Release layer-forming composition, laminate, and method for manufacturing laminate

Abstract

A laminate comprising a support that can transmit active energy rays, a release layer that is on the support, and a resin layer that is on the release layer, wherein the release layer is formed from a release layer-forming composition containing a film-forming component and a solvent, the resin layer is formed from a resin layer precursor, the release layer has a cleavage structure in which a chemical bond is cleaved by absorbing the active energy rays, the film-forming component has a first reactive group, and the resin layer precursor has a second reactive group capable of reacting with the first reactive group.

Description

[Technical Field]

[0001] The present invention relates to a release layer-forming composition, a laminate, and a method for producing the laminate. [Background technology]

[0002] In recent years, electronic devices have been required to be thin, lightweight, and flexible, which has led to the need to use lightweight, flexible plastic substrates instead of conventional heavy, fragile, and inflexible glass substrates.

[0003] In particular, new generation displays require the development of active matrix full-color TFT display panels using lightweight flexible plastic substrates (hereinafter also referred to as resin substrates). For touch panel displays, materials that support flexibility, such as transparent electrodes and resin substrates for touch panels used in combination with display panels, have been developed. For transparent electrodes, alternative transparent electrode materials have been proposed, replacing the conventionally used ITO, such as bendable transparent conductive polymers such as PEDOT, metal nanowires, and mixtures thereof (Patent Documents 1 to 4).

[0004] Meanwhile, the substrate of touch panel films has also changed from glass to sheets made of plastics such as polyethylene terephthalate (PET), polyimide, cycloolefin, and acrylic, and transparent flexible touch screen panels with flexibility have been developed (Patent Documents 5 to 7).

[0005] Generally, to ensure stable production, flexible touch screen panels are produced by forming a release (adhesive) layer on a support substrate such as a glass substrate, forming a device composed of a resin substrate or the like on top of that, and then peeling the device off the adhesive layer (Patent Document 8). Devices made of resin substrates and fabricated on this release layer must not peel from the support substrate during processing, but require low peeling force when peeling. Peeling from the support substrate during the fabrication process can significantly reduce yield. This problem applies not only to flexible touchscreen panels, but also to devices that use resin substrates in general. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2012 / 147235 [Patent Document 2] Japanese Patent Application Laid-Open No. 2009-283410 [Patent Document 3] Special Publication No. 2010-507199 [Patent Document 4] Japanese Patent Application Laid-Open No. 2009-205924 [Patent Document 5] International Publication No. 2017 / 002664 [Patent Document 6] Japanese Patent Application Laid-Open No. 2016-160338 [Patent Document 7] Japanese Patent Application Laid-Open No. 2015-166145 [Patent Document 8] Japanese Patent Application Laid-Open No. 2016-531358 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made to solve the above-mentioned problems, and aims to provide a laminate that is difficult to peel off during the production of a device or the like, but that can be easily peeled off by irradiating it with active energy rays after the production of the device or the like. Another object of the present invention is to provide a method for producing the laminate, a method for producing an electronic device using the laminate, and a release layer-forming composition used in producing the laminate. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, and have completed the present invention having the following gist. That is, the present invention includes the following. [1] A laminate having a support that is transparent to active energy rays, a release layer on the support, and a resin layer on the release layer, the release layer is formed from a release layer-forming composition containing a film-forming component and a solvent, the resin layer is formed from a resin layer precursor, the release layer has a cleavage structure that absorbs the active energy ray to cleave a chemical bond, the film-forming component has a first reactive group; the resin layer precursor has a second reactive group capable of reacting with the first reactive group; Laminate. [2] The laminate according to [1], which satisfies at least one of 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 structures that can react with each other to form the cleavage structure. [3] The laminate according to [1] or [2], wherein the cleavage structure includes 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. [4] The cleavage structure includes 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 a structure represented by the following formula (2): The acetophenone structure is a structure represented by the following formula (3): The laminate according to [3]. [ka] (In formula (1), R 1 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, a heterocycle-containing 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 heterocycle-containing group have been replaced with 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, n1 represents 0 or 1; n2 represents 0 or 1. In formula (2), R 11 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, a heterocycle-containing 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 heterocycle-containing group have been replaced with 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 heterocycle-containing group having 2 to 30 carbon atoms, n11 represents 0 or 1; n12 represents an integer of 0 to 3, and 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, and 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. [5] The above condition (A) is satisfied, the film-forming component comprises a polymer and a crosslinker; the crosslinker has the first reactive group and the cleavage structure; The laminate according to any one of [2] to [4]. [6] The above condition (A) is satisfied, the film-forming component comprises a polymer and a crosslinker; the polymer has the cleavage structure, the crosslinker has the first reactive group; The laminate according to any one of [2] to [4]. [7] The above condition (B) is satisfied, the film-forming component comprises a polymer and a crosslinker; the polymer has one of two moieties capable of reacting with each other to form the cleavage structure, the crosslinker has the first reactive group; The laminate according to any one of [2] to [4]. [8] The laminate according to any one of [1] to [7], wherein the first reactive group and the second reactive group are the same reactive group. [9] A step of forming a release layer on a support that is transparent to active energy rays; forming a resin layer precursor on the release layer; converting the resin layer precursor into a resin layer; A method for producing a laminate, comprising: the release layer has a cleavage structure that absorbs the active energy ray to cleave a chemical bond, the film-forming component has a first reactive group; the resin layer precursor has a second reactive group capable of reacting with the first reactive group; A method for manufacturing a laminate.

[10] The method for producing a laminate according to [9], which satisfies at least one of 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 structures that can react with each other to form the cleavage structure.

[11] The method for producing a laminate according to [9] or

[10] , wherein the cleavage structure includes 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.

[12] The cleavage structure includes 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 a structure represented by the following formula (2): The acetophenone structure is a structure represented by the following formula (3):

[11] A method for producing the laminate described in

[11] . [ka] (In formula (1), R 1 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, a heterocycle-containing 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 heterocycle-containing group have been replaced with 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 R3 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, n1 represents 0 or 1; n2 represents 0 or 1. In formula (2), R 11 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, a heterocycle-containing 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 heterocycle-containing group have been replaced with 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 heterocycle-containing group having 2 to 30 carbon atoms, n11 represents 0 or 1; n12 represents an integer of 0 to 3, and 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 heterocycle-containing group having 2 to 30 carbon atoms, n21 represents an integer of 0 to 4, and 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.

[13] The above condition (A) is satisfied, the film-forming component comprises a polymer and a crosslinker; the crosslinker has the first reactive group and the cleavage structure; The method for producing a laminate according to any one of

[10] to

[12] .

[14] The above condition (A) is satisfied, the film-forming component comprises a polymer and a crosslinker; the polymer has the cleavage structure, the crosslinker has the first reactive group; The method for producing a laminate according to any one of

[10] to

[12] .

[15] The condition (B) is satisfied, the film-forming component comprises a polymer and a crosslinker; the polymer has one of two moieties capable of reacting with each other to form the cleavage structure, the crosslinker has the first reactive group; The method for producing a laminate according to any one of

[10] to

[12] .

[16] The method for producing a laminate according to any one of [9] to

[15] , wherein the first reactive group and the second reactive group are the same reactive group.

[17] The method for producing a laminate according to any one of [9] to

[16] , wherein the resin layer precursor is formed from a composition for forming a resin layer containing a resin and a crosslinking agent having the second reactive group.

[18] A step of forming at least one of a photoelectric conversion element, a display element, a member for a display element, and an electronic circuit on the resin layer of either the laminate according to any one of [1] to [8] and the laminate produced by the method for producing a laminate according to any one of [9] to

[17] ; a peeling step of irradiating the laminate with active energy rays from the support side toward the release layer, thereby peeling the support from the resin layer; A method for manufacturing an electronic device, comprising:

[19] A release layer-forming composition used in either the production of the laminate according to [2] or the production method of the laminate according to

[10] , Contains a film-forming component and a solvent, At least one of the following conditions (A) and (B) is satisfied: the film-forming component has a first reactive group; A release layer-forming composition. Condition (A): The film-forming component has the cleavage structure. Condition (B): The film-forming component has two types of partial structures that can react with each other to form the cleavage structure.

[20] The composition for forming a release layer according to

[19] , wherein the cleavage structure includes 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.

[21] The cleavage structure includes 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 a structure represented by the following formula (2): The acetophenone structure is a structure represented by the following formula (3):

[20] The composition for forming a release layer according to

[20] . [ka] (In formula (1), R 1 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, a heterocycle-containing 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 heterocycle-containing group have been replaced with 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, n1 represents 0 or 1; n2 represents 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 heterocycle-containing 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 heterocycle-containing group have been replaced with 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 heterocycle-containing group having 2 to 30 carbon atoms, n11 represents 0 or 1; n12 represents an integer of 0 to 3, and 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 heterocycle-containing group having 2 to 30 carbon atoms, n21 represents an integer of 0 to 4, and 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.

[22] The above condition (A) is satisfied, the film-forming component comprises a polymer and a crosslinker; the crosslinker has the first reactive group and the cleavage structure; The composition for forming a release layer according to any one of

[19] to

[21] .

[23] The above condition (A) is satisfied, the film-forming component comprises a polymer and a crosslinker; the polymer has the cleavage structure, the crosslinker has the first reactive group; The composition for forming a release layer according to any one of

[19] to

[21] .

[24] The condition (B) is satisfied, the film-forming component comprises a polymer and a crosslinker; the polymer has one of two moieties capable of reacting with each other to form the cleavage structure, the crosslinker has the first reactive group; The composition for forming a release layer according to any one of

[19] to

[21] .

[25] The composition for forming a release layer according to any one of

[19] to

[24] , wherein the first reactive group and the second reactive group possessed by the resin layer precursor are the same reactive group. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a laminate that is difficult to peel during the fabrication of a device or the like, but that can be easily peeled off by irradiating it with active energy rays after the fabrication of the device or the like. Furthermore, according to the present invention, it is possible to provide a method for producing the laminate, a method for producing an electronic device using the laminate, and a release layer-forming composition used in producing the laminate. DETAILED DESCRIPTION OF THE INVENTION

[0010] (Laminate) The laminate of the present invention has a support, a release layer, and a resin layer.

[0011] <Support> The support is not particularly limited as long as it is transparent to active energy rays. Examples of materials for the support include glass, resin, etc. Among these, glass is preferred because of its low flexibility.

