 H-NMR (500MHz, CDCl3):δ 8.17(s,3H),3.95-3.85(m,6H),3.83(dd,3H,J=3.0Hz,11.5Hz),3.44(dd,3H,J=6.5Hz,1 1.5Hz),3.15-3.19(m,3H),2.78-2.85(m,9H),2.63(dd,3H,J=3.5Hz,3.0Hz),2.45(s,9H) [ka]

[0158] [3] Preparation of adhesive composition [Preparation Example 1] 29.7 g of liquid bisphenol-type epoxy resin jER-828 (Mitsubishi Chemical Corporation) and 0.3 g of (4-acetoxyphenyl)methyl(2-methylbenzyl)sulfonium tetrakis(pentafluorophenyl)borate (Sanshin Chemical Industry Co., Ltd., trade name: SI-B2A) were mixed with 70 g of PGME as a solvent to prepare an adhesive composition (Ad-1) with a solid content concentration of 30.0% by mass.

[0159] [Preparation Example 2] Adhesive composition (Ad-2) was prepared by mixing 29.97 g of liquid bisphenol-type epoxy resin jER-828 (Mitsubishi Chemical Corporation) and 0.03 g of (4-acetoxyphenyl)benzyl(methyl)sulfonium tetrakis(pentafluorophenyl)borate (Sanshin Chemical Industry Co., Ltd., trade name: SI-B3A).

[0160] [4] Preparation of a composition for forming a primer layer [Example 1-1] A mixture was obtained by mixing 100 parts by mass of (PA-1) as a polymer, 20 parts by mass of PL as a crosslinking agent, 1 part by mass of PPTS as a curing catalyst, and 1 part by mass of TGS as a silane coupling agent. To the obtained mixture, NMP and BCS were added as solvents in a mass ratio of NMP:BCS = 80:20 to prepare a primer layer forming composition (A-1) with a solid content concentration of 3.0% by mass.

[0161] [Examples 1-2 to 1-8, Comparative Examples 1-1 and 1-2] Primer layer-forming compositions A-2 to A-10 were prepared in the same manner as in Example 1-1, except that the types and amounts of each component were as shown in Table 1.

[0162] [Table 1]

[0163] [5] Preparation and evaluation of a primer layer on a glass substrate [Example 2-1] Using a spin coater (conditions: rotation speed 800 rpm for approximately 30 seconds), a primer layer forming composition (A-1) was applied onto a glass substrate (Corning Eagle XG, 100 mm × 100 mm × 0.7 mm) as the adherend. The resulting coating was heated on a hot plate at 80°C for 2 minutes, and then on a hot plate at 150°C for 10 minutes to form a primer layer approximately 0.1 μm thick on the glass substrate. Subsequently, using a spin coater (conditions: rotation speed 500 rpm for approximately 30 seconds), an adhesive composition (Ad-1) was applied to the entire surface of the glass substrate where the primer layer had been formed. The resulting coating was heated on a hot plate at 80°C for 2 minutes, and then on a hot plate at 150°C for 30 minutes to form an adhesive layer approximately 2 μm thick on the primer layer, obtaining a glass substrate with adhesive and primer layers.

[0164] [Examples 2-2 to 2-7, Comparative Examples 2-1 and 2-2] Glass substrates with adhesive layers and primer layers for Examples 2-2 to 2-7, Comparative Examples 2-1 and 2-2 were obtained in the same manner as in Example 2-1, except that primer layer forming compositions (A-2) to (A-7), (A-9), and (A-10) were used instead of primer layer forming composition (A-1).

[0165] [6] Preparation and evaluation of adhesive layers on glass substrates [Comparative Example 2-3] An adhesive composition (Ad-1) was applied to a glass substrate (Corning Eagle XG, 100 mm × 100 mm × 0.7 mm) using a spin coater (conditions: rotation speed 500 rpm for approximately 30 seconds). The resulting coating was heated on a hot plate at 80°C for 2 minutes, and then heated on a hot plate at 150°C for 30 minutes to form an adhesive layer approximately 2 μm thick on the glass substrate, obtaining a glass substrate with an adhesive layer.

[0166] [7] Preparation and evaluation of a primer layer on a film substrate [Examples 2-8] Using a bar coater, the primer layer-forming composition (A-8) was applied to the uncoated side of an ozone-treated polyester (PET) film substrate (CosmoShine® A4100, manufactured by Toyobo Co., Ltd., 50 μm thick) to a wet film thickness of 4 μm. The resulting coating was heated in a heat-circulating oven at 150°C for 10 minutes to form a primer layer approximately 0.1 μm thick on the PET film substrate. Subsequently, using a bar coater, the adhesive composition (Ad-1) was applied to the entire surface of the PET film substrate where the primer layer had formed to a wet film thickness of 10 μm. The resulting coating was heated in a heat-circulating oven at 150°C for 30 minutes to form an adhesive layer approximately 3 μm thick on the primer layer, obtaining a PET film substrate with adhesive and primer layers.

