CN118103209A

CN118103209A - Composition for forming release layer, laminate, and method for producing laminate

Info

Publication number: CN118103209A
Application number: CN202280069688.1A
Authority: CN
Inventors: 伊藤润; 武山敏明
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2021-10-26
Filing date: 2022-09-15
Publication date: 2024-05-28
Also published as: TW202323041A; WO2023074171A1

Abstract

The present invention relates to a laminate, which has: a support having transparency to active energy rays, a release layer on the support, and a resin layer on the release layer, wherein the release layer is formed from a composition for forming a release layer 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 capable of absorbing the active energy rays and causing cleavage of chemical bonds, 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

Composition for forming release layer, laminate, and method for producing laminate

Technical Field

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

Background

In recent years, in addition to characteristics such as thickness reduction and weight reduction, electronic devices are required to have a function of being bendable. Accordingly, a lightweight flexible plastic substrate is required to be used instead of the conventional heavy, fragile, and inflexible glass substrate.

In particular, in a new-generation display, development of an active matrix full-color TFT display panel using a lightweight flexible plastic substrate (hereinafter, also referred to as a resin substrate) is demanded. In addition, materials corresponding to flexibility such as transparent electrodes and resin substrates of touch panels used in combination with display panels have been developed for touch panel type displays. As the transparent electrode, conventionally used ITO has been proposed as another transparent electrode material such as a transparent conductive polymer capable of being bent such as PEDOT, a metal nanowire, or a mixed system thereof (patent documents 1 to 4).

On the other hand, a transparent flexible touch panel having flexibility has been developed in which a substrate of a touch panel film is changed from glass to a sheet made of plastic such as polyethylene terephthalate (PET), polyimide, cycloolefin, or acrylic (patent documents 5 to 7).

In general, in order to stably produce a flexible touch panel, a release (adhesive) layer is formed on a support substrate such as a glass substrate, a device made of a resin substrate or the like is formed thereon, and then the device is released from the adhesive layer to produce the flexible touch panel (patent document 8).

A device made of a resin substrate or the like formed on the release layer cannot be peeled from the support substrate in the process, but a low peeling force is required for peeling. In particular, when the support substrate is peeled off in the production process, the yield may be greatly reduced. The problem is not limited to the flexible touch panel, and is encountered in devices using a resin substrate.

Prior art literature

Patent literature

Patent document 1: international publication No. 2012/147235

Patent document 2: japanese patent laid-open No. 2009-283410

Patent document 3: japanese patent application laid-open No. 2010-507199

Patent document 4: japanese patent laid-open No. 2009-205924

Patent document 5: international publication No. 2017/002664

Patent document 6: japanese patent laid-open publication 2016-160338

Patent document 7: japanese patent application laid-open No. 2015-166145

Patent document 8: japanese patent laid-open publication 2016-531358

Disclosure of Invention

Technical problem to be solved by the invention

The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a laminate which is less likely to be peeled off during the production of a device or the like, and which is easily peeled off by irradiation with active energy rays after the production of a device or the like.

The present invention also provides a method for producing the laminate, a method for producing an electronic device using the laminate, and a composition for forming a release layer used for producing the laminate.

Technical scheme for solving technical problems

The present inventors have conducted intensive studies to solve the above-described problems, and as a result, have found that the above-described problems can be solved, and have completed the present invention having the following gist.

Namely, the present invention includes the following.

[1] A laminate, comprising: a support having a transmission of active energy rays, a release layer on the support, and a resin layer on the release layer,

The release layer is formed from a composition for forming a release layer 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 capable of absorbing the active energy rays to undergo chemical bond cleavage,

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.

[2] The laminate according to [1], which satisfies at least any one of the following conditions (A) and (B).

Condition (a): the film forming component has the fracture structure.

Condition (B): the film forming component has 2 partial structures capable of reacting with each other to form the cleavage structure.

[3] The laminate according to [1] or [2], wherein the cleavage structure comprises at least any one of an oxime ester structure, an oxime ether structure, an o-nitrobenzyl structure, an acetophenone structure, an alkylbenzene ketone structure, a pyrenylmethyl structure, a coumarin ylmethyl (Coumarinyl Methyl) structure, an aminoalkyl ketone structure, and a benzyl ketal (benzylketal) structure.

[4] The laminate according to [3], wherein the cleavage structure comprises at least any 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 shown in the following formula (1),

The o-nitrobenzyl structure is shown in the following formula (2),

The acetophenone structure is shown in the following formula (3).

[ Chemical 1]

(In the 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 heterocyclic group having 2 to 30 carbon atoms, or a group in which 1 or not adjacent 2 or more of the hydrocarbon groups or methylene groups in the heterocyclic group are replaced with a 2-valent group selected from the group I,

Group I is-O-, -C (=O) O-, -N (-R ³)-、-N(-R³)C(＝O)-、-S-、-C(＝S)-、-SO₂ -, -SC (=O) -and-OC (=S) -, R ³ represents hydrogen atom or hydrocarbon group having 1-30 carbon atoms,

N1 represents 0 or 1 and is preferably selected from the group consisting of,

N2 represents 0 or 1.

In the 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 heterocyclic group having 2 to 30 carbon atoms, or a group in which 1 or not adjacent 2 or more of the hydrocarbon groups or methylene groups in the heterocyclic group are replaced with a 2-valent group selected from the group I,

R ¹² represents a halogen atom, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms,

N11 represents a group consisting of 0 and 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 the 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 the formulas (1) to (3), the bonding bond is represented. )

[5] The laminate according to any one of [2] to [4], which satisfies the condition (A),

The film forming component comprises a polymer and a cross-linking agent,

The crosslinker has the first reactive group and the cleavage structure.

[6] The laminate according to any one of [2] to [4], which satisfies the condition (A),

The film forming component comprises a polymer and a cross-linking agent,

The polymer has the above-mentioned broken structure,

The crosslinker has the first reactive group.

[7] The laminate according to any one of [2] to [4], which satisfies the condition (B),

The film forming component comprises a polymer and a cross-linking agent,

The polymer has one of 2 partial structures capable of reacting with each other to form the cleavage structure,

The crosslinker has the first reactive group.

[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 method for producing a laminate, comprising the steps of: a step of forming a release layer on a support having a transmission property for active energy rays,

A step of forming a resin layer precursor on the release layer, and

A step of converting the resin layer precursor into a resin layer,

The film forming component has a first reactive group,

[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 fracture structure.

[11] The method for producing a laminate according to [9] or [10], wherein the cleavage structure comprises at least any one of an oxime ester structure, an oxime ether structure, an o-nitrobenzyl structure, an acetophenone structure, an alkyl benzophenone structure, a pyrenylmethyl structure, a coumarin ylmethyl structure, an aminoalkylbenzophenone structure, and a benzyl ketal structure.

[12] The method for producing a laminate according to [11], wherein the cleavage structure comprises at least any one of the oxime ester structure, the oxime ether structure, the o-nitrobenzyl structure and the acetophenone structure,

The o-nitrobenzyl structure is shown in the following formula (2),

The acetophenone structure is shown in the following formula (3).

[ Chemical 2]

N1 represents 0 or 1 and is preferably selected from the group consisting of,

N2 represents 0 or 1.

N11 represents a group consisting of 0 and 1,

N22 represents 0 or 1.

In the formulas (1) to (3), the bonding bond is represented. )

[13] The method for producing a laminate according to any one of [10] to [12], which satisfies the condition (A),

The film forming component comprises a polymer and a cross-linking agent,

The crosslinker has the first reactive group and the cleavage structure.

[14] The method for producing a laminate according to any one of [10] to [12], which satisfies the condition (A),

The film forming component comprises a polymer and a cross-linking agent,

The polymer has the above-mentioned broken structure,

The crosslinker has the first reactive group.