[0012] The support is, for example, in the form of a plate. The thickness of the plate-shaped support is not particularly limited, but is preferably 0.1 mm to 10 mm, more preferably 0.2 mm to 5 mm, and particularly preferably 0.3 mm to 2 mm.

[0013] The transmittance of the support to active energy rays is, for example, preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more, for light with a wavelength of 365 nm.

[0014] 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 wavelengths of ultraviolet rays 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. As the active energy ray, a laser beam may be used, but it is preferable not to use a laser beam since the laser beam may damage the support and the resin layer.

[0015] <Release layer> The release layer is formed from a release layer-forming composition containing a film-forming component and a solvent. The release layer has a cleavage structure that absorbs active energy rays to cleave chemical bonds. The release layer is disposed between the support and the resin layer. The release layer is a layer obtained, for example, by applying and heating a composition for forming a release layer.

[0016] <<Composition for forming release layer>> The release layer-forming composition contains a film-forming component and a solvent. The release layer-forming composition is used, for example, in the production of the laminate of the present invention. The release layer-forming composition is also used, for example, in the production method of the laminate of the present invention. Such a release layer-forming composition is also within the scope of the present invention. The release layer-forming composition is a composition for forming a release layer having a cleavage structure, which is a structure in which chemical bonds are cleaved upon absorption of active energy rays. The laminate of the present invention or the composition for forming a release layer of the present invention satisfies at least one of the following conditions (A) and (B). Condition (A): The film-forming component has a cleavable structure. Condition (B): The film-forming component has two types of partial structures that can react with each other to form a cleavage structure.

[0017] When the release layer has a cleavage structure, the cleavage structure is cleaved when the release layer is irradiated with active energy rays, reducing the adhesiveness between the support and the resin layer due to the release layer, and as a result, the support and the resin layer can be easily separated.

[0018] <<<cleavage structure>>> The cleavage structure is not particularly limited as long as it is a structure that absorbs active energy rays and cleaves chemical bonds. Examples of the cleavage structure include a cleavage structure that undergoes reversible cleavage and a cleavage structure that undergoes irreversible cleavage, and among these, a cleavage structure that undergoes irreversible cleavage is preferred. Irreversible cleavage refers to cleavage by an irreversible chemical reaction. If the cleavage is reversible, there is a risk that the chemical bond may unintentionally recombine after the cleavage, which may result in a decrease in the ease of separation between the support and the resin layer. In this respect, the cleavage structure is preferably an irreversible cleavage structure.

[0019] Examples of the active energy rays absorbed by the cleavage structure include ultraviolet rays, electron beams, and X-rays, with ultraviolet rays being particularly preferred. Examples of the wavelength of ultraviolet rays 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. As the active energy ray, a laser beam may be used, but it is preferable not to use a laser beam since the laser beam may damage the support and the resin layer.

[0020] The chemical bond cleaved in the cleavage structure is usually a covalent bond. Examples of the cleaved covalent bond include a covalent bond between two heteroatoms and a covalent bond between a heteroatom and a carbon atom. Examples of the heteroatom include an oxygen atom and a nitrogen atom.

[0021] The cleavage structure preferably includes 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, and more preferably includes at least one of an oxime ester structure, an oxime ether structure, an o-nitrobenzyl structure, and an acetophenone structure. These cleavage structures are cleaved by low-energy active energy rays, and therefore the support and the resin layer can be separated with low energy.

[0022] An example of the cleavage of the cleavage structure is shown below. Below is an example of the cleavage of an oxime ester structure. [ka]

[0023] Below is an example of the cleavage of an o-nitrobenzyl structure. [ka]

[0024] Below is an example of the cleavage of an acetophenone structure. [ka]

[0025] Below is an example of the cleavage of a pyrenylmethyl structure. [ka]

[0026] Below is an example of the cleavage of a coumarinylmethyl structure. [ka]

[0027] The oxime ester structure or oxime ether structure includes, for example, a structure represented by the following formula (1). An example of the o-nitrobenzyl structure is a structure represented by the following formula (2). An example of the acetophenone structure is a structure represented by the following formula (3).

[0028] [ka] (In formula (1), R 1 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, a heterocycle-containing 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 heterocycle-containing group have been replaced with 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, n1 represents 0 or 1; n2 represents 0 or 1. In formula (2), R 11 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, a heterocycle-containing 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 heterocycle-containing group have been replaced with 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 heterocycle-containing group having 2 to 30 carbon atoms, n11 represents 0 or 1; n12 represents an integer of 0 to 3, and 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 heterocycle-containing group having 2 to 30 carbon atoms, n21 represents an integer of 0 to 4, and 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.

[0029] -C1 to C30 hydrocarbon group- The hydrocarbon group having 1 to 30 carbon atoms is not particularly limited, and examples thereof include an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a cycloalkylalkyl group having 4 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an arylalkyl group having 7 to 30 carbon atoms. When the hydrocarbon group having 1 to 30 carbon atoms has a substituent, the total number of carbon atoms is 1 to 30.

[0030] The alkyl group having 1 to 30 carbon atoms may be linear or branched. Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, and an icosyl group. Examples of branched alkyl groups include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an iso-amyl group, a tert-amyl group, an iso-octyl group, a 2-ethylhexyl group, a tert-octyl group, an iso-nonyl group, and an iso-decyl group. Of these, straight chain ones 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, since this will improve the decomposition property of the release layer by active energy rays.

[0031] The alkenyl group having 2 to 30 carbon atoms may be linear or cyclic. When the alkenyl group is linear, it may be a terminal alkenyl group having an unsaturated bond at the terminal, or an internal alkenyl group having an unsaturated bond inside. Examples of the terminal alkenyl group having 2 to 30 carbon atoms include a vinyl group, a 2-propenyl group, a 3-butenyl group, a 4-pentenyl group, and a 5-hexenyl group. Examples of internal alkenyl groups include 2-butenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, and 4-dodecenyl groups. Examples of the cyclic alkenyl group include a 3-cyclohexenyl group, a 2,5-cyclohexadienyl-1-methyl group, and a 4,8,12-tetradecatrienylallyl group. Among these, alkenyl groups having 2 to 10 carbon atoms are preferred because they provide better decomposition of the release layer by active energy rays.

[0032] The cycloalkyl group having 3 to 30 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having a total of 3 to 30 carbon atoms. Examples of the saturated monocyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group. Examples of the saturated polycyclic alkyl group include an adamantyl group, a decahydronaphthyl group, an octahydropentalene group, a bicyclo[1.1.1]pentanyl group, and a tetradecahydroanthracenyl group. Among these, cycloalkyl groups having 3 to 10 carbon atoms are preferred because they provide better decomposition of the release layer by active energy rays.

[0033] The cycloalkylalkyl group having 4 to 30 carbon atoms means a group in which a hydrogen atom of an alkyl group is substituted with a cycloalkyl group and which has a total of 4 to 30 carbon atoms. The cycloalkyl group in the cycloalkylalkyl group may be monocyclic or polycyclic, and a methylene group in the alkyl group in the cycloalkylalkyl group may be replaced with -CH=CH-. Examples of the cycloalkylalkyl group having 4 to 30 carbon atoms and in which the cycloalkyl group is a single ring include a cycloalkylmethyl group, a cycloalkylethyl group, a cycloalkylpropyl group, and a cycloalkylpropyl group. Examples of the cycloalkylmethyl group include a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cycloheptylmethyl group, a cyclooctylmethyl group, a cyclononylmethyl group, and a cyclodecylmethyl group. Examples of the cycloalkylethyl group include a 2-cyclobutylethyl group, a 2-cyclopentylethyl group, a 2-cyclohexylethyl group, a 2-cycloheptylethyl group, a 2-cyclooctylethyl group, a 2-cyclononylethyl group, and a 2-cyclodecylethyl group. Examples of the cycloalkylpropyl group include a 3-cyclobutylpropyl group, a 3-cyclopentylpropyl group, a 3-cyclohexylpropyl group, a 3-cycloheptylpropyl group, a 3-cyclooctylpropyl group, a 3-cyclononylpropyl group, and a 3-cyclodecylpropyl group. Examples of the cycloalkylbutyl group include a 4-cyclobutylbutyl group, a 4-cyclopentylbutyl group, a 4-cyclohexylbutyl group, a 4-cycloheptylbutyl group, a 4-cyclooctylbutyl group, a 4-cyclononylbutyl group, and a 4-cyclodecylbutyl group. Examples of the cycloalkylalkyl group having 4 to 20 carbon atoms and in which the cycloalkyl group is polycyclic include a bicyclo[1.1.0]butyl group, a bicyclo[1.1.1]pentyl group, a bicyclo[2.1.0]pentyl group, a bicyclo[3.1.0]hexyl group, a bicyclo[2.1.1]hexyl group, a bicyclo[2.2.0]hexyl group, a bicyclo[4.1.0]heptyl group, a bicyclo[3.2.0]heptyl group, a bicyclo[4.1.0]butyl group, a bicyclo[4.1.1]pentyl group, a bicyclo[4.1.0]pentyl ... Examples include cyclo[3.1.1]heptyl, bicyclo[2.2.1]heptyl, bicyclo[5.1.0]octyl, bicyclo[4.2.0]octyl, bicyclo[4.1.1]octyl, bicyclo[3.3.0]octyl, bicyclo[3.2.1]octyl, bicyclo[2.2.2]octyl, spiro[4.4]nonanyl, spiro[4.5]decanyl, and tricyclodecanyl. Among these, cycloalkylalkyl groups having 4 to 10 carbon atoms are preferred because they provide better decomposition of the release layer by active energy rays.

[0034] 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 one in which an aryl group having a monocyclic structure and another aryl group having a monocyclic structure are linked together, or one in which an aryl group having a monocyclic structure and an aryl group having a fused ring structure are linked together, or one in which an aryl group having a fused ring structure and another aryl group having a fused ring structure are linked together. Examples of the aryl group having a monocyclic structure include a phenyl group and a biphenylyl group. Examples of the aryl group having a fused ring structure include a naphthyl group, an anthryl group, and a phenanthrenyl group. One or more hydrogen atoms of the aryl group having 6 to 30 carbon atoms may be substituted with a substituent. Examples of the substituent include the above-mentioned alkyl group, alkenyl group, carboxy group, and halogen atoms. Examples of the aryl group having 6 to 30 carbon atoms and having a substituent include substituted aryl groups with a monocyclic structure, 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 provide better decomposition of the release layer by active energy rays.