[0167] [Examples 2-9] Using a bar coater, the primer layer-forming composition (A-8) was applied to an ozone-treated polyimide (PI) film substrate (Kapton® 300H, manufactured by Toray DuPont, Ltd., 75 μm thick) to a wet film thickness of 4 μm. The resulting coating was heated in a heat-circulating oven at 150°C for 10 minutes to form a primer layer approximately 0.1 μm thick on the PI film substrate. Subsequently, using a bar coater, the adhesive composition (Ad-1) was applied to the entire surface of the PI film substrate where the primer layer had formed to a wet film thickness of 10 μm. The resulting coating was heated in a heat-circulating oven at 150°C for 30 minutes to form an adhesive layer approximately 3 μm thick on the primer layer, obtaining a PI film substrate with adhesive and primer layers.

[0168] [8] Preparation and evaluation of adhesive layers on film substrates [Comparative Example 2-4] Using a bar coater, the adhesive composition (Ad-1) was applied to the uncoated side of an ozone-treated polyester (PET) film substrate (CosmoShine® A4100, manufactured by Toyobo Co., Ltd., 50 μm thick) to a wet film thickness of 10 μm. The resulting coating was heated in a heat-circulating oven at 150°C for 30 minutes to form an adhesive layer approximately 3 μm thick on the PET film substrate, obtaining a PET film substrate with an adhesive layer.

[0169] [Evaluation of adhesive strength] For the glass substrates with adhesive and primer layers obtained in Examples 2-1 to 2-7, Comparative Examples 2-1 and 2-2, and the glass substrate with adhesive layer obtained in Comparative Example 2-3, ultraviolet light at a rate of 2000 mJ / cm² was applied to half of the surface where the adhesive layer was formed using a high-pressure mercury lamp, through a cut filter that absorbs light with a wavelength of 300 nm or less. 2 The substrate was irradiated at a wavelength of 365 nm. Subsequently, 25 mm x 50 mm strips were cut into both the exposed and unexposed areas using a cutter. Furthermore, cellophane tape (registered trademark) (manufactured by Nichiban Co., Ltd., CT-24) was applied to the adhesive layer, and the adhesive strength was measured by peeling it off using an Autograph AGS-X500N (manufactured by Shimadzu Corporation) at a peeling angle of 90° and a peeling speed of 300 mm / min. In cases where the adhesive layer could not be peeled off the glass substrate, peeling occurred at the interface between the adhesive layer and the cellophane tape (registered trademark), and the adhesive strength at that time was approximately 8.0 N / 25 mm, so it was classified as "unpeelable (>8.0)". The evaluation result is "adhesive strength," and the results for the exposed and unexposed areas are summarized in Table 2.

[0170] In the PET film substrates with adhesive and primer layers obtained in Example 2-8, and the PET film substrates with adhesive layers obtained in Comparative Example 2-4, ultraviolet light at a rate of 2000 mJ / cm² was applied to half of the surface where the adhesive layer was formed, using a high-pressure mercury lamp and a cut filter that absorbs light with a wavelength of 300 nm or less. 2The material was irradiated at a wavelength of 365 nm. Subsequently, 25 mm x 50 mm strips were cut into both the exposed and unexposed areas using a cutter. The cuts reached the PET film substrate, but care was taken to prevent the PET film substrate from tearing along the cuts when peeling off the cellophane tape (registered trademark). Furthermore, after applying cellophane tape (registered trademark) (CT-24, manufactured by Nichiban Co., Ltd.) to the adhesive layer, the adhesive strength was measured by peeling it off using an Autograph AGS-X500N (manufactured by Shimadzu Corporation) at a peeling angle of 90° and a peeling speed of 300 mm / min. For samples where the adhesive layer could not be peeled off the PET film substrate, peeling occurred at the interface between the adhesive layer and the cellophane tape (registered trademark), and the adhesive strength at that time was approximately 8.0 N / 25 mm, so it was classified as "unpeelable (>8.0)". The evaluation result is "adhesive strength," and the results for the exposed and unexposed areas are summarized in Table 2.