[15] The method for producing a laminate according to any one of [10] to [12], which satisfies the condition (B),

The film forming component comprises a polymer and a cross-linking agent,

The crosslinker has the first reactive group.

[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 resin layer-forming composition containing a resin and a crosslinking agent having the second reactive group.

[18] A method for manufacturing an electronic device, comprising: 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 one of the laminate of any one of [1] to [8] and the laminate produced by the method for producing a laminate of any one of [9] to [17], and

And a peeling step of irradiating the support side of the laminate with the active energy rays toward the peeling layer to peel the support from the resin layer.

[19] A composition for forming a release layer, which is used for any one of the production of a laminate according to [2] and the production method of a laminate according to [10],

Wherein the composition for forming a release layer contains a film-forming component and a solvent,

Which satisfies at least any one of the following conditions (A) and (B),

Condition (a): the film forming component has the fracture structure.

The film forming component has a first reactive group.

[20] The composition for forming a release layer according to [19], wherein the cleavage structure comprises at least any one of an oxime ester structure, an oxime ether structure, an o-nitrobenzyl structure, an acetophenone structure, an alkylbenzene ketone structure, a pyrenylmethyl structure, a coumarin ylmethyl structure, an aminoalkyl ketone structure, and a benzyl ketal structure.

[21] The composition for forming a release layer according to [20], wherein the cleavage structure comprises at least any one of the oxime ester structure, the oxime ether structure, the o-nitrobenzyl structure and the acetophenone structure,

The o-nitrobenzyl structure is shown in the following formula (2),

The acetophenone structure is shown in the following formula (3).

[ Chemical 3]

N1 represents 0 or 1 and is preferably selected from the group consisting of,

N2 represents 0 or 1.

N11 represents a group consisting of 0 and 1,

N22 represents 0 or 1.

In the formulas (1) to (3), the bonding bond is represented. )

[22] The composition for forming a release layer according to any one of [19] to [21], which satisfies the condition (A),

The film forming component comprises a polymer and a cross-linking agent,

The crosslinker has the first reactive group and the cleavage structure.

[23] The composition for forming a release layer according to any one of [19] to [21], which satisfies the condition (A),

The film forming component comprises a polymer and a cross-linking agent,

The polymer has the above-mentioned broken structure,

The crosslinker has the first reactive group.

[24] The composition for forming a release layer according to any one of [19] to [21], which satisfies the condition (B),

The film forming component comprises a polymer and a cross-linking agent,

The crosslinker has the first reactive group.

[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 of the resin layer precursor are the same reactive group.

Effects of the invention

According to the present invention, it is possible to provide a laminate which is not easily peeled off during the production of a device or the like, but which is easily peeled off by irradiation of active energy rays after the production of a device or the like.

Further, according to the present invention, a method for producing the laminate, a method for producing an electronic device using the laminate, and a composition for forming a release layer used for producing the laminate can be provided.

Detailed Description

(Laminate)

The laminate of the present invention comprises a support, a release layer, and a resin layer.

< Support body >)

The support is not particularly limited as long as it has a transmittance for active energy rays.

Examples of the material of the support include glass and resin. Among them, glass is preferable from the viewpoint of low bendability.

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

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, of light having a wavelength of 365 nm.

Examples of the active energy ray (active energy ray absorbed by the fracture structure) include ultraviolet rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable. The wavelength of ultraviolet light is, for example, 300nm to 380nm.

Examples of the light source used for ultraviolet irradiation include solar rays, 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 may be used, but in the case of using a laser, there is a possibility that damage may be caused to the support and the resin layer, and therefore, it is not preferable to use a laser.

< Peel-off layer >

The release layer is formed from a composition for forming a release layer, which contains a film-forming component and a solvent.

The release layer has a cleavage structure capable of absorbing active energy rays to cause cleavage of chemical bonds.

The release layer is disposed between the support and the resin layer.

The release layer is, for example, a layer obtained by applying a composition for forming a release layer and heating the same.

Composition for forming release layer

The composition for forming a release layer contains a film-forming component and a solvent.

The composition for forming a release layer is used, for example, for producing the laminate of the present invention. The composition for forming a release layer is used, for example, in the method for producing a laminate of the present invention. Such a composition for forming a release layer is also an object of the present invention.

The composition for forming a release layer is a composition for forming a release layer having a broken structure. The cleavage structure is a structure capable of absorbing active energy rays to cause cleavage of chemical bonds.

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 broken structure.

Condition (B): the film-forming component has 2 partial structures capable of reacting with each other to form a cleavage structure.

By providing the release layer with a fracture structure, if the release layer is irradiated with active energy rays, the adhesiveness between the support and the resin layer due to the release layer is reduced due to fracture of the fracture structure. As a result, the support and the resin layer can be easily separated.

Fracture structure

The cleavage structure is not particularly limited as long as it is a structure capable of absorbing active energy rays and causing cleavage of chemical bonds.

Examples of the cleavage structure include a cleavage structure that is reversibly cleaved and a cleavage structure that is irreversibly cleaved, and among these cleavage structures, a cleavage structure that is irreversibly cleaved is preferable. Irreversible cleavage refers to cleavage caused by an irreversible chemical reaction.

If the cleavage is reversible, after the occurrence of the cleavage of the chemical bond, the chemical bond may be unintentionally re-bonded, and as a result, the releasability of the support from the resin layer may be reduced. In this respect, the fracture structure is preferably a fracture structure that irreversibly breaks.

Examples of the active energy rays absorbed by the fracture structure include ultraviolet rays, electron beams, and X-rays, and ultraviolet rays are particularly preferred. The wavelength of ultraviolet light is, for example, 300 to 380nm.

The chemical bonds broken in the broken structure are typically covalent bonds. Examples of the broken covalent bond include a covalent bond between 2 heteroatoms, a covalent bond between a heteroatom and a carbon atom, and the like. Examples of the hetero atom include an oxygen atom and a nitrogen atom.

As the cleavage structure, at least any one of an oxime ester structure, an oxime ether structure, an o-nitrobenzyl structure, an acetophenone structure, an alkylbenzene ketone structure, a pyrenylmethyl structure, a coumarin ylmethyl structure, an aminoalkyl ketone structure, and a benzyl ketal structure is preferably contained, and at least any one of an oxime ester structure, an oxime ether structure, an o-nitrobenzyl structure, and an acetophenone structure is more preferably contained.

These fracture structures are broken by active energy rays of low energy, and therefore separation of the support and the resin layer can be performed at low energy.

Here, an example of breaking of the breaking structure is shown below. The following is an example of cleavage of the oxime ester structure.

[ Chemical 4]

The following is an example of cleavage of the o-nitrobenzyl structure.

[ Chemical 5]

The following is an example of cleavage of acetophenone structure.

[ Chemical 6]

The following is an example of cleavage of pyrenylmethyl structure.

[ Chemical 7]

The following is an example of cleavage of the coumarin-based methyl structure.

[ Chemical 8]

Examples of the oxime ester structure or oxime ether structure include a structure represented by the following formula (1).

Examples of the o-nitrobenzyl structure include a structure represented by the following formula (2).

Examples of the acetophenone structure include a structure represented by the following formula (3).

[ Chemical 9]

N1 represents 0 or 1 and is preferably selected from the group consisting of,

N2 represents 0 or 1.

N11 represents a group consisting of 0 and 1,

N22 represents 0 or 1.

In the formulas (1) to (3), the bonding bond is represented. )

Hydrocarbon radicals having 1 to 30 carbon atoms

The hydrocarbon group having 1 to 30 carbon atoms is not particularly limited, and examples thereof include: alkyl group having 1 to 30 carbon atoms, alkenyl group having 2 to 30 carbon atoms, cycloalkyl group having 3 to 30 carbon atoms, cycloalkylalkyl group having 4 to 30 carbon atoms, aryl group having 6 to 30 carbon atoms, aralkyl group having 7 to 30 carbon atoms, and the like. When the hydrocarbon group having 1 to 30 carbon atoms has a substituent, the number of carbon atoms is 1 to 30 as a whole.