[0035] The arylalkyl group having 7 to 30 carbon atoms means a group in which one or more hydrogen atoms of an alkyl group have been substituted with the above aryl group. Examples of the arylalkyl group having 7 to 30 carbon atoms include a phenylalkyl group and a naphthylalkyl group. Examples of the phenylalkyl group include a benzyl group, a 2-methylbenzyl group, a 3-methylbenzyl group, a 4-methylbenzyl group, an α-dimethylbenzyl group, a 2-phenylethyl group, a 2-phenylpropyl group, a 3-phenylpropyl group, a diphenylmethyl group, a triphenylmethyl group, and a triphenylpropyl group. Examples of naphthylalkyl groups include naphthylpropyl groups. Among these, arylalkyl groups having 7 to 10 carbon atoms are preferred because they provide better decomposition of the release layer by active energy rays.

[0036] -C2-C30 heterocycle-containing group (heterocycle-containing group having 2-30 carbon atoms)- The heterocycle in the heterocycle-containing group having 2 to 30 carbon atoms may have a monocyclic structure or a condensed ring structure. One or more hydrogen atoms in the heterocycle may be substituted with an alkyl group having 1 to 6 carbon atoms. Furthermore, the heterocycles may be bonded via an alkylene group having 1 to 6 carbon atoms to form a heterocyclic group having a condensed ring structure. Examples of heterocycle-containing groups containing a monocyclic heterocycle include pyrrolyl, pyridyl, pyridylethyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyranylethyl, pyrazolyl, triazyl, triazylmethyl, pyrrolidyl, imidazolyl, triazolyl, furyl, furanyl, thienyl, thiophenyl, thiadiazolyl, thiazolyl, oxazolyl, isothiazolyl, isoxazolyl, yulolidyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinon-1-yl, 2-piperidon-1-yl, 2,4-dioxyimidazolidin-3-yl, and 2,4-dioxyoxazolidin-3-yl groups. Examples of heterocycle-containing groups having a fused heterocycle structure include a quinolyl group, an isoquinolyl group, a benzimidazolyl group, a benzofuranyl group, a benzothiophenyl group, a benzothiazolyl group, a benzoxazolyl group, and an indolyl group.

[0037] Examples of the heterocycle-containing group include the following groups. [ka] (In the above formula, each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, each Z independently represents a single bond or an alkylene group having 1 to 6 carbon atoms, and * represents a bond.) Examples of the alkyl group having 1 to 6 carbon atoms for R include those having 1 to 6 carbon atoms among the alkyl groups having 1 to 30 carbon atoms exemplified above. Examples of the alkylene group having 1 to 6 carbon atoms for Z include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.

[0038] <<<Two substructures that can react with each other to form cleavage structures>>> The two types of partial structures that can react with each other to form a cleavage structure are not particularly limited, and examples of the cleavage structure that can be formed include an oxime ester structure, an o-nitrobenzyl structure, an alkylphenone structure, a pyrenylmethyl structure, a coumarinylmethyl structure, an aminoalkylphenone structure, and a benzyl ketal structure.

[0039] An example of two moieties that can react with each other to form a cleavage structure is shown below. The cleaved structure formed is an o-nitrobenzyl structure. One of the two partial structures is an o-nitrobenzyl alcohol structure, an example of which is the following structure. [ka] (In the formula, * represents a bond.)

[0040] The other of the two partial structures is, for example, an epoxy group, a methylol group, an alkoxymethyl group, an isocyanate group, or a blocked isocyanate group, and an example of one of these is the following structure. [ka] (In the formula, * represents a bond.)

[0041] These two partial structures react with each other to form the following cleavage structure (o-nitrobenzyl structure). [ka] (In the formula, * represents a bond.)

[0042] Such a reaction can be carried out, for example, by applying a release layer-forming composition containing an acid catalyst onto an article to be coated, and then heating the composition. Examples of the acid catalyst include the curing catalysts described below.

[0043] <<<Film-forming components>>> The film-forming component is a component that constitutes the release layer when the release layer is formed from the release layer-forming composition. Examples of the film-forming component include a component that exists in the release layer as it is, a component that exists in the release layer as a reaction product with other components, and a component used as an auxiliary (e.g., a curing catalyst) that assists the reaction of other components. In other words, the film-forming component is a general term for all components of the release layer-forming composition other than the solvent.

[0044] The film-forming component has a first reactive group.

[0045] Examples of the film-forming component include a polymer and a crosslinking agent. For example, the polymer may have the first reactive groups, the crosslinker may have the first reactive groups, or both the polymer and the crosslinker may have the first reactive groups.

[0046] When the condition (A) is satisfied, the film-forming component may contain a polymer. In this case, for example, the polymer has 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. The polymer may have a first reactive group and a cleavage structure, or may have a cleavage structure without a first reactive group.

[0047] When the condition (A) is satisfied, 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. The crosslinking agent may have a first reactive group and a cleavage structure, or may have a cleavage structure without having a first reactive group.

[0048] When the condition (A) is satisfied, the film-forming component may contain a polymer and a crosslinking agent, where, for example, at least one of the polymer and the crosslinking agent has a cleavage structure. In the combination of the polymer and the crosslinking agent in the film-forming component, only the polymer may have a cleavage structure, only the crosslinking agent may have a cleavage structure, or both the polymer and the crosslinking agent may have a cleavage structure.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 a cleavage structure.In addition, 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. The film-forming component includes, for example, a polymer and a crosslinking agent, and the crosslinking agent has a first reactive group and a cleavable structure. The film-forming component contains, for example, a polymer and a crosslinking agent, where the polymer has a cleavable structure and the crosslinking agent has a first reactive group.

[0049] When condition (B) is satisfied, the film-forming component may contain a polymer and a crosslinking agent. In this case, for example, the polymer has one of two partial structures that can react with each other to form a cleavage structure, and the crosslinking agent has the other of the two partial structures. 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 partial structures. 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 the other of the two partial structures. The film-forming component contains, for example, a polymer and a crosslinking agent, and the polymer has one of two partial structures that can react with each other to form a cleavage structure. The crosslinking agent has the other of the two partial structures. The crosslinking agent also has a first reactive group. Here, the other of the two partial structures possessed by the crosslinking agent and the first reactive group may be the same reactive group or different reactive groups. For example, an alkoxyalkyl group can be the other of the two partial structures or the first reactive group.

[0050] When condition (B) is satisfied, the film-forming component may contain two or more polymers, where, for example, at least one of the two or more polymers has one of two partial structures capable of reacting with each other to form a cleavage structure, and at least one of the remaining polymers has the other of the two partial structures.

[0051] When condition (B) is satisfied, the film-forming component may contain two or more crosslinking agents, where, for example, at least one of the two or more crosslinking agents has one of two partial structures capable of reacting with each other to form a cleavage structure, and at least one of the remaining crosslinking agents has the other of the two partial structures.

[0052] -polymer- The polymer may or may not have a cleaved structure.

[0053] --Polymers with cleavage structures-- When the polymer has a cleavage structure, the cleavage structure may be located in the main chain of the polymer or in a side chain of the polymer, and among these, a polymer having the cleavage structure in the main chain is preferred in that a large number of cleavage structures can be introduced into the polymer.

[0054] In a polymer having a cleavage structure in the main chain, the cleavage structure may exist in all or some of the repeating units of the polymer. The molar ratio of the repeating units having the 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 a polymer having a cleavage structure in a side chain, the cleavage structure may be present in all or part of the repeating units of the polymer. The molar ratio of the repeating units having the cleavage structure 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.

[0055] When a polymer has one of two moieties that can react with each other to form a cleavage structure, that one is usually located in a side chain of the polymer. In a polymer having, in its side chain, one of two partial structures capable of reacting with each other to form a cleavage structure, the partial structure may be present in all or some of the repeating units of the polymer. The molar ratio of the repeating units having the partial structure 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.

[0056] Examples of these polymers include condensation polymers such as polyester, polyamide, polyimide and polyamic acid, polyurethane, and vinyl polymers.

[0057] Examples of polymers having a cleavage structure in the main chain include polymers having a repeating unit represented by the following formula (11) or formula (12). [ka] (In formula (11), R 1 , and n1 are R in formula (1), 1 , and n1. R 101 represents a divalent organic group. 102 represents a divalent organic group. In formula (12), R 11 , R 12 , and n12 are R in formula (2), respectively. 11 , R 12 , and n12. R 111 represents a divalent organic group. 112 represents a divalent organic group. m1 represents 0 or 1.

[0058] R 101 Examples of the divalent organic group include divalent organic groups having 1 to 30 carbon atoms. Examples of the divalent organic group having 1 to 30 carbon atoms include divalent aromatic hydrocarbon groups which may have a substituent. Examples of the divalent aromatic hydrocarbon group include a phenylene group and a naphthylene group. Examples of the substituent include a hydrogen atom, a halogen atom, a nitro group, a cyano group, and a hydrocarbon group having 1 to 10 carbon atoms.

[0059] R 102 Examples of the divalent organic group include divalent organic groups having 1 to 30 carbon atoms. Examples of the divalent organic group 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 aliphatic hydrocarbon groups in R2 and R3 may each have 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms.

[0060] R 111 Examples of the group include a divalent organic group represented by the following formula (12-1). [ka] (In formula (12-1), R 11 is R in Equation (12). 11 * represents a bond.)

[0061] R 112 Examples of the group include divalent organic groups having 1 to 30 carbon atoms. In equation (12), when m1 is 1, R 112 Examples of the group include a divalent organic group represented by any one of the above formulas (K-1) to (K-13). In equation (12), when m is 0, R 112 Examples of the divalent organic group include divalent organic groups having 1 to 30 carbon atoms. Examples of the divalent organic group having 1 to 30 carbon atoms include divalent aromatic hydrocarbon groups which may have a substituent. Examples of the divalent aromatic hydrocarbon group include a phenylene group and a naphthylene group. Examples of the substituent include a hydrogen atom, a halogen atom, a nitro group, a cyano group, and a hydrocarbon group having 1 to 30 carbon atoms.