[0171] In the PI film substrate with adhesive layer and primer layer obtained in Example 2-9, ultraviolet light at a rate of 2000 mJ / cm² was applied to half of the surface where the adhesive layer was formed, using a high-pressure mercury lamp and a cut filter that absorbs light with a wavelength of 300 nm or less. 2 The substrate was irradiated at a wavelength of 365 nm. Subsequently, 25 mm x 50 mm strips were cut into both the exposed and unexposed areas using a cutter. The cuts reached the PI film substrate, but care was taken to prevent the PI film substrate from tearing along the cuts when peeling off the cellophane tape (registered trademark). Furthermore, after applying cellophane tape (registered trademark) (CT-24, manufactured by Nichiban Co., Ltd.) to the adhesive layer, the adhesive strength was measured by peeling it off using an Autograph AGS-X500N (manufactured by Shimadzu Corporation) at a peeling angle of 90° and a peeling speed of 300 mm / min. In cases where the adhesive layer could not be peeled off the PI film substrate, peeling occurred at the interface between the adhesive layer and the cellophane tape (registered trademark), and the adhesive strength at that time was approximately 8.0 N / 25 mm, so it was classified as "Not peelable (>8.0)". The evaluation result is "Adhesive strength," and the results for the exposed and unexposed areas are summarized in Table 2.

[0172] [Table 2]

[0173] As shown in Table 2, the primer layer in the example showed that the adhesive layer could not be peeled off before exposure, but after exposure, the adhesive layer could be peeled off, indicating low adhesive strength. On the other hand, in the comparative example, the adhesive layer could not be peeled off regardless of whether or not exposure was performed.

[0174] [9] Deconstruction test of adhesive substrate [Example 3-1] Using a spin coater (conditions: rotation speed 800 rpm for approximately 30 seconds), the primer layer forming composition (A-1) was applied onto a quartz substrate (40 mm × 40 mm × 1.0 mm) as the adherend. The resulting coating was heated on a hot plate at 80°C for 2 minutes, and then on a hot plate at 150°C for 10 minutes to form a primer layer approximately 0.1 μm thick on the quartz substrate. Subsequently, using a dispenser (electric dispenser Tofutty, manufactured by Icams Lab Co., Ltd.), 0.5 μL of adhesive composition (Ad-2) was dispensed onto the surface of the quartz substrate where the primer layer had formed. Two evaluation substrates were fabricated by placing another quartz substrate (40 mm × 40 mm × 1.0 mm) on the surface from which the adhesive composition (Ad-2) was dispensed, so that the adhesive thickness was 50 μm, and then heating in an oven at 150°C for 60 minutes, resulting in a layered structure of quartz substrate, primer layer, adhesive layer, and quartz substrate. Visual inspection of the fabricated evaluation substrates confirmed that the two quartz substrates were bonded together. On only one of the two evaluation substrates, ultraviolet light at 2000 mJ / cm² was applied using a high-pressure mercury lamp through a cut filter that absorbs light with a wavelength of 300 nm or less. 2 The substrates were irradiated at a wavelength of 365 nm. Afterwards, when the two quartz substrates of each of the two evaluation substrates were peeled apart, the adhesive layer remained on both quartz substrates of the evaluation substrate that had not been exposed. On the other hand, in the evaluation substrate exposed using a high-pressure mercury lamp, no adhesive layer remained on the quartz substrate where the primer layer had formed, and it was possible to disassemble it without leaving any trace of the adhesive layer.

[0175] [Comparative Example 3-1] Two evaluation substrates were prepared in the same manner as in Example 3-1, except that the primer layer-forming composition was not applied, by laminating a quartz substrate, an adhesive layer, and another quartz substrate in that order. On only one of the two evaluation substrates, ultraviolet light at 2000 mJ / cm² was applied using a high-pressure mercury lamp through a cut filter that absorbs light with a wavelength of 300 nm or less. 2 The substrates were irradiated at a wavelength of 365 nm. Afterwards, when the two quartz substrates on each of the two evaluation substrates were peeled off, an adhesive layer remained on both of the two quartz substrates on the two evaluation substrates, regardless of whether or not they had been exposed to light.

Claims

1. A primer layer forming composition for forming a primer layer having a cleavage structure in which chemical bonds irreversibly cleave in response to external stimuli, It contains a film-forming component and a solvent, The aforementioned film-forming component contains a polymer and a crosslinking agent, The film-forming component has two types of substructures that can react with each other to form the cracked structure, The polymer and the crosslinking agent each have one of two substructures that can react with each other to form the cleavage structure. The polymer and the other crosslinking agent have the other of the two types of substructures, The aforementioned cleavage structure is an o-nitrobenzyl structure, One of the two types of substructures is an o-nitrobenzyl alcohol structure, and the other of the two types of substructures is an epoxy group, a methylol group, an alkoxymethyl group, an isocyanate group, or a blocked isocyanate group. Composition for forming a primer layer.