The alkyl group having 1 to 30 carbon atoms may be linear or branched.

Examples of the linear alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and eicosyl groups.

Examples of the branched alkyl group include isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, tert-pentyl, isooctyl, 2-ethylhexyl, tert-octyl, isononyl, isodecyl and the like.

Among them, a linear alkyl group is preferable.

Further, from the viewpoint that the degradability of the release layer by the active energy ray becomes more excellent, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.

The alkenyl group having 2 to 30 carbon atoms may be chain-shaped or cyclic. When the alkenyl group is chain, the alkenyl group may be a terminal alkenyl group having an unsaturated bond at the terminal, or may be an internal alkenyl group having an unsaturated bond in the interior.

Examples of the terminal alkenyl group having 2 to 30 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 4-pentenyl, and 5-hexenyl.

Examples of the internal alkenyl group include a 2-butenyl group, a 3-pentenyl group, a 2-hexenyl group, a 3-hexenyl group, a 2-heptenyl group, a 3-heptenyl group, a 4-heptenyl group, a 3-octenyl group, a 3-nonenyl group, a 4-decenyl group, a 3-undecenyl group, and a 4-dodecenyl group.

Examples of the cyclic alkenyl group include 3-cyclohexenyl, 2, 5-cyclohexadienyl-1-methyl, and 4,8, 12-tetradecatrienyl allyl.

Among them, alkenyl groups having 2 to 10 carbon atoms are preferable from the viewpoint that the degradability of the release layer by active energy rays becomes more excellent.

Cycloalkyl having 3 to 30 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 30 carbon atoms as a whole.

Examples of the saturated monocyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl.

Examples of the saturated polycyclic alkyl group include adamantyl, decalinyl, octahydropentylene (Octahydropentalene group), bicyclo [1.1.1] pentyl, tetradecyl, and the like.

Among them, cycloalkyl groups having 3 to 10 carbon atoms are preferable from the viewpoint that the degradability of the release layer by active energy rays becomes more excellent.

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 the whole has 4 to 30 carbon atoms.

Cycloalkyl groups in cycloalkylalkyl groups may be monocyclic or polycyclic. In addition, the methylene group of the alkyl group in the cycloalkylalkyl group may be replaced by-ch=ch-.

Examples of the cycloalkylalkyl group having 4 to 30 carbon atoms 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 cyclopropylmethyl group, cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, cycloheptylmethyl group, cyclooctylmethyl group, cyclononylmethyl group, and 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 3-cyclobutylpropyl group, 3-cyclopentylpropyl group, 3-cyclohexylpropyl group, 3-cycloheptylpropyl group, 3-cyclooctylpropyl group, 3-cyclononylpropyl group, and 3-cyclodecylpropyl group.

Examples of the cycloalkylbutyl group include 4-cyclobutyl group, 4-cyclopentylbutyl group, 4-cyclohexylbutyl group, 4-cycloheptylbutyl group, 4-cyclooctylbutyl group, 4-cyclononylbutyl group, and 4-cyclodecylbutyl group.

Examples of the cycloalkylalkyl group having 4 to 20 carbon atoms in which the cycloalkyl group is polycyclic include bicyclo [1.1.0] butyl group, bicyclo [1.1.1] pentyl group, bicyclo [2.1.0] pentyl group, bicyclo [3.1.0] hexyl group, bicyclo [2.1.1] hexyl group, bicyclo [2.2.0] hexyl group, bicyclo [4.1.0] heptyl group, bicyclo [3.2.0] heptyl group, bicyclo [3.1.1] heptyl group, bicyclo [2.2.1] heptyl group, bicyclo [5.1.0] octyl group, bicyclo [4.2.0] octyl group, bicyclo [4.1.1] octyl group, bicyclo [3.3.0] octyl group, bicyclo [3.2.1] octyl group, bicyclo [2.2.2] octyl group, spiro [4,4] nonyl group, spiro [4,5] decyl group, and tricyclodecyl group.

Among them, cycloalkylalkyl groups having 4 to 10 carbon atoms are preferable from the viewpoint that the degradability of the release layer by active energy rays becomes more excellent.

The aryl group having 6 to 30 carbon atoms may have a monocyclic structure or a condensed ring structure. The aryl group may be a group in which an aryl group having a single ring structure is connected to an aryl group having a single ring structure, a group in which an aryl group having a single ring structure is connected to an aryl group having a fused ring structure, or a group in which an aryl group having a fused ring structure is connected to an aryl group having a fused ring structure.

Examples of the aryl group having a monocyclic structure include phenyl and biphenyl.

Examples of the aryl group having a condensed ring structure include naphthyl group, anthryl group, phenanthryl group and the like.

1 Or 2 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 alkyl group, the alkenyl group, the carboxyl group, and the halogen atom. Examples of the aryl group having a substituent having 6 to 30 carbon atoms include substituted aryl groups having a monocyclic structure such as tolyl, xylyl, ethylphenyl, 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl and 2,4, 6-trimethylphenyl.

Among them, from the viewpoint that the degradability of the release layer by active energy rays becomes more excellent, an aryl group having 6 to 10 carbon atoms is preferable.

The arylalkyl group having 7 to 30 carbon atoms is a group in which 1 or 2 or more hydrogen atoms of the alkyl group are substituted with the aryl group.

Examples of the arylalkyl group having 7 to 30 carbon atoms include phenylalkyl groups and naphthylalkyl groups.

Examples of the phenylalkyl group include benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, α -dimethylbenzyl, 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, diphenylmethyl, triphenylmethyl, and triphenylpropyl.

Examples of the naphthylalkyl group include naphthylpropyl group and the like.

Among them, from the viewpoint that the degradability of the release layer by active energy rays becomes more excellent, an arylalkyl group having 7 to 10 carbon atoms is preferable.

Heterocyclic group (group having 2 to 30 carbon atoms of the heterocyclic ring) containing 2 to 30 carbon atoms

The heterocycle in the heterocyclic group having 2 to 30 carbon atoms may have a monocyclic structure or a condensed ring structure. In addition, 1 or 2 or more hydrogen atoms of the heterocyclic ring may be substituted with an alkyl group having 1 to 6 carbon atoms. The heterocyclic ring may be a heterocyclic group having a condensed ring structure formed by bonding through an alkylene group having 1 to 6 carbon atoms.

Examples of the heterocyclic group containing a monocyclic heterocycle include a pyrrolyl group, a pyridyl group, a pyridylethyl group, a pyrimidinyl group, a pyridazinyl group, a piperazinyl group, a piperidyl group, a pyranyl group, a pyranylethyl group, a pyrazolyl group, a triazinylmethyl group, a pyrrolidinyl group, an imidazolyl group, a triazolyl group, a furyl group (furyl group), a furyl group (furanyl group), a thienyl group, a thiophenyl group, a thiadiazolyl group, a thiazolyl group, an oxazolyl group, an isothiazolyl group, an isoxazolyl group, a julolidine group (julolidyl group), a morpholinyl group, a thiomorpholinyl group, a 2-pyrrolidone-1-yl group (2-pyrrolidinone-1-yl) and a 2-piperidone-1-yl group (2-piperidone-1-yl) and a 2, 4-dioxazolid-3-yl group (2, 4-dioxyoxazolidin-3-yl) and the like.

Examples of the heterocyclic group containing a heterocyclic ring having a condensed ring structure include quinolinyl, isoquinolinyl, benzimidazolyl, benzofuranyl, benzothienyl, benzothiazolyl, benzoxazolyl, indolyl and the like.