[0062] An example of a polymer having a cleavage structure in the main chain is shown below. [ka] (In the formula, n represents an integer of 1 or more.) This polymer has an o-nitrobenzyl structure located in the main chain. In this polymer, the o-nitrobenzyl structure is present in all of the repeating units of the polymer. This polymer can be obtained, for example, by condensation polymerization of 2-nitro-m-xylylene glycol and isophthaloyl chloride, and the resulting polymer is a type of polyester. Furthermore, by reacting (2-nitro-1,3-phenylene)dimethanol with diisocyanate, polyurethane having an o-nitrobenzyl structure in the main chain can be obtained.

[0063] Furthermore, a polyurethane having an oxime ester structure in the main chain can be obtained by reacting a compound having two oxime groups (>C=N-OH) such as those having the following structure with a diisocyanate compound. [ka]

[0064] An example of a polymer having a cleavage structure in the side chain is shown below. [ka] This polymer has an acetophenone structure located in the side chain. In this polymer, n mol % (n+m=50) of all repeating units are repeating units having an acetophenone structure. This polymer is a type of vinyl polymer and can be obtained, for example, by radical polymerization of monomers having polymerizable unsaturated double bonds corresponding to the respective repeating units.

[0065] Here, an example in which one of two partial structures capable of reacting with each other to form a cleavage structure is present in the side chain of the polymer is shown below. [ka] This polymer has a moiety capable of forming an o-nitrobenzyl structure located on the side chain. In this polymer, 20 mol % of all repeating units are repeating units having this partial structure. This polymer is a type of vinyl polymer and can be obtained, for example, by radical polymerization of monomers having polymerizable unsaturated double bonds corresponding to the respective repeating units.

[0066] --Polymer without cleavage structure-- The polymer without a cleavage structure is not particularly limited, and for example, a known polymer can be used. Examples of known polymers include condensation polymers such as polyester, polyamide, polyimide and polyamic acid, polyurethane, and vinyl polymer.

[0067] ---Polyurethane--- An example of a polyurethane having no cleavage structure is a reaction product of a diol and a diisocyanate. The diol is not particularly limited, and examples thereof include diols having 1 to 30 carbon atoms. The diol may or may not have an aromatic hydrocarbon group, but preferably has an aromatic hydrocarbon group. Examples of the aromatic ring in the aromatic hydrocarbon group include a benzene ring and a naphthalene ring. The diisocyanate is not particularly limited, and examples thereof include diisocyanates having a carbon number of 3 to 30. Preferred diisocyanates are, for example, diisocyanates 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 aliphatic hydrocarbon groups in R2 and R3 may each have 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms.

[0068] ---Condensation polymers--- An example of a polymer that does not have a cleavage structure is a condensation polymer having a repeating unit represented by the following formula (A1). [ka] (In formula (A1), A 1 , A 2 , A 3 , A 4 , A 5 and A 6 are each independently a hydrogen atom, a methyl group, or an ethyl group, X 1 is a group represented by the following formula (A1-1), (A1-2), (A1-3) or (A1-4), Q 1 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 are each independently a hydrogen atom, 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 an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 6 carbon atoms. 1 and R 2 may be bonded to each other to form a ring having 3 to 6 carbon atoms together with the carbon atoms to which they are bonded. R 3is 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 an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 6 carbon atoms. * represents a bond. *1 represents a bond to a carbon atom. *2 represents a bond to a nitrogen atom. [ka] (In formulas (A1-5) and (A1-6), X 2 is a group represented by formula (A1-1), formula (A1-2) or formula (A1-4). Q 2 is an alkylene group having 1 to 10 carbon atoms, a phenylene group, a naphthylene group, or an anthrylene group. The phenylene group, naphthylene group, and anthrylene group may be substituted with at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 6 carbon atoms. n 1 and n 2 are each independently 0 or 1. *1 is A 3 *2 represents the bond that bonds to the carbon atom that bonds to A. 4 represents the bond that bonds to the carbon atom that bonds to

[0069] A 1 ~A 6 are preferably all hydrogen atoms.

[0070] In formula (A1-5), for example, X 2 When is a group represented by formula (A1-2), the structure is represented by formula (A1-5-1) below. [ka] (In formula (A1-5-1), R 1 and R 2is R in formula (A1-2). 1 and R 2 are the same as

[0071] In formula (A1-6), Q 2 is a phenylene group, a naphthylene group, or an anthrylene group, their bonding positions are not particularly limited. That is, for example, the phenylene group may be bonded at the 1st and 2nd positions, or at the 1st and 3rd positions, the naphthylene group may be bonded at the 1st and 2nd positions, or at the 1st and 4th positions, the anthrylene group may be bonded at the 1st and 2nd positions, or at the 1st and 4th positions, or at the 9th and 10th positions, and any of these may be used.

[0072] The alkyl group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, an isopropyl group, an n-butyl group, and a cyclohexyl group. The alkenyl group having 3 to 6 carbon atoms may be linear, branched, or cyclic, and examples thereof include a 2-propenyl group and a 3-butenyl group. The alkoxy group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and examples thereof include a methoxy group, an ethoxy group, an isopropoxy group, an n-pentyloxy group, and a cyclohexyloxy group. The alkylthio group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and examples thereof include a methylthio group, an ethylthio group, an isopropylthio group, an n-pentylthio group, and a cyclohexylthio group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Also, R 1 and R 2 Examples of the ring having 3 to 6 carbon atoms formed by bonding include a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring.

[0073] The alkylene group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and examples thereof include a methylene group, an ethylene group, a propylene group, a pentamethylene group, a cyclohexylene group, and a 2-methylpropylene group.

[0074] In addition, in formula (A1), X 1 When X is a group represented by formula (A1-2), the structure is represented by formula (A2) below. 1 When R is a group represented by formula (A1-3), the structure is represented by formula (A3) below. 3 However, it is preferably a 2-propenyl group. [ka] (In formulas (A2) and (A3), A 1 ~A 6 , and Q 1 is A in formula (A1) 1 ~A 6 , and Q 1 are the same as R 1 and R 2 is R in formula (A1-2). 1 and R 2 are the same as R 3 is R in formula (A1-3) 3 is the same as

[0075] In formula (A1), Q 1 From the viewpoint of the heat resistance of the condensation polymer, it is preferable that Q contains a cyclic structure. 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).

[0076] As the repeating unit represented by formula (A1), those represented by the following formulae (A4) to (A22) are preferred: In the following formulae, Me is a methyl group, and Et is an ethyl group. [ka] [ka] [ka] [ka] [ka] The condensation polymer having a repeating unit represented by the formula (A1) can be synthesized, for example, by referring to WO 2005 / 098542.

[0077] ---Vinyl polymer--- The vinyl polymer refers to a polymer obtained by polymerizing a monomer having a polymerizable unsaturated double bond, such as an acrylic acid ester, a methacrylic acid ester, or styrene. A vinyl polymer having no cleavage structure can be obtained, for example, by polymerizing a monomer having a polymerizable unsaturated double bond having no cleavage structure.

[0078] Examples of the monomer having a polymerizable unsaturated double bond include a monomer having a carboxy group, a monomer having an epoxy group, an acrylic acid ester compound, a methacrylic acid ester compound, a maleimide compound, an acrylamide compound, acrylonitrile, maleic anhydride, a styrene compound, and a vinyl compound.

[0079] Examples of monomers having a carboxy 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. As these monomers, for example, commercially available products such as "Light Ester HO-MS," "Light Acrylate HOA-MS(N)," "Light Acrylate HOA-HH(N)," and "Light Acrylate HOA-MPL(N)" (all of which are product names manufactured by Kyoeisha Chemical Co., Ltd.), Aronix (registered trademark) M-5300, Aronix (registered trademark) M-5400 (all of which are product names manufactured by Toagosei Co., Ltd.), A-SA, and SA (all of which are product names manufactured by Shin-Nakamura Chemical Co., Ltd.) can be used.

[0080] Examples of monomers having an epoxy group include glycidyl methacrylate, glycidyl acrylate, 4-hydroxybutyl methacrylate glycidyl ether, allyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.

[0081] Examples of acrylic acid ester compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthrylmethyl 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.

[0082] Examples of methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl 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.

[0083] Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0084] Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

[0085] Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, and vinyl carbazole.

[0086] The vinyl polymer can be obtained by a known method, for example, by radical polymerization of one or more monomers having a polymerizable unsaturated double bond.

[0087] The polymer preferably has reactive groups capable of reacting with a crosslinking agent. For example, when the crosslinking agent has an epoxy group, examples of the reactive group include an epoxy group, an amino group, a carboxy group, and a phenolic hydroxyl group. For example, when the crosslinking agent has an alkoxymethyl group or a methylol group, the reactive group may be an alkoxymethyl group, a methylol group, or the like. For example, when the crosslinking agent has an isocyanate group, examples of the reactive group include a carboxy group and a hydroxy group.

[0088] The molecular weight of the polymer (polymer with cleavage structure and polymer without 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.

[0089] The content of the polymer in the release layer-forming composition is not particularly limited, but is preferably 10% by mass to 99.5% by mass, more preferably 30% by mass to 95% by mass, and particularly preferably 50% by mass to 90% by mass, based on the film-forming components. These contents may be the content of only the polymer having a cleavage structure, the content of only the polymer not having a cleavage structure, or the total content of the polymer having a cleavage structure and the polymer not having a cleavage structure.

[0090] -Crosslinking agent- The crosslinking agent may or may not have a cleavage structure. When the crosslinking agent has a cleavage structure, the number of cleavage structures contained in the crosslinking agent may be one or may be two or more. When the crosslinking agent has one or the other of two partial structures that can react with each other to form a cleavage structure, the number of such partial structures contained in the crosslinking agent may be one or two or more.

[0091] Examples of the crosslinking agent include epoxy compounds, methylol compounds, and isocyanate compounds. An epoxy compound is a compound having two or more epoxy groups. The methylol compound is a compound having at least one of a methylol group and an alkoxymethyl group, and the total number of methylol groups and alkoxymethyl groups is two or more. The isocyanate compound is a compound having at least one of an isocyanate group and a blocked isocyanate group, and the total number of isocyanate groups and blocked isocyanate groups is two or more.

[0092] --Crosslinking agent having a cleavage structure-- Examples of the crosslinking agent having a cleavage structure include an epoxy compound, a methylol compound, and an isocyanate compound. The number of cleavage structures contained in the crosslinking agent having a cleavage structure may be one or two or more. The crosslinking agent having a cleavage structure is represented by, for example, the following formula (B1) or (B2).