2. The aforementioned external stimulus is an active energy ray, The aforementioned cleavage structure is a cleavage structure in which the chemical bond is irreversibly cleaved by absorbing the aforementioned active energy rays. The primer layer forming composition according to claim 1.

3. The primer layer forming composition according to claim 2, wherein the active energy ray is not laser light.

4. A primer layer forming composition according to claim 1 or 2, which is a composition for forming the primer layer adjacent to the adhesive layer.

5. The o-nitrobenzyl structure is a structure represented by the following formula (2): The primer layer forming composition according to claim 1. 【Chemistry 1】 (In formula (2), R １１ This represents a hydrogen atom, halogen atom, nitro group, cyano group, hydrocarbon group having 1 to 30 carbon atoms, heterocyclic group having 2 to 30 carbon atoms, or a group in which one or more non-adjacent methylene groups in the hydrocarbon group or heterocyclic group are replaced by a divalent group selected from group I below. Group I consists of -O-, -C(=O)-, -C(=O)O-, and -N(-R ３ )-,-N(-R ３ )C(=O)-, -S-, -C(=S)-, -SO ２ -, -SC(=O)-, and -OC(=S)-, R ３ This represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. R １２ This represents a halogen atom, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms. n11 represents 0 or 1, n12 represents an integer from 0 to 3, and if n12 is 2 or 3, R １２ They may be the same or they may be different. * indicates a bonding operation.

6. The first object to be attached, The second adherend and, A primer layer located between the first adherend and the second adherend, A laminate comprising an adhesive layer located between the first adherend and the second adherend and in contact with the primer layer, The primer layer is formed from a primer layer forming composition containing a film-forming component and a solvent. The primer layer has a cleavage structure in which chemical bonds irreversibly cleave in response to external stimuli. The aforementioned film-forming component contains a polymer and a crosslinking agent, The film-forming component has two types of substructures that can react with each other to form the cracked structure, The polymer and the crosslinking agent each have one of two substructures that can react with each other to form the cleavage structure. The polymer and the other crosslinking agent have the other of the two types of substructures, The aforementioned cleavage structure is an o-nitrobenzyl structure, One of the two types of substructures is an o-nitrobenzyl alcohol structure, and the other of the two types of substructures is an epoxy group, a methylol group, an alkoxymethyl group, an isocyanate group, or a blocked isocyanate group. Laminated structure.

7. The aforementioned external stimulus is an active energy ray, The aforementioned cleavage structure is a cleavage structure in which the chemical bond is irreversibly cleaved by absorbing the activation energy rays. At least one of the first adherend and the second adherend is permeable to the active energy rays. The laminate according to claim 6.

8. The laminate according to claim 7, wherein the active energy ray is not laser light.

9. The o-nitrobenzyl structure is a structure represented by the following formula (2): The laminate according to claim 6. 【Chemistry 2】 (In formula (2), R １１ This represents a hydrogen atom, halogen atom, nitro group, cyano group, hydrocarbon group having 1 to 30 carbon atoms, heterocyclic group having 2 to 30 carbon atoms, or a group in which one or more non-adjacent methylene groups in the hydrocarbon group or heterocyclic group are replaced by a divalent group selected from group I below. Group I is -O-, -C(=O)-, -C(=O)O-, -N(-R ３ ), -N(-R ３ ), -N(-R ２ ), -C(=O)-, -S-, -C(=S)-, -SO ３ -, -SC(=O)-, and -OC(=S)-, and R R １２ This represents a halogen atom, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms. n11 represents 0 or 1, n12 represents an integer from 0 to 3, and if n12 is 2 or 3, R １２ They may be the same or they may be different. * indicates a bonding operation.

10. A separation step of applying an external stimulus to the primer layer in the laminate according to any one of claims 6 to 9 to separate the first adherend and the second adherend, A method for disassembling a laminate, including the following.

11. The aforementioned external stimulus is an active energy ray, The aforementioned cleavage structure is a cleavage structure in which the chemical bond is irreversibly cleaved by absorbing the activation energy rays. At least one of the first adherend and the second adherend is permeable to the active energy rays. A method for disassembling a laminate according to claim 10.

12. The method for decomposing a laminate according to claim 11, wherein the active energy ray is not laser light.

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