Examples of the heterocyclic group include the following groups.

[ Chemical 10]

(Wherein R is each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Z is each independently a single bond or an alkylene group having 1 to 6 carbon atoms; and X is a bond.)

Examples of the alkyl group having 1 to 6 carbon atoms in R include the alkyl groups having 1 to 6 carbon atoms in the alkyl groups exemplified above as the alkyl groups having 1 to 30 carbon atoms.

Examples of the alkylene group having 1 to 6 carbon atoms in Z include methylene, ethylene, propylene, butylene, pentylene, and hexylene.

2 Partial structures capable of reacting with each other to form a fracture structure

The 2 kinds of partial structures capable of reacting with each other to form a cleavage structure are not particularly limited. Examples of the cleavage structure to be formed include an oxime ester structure, an o-nitrobenzyl structure, an alkylbenzene ketone structure, a pyrenylmethyl structure, a coumarin ylmethyl structure, an aminoalkyl ketone structure, and a benzyl ketal structure.

The following is an example of 2 partial structures that can react with each other to form a cleavage structure.

The formed cleavage structure is an o-nitrobenzyl structure.

One of the 2 partial structures is an o-nitrobenzyl alcohol structure, and if one example is given, the following structure is given.

[ Chemical 11]

(Wherein, represents a bond.)

The other of the 2 partial structures is, for example, an epoxy group, a hydroxymethyl group, an alkoxymethyl group, an isocyanate group, or a blocked isocyanate group, and if one of them is exemplified, the following structure is given.

[ Chemical 12]

(Wherein, represents a bond.)

By the mutual reaction of these 2 partial structures, the following cleavage structure (o-nitrobenzyl structure) is formed.

[ Chemical 13]

(Wherein, represents a bond.)

Such a reaction can be performed, for example, by applying a release layer-forming composition containing an acid catalyst to an object and then heating the same.

Examples of the acid catalyst include a curing catalyst described below.

Film forming component

The film-forming component is a component constituting the release layer when the release layer is formed from the composition for forming a release layer. Examples of the film-forming component include a component existing in the release layer in an original state, a component existing in the release layer as a reaction product with other components, a component used as an auxiliary agent (for example, a curing catalyst) for assisting a reaction of other components, and the like.

In other words, the film-forming component is a generic term for all components except the solvent in the composition for forming a release layer.

The film forming component has a first reactive group.

Examples of the film-forming component include a polymer and a crosslinking agent.

For example, the polymer may have a first reactive group, the crosslinker may have a first reactive group, and both the polymer and the crosslinker may have a first reactive group.

In the case where the condition (a) is satisfied, the film-forming component may contain a polymer. At this time, for example, the polymer has a broken structure. In this case, for example, the film-forming component contains 2 or more polymers, and at least 1 of the 2 or more polymers may have a broken structure.

The polymer may have the first reactive group and the cleavage structure, or may have the cleavage structure without the first reactive group.

When the condition (a) is satisfied, the film-forming component may contain a crosslinking agent. At this time, for example, the crosslinking agent has a broken structure. In this case, the film-forming component contains 2 or more kinds of crosslinking agents, and at least 1 of the 2 or more kinds of 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 the first reactive group.

In the case where the condition (a) is satisfied, the film-forming component may contain a polymer and a crosslinking agent. At this time, for example, at least any one of the polymer and the crosslinking agent has a broken 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 contains 2 or more polymers, and at least 1 of the 2 or more polymers may have a cleavage structure. In this case, the film-forming component contains 2 or more kinds of crosslinking agents, and at least 1 of the 2 or more kinds of crosslinking agents may have a cleavage structure.

The film forming component, for example, contains a polymer and a crosslinking agent having a first reactive group and a cleavage structure.

The film-forming component contains, for example, a polymer having a broken structure and a crosslinking agent having a first reactive group.

In the case where the condition (B) is satisfied, the film-forming component may contain a polymer and a crosslinking agent. At this time, for example, the polymer has one of 2 partial structures capable of reacting with each other to form a cleavage structure, and the crosslinking agent has the other of 2 partial structures. In this case, the film-forming component contains 2 or more polymers, and at least 1 of the 2 or more polymers may have one of 2 partial structures. In this case, the film-forming component contains 2 or more kinds of crosslinking agents, and at least 1 of the 2 or more kinds of crosslinking agents may have another one of the 2 kinds of partial structures.

The film-forming component contains, for example, a polymer and a crosslinking agent, and has one of 2 partial structures in which the polymer can react with each other to form a cleavage structure. Moreover, the crosslinking agent has another one of the 2 partial structures. In addition, the crosslinker has a first reactive group. Here, the other of the 2 partial structures of the crosslinking agent and the first reactive group may be the same reactive group or may be different reactive groups. For example, an alkoxyalkyl group can be another of the 2 partial structures, and can also be the first reactive group.

When the condition (B) is satisfied, the film-forming component may contain 2 or more polymers. At this time, for example, at least 1 of the 2 or more polymers has one of 2 partial structures capable of reacting with each other to form a cleavage structure, and at least 1 of the remaining polymers has the other of 2 partial structures.

When the condition (B) is satisfied, the film-forming component may contain 2 or more kinds of crosslinking agents. At this time, for example, at least 1 of the 2 or more crosslinking agents has one of 2 partial structures capable of reacting with each other to form a cleavage structure, and at least 1 of the remaining crosslinking agents has the other of 2 partial structures.

Polymer-

The polymer may or may not have a broken structure.

Polymers having a broken structure

In the case of polymers having a cleavage structure, the cleavage structure may be located in the main chain of the polymer or in the side chain of the polymer. Among them, a polymer having a backbone with a cleavage structure is preferable in that a cleavage structure can be introduced into the polymer in a large amount.

In the polymer having a backbone with a cleavage structure, the cleavage structure may be present in all of the repeating units of the polymer, or may be present in a part thereof. The molar ratio of the repeating units having a cleavage structure to the entire 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 the polymer having a side chain having a cleavage structure, the cleavage structure may be present in all the repeating units of the polymer, or the cleavage structure may be present in a part. The molar ratio of the repeating units having a cleavage structure to the entire 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.

In the case of polymers having one of 2 partial structures capable of reacting with each other to form a broken structure, the one is typically located in a side chain of the polymer.

In a polymer having one of 2 partial structures in a side chain capable of reacting with each other to form a cleavage structure, the partial structure may exist in all of the repeating units of the polymer, and the partial structure may also exist in a part 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.

Examples of the polymer include condensation polymers such as polyesters, polyamides, polyimides, and polyamic acids, polyurethanes, and vinyl polymers.

Examples of the polymer having a backbone having a cleavage structure include polymers having a repeating unit represented by the following formula (11) or formula (12).

[ Chemical 14]

(In the formula (11), R ¹ and n1 are the same as R ¹ and n1 in the formula (1), respectively. R ¹⁰¹ represents a 2-valent organic group. R ¹⁰² represents a 2-valent organic group.

In formula (12), R ¹¹、R¹² and n12 are the same as R ¹¹、R¹² and n12 in formula (2), respectively. R ¹¹¹ represents a 2-valent organic group. R ¹¹² represents a 2-valent organic group. m1 represents 0 or 1. )

Examples of R ¹⁰¹ include a 2-valent organic group having 1 to 30 carbon atoms. Examples of the 2-valent organic group having 1 to 30 carbon atoms include 2-valent aromatic hydrocarbon groups which may have a substituent. Examples of the 2-valent aromatic hydrocarbon group include phenylene and naphthylene. 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.

Examples of R ¹⁰² include a 2-valent organic group having 1 to 30 carbon atoms. Examples of the 2-valent organic group having 1 to 30 carbon atoms include 2-valent organic groups represented by any one of the following formulas (K-1) to (K-13).