[0093] [ka] (In formula (B1), X represents a cleavage structure. L 1 and L 2 Each of Y independently represents a single bond or a linking group. 1 and Y 2each independently represents an epoxy group, an alkoxyalkyl group, a methylol group, or an isocyanate group. In formula (B2), n represents an integer of 3 to 6. Z represents an n-valent group. Each X independently represents a cleavage structure. Each L independently represents a single bond or a linking group. Each Y independently represents an epoxy group, an alkoxyalkyl group, a methylol group, or an isocyanate group.

[0094] X (cleavage structure) in formula (B1) and formula (B2) is, for example, a structure represented by any one of formulas (1) to (3). The linking group in formula (B1) and formula (B2) is not particularly limited as long as it is a divalent group. Examples of the linking group include divalent groups having 1 to 20 atoms. Z in formula (B2) is not particularly limited as long as it is an n-valent group. Examples of Z include n-valent groups having 5 to 30 atoms.

[0095] Specific examples of the crosslinking agent having a cleavable structure include the following compounds. [ka]

[0096] --Crosslinking agent without cleavage structure-- Examples of epoxy compounds that can be used as crosslinking agents without a cleavage structure include 1,2,7,8-diepoxyoctane, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,6-dimethylolperfluorohexane diglycidyl ether, (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol triglycidyl ether, diglycerol polyglycidyl ether, and trimethylolethane. Diglycidyl 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-glycidyloxyphenyl)ethane (epoxyphenyl)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-epoxycyclopentyl (3,4-epoxycyclohexyl)methyl cyclohexanecarboxylate, (4,5-epoxy-2-methylcyclohexyl)methyl 4,5-epoxy-2-methylcyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl) adipate, 1,2-epoxy-4-(epoxyethyl)cyclohexane, 4-(spiro[3,4-epoxycyclohexane-1,5'-[1,3]dioxane]-2'-yl)-1,2-epoxycyclohexane, diglycidyl adipate, diglycidyl phthalate, diglycidyl tetrahydrophthalate, 1,Diglycidyl 2-cyclohexanedicarboxylate, 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 -triazine-1,3,5-triyl)trippropanoate, 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), 2,2-bis(glycidyloxymethyl)butyl 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctanoate, 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, dicyclopentadiene novolac type epoxy resin, etc. Commercially available epoxy compounds include, for example, TEPIC (registered trademark)-G, S, SS, SP, L, HP, VL, FL, PAS B22, PAS B26, PAS B26L, UC, FOLDI (registered trademark)-E201 [all manufactured by Nissan Chemical Industries, Ltd.], jER (registered trademark) 828, 807, YX8000, 157S70 [all manufactured by Mitsubishi Chemical Corporation], Rikaresin (registered trademark) DME100 [manufactured by New Japan Chemical Co., Ltd.], Celloxide 2021P [manufactured by Daicel Corporation], EPICLON (registered trademark) HP-4700, HP-4710, HP-7200L [all manufactured by DIC Corporation], AV Light (registered trademark) TEP-G [manufactured by Asahi Organic Chemicals Co., Ltd.], and the like.

[0097] Examples of methylol compounds as crosslinking agents without a cleavage structure include alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, alkoxymethylated melamine, tetra(alkoxymethyl)bisphenol, and tetra(hydroxymethyl)bisphenol. Examples of alkoxymethylated glycolurils include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 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. Commercially available products include glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resin (trade name: UFR (registered trademark) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea / formaldehyde resins (high condensation type, trade names: Beckamin (registered trademark) J-300S, P-955, N) manufactured by DIC Corporation. Examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine, etc. Commercially available products include those manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123) and those manufactured by Sanwa Chemical Co., Ltd. (trade names: Nikalac (registered trademark) BX-4000, BX-37, BL-60, and BX-55H). Examples of alkoxymethylated melamine include hexamethoxymethyl melamine, etc. Commercially available products include methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, and 350) and butoxymethyl type melamine compounds (trade names: Mycoat (registered trademark) 506 and 508) manufactured by Mitsui Cytec Co., Ltd., methoxymethyl type melamine compounds (trade names: Nikalac (registered trademark) MW-30, MW-22, MW-11, MW-100LM, MS-001, MX-002, MX-730, MX-750, and MX-035) manufactured by Sanwa Chemical Co., Ltd., and butoxymethyl type melamine compounds (trade names: Nikalac (registered trademark) MX-45, MX-410, and MX-302) manufactured by Sanwa Chemical Co., Ltd. Examples of tetra(alkoxymethyl)bisphenols and tetra(hydroxymethyl)bisphenols include tetra(alkoxymethyl)bisphenol A, tetra(hydroxymethyl)bisphenol A, and the like.

[0098] When condition (B) is satisfied, a crosslinking agent having no cleavage structure can become a crosslinking agent having one or the other of two partial structures capable of forming a cleavage structure by reacting with each other. For example, an epoxy group, an alkoxymethyl group, a methylol group, an isocyanate group, etc. may react with the other of two partial structures capable of forming a cleavage structure to form a cleavage structure.

[0099] The molecular weight of the crosslinking agent (a crosslinking agent having a cleavage structure and a crosslinking agent not having a cleavage structure) is not particularly limited, but is preferably 2,000 or less, more preferably 1,500 or less.

[0100] The content of the crosslinking agent in the release layer-forming composition is not particularly limited, but is preferably 1% by mass to 100% by mass, more preferably 3% by mass to 80% by mass, and particularly preferably 5% by mass to 50% by mass relative to the polymer. These contents may be the content of only the crosslinking agent having a cleavage structure, the content of only the crosslinking agent not having a cleavage structure, or the total content of the crosslinking agent having a cleavage structure and the crosslinking agent not having a cleavage structure.

[0101] -Other ingredients- The release layer-forming composition may contain other components as film-forming components in addition to the polymer and the crosslinking agent, such as a curing catalyst, a surfactant, and a silane coupling agent.

[0102] --Curing catalyst-- The curing catalyst is effective in promoting the thermosetting reaction in forming a release layer using the release layer-forming composition. Examples of the curing catalyst include an acid and a thermal acid generator. The thermal acid generator is preferably a compound that thermally decomposes at a temperature of 80°C to 250°C to generate an acid.

[0103] Examples of the acid include sulfonic acids such as hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic 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, and dodecylbenzenesulfonic acid, as well as hydrates and salts thereof.

[0104] 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-phenylene tris(methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morpholinium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p-toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-tosylate, N-ethyl-4-toluenesulfonamide, and compounds represented by the following formulae [TAG-1] to [TAG-41]. [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0105] Examples of the thermal acid generator include onium salts such as iodonium salts, sulfonium salts, phosphonium salts, and selenium salts.

[0106] Examples of the iodonium in the iodonium salt 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 of the above iodonium such as chloride, bromide, mesylate, tosylate, trifluoromethanesulfonate, tetrafluoroborate, tetrakis(pentafluorophenyl)borate, hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate.

[0107] Examples of the sulfonium in the sulfonium salt 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 arylsulfonium salts of the above sulfoniums, such as chloride, bromide, trifluoromethanesulfonate, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, tetrakis(pentafluorophenyl)borate, and hexafluoroantimonate.

[0108] Examples of the phosphonium in the phosphonium salt include tetraphenylphosphonium, ethyltriphenylphosphonium, tetra(p-methoxyphenyl)phosphonium, ethyltri(p-methoxyphenyl)phosphonium, and benzyltriphenylphosphonium. Examples of the phosphonium salt include aryl phosphonium salts of the above phosphoniums, such as chlorides, bromides, tetrafluoroborates, hexafluorophosphates, and hexafluoroantimonates.

[0109] Selenium salts include triarylselenium salts such as triphenylselenium hexafluorophosphate.

[0110] The content of the acid or thermal acid generator in the composition for forming a release layer is preferably 0.01% by mass to 15% by mass, more preferably 0.1% by mass to 10% by mass, based on the polymer.

[0111] --Surfactants-- Adding a surfactant to the release layer-forming composition can improve the coatability of the release layer-forming composition. Examples of the surfactant include known surfactants such as nonionic surfactants, fluorine-based surfactants, and silicone-based surfactants. The surfactants can be used alone or in combination of two or more.

[0112] 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.

[0113] Examples of fluorine-based surfactants include F-TOP (registered trademark) EF301, EF303, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac (registered trademark) F171, F173, F554, F559, F563, R-30, R-40, R-40-LM, and DS-21 (manufactured by DIC Corporation), FLUORAD (registered trademark) FC430 and FC431 (manufactured by 3M), Asahiguard (registered trademark) AG710, and Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by AGC Corporation).

[0114] Examples of silicone surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0115] When the release layer-forming composition contains a surfactant, the content thereof is preferably 0.0001% by mass to 1% by mass, and more preferably 0.001% by mass to 0.5% by mass, based on the polymer.

[0116] --Silane coupling agent-- By adding a silane coupling agent to the release layer-forming composition, the adhesion of the release layer-forming composition to the substrate can be improved.

[0117] Examples of the silane coupling agent 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, and diethoxy(3-(meth)acryloyloxypropyl)silane; (meth)acrylic 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;Examples of suitable silane coupling agents include mercapto-based silane coupling agents such as 3-mercaptopropyltrimethoxysilane, triethoxy(3-mercaptopropyl)silane, (3-mercaptopropyl)(dimethoxy)(methyl)silane, and diethoxy(3-mercaptopropyl)(methyl)silane; sulfide-based silane coupling agents such as bis(3-trimethoxysilylpropyl)tetrasulfide and bis(3-triethoxysilylpropyl)tetrasulfide; and isocyanate-based silane coupling agents such as 3-isocyanatopropyltrimethoxysilane and triethoxy(3-isocyanatopropyl)silane. Among these, a silane coupling agent having the same reactive group as the crosslinking agent is preferred. For example, when the crosslinking agent has an epoxy group, an epoxy-based silane coupling agent is preferred as the silane coupling agent.

[0118] When the release layer-forming composition contains a silane coupling agent, the content thereof is preferably 0.1% by mass to 5% by mass, more preferably 0.3% by mass to 3% by mass, based on the polymer.

[0119] <<<Solvent>>> 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, and cyclic compound solvents having 3 to 20 carbon atoms.

[0120] Examples of glycol ether solvents include ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether, and propylene glycol monopropyl ether. Examples of the ester solvent include ethyl lactate, γ-butyrolactone, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate. Examples of ketone solvents include methyl ethyl ketone, cyclohexanone, cyclopentanone, and benzophenone. Examples of the cyclic compound solvent include N-methylpyrrolidone and γ-butyrolactone. These can be used alone or in combination of two or more.

[0121] The content of the solvent in the composition for forming a release layer is preferably an amount that results in a concentration of the film-forming components of the composition for forming a release layer of 0.1% by mass to 40% by mass, more preferably an amount that results in a concentration of 0.5% by mass to 20% by mass, and particularly preferably an amount that results in a concentration of 0.5% by mass to 10% by mass.

[0122] The method for preparing the composition for forming the release layer is not particularly limited, and any known method capable of uniformly mixing the components can be used.

[0123] The thickness of the release 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] <Resin layer> The resin layer is formed from a resin layer precursor. The resin layer precursor is formed from, for example, a resin layer-forming composition. The resin layer precursor is, for example, a layer obtained by applying a resin layer-forming composition.

[0125] The resin layer precursor has a second reactive group that can react with the first reactive group. The release layer has the first reactive group and the resin layer precursor has the second reactive group, thereby improving the adhesion between the release layer and the resin layer.

[0126] The first reactive group and the second reactive group may be the same reactive group or different reactive groups. When the first reactive group and the second reactive group are the same reactive group, the combination of the first reactive group and the second reactive group may be, for example, a combination in which both the first reactive group and the second reactive group are epoxy groups. At least one of the epoxy groups of the first reactive group and the second reactive group may be an alicyclic epoxy group. When the first reactive group and the second reactive group are different reactive groups, an example of the combination of the first reactive group and the second reactive group is a combination in which the first reactive group is an alkoxyalkyl group and the second reactive group is an epoxy group.

[0127] <<Composition for forming resin layer>> The resin layer-forming composition contains, for example, a resin and a crosslinking agent having a second reactive group.

[0128] Examples of the resin include polyethylene terephthalate, polyethylene naphthalate, polypropylene, cycloolefin polymer, polyamide, polyethersulfone, polymethyl methacrylate, polycarbonate, polyarylate, polyimide, and polyurethane.

[0129] The crosslinking agent having a second reactive group is not particularly limited, but examples thereof include epoxy compounds. The epoxy compound is not particularly limited as long as it is a compound having two or more epoxy groups, and examples thereof include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, and hydrogenated bisphenol S diglycidyl ether. bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis(3,4- Examples of the epoxy ether include 3,4-epoxycyclohexane, dicyclopentadiene diepoxide, di(3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis(3,4-epoxycyclohexanecarboxylate), 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ethers; polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to phenol, cresol, butylphenol, or these; glycidyl esters of higher fatty acids; silicone epoxy, and derivatives thereof.

[0130] Commercially available epoxy compounds include, for example, "Celloxide 2021P" (manufactured by Daicel Corporation), "Celloxide 2081" (manufactured by Daicel Corporation), "Epolead PB3600" (manufactured by Daicel Corporation), "Epolead PB4700" (manufactured by Daicel Corporation), and "Epolead GT401" (manufactured by Daicel Corporation).

[0131] The resin layer-forming composition may contain a solvent. Examples of the solvent include alcohol-based solvents such as methanol, ethanol, 2-propanol, 1-butanol, and 2-butanol; ether-based solvents such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, and propylene glycol monomethyl ether; ketone-based solvents such as acetone, 2-butanone, and methyl isobutyl ketone; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and dimethyl sulfoxide. ester-based solvents such as methyl acetate, ethyl acetate, and n-butyl acetate; nitrile-based solvents such as acetonitrile and benzonitrile; hydrocarbon solvents such as n-pentane, n-hexane, n-heptane, octane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, and mesitylene; halogenated hydrocarbon solvents such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, trichloroethane, monochlorobenzene, and dichlorobenzene; and water. These solvents may be used alone or in combination.

[0132] The resin content in the resin layer-forming composition is not particularly limited, but is preferably 30% by mass to 95% by mass, more preferably 45% by mass to 90% by mass, and particularly preferably 60% by mass to 85% by mass, based on the non-volatile content in the resin layer-forming composition. The content of the crosslinking agent having a second reactive group in the composition for forming a resin layer is not particularly limited, but is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 55% by mass, and particularly preferably 15% by mass to 40% by mass, relative to the non-volatile content in the composition for forming a resin layer.

[0133] The thickness of the resin layer is not particularly limited, but is preferably 0.1 μm to 50 μm, more preferably 0.5 μm to 30 μm, and particularly preferably 1 μm to 20 μm.

[0134] The laminate has, for example, a support, a release layer, and a resin layer in this order. In the laminate, the release layer and the resin layer are in contact with each other. In the laminate, the support and the release layer may be in contact with each other, or another layer may be interposed between the support and the release layer.

[0135] (Method of manufacturing laminate) The method for producing the laminate of the present invention includes the following steps (1) to (3). Step (1): A step of forming a release layer on a support that is transparent to active energy rays. Step (2): Forming a resin layer precursor on the release layer Step (3): A step of converting the resin layer precursor into a resin layer The release layer has a cleavage structure that absorbs active energy rays to cleave chemical bonds. The film-forming component has a first reactive group. The resin layer precursor has a second reactive group that can react with the first reactive group.

[0136] Specific examples and preferred examples of the support are the same as those of the support in the description of the laminate of the present invention. Specific examples and preferred examples of the release layer are the same as those of the release layer in the description of the laminate of the present invention. Specific examples and preferred examples of the resin layer precursor are the same as the specific examples and preferred examples of the resin layer precursor in the description of the laminate of the present invention. Specific examples and preferred examples of the resin layer are the same as the specific examples and preferred examples of the resin layer in the description of the laminate of the present invention.

[0137] <Process (1)> In step (1), the release layer is formed, for example, by applying a composition for forming a release layer and heating it.

[0138] The coating method is not particularly limited, and examples thereof include cast coating, spin coating, blade coating, dip coating, roll coating, bar coating, die coating, inkjet printing, and printing methods (relief printing, intaglio printing, lithography, screen printing, etc.).

[0139] Heating is performed, for example, to evaporate the solvent contained in the release layer-forming composition. Heating is also performed, for example, to form a crosslinked structure in the release layer. Furthermore, for example, when the film-forming component contained in the release layer-forming composition satisfies condition (B), heating is carried out to cause the two types of partial structures to react with each other to form a cleavage structure.

[0140] The heating temperature is not particularly limited. The heating temperature for evaporating the solvent contained in the release layer-forming composition is, for example, 40° C. to 100° C. The heating time is, for example, 1 minute to 1 hour. The heating temperature for forming a crosslinked structure in the release layer can be, for example, 120° C. to 200° C. The heating time can be, for example, 5 minutes to 2 hours. The heating temperature and time for reacting two types of partial structures with each other to form a cleavage structure can be appropriately selected depending on the type of reaction. The heating may also serve as heating for evaporating a solvent, heating for forming a crosslinked structure, etc. Heating may be carried out in stages, for example, by heating to 40°C to 100°C in the first stage and then heating to 120°C to 200°C in the second stage to form a release layer. Examples of heating devices include a hot plate and an oven. The heating atmosphere may be air or an inert gas, and may be atmospheric pressure or reduced pressure.

[0141] When the release layer-forming composition contains a polymer and a crosslinking agent, at least one of the polymer and the crosslinking agent reacts to form a crosslinked structure when the release layer is formed, for example.

[0142] <Process (2)> In step (2), the resin layer precursor is formed, for example, by applying a resin layer-forming composition and heating it.

[0143] The coating method is not particularly limited, and examples thereof include cast coating, spin coating, blade coating, dip coating, roll coating, bar coating, die coating, inkjet printing, and printing methods (relief printing, intaglio printing, lithography, screen printing, etc.). The heating temperature is not particularly limited as long as it is a temperature at which the solvent contained in the resin layer-forming composition can be evaporated, and may be, for example, 40°C to 100°C. The heating time is not particularly limited, and may be, for example, 1 minute to 1 hour. Examples of heating devices include a hot plate and an oven. The heating atmosphere may be air or an inert gas, and may be atmospheric pressure or reduced pressure.

[0144] <Process (3)> In step (3), the conversion from the resin layer precursor to the resin layer is carried out, for example, by heating the resin layer precursor.

[0145] The heating temperature is not particularly limited, and may be, for example, 120°C to 200°C. The heating time is not particularly limited, and may be, for example, 5 minutes to 2 hours. Examples of heating devices include a hot plate and an oven. The heating atmosphere may be air or an inert gas, and may be atmospheric pressure or reduced pressure.

[0146] When the resin layer precursor is converted into the resin layer, for example, a reaction takes place between the first reactive group of the release layer and the second reactive group of the resin layer precursor.

[0147] (Electronic device manufacturing method) The method for producing an electronic device of the present invention includes the following steps (I) and (II). Step (I): A step of forming at least one of a photoelectric conversion element, a display element, a member for a display element, and an electronic circuit on the resin layer of the laminate of the present invention or a laminate produced by the method for producing a laminate of the present invention. Step (II): A step of irradiating the release layer with active energy rays from the support side of the laminate, thereby peeling the support from the resin layer.

[0148] <Process (I)> In the step (I), the method for forming at least one of a photoelectric conversion element, a display element, a member for a display element, and an electronic circuit on the resin layer is not particularly limited, and known methods can be used. Examples of photoelectric conversion elements include light-emitting elements that convert electrical energy into light and light-receiving elements that convert light into electrical energy. Examples of light-emitting elements include light-emitting diodes and semiconductor lasers. Examples of light-receiving elements include photodiodes and phototransistors. Examples of display elements include liquid crystal display elements, inorganic EL (Electro Luminescence), and organic EL. Examples of display element members include transparent electrodes and color filters for touch panels. Examples of the electronic circuit include a capacitor and a transistor.

[0149] <Process (II)> In step (II), the amount of active energy rays irradiated toward the release layer is not particularly limited, and examples thereof include an irradiation amount that can reduce the peeling force of the release layer to an extent that the support can be peeled from the resin layer without damaging the support or the resin layer. Such an irradiation dose is, for example, 500 to 10,000 mJ / cm 2 (365nm equivalent). [Example]

[0150] The present invention will be explained in more detail below by way of synthesis examples, preparation examples, working examples and comparative examples, but the present invention is not limited to the following examples.