[ 15]

( In the formula (K-5), R ₂ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms. In the formula (K-13), R ₃ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms. * Representing a bond. )

The aliphatic hydrocarbon groups in R ₂ and R ₃ may have 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms.

Examples of R ¹¹¹ include a 2-valent organic group represented by the following formula (12-1).

[ 16]

( In formula (12-1), R ¹¹ is the same as R ¹¹ in formula (12). * Representing a bond. )

Examples of R ¹¹² include a 2-valent organic group having 1 to 30 carbon atoms.

In the formula (12), when m1 is 1, R ¹¹² is, for example, a 2-valent organic group represented by any one of the above formulas (K-1) to (K-13).

In the formula (12), when m is 0, R ¹¹² is, for example, a 2-valent organic group having 1 to 30 carbon atoms. Examples of the 2-valent organic group having 1 to 30 carbon atoms include 2-valent aromatic hydrocarbon groups which may have a substituent. Examples of the 2-valent aromatic hydrocarbon group include phenylene and naphthylene. 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.

Here, an example of a polymer having a main chain with a broken structure is shown below.

[ Chemical 17]

(Wherein n represents an integer of 1 or more.)

The polymer is a polymer with an o-nitrobenzyl structure in the main chain.

In this polymer, the ortho-nitrobenzyl structure is present in all the repeating units of the polymer.

The polymer can be obtained, for example, by polycondensation of 2-nitro-isophthaloyl dichloride (2-nitro-m-xyleneglycol) with isophthaloyl dichloride. The polymers obtained are 1 of the polyesters.

In addition, by reacting (2-nitro-1, 3-phenylene) dimethanol with diisocyanate, it is possible to obtain polyurethane having an o-nitrobenzyl structure in the main chain.

In addition, by reacting a compound having 2 oxime groups (> c=n—oh) having the following structure with a diisocyanate compound, a polyurethane having an oxime ester structure in the main chain can be obtained.

[ Chemical 18]

Here, an example of a polymer having a side chain with a broken structure is shown below.

[ Chemical 19]

The polymer is a polymer with acetophenone structure at a side chain.

In this polymer, n mol% (n+m=50) of all the repeating units are repeating units having an acetophenone structure.

The polymer is 1 kind of vinyl polymer. The polymer can be obtained, for example, by radical polymerization of a monomer having a polymerizable unsaturated double bond corresponding to each repeating unit.

Here, an example of one of 2 partial structures having a cleavage structure in a side chain of a polymer, which can react with each other, is shown below.

[ Chemical 20]

The polymer is a polymer with a part of a structure capable of forming an o-nitrobenzyl structure positioned at a side chain.

In this polymer, 20 mol% of the total repeating units are repeating units having the partial structure.

Polymers without broken structures

The polymer having no cleavage structure is not particularly limited, and for example, a known polymer can be used.

Examples of the known polymer include condensation polymers such as polyesters, polyamides, polyimides, and polyamic acids, polyurethanes, and vinyl polymers.

Polyurethane-polyurethane

Examples of the polyurethane having no cleavage structure include 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, and 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 3 to 30 carbon atoms. The diisocyanate is preferably, for example, a diisocyanate represented by the following formula.

[ Chemical 21]

(Wherein R ₂ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R ₃ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms.

Condensation polymers

Examples of the polymer having no cleavage structure include a condensation polymer having a repeating unit represented by the following formula (A1).

[ Chemical 22]

(In the formula (A1), A ¹、A²、A³、A⁴、A⁵ 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). )

[ Chemical 23]

(In the formulae (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, which may be substituted with at least 1 group selected from 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 hydroxyl group and an alkylthio group having 1 to 6 carbon atoms, R ¹ and R ² may be bonded to each other and form a ring having 3 to 6 carbon atoms together with the carbon atoms to which they are bonded.

R ³ is alkyl group with 1-6 carbon atoms, alkenyl group with 3-6 carbon atoms, benzyl or phenyl. The phenyl group may be substituted with at least 1 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 hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms.

* Representing a bond. *1 represents a bond to a carbon atom. *2 represents a bond to a nitrogen atom. )

[ Chemical 24]

(In the formulae (A1-5) and (A1-6), X ² is a group represented by the formula (A1-1), the formula (A1-2) or the formula (A1-4).

Q ² is an alkylene group having 1 to 10 carbon atoms, a phenylene group, a naphthylene group or an anthracenylene group. The phenylene group, the naphthylene group and the anthrylene group may be substituted with at least 1 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 hydroxyl group and an alkylthio group having 1 to 6 carbon atoms.

N ¹ and n ² are each independently 0 or 1.

*1 Represents a bond to a carbon atom bonded to a ³. *2 represents a bond to a carbon atom bonded to a ⁴. )

Preferably all of A ¹～A⁶ are hydrogen atoms.

In the formula (A1-5), for example, when X ² is a group represented by the formula (A1-2), the structure is represented by the following formula (A1-5-1).

[ Chemical 25]

(In the formula (A1-5-1), R ¹ and R ² are the same as R ¹ and R ² in the formula (A1-2), respectively.)

In the formula (A1-6), in the case where Q ² is a phenylene group, a naphthylene group or an anthracenylene group, the bonding position thereof is not particularly limited. That is, for example, it can be any of the case where phenylene is bonded at 1-position and 2-position, the case where 1-position and 3-position are bonded, or the case where 1-position and 4-position are bonded, the case where 1-position and 5-position are bonded, or the case where 2-position and 3-position are bonded, the case where anthracene is bonded at 1-position and 2-position, the case where 1-position and 4-position are bonded, or the case where 9-position and 10-position are bonded, and the like.

The alkyl group having 1 to 6 carbon atoms may be any of linear, branched, and cyclic, and examples thereof include methyl, ethyl, isopropyl, n-butyl, and cyclohexyl.

The alkenyl group having 3 to 6 carbon atoms may be any of a straight chain, a branched chain, and a cyclic one, and examples thereof include a 2-propenyl group, a 3-butenyl group, and the like.

The alkoxy group having 1 to 6 carbon atoms may be any of a straight chain, branched, and cyclic, and examples thereof include methoxy, ethoxy, isopropoxy, n-pentyloxy, and cyclohexyloxy.

The alkylthio group having 1 to 6 carbon atoms may be any of a straight-chain, branched, and cyclic one, 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.

Examples of the ring having 3 to 6 carbon atoms formed by bonding R ¹ to R ² include a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring.

The alkylene group having 1 to 10 carbon atoms may be any of a straight chain, branched chain, and cyclic group, and examples thereof include methylene, ethylene, propylene, pentamethylene, cyclohexylene, and 2-methylpropylene.

In the formula (A1), when X ¹ is a group represented by the formula (A1-2), the structure is represented by the following formula (A2), and when X ¹ is a group represented by the formula (A1-3), the structure is represented by the following formula (A3). In the formula (A3), R ³ is preferably 2-propenyl.

[ Chemical 26]

( In the formulas (A2) and (A3), a ¹～A⁶ and Q ¹ are the same as a ¹～A⁶ and Q ¹ in the formula (A1), respectively. R ¹ and R ² are the same as R ¹ and R ² in the formula (A1-2), respectively. R ³ is the same as R ³ in the formula (A1-3). )

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

The repeating unit represented by the formula (A1) is preferably a repeating unit represented by the following formulas (A4) to (a 22). In the following formula, me is methyl and Et is ethyl.

[ Chemical 27]

[ Chemical 28]

[ Chemical 29]

[ Chemical 30]

[ 31]

The condensation polymer having the repeating unit represented by the formula (A1) can be synthesized, for example, by referring to International publication No. 2005/098542.

Vinyl polymer

The vinyl polymer is a polymer obtained by polymerizing a monomer having a polymerizable unsaturated double bond such as acrylate, methacrylate, and styrene.