[0151] The compounds used in the following synthesis examples, preparation examples and working examples are as follows. [solvent] PGME: Propylene glycol monomethyl ether NMP: N-methylpyrrolidone BCS: Ethylene glycol monobutyl ether THF: tetrahydrofuran CHN: Cyclohexanone DMF: N,N-dimethylformamide DMSO: dimethyl sulfoxide [Crosslinking agent] PL: 1,3,4,6-tetrakis(methoxyethyl)glycoluril (Allnex, trade name: POWDERLINK 1174) TP: 1,3,5-triglycidyl isocyanurate (Nissan Chemical Industries, Ltd., trade name: TEPIC (registered trademark)-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)

[0152] The weight average molecular weight (Mw) of the polymer was measured using a GPC apparatus manufactured by Shimadzu Corporation (column: Shodex (registered trademark) KF803L and KF804L (manufactured by Showa Denko K.K.); eluent: THF, flow rate: 1.0 mL / min, column temperature: 40°C, Mw: value converted into standard polystyrene).

[0153] Also, 1 H-NMR measurements were performed using AVANCE III HD manufactured by Bruker, a measurement frequency of 500 MHz, a measurement solvent of deuterated chloroform manufactured by Kanto Chemical Co., Ltd. or deuterated DMSO manufactured by Kanto Chemical Co., Ltd., and an internal standard of tetramethylsilane (δ=0.00 ppm).

[0154] [1] Polymer synthesis [Synthesis Example 1] 5.00 g (28.87 mmol) of N-phenylmaleimide, 3.34 g (32.08 mmol) of styrene, 0.46 g (3.21 mmol) of glycidyl methacrylate, and 0.21 g of azobisisobutyronitrile as a polymerization catalyst were dissolved in 80.0 g of THF and reacted at 60 °C for 20 hours to obtain a polymer solution. The resulting polymer solution was slowly added dropwise to 500 g of methanol to precipitate a solid. The precipitated solid was filtered and dried under reduced pressure to obtain polymer (PA-1) without cleavage structures. The Mw of polymer (PA-1) was 21,000. [ka]

[0155] [Synthesis Example 2] 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 were dissolved in 50.0 g of PGME and reacted at 80°C for 20 hours to obtain a polymer solution. The resulting polymer solution was slowly added dropwise to 400 g of hexane to precipitate a solid. The precipitated solid was filtered and dried under reduced pressure to obtain a polymer (PA-2) containing no cleavage structures. The Mw of the polymer (PA-2) was 22,000. [ka]

[0156] [Synthesis Example 3] 4.58 g of 2-nitro-4-bromobenzyl alcohol and 3.23 g of 4-vinylphenylboronic acid were added to 9.9 g of potassium carbonate, 28 mL of water, 12 mL of ethanol, and 48 mL of toluene, and the mixture was stirred under nitrogen. 0.71 g of tetrakistriphenylphosphine palladium was then added and the reaction was carried out at 80°C for 4 hours. After the reaction was complete, the mixture was separated and extracted with chloroform, and concentrated and dried to obtain 6.35 g of a crude product. Column purification yielded 4.30 g of a monomer having a partial structure capable of forming a cleavage structure. 1 The results of H-NMR are shown below. 1 H-NMR (500MHz, CDCl3):δ 8.32(d,1H,J=2.0Hz),7.89(dd,1H,J=8.0,1.0Hz),7.80(d,1H,J=8.0Hz),7.59(d,2H,J=8.0Hz),7.53(d,2H,J=8.0Hz),6. 77(dd,1H,J=17.5,11.0Hz),5.83(d,1H,J=17.5Hz),5.33(d,1H,J=11.0Hz),5.01(d,2H,J=6.5Hz),2.58(t,1H,J=6.5Hz),

[0157] 1.18 g (4.62 mmol) of the resulting monomer, 2.00 g (11.55 mmol) of N-phenylmaleimide, 0.72 g (6.93 mmol) of styrene, and 0.08 g of azobisisobutyronitrile as a polymerization catalyst were dissolved in 35.8 g of THF and reacted at 60 °C for 20 hours to obtain a polymer solution. The resulting polymer solution was slowly added dropwise to 300 g of methanol to precipitate a solid. The precipitated solid was filtered and dried under reduced pressure to obtain polymer (PA-3), which contains a partial structure in the side chain that can react with PL to form a cleavage structure. The Mw of polymer (PA-3) was 22,000. [ka]

[0158] [Synthesis Example 4] 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 continued under ice cooling until the bubbling subsided, and then the reaction was continued at room temperature overnight. After the reaction was completed, the mixture was cooled on ice and quenched with ice water. Ethyl acetate was added, and the mixture was extracted and washed with saturated brine. 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 H-NMR 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).

[0159] 2.40 g (13.10 mmol) of the resulting 2-nitro-m-xylylene glycol, 2.24 g (12.84 mmol) of tolylene-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 resulting polymer solution was slowly added dropwise to 300 g of methanol to precipitate a solid. The precipitated solid was filtered and dried under reduced pressure to obtain a polymer (PA-4) containing a cleavage structure in the main chain. The Mw of the polymer (PA-4) was 18,000. [ka]

[0160] [Synthesis Example 5] 2.40 g of 2-nitro-m-xylylene glycol was obtained using a method similar to that of Synthesis Example 4. 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 slowly added dropwise to 300 g of methanol to precipitate a solid. The precipitated solid was filtered and dried under reduced pressure to obtain a polymer (PA-5) containing a cleavage structure in the main chain. The Mw of the polymer (PA-5) was 3,100. [ka]

[0161] [Synthesis Example 6] 12.05 g of 1,4-diacetylbenzene and 12.46 g of hydroxylamine hydrochloride were added to 60 mL of DMF and reacted for 3 hours at 80° C. After the reaction was completed, 200 mL of water was added, and the solid was filtered, washed three times with water, and then dried to obtain 14.07 g of diol. 1 The results of H-NMR are shown below. 1H-NMR (500MHz, DMSO-d6): δ 11.26(s,2H),7.67(s,4H),2.17(s,6H).

[0162] 1.70 g (8.84 mmol) of the resulting diol, 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 resulting polymer solution was slowly added dropwise to 300 g of methanol to precipitate a solid. The precipitated solid was filtered and dried under reduced pressure to obtain a polymer (PA-6) containing a cleavage structure in the main chain. [ka]

[0163] [Synthesis Example 7] 4.00 g (28.97 mmol) of p-xylylene glycol, 4.54 g (26.08 mmol) of tolylene-2,4-diisocyanate, and 0.02 g of dibutyltin dilaurate as a polymerization catalyst were dissolved in 34.2 g of THF and reacted under reflux for 20 hours to obtain a polymer solution. The resulting polymer solution was slowly added dropwise to 300 g of methanol to precipitate a solid. The precipitated solid was filtered and dried under reduced pressure to obtain a polymer (PA-7) containing no cleavage structures. The Mw of the polymer (PA-7) was 21,000. [ka]

[0164] [2] Synthesis of crosslinking agent [Synthesis Example 8] 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, and the solid was filtered, washed three times with water, and dried to yield 11.96 g of 1,3,5-triacetylbenzene oxime. 1.81 g of the resulting 1,3,5-triacetylbenzene oxime and 2.93 g of 2-allyloxypropionic acid were added to 40 mL of THF and stirred. 5.43 g of 1-(dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 4.46 g of 1-hydroxybenzotriazole were added and reacted overnight at room temperature. After the reaction was complete, the mixture was separated and extracted with ethyl acetate, washed with aqueous sodium bicarbonate, and then concentrated and dried to yield 4.12 g of crude product. The resulting crude product was purified by column chromatography to yield 3.78 g of 1,3,5-triacetylbenzene oxime 2-allyloxypropionic acid ester. 60 mL of chloroform was added to 3.78 g of the resulting 1,3,5-triacetylbenzene oxime 2-allyloxypropionate, and the mixture was stirred under ice cooling. 6.28 g of m-chloroperbenzoic acid was then added and the mixture was allowed to react overnight. After the reaction was complete, the mixture was separated and extracted with chloroform, washed three times with aqueous sodium bicarbonate, and then concentrated and dried to obtain 5.8 g of a crude product. The resulting crude product was purified using a column to obtain 2.0 g of crosslinker (B-1) containing a cleavage structure. 1 The results of H-NMR 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,11 .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]

[0165] [3] Preparation of composition for forming resin substrate [Preparation Example 1] Preparation of composition F1 for forming resin substrate 10 g of Zeonor (registered trademark) 1020R (a cycloolefin polymer manufactured by Zeon Corporation) and 3 g of Epolead (registered trademark) GT401 (an epoxy compound manufactured by Daicel Corporation) were added to an eggplant flask containing 100 g of carbon tetrachloride. The solution was stirred for 24 hours under a nitrogen atmosphere to dissolve the solution, thereby preparing a composition F1 for forming a resin substrate.

[0166] [4] Preparation of release layer-forming composition [Example 1-1] A mixture was obtained by mixing 100 parts by mass of (PA-1) as a polymer, 30 parts by mass of B-1 as a crosslinking agent, and 1 part by mass of SI as a curing catalyst. CHN was added to the mixture as a solvent to prepare a release layer-forming composition (A-1) with a solid content of 5.0% by mass.

[0167] [Examples 1-2 to 1-7, Comparative Examples 1-1 and 1-2] Compositions A-2 to A-9 for forming a release layer were prepared in the same manner as in Example 1-1, except that the types and amounts of the components were as shown in Table 1.

[0168] [Table 1]

[0169] [5] Preparation and evaluation of the release layer [Example 2-1] Using a spin coater (conditions: rotation speed 800 rpm, approximately 30 seconds), the release layer-forming composition (A-1) was applied to a glass substrate (Corning Eagle XG, 100 mm x 100 mm x 0.7 mm) as a base. The resulting coating was heated on a hot plate at 80°C for 2 minutes, then at 150°C for 10 minutes, forming a release layer approximately 0.1 μm thick on the glass substrate. Subsequently, using a spin coater (conditions: rotation speed 500 rpm, approximately 30 seconds), the resin substrate-forming composition F1 was applied to the entire surface of the glass substrate on which the release layer had been formed. The resulting coating was heated on a hot plate at 80°C for 2 minutes to form a resin precursor, which was then heated on a hot plate at 150°C for 30 minutes to form a resin substrate (resin layer) approximately 3 μm thick on the release layer, yielding a glass substrate with a resin substrate and release layer.