The vinyl polymer having no cleavage structure is obtained by polymerizing, for example, a monomer having a polymerizable unsaturated double bond having no cleavage structure.

Examples of the monomer having a polymerizable unsaturated double bond include a monomer having a carboxyl group, a monomer having an epoxy group, an acrylate compound, a methacrylate compound, a maleimide compound, an acrylamide compound, acrylonitrile, maleic anhydride, a styrene compound, and a vinyl compound.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, mono- (2- (acryloyloxy) ethyl) hexahydrophthalate, mono- (2- (methacryloyloxy) ethyl) hexahydrophthalate, mono- (2- (acryloyloxy) ethyl) succinate, mono- (2- (methacryloyloxy) ethyl) succinate, N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide, and ω -carboxyl-polycaprolactone mono (meth) acrylate.

Examples of such monomers include the following commercially available monomers: "LIGHT ESTER HO-MS", "LIGHT ACRYLATE HOA-MS (N)", "LIGHT ACRYLATE HOA-HH (N)", and "LIGHT ACRYLATE HOA-MPL (N)" (above, trade name manufactured by Kabushiki Kaisha chemical Co., ltd.), ARONIX (registered trademark) M-5300, ARONIX (registered trademark) M-5400 (above, trade name manufactured by east Asian Synthesis Co., ltd.), A-SA, SA (above, trade name manufactured by Xinzhongcun chemical industry Co., ltd.).

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

Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthalene acrylate, anthracene methyl acrylate, phenyl acrylate, 2-trifluoroethyl acrylate, t-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, 8-ethyl-8-tricyclodecyl acrylate, and the like.

Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthalene methacrylate, anthracene methacrylate, phenyl methacrylate, 2-trifluoroethyl methacrylate, t-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, gamma-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.

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

Examples of the styrene compound include styrene, methyl styrene, chlorostyrene, and bromostyrene.

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

The vinyl polymer can be obtained by a known method, for example, by radical polymerization of 1 or 2 or more monomers having polymerizable unsaturated double bonds.

The polymer preferably has reactive groups capable of reacting with the 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 carboxyl group, and a phenolic hydroxyl group.

For example, when the crosslinking agent has an alkoxymethyl group or a hydroxymethyl group, examples of the reactive group include an alkoxymethyl group and a hydroxymethyl group.

For example, when the crosslinking agent has an isocyanate group, examples of the reactive group include a carboxyl group and a hydroxyl group.

The molecular weight of the polymer (polymer having a broken structure, polymer not having a broken structure) is not particularly limited, and the weight average molecular weight based on GPC (gel permeation chromatography) is preferably 2000 to 100000, more preferably 2500 to 50000.

The content of the polymer in the composition for forming a release layer is not particularly limited, but is preferably 10 to 99.5% by mass, more preferably 30 to 95% by mass, and particularly preferably 50 to 90% by mass, relative to the film-forming component. These contents may be only the content of the polymer having a broken structure, may be only the content of the polymer not having a broken structure, or may be the total content of the polymer having a broken structure and the polymer not having a broken structure.

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 1 or 2 or more.

In the case where the crosslinking agent has one or the other of 2 partial structures capable of reacting with each other to form a cleavage structure, the number of the partial structures contained in the crosslinking agent may be 1 or 2 or more.

Examples of the crosslinking agent include epoxy compounds, methylol compounds, and isocyanate compounds.

The epoxy compound is a compound having 2 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 of the methylol group and the alkoxymethyl group is 2 or more.

The isocyanate compound has at least one of an isocyanate group and a blocked isocyanate group, and the total of the isocyanate group and the blocked isocyanate group is 2 or more.

Crosslinking agents having a cleavage structure

Examples of the crosslinking agent having a cleavage structure include epoxy compounds, methylol compounds, and isocyanate compounds.

The crosslinking agent having a cleavage structure may have 1 cleavage structure or may have 2 or more cleavage structures.

The crosslinking agent having a cleavage structure is represented by, for example, the following formula (B1) or formula (B2).

[ Chemical 32]

(In the formula (B1), X represents a cleavage structure, L ¹ and L ² each independently represent a single bond or a linking group, and Y ¹ and Y ² each independently represent an epoxy group, an alkoxyalkyl group, a hydroxymethyl group, or an isocyanate group.

In the formula (B2), n represents an integer of 3 to 6. Z represents an n-valent group. X each independently represents a cleavage structure. Each L independently represents a single bond or a linking group. Y each independently represents an epoxy group, an alkoxyalkyl group, a hydroxymethyl group or an isocyanate group. )

The X (cleavage structure) in the formulae (B1) and (B2) is, for example, a structure represented by any one of the formulae (1) to (3).

The linking group in the formula (B1) and the formula (B2) is not particularly limited as long as it is a 2-valent group. Examples of the linking group include a 2-valent group having 1 to 20 atoms.

Z in the 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.

Specific examples of the crosslinking agent having a cleavage structure include the following compounds.

[ 33]

/>

Crosslinking agents without cleavage structures

Examples of the epoxy compound having no crosslinking agent having a cleavage structure include 1,2,7, 8-diglycidyl octane, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1, 6-dimethylol perfluorohexane diglycidyl ether, (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol triglycidyl ether, diglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol polyglycidyl ether, and, Sorbitol polyglycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether, resorcinol diglycidyl ether, bis (2, 7-diglycidyl oxynaphthalen-1-yl) methane, 1, 2-tetrakis (4-glycidyloxyphenyl) ethane, 1, 3-tris (4-glycidyloxyphenyl) 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-epoxycyclohexane carboxylate), 3, 4-epoxycyclohexane carboxylate (3, 4-epoxycyclohexyl) methyl ester, 4, 5-epoxy-2-methylcyclohexane carboxylate (4, 5-epoxy-2-methylcyclohexyl) methyl ester, bis (3, 4-epoxycyclohexylmethyl) adipate, 1, 2-epoxy-4- (epoxyethyl) cyclohexane, 4- (spiro [3, 4-epoxycyclohexane-1, 5'- [1,3] dioxan ] -2' -yl) -1, 2-epoxycyclohexane, diglycidyl adipate, diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl 1, 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 '-diglycidyl N' - (2, 3-dipropyloxypropyl) isocyanurate, 1,3, 5-tris (2- (2, 2-bis (glycidyloxymethyl) butoxycarbonyl) ethyl) isocyanurate, Tris (2, 2-bis (glycidoxymethyl) butyl) 3,3 '- (2, 4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tripropionate, N, N-diglycidyl-4-glycidoxylaniline, N, N, N', N '-tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane, 4' -methylenebis (N, N-diglycidyl aniline), 2- (4, 4-dimethylpentan-2-yl) -5, 7-trimethyloctanic acid 2, 2-bis (glycidoxymethyl) butyl, Phenol novolac type epoxy resins, cresol novolac type epoxy resins, naphthol novolac type epoxy resins, anthracene novolac type epoxy resins, biphenyl novolac type epoxy resins, xylenol novolac type epoxy resins, triphenol methane novolac type epoxy resins, tetraphenol novolac type epoxy resins, dicyclopentadiene novolac type epoxy resins, and the like.

Examples of the commercial products of the epoxy compound include TEPIC (registered trademark) -G, TEPIC (registered trademark) -S, TEPIC (registered trademark) -SS, TEPIC (registered trademark) -SP, TEPIC (registered trademark) -L, TEPIC (registered trademark) -HP, TEPIC (registered trademark) -VL, TEPIC (registered trademark) -FL, TEPIC (registered trademark) -PAS B22, TEPIC (registered trademark) -PAS B26L, TEPIC (registered trademark) -UC, FOLDI (registered trademark) -E201[ all manufactured by daily chemical corporation ], jER (registered trademark) 828, jER (registered trademark) 807, jER (registered trademark) YX8000, jER (registered trademark) 157S70[ all manufactured by mitsubishi chemical corporation ], RIKARESIN (registered trademark) DME 100[ manufactured by new japan physicochemical corporation ], CELLOXIDE p [ daicel (registered trademark) manufactured ], EPICLON (registered trademark) HP-4700, EPICLON HP-4710, EPICLON HP-7200 ] and DIC [ manufactured by jik corporation ], and the like.

Examples of the methylol compound having no cleavage structure as the crosslinking agent include alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, alkoxymethylated melamine, tetra (alkoxymethyl) bisphenol, and tetra (hydroxymethyl) bisphenol.

Examples of alkoxymethylated glycolurils include 1,3,4, 6-tetra (methoxymethyl) glycoluril, 1,3,4, 6-tetra (butoxymethyl) glycoluril, 1,3,4, 6-tetra (hydroxymethyl) glycoluril, 1, 3-bis (hydroxymethyl) urea, 1, 3-tetra (butoxymethyl) urea, 1, 3-tetra (methoxymethyl) urea, 1, 3-bis (hydroxymethyl) -4, 5-dihydroxy-2-imidazolidinone, and 1, 3-bis (methoxymethyl) -4, 5-dimethoxy-2-imidazolidinone. Examples of the commercial products include glycoluril compounds (trade name: CYMEL (registered trademark) 1170, POWDER LINK (registered trademark) 1174) manufactured by MITSUI-CYTEC corporation, methylated urea resins (trade name: UFR (registered trademark) 65), butylated urea resins (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11 HV), urea/formaldehyde resins (high condensation type, trade name: BECKAMINE (registered trademark) J-300S, BECKAMINE P-955, BECKAMINE N) manufactured by DIC corporation, and the like.

Examples of the alkoxymethylated benzoguanamine include tetramethoxymethyl benzoguanamine and the like. Examples of the commercial products include MITSUI-CYTEC Co., ltd (trade name: CYMEL (registered trademark) 1123), and Sanhe chemical Co., ltd (trade name: NIKALAC (registered trademark) BX-4000, NIKALAC BX-37, NIKALAC BL-60, NIKALAC BX-55H).

Examples of the alkoxymethylated melamine include hexamethoxymethyl melamine. Examples of the commercial products include methoxymethyl melamine compounds (trade names: CYMEL (registered trademark) 300, CYMEL 301, CYMEL 303, and CYMEL 350) manufactured by MITSUI-CYTEC corporation, butoxymethyl melamine compounds (trade names: MYCOAT (registered trademark) 506 and MYCOAT) and methoxymethyl melamine compounds (trade names: NIKALAC (registered trademark) )MW-30、NIKALAC MW-22、NIKALAC MW-11、NIKALAC MW-100LM、NIKALAC MS-001、NIKALAC MX-002、NIKALAC MX-730、NIKALAC MX-750、NIKALAC MX-035)、 butoxymethyl melamine compounds (trade names: NIKALAC (registered trademark) MX-45, NIKALAC MX-410, and NIKALAC MX-302) manufactured by Sanand chemical corporation.

Examples of the tetra (alkoxymethyl) bisphenol and the tetra (hydroxymethyl) bisphenol include tetra (alkoxymethyl) bisphenol a, tetra (hydroxymethyl) bisphenol a, and the like.

When the condition (B) is satisfied, the crosslinking agent having no cleavage structure can be one having one or the other of 2 partial structures capable of reacting with each other to form a cleavage structure. For example, an epoxy group, an alkoxymethyl group, a hydroxymethyl group, an isocyanate group, or the like can sometimes react with another one of the 2 partial structures that can form a cleavage structure to form a cleavage structure.

The molecular weight of the crosslinking agent (crosslinking agent having a broken structure, crosslinking agent not having a broken structure) is not particularly limited, but is preferably 2000 or less, more preferably 1500 or less.

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

Other ingredients-

The composition for forming a release layer may contain other components than the polymer and the crosslinking agent as film-forming components. Examples of the other component include a curing catalyst, a surfactant, and a silane coupling agent.

Curing catalyst

The curing catalyst is effective for promoting the heat curing reaction in the formation of the release layer using the composition for forming a release layer.

Examples of the curing catalyst include acids and thermal acid generators.

As the thermal acid generator, a compound which thermally cracks at a temperature of 80 to 250℃to generate an acid is preferable.

Examples of the acid include 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, mesitylene sulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1h,2 h-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, and the like, and hydrates and salts thereof.

Examples of the compound (thermal acid generator) which generates an acid by heat include bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2, 3-phenylene tris (methylsulfonate), pyridinium p-toluenesulfonate, morpholinium p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, isobutyl p-toluenesulfonate, methyl p-toluenesulfonate, phenethyl p-toluenesulfonate, cyanomethyl p-toluenesulfonate, 2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, N-ethyl-4-toluenesulfonamide, and compounds represented by the following formulae [ TAG-1] to [ TAG-41 ].

[ Chemical 34]

[ 35]

[ 36]

[ 37]

[ 38]

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[ 39]

[ 40]

Examples of the thermal acid generator include onium salts such as iodonium salts, sulfonium salts, phosphonium salts, and selenonium salts.

Examples of iodonium salts include diphenyliodonium, 4 '-dichlorodiphenyliodonium, 4' -dimethoxydiphenyliodonium, 4 '-di-t-butyldiphenyliodonium, 4-methylphenyl (4- (2-methylpropyl) phenyl) iodonium, 3' -dinitrophenyliodonium, 4- (1-ethoxycarbonylethoxy) phenyl (2, 4, 6-trimethylphenyl) iodonium, and 4-methoxyphenyl (phenyl) iodonium.

Examples of the iodonium salt include diaryliodonium salts such as chloride, bromide, methanesulfonate, toluenesulfonate (tosylate), trifluoromethanesulfonate, tetrafluoroborate, tetrakis (pentafluorophenyl) borate, hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate of the iodonium salts described above.

Examples of sulfonium salts include triphenylsulfonium, diphenyl (4-t-butylphenyl) sulfonium, tris (4-t-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, benzyl (4-acetoxyphenyl) (methyl) sulfonium, and the like.

Examples of the sulfonium salt include aryl sulfonium salts such as chloride, bromide, trifluoromethanesulfonate, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, tetrakis (pentafluorophenyl) borate, and hexafluoroantimonate of the above sulfonium.

Examples of the phosphonium in the phosphonium salt include tetraphenylphosphonium, ethyltriphenylphosphonium, tetrakis (p-methoxyphenyl) phosphonium, ethyltris (p-methoxyphenyl) phosphonium, and benzyltriphenylphosphonium.

Examples of the phosphonium salt include aryl phosphonium salts such as chlorides, bromides, tetrafluoroborates, hexafluorophosphates, and hexafluoroantimonates of the above-mentioned phosphonium salts.

Examples of the selenonium salt include triarylselenonium salts such as triphenylselenonium hexafluorophosphate.

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

Surfactant-a-

By adding a surfactant to the composition for forming a release layer, the coatability of the composition for forming a release layer can be improved.

The surfactant may be a known surfactant such as a nonionic surfactant, a fluorine-based surfactant, or a silicone-based surfactant.

The surfactant can be used alone or in combination of 1 or more than 2.

Examples of the nonionic surfactant 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 octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate and other polyoxyethylene sorbitan fatty acid esters.

Examples of the fluorine-based surfactant include EFTOP (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi materials electronics chemical corporation), MEGAFAC (registered trademark) F171, F173, F554, F559, F563, R-30, R-40-LM, DS-21 (manufactured by DIC corporation), FLUORAD (registered trademark) FC430, FC431 (manufactured by 3M corporation), asahiguard (registered trademark) AG710, SURFLON (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC corporation), and the like.