[0170] [Examples 2-2 to 2-7, Comparative Examples 2-1 and 2-2] Examples 2-2 to 2-7 and Comparative Examples 2-1 and 2-2 were obtained in the same manner as Example 2-1, except that compositions (A-2) to (A-9) for forming a release layer were used instead of composition (A-1) for forming a release layer, and the heating temperature using a hot plate was changed to the temperature listed in the "Heating temperature" column of Table 2.

[0171] [Comparative Example 2-3] Using a spin coater (conditions: rotation speed 500 rpm for approximately 30 seconds), the resin substrate-forming composition F1 was applied onto a glass substrate (Corning Eagle XG, 100 mm × 100 mm × 0.7 mm) as a base. The resulting coating film 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 a resin substrate with a thickness of approximately 3 μm on the glass substrate, thereby obtaining a glass substrate with a resin substrate.

[0172] [Evaluation of peeling force] For the glass substrates with a resin substrate and a release layer obtained in Examples 2-1 to 2-7 and Comparative Examples 2-1 and 2-2, and the glass substrate with a resin substrate obtained in Comparative Example 2-3, ultraviolet light was applied at 2000 mJ / cm from a high-pressure mercury lamp to half of the surface on which the resin substrate was formed, through a cut filter that absorbs light with a wavelength of 300 nm or less. 2 The glass substrate was irradiated with 1000 kJ / cm² (365 nm equivalent). Then, 25 mm x 50 mm strips were cut using a cutter in each of the exposed and unexposed areas. Cellotape (registered trademark) (CT-24, manufactured by Nichiban Co., Ltd.) was then applied to the resin substrate, and the resin substrate was peeled off at a peel angle of 90° and a peel speed of 300 mm / min using an autograph AGS-X500N (manufactured by Shimadzu Corporation), and the peel strength was measured. When the resin substrate could not be peeled off from the glass substrate, peeling occurred at the interface between the resin substrate and the Cellotape (registered trademark). The peel strength at this time was approximately 8.0 N / 25 mm, and the result was rated as "unpeelable (>8.0)." The evaluation results were reported as "peel strength," and the results for the exposed and unexposed areas are summarized in Table 2.

[0173] [Table 2]

[0174] From the results shown in Table 2, in the Examples, the resin substrate was either not peelable or showed a high peel strength before exposure, whereas after exposure the resin substrate was peelable and showed a low peel strength. On the other hand, in the comparative example, the resin substrate could not be peeled off regardless of whether it was exposed to light or not.

Claims

1. A laminate comprising a support that is transparent to active energy rays, a release layer on the support, and a resin layer on the release layer, the release layer has a cleavage structure that absorbs the active energy ray to cleave a chemical bond, a first reactive group of the release layer reacts with a second reactive group of the resin layer at an interface between the release layer and the resin layer; the first reactive group and the second reactive group are both epoxy groups, or the first reactive group is an alkoxyalkyl group and the second reactive group is an epoxy group; Laminate.

2. The laminate according to claim 1, wherein the cleavage structure includes 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 benzil ketal structure.

3. the cleavage structure includes 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 a structure represented by the following formula (2): The acetophenone structure is a structure represented by the following formula (3): The laminate according to claim 2 . 【Chemistry 1】 (In formula (1), R １ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, a heterocycle-containing 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 heterocycle-containing group have been replaced with a divalent group selected from the following Group I: Group I includes —O—, —C(═O)—, —C(═O)O—, —N(—R ３ ) -, -N(-R ３ )C(=O)-, -S-, -C(=S)-, -SO ２ -, -SC(=O)-, and -OC(=S)-, and R ３ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, n1 represents 0 or 1; n2 represents 0 or 1. In formula (2), R １１ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, a heterocycle-containing 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 heterocycle-containing group have been replaced with a divalent group selected from the following Group I: Group I includes —O—, —C(═O)—, —C(═O)O—, —N(—R ３ ) -, -N(-R ３ )C(=O)-, -S-, -C(=S)-, -SO ２ -, -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 heterocycle-containing group having 2 to 30 carbon atoms, n11 represents 0 or 1; n12 represents an integer of 0 to 3, and 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 heterocycle-containing group having 2 to 30 carbon atoms, n21 represents an integer of 0 to 4, and 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.

4. The laminate according to claim 1 , wherein the first reactive group and the second reactive group are the same reactive group.

5. a step of forming a release layer on a support that is transparent to active energy rays from a release layer-forming composition that contains a film-forming component and a solvent; forming a resin layer precursor on the release layer; converting the resin layer precursor into a resin layer; A method for producing a laminate, comprising: the release layer has a cleavage structure that absorbs the active energy ray to cleave a chemical bond, the film-forming component has a first reactive group; the resin layer precursor has a second reactive group capable of reacting with the first reactive group, the first reactive group and the second reactive group are both epoxy groups, or the first reactive group is an alkoxyalkyl group and the second reactive group is an epoxy group; A method for manufacturing a laminate.

6. The method for producing a laminate according to claim 5 , which satisfies at least one of 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 structures that can react with each other to form the cleavage structure.

7. 6. The method for producing a laminate according to claim 5, wherein the cleavage structure includes 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.

8. the cleavage structure includes 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 a structure represented by the following formula (2): The acetophenone structure is a structure represented by the following formula (3): A method for producing the laminate according to claim 7. 【Chemistry 2】 (In formula (1), R １ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, a heterocycle-containing 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 heterocycle-containing group have been replaced with a divalent group selected from the following Group I: Group I includes —O—, —C(═O)—, —C(═O)O—, —N(—R ３ ) -, -N(-R ３ )C(=O)-, -S-, -C(=S)-, -SO ２ -, -SC(=O)-, and -OC(=S)-, and R ３ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, n1 represents 0 or 1; n2 represents 0 or 1. In formula (2), R １１ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, a heterocycle-containing 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 heterocycle-containing group have been replaced with a divalent group selected from the following Group I: Group I includes —O—, —C(═O)—, —C(═O)O—, —N(—R ３ ) -, -N(-R ３ )C(=O)-, -S-, -C(=S)-, -SO ２ -, -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 heterocycle-containing group having 2 to 30 carbon atoms, n11 represents 0 or 1; n12 represents an integer of 0 to 3, and 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 heterocycle-containing group having 2 to 30 carbon atoms, n21 represents an integer of 0 to 4, and 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.

9. The condition (A) is satisfied, the film-forming component comprises a polymer and a crosslinker; the crosslinker has the first reactive group and the cleavage structure; A method for producing the laminate according to claim 6.

10. The condition (A) is satisfied, the film-forming component comprises a polymer and a crosslinker; the polymer has the cleavage structure, the crosslinker has the first reactive group; A method for producing the laminate according to claim 6.

11. The condition (B) is satisfied, the film-forming component comprises a polymer and a crosslinker; the polymer has one of two moieties capable of reacting with each other to form the cleavage structure, the crosslinker has the first reactive group; A method for producing the laminate according to claim 6.

12. The method for producing a laminate according to claim 5 , wherein the first reactive group and the second reactive group are the same reactive group.

13. The method for producing a laminate according to claim 5 , wherein the resin layer precursor is formed from a resin layer-forming composition containing a resin and a crosslinking agent having the second reactive group.

14. A step of forming at least one of a photoelectric conversion element, a display element, a member for a display element, and an electronic circuit on the resin layer of any of the laminates according to any one of claims 1 to 4 and the laminates manufactured by the manufacturing method of a laminate according to any one of claims 5 to 13; a step of irradiating the active energy rays from the support side of the laminate toward the release layer, thereby peeling the support from the resin layer; A method for manufacturing an electronic device, comprising:

15. A peeling layer-forming composition used in the method for producing the laminate according to claim 6, Contains a film-forming component and a solvent, At least one of the following conditions (A) and (B) is satisfied: the film-forming component has a first reactive group; A release layer-forming composition. Condition (A): The film-forming component has the cleavage structure. Condition (B): The film-forming component has two types of partial structures that can react with each other to form the cleavage structure.

16. The release layer-forming composition according to claim 15, wherein the cleavage structure includes 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 benzil ketal structure.

17. the cleavage structure includes 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 a structure represented by the following formula (2): The acetophenone structure is a structure represented by the following formula (3): The release layer-forming composition according to claim 16 . 【Transformation 3】 (In formula (1), R １ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, a heterocycle-containing 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 heterocycle-containing group have been replaced with a divalent group selected from the following Group I: Group I includes —O—, —C(═O)—, —C(═O)O—, —N(—R ３ ) -, -N(-R ３ )C(=O)-, -S-, -C(=S)-, -SO ２ -, -SC(=O)-, and -OC(=S)-, and R ３ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, n1 represents 0 or 1; n2 represents 0 or 1. In formula (2), R １１ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, a heterocycle-containing 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 heterocycle-containing group have been replaced with a divalent group selected from the following Group I: Group I includes —O—, —C(═O)—, —C(═O)O—, —N(—R ３ ) -, -N(-R ３ )C(=O)-, -S-, -C(=S)-, -SO ２ -, -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 heterocycle-containing group having 2 to 30 carbon atoms, n11 represents 0 or 1; n12 represents an integer of 0 to 3, and 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 heterocycle-containing group having 2 to 30 carbon atoms, n21 represents an integer of 0 to 4, and 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.

18. The condition (A) is satisfied, the film-forming component comprises a polymer and a crosslinker; the crosslinker has the first reactive group and the cleavage structure; The release layer-forming composition according to claim 15 .

19. The condition (A) is satisfied, the film-forming component comprises a polymer and a crosslinker; the polymer has the cleavage structure, the crosslinker has the first reactive group; The release layer-forming composition according to claim 15 .

20. The condition (B) is satisfied, the film-forming component comprises a polymer and a crosslinker; the polymer has one of two moieties capable of reacting with each other to form the cleavage structure, the crosslinker has the first reactive group; The release layer-forming composition according to claim 15 .

21. The release layer-forming composition according to claim 15 , wherein the first reactive group and the second reactive group of the resin layer precursor are the same reactive group.

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