Examples of the silicone surfactant include an organosiloxane polymer KP341 (manufactured by singe chemical industry co., ltd.).

When the release layer-forming composition contains a surfactant, the content thereof is preferably 0.0001 to 1% by mass, more preferably 0.001 to 0.5% by mass, relative to the polymer.

Silane coupling agent

By adding a silane coupling agent to the composition for forming a release layer, adhesion between the composition for forming a release layer and a coating object can be improved.

Examples of the silane coupling agent include vinyl silane coupling agents such as trimethoxy (vinyl) silane, triethoxy (vinyl) silane, trimethoxy (4-vinylphenyl) silane, and triethoxy (4-vinylphenyl) silane; (meth) acrylic silane coupling agents such as 3- (meth) acryloxypropyl trimethoxysilane, triethoxy (3- (meth) acryloxypropyl) silane, 3- (meth) acryloxypropyl (dimethoxy) (meth) silane, and diethoxy (3- (meth) acryloxypropyl) (meth) silane; epoxy silane coupling agents such as 3-glycidoxypropyl trimethoxysilane, triethoxy (3-glycidoxypropyl) silane, 3-glycidoxypropyl (dimethoxy) (methyl) silane, diethoxy (3-glycidoxypropyl) (methyl) silane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, and 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane; amine-based silane coupling agents such as 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl triethoxysilane, N- (2-aminoethyl) -3-aminopropyl (dimethoxy) (methyl) silane, N- (2-aminoethyl) -3-aminopropyl (diethoxy) (methyl) silane, N- (1-methylpentylene) -3-trimethoxysilylpropylamine, 3-triethoxysilyl-N- (1-methylpentylene) propylamine, N- (1, 3-dimethylbutylidene) -3-trimethoxysilylpropylamine, N- (1, 3-dimethylbutylidene) -3-triethoxysilylpropylamine, N-phenyl-3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyl triethoxysilane; ureido silane coupling agents such as 3-ureidopropyltrimethoxysilane and triethoxy (3-ureidopropyl) silane; mercapto silane coupling agents such as 3-mercaptopropyl trimethoxysilane, 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; isocyanate-based silane coupling agents such as 3-isocyanatopropyl trimethoxysilane and triethoxy (3-isocyanatopropyl) silane.

Among them, a silane coupling agent having the same reactive group as that of the crosslinking agent is preferable. For example, when the crosslinking agent has an epoxy group, an epoxy-based silane coupling agent is preferable as the silane coupling agent.

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

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.

Examples of the 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 solvents include ethyl lactate, γ -butyrolactone, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate.

Examples of the ketone solvent include methyl ethyl ketone, cyclohexanone, cyclopentanone, and benzophenone.

Examples of the cyclic compound solvent include N-methylpyrrolidone and γ -butyrolactone.

They can be used singly or in combination of 1 or more than 2.

The concentration of the film-forming component in the composition for forming a release layer is preferably 0.1 to 40% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 0.5 to 10% by mass.

The method for producing the composition for forming a release layer is not particularly limited, and a known method that can uniformly mix the components can be used.

The thickness of the release layer is not particularly limited, but is preferably 0.01 μm to 10. Mu.m, more preferably 0.03 μm to 5. Mu.m, particularly preferably 0.05 μm to 1. Mu.m.

< Resin layer >)

The resin layer is formed from a resin layer precursor.

The resin layer precursor is formed, for example, from a resin layer-forming composition.

The resin layer precursor is, for example, a layer obtained by applying a composition for forming a resin layer.

By providing the release layer with the first reactive group, the resin layer precursor is provided with the second reactive group, and the adhesion between the release layer and the resin layer is improved.

The first reactive group and the second reactive group may be the same reactive group or may be different reactive groups.

As a combination of the first reactive group and the second reactive group when the first reactive group and the second reactive group are the same reactive group, for example, a combination in which both the first reactive group and the second reactive group are epoxy groups can be cited. At least any one of the first reactive group and the second reactive group may be an alicyclic epoxy group.

As a combination of the first reactive group and the second reactive group when the first reactive group and the second reactive group are different reactive groups, for example, a combination in which the first reactive group is an alkoxyalkyl group and the second reactive group is an epoxy group can be given.

Composition for forming resin layer

The resin layer-forming composition contains, for example, a resin and a crosslinking agent having a second reactive group.

Examples of the resin include polyethylene terephthalate, polyethylene naphthalate, polypropylene, cycloolefin polymer, polyamide, polyether sulfone, polymethyl methacrylate, polycarbonate, polyarylate, polyimide, polyurethane, and the like.

The crosslinking agent having the second reactive group is not particularly limited, and examples thereof include epoxy compounds.

The epoxy compound is not particularly limited as long as it has 2 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, hydrogenated bisphenol S diglycidyl ether, 3, 4-epoxycyclohexylmethyl-3 ',4' -epoxycyclohexane carboxylate, 2- (3, 4-epoxycyclohexyl-5, 5-spiro-3, 4-epoxycyclohexane-m-dioxane, bis (3, 4-epoxycyclohexylmethyl) adipate, bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexyl-3 ',4' -epoxy-6 ' -methylcyclohexane carboxylate, methylenebis (3, 4-epoxycyclohexane), dicyclopentadiene diglycidyl ether, 3, 4-epoxycyclohexane diglycidyl ether, triglycidyl ether, 1, 4-epoxycyclohexane diglycidyl ether, triglycidyl ether; polyglycidyl ethers of polyether polyols obtained by adding 1 or 2 or more alkylene oxides to aliphatic polyols such as ethylene glycol, propylene glycol and glycerin; diglycidyl esters of aliphatic long chain dibasic acids; monoglycidyl ethers of phenol, cresol, butylphenol or polyether alcohols obtained by adding alkylene oxides thereto; glycidyl esters of higher fatty acids; silicone epoxy resins (Japanese コ) and derivatives thereof.

Examples of the commercial products of the epoxy compound include "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).

The resin layer-forming composition may contain a solvent.

Examples of the solvent include alcohol solvents such as methanol, ethanol, 2-propanol, 1-butanol, and 2-butanol; ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, 1, 4-dioxane, and propylene glycol monomethyl ether; ketone solvents such as acetone, 2-butanone, and methyl isobutyl ketone; aprotic polar solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and dimethylsulfoxide; ester solvents such as methyl acetate, ethyl acetate, and n-butyl acetate; nitrile 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; dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, trichloroethane, monochlorobenzene, dichlorobenzene and other halogenated hydrocarbon solvents, water and the like.

These solvents may be used singly or in combination of two or more.

The content of the resin in the resin layer-forming composition is not particularly limited, but is preferably 30 to 95% by mass, more preferably 45 to 90% by mass, and particularly preferably 60 to 85% by mass, relative to the nonvolatile component in the resin layer-forming composition.

The content of the crosslinking agent having the second reactive group in the resin layer-forming composition is not particularly limited, but is preferably 5 to 70% by mass, more preferably 10 to 55% by mass, and particularly preferably 15 to 40% by mass, relative to the nonvolatile component in the resin layer-forming composition.

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

The laminate includes, for example, a support, a release layer, and a resin layer in this order.

In the laminate, the release layer is in contact with the resin layer.

In the laminate, the support and the release layer may be in contact, or another layer may be present between the support and the release layer.

(Method for producing laminate)

The method for producing a laminate of the present invention comprises the following steps (1) to (3).

Step (1): a step of forming a release layer on a support having a transmission property for active energy rays,

Step (2): a step of forming a resin layer precursor on the release layer,

Step (3): a step of converting the resin layer precursor into a resin layer,

The film forming component has a first reactive group.

Specific examples and preferred examples of the support are the same as those 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 those in the description of the laminate of the present invention.

Specific examples and preferred examples of the resin layer are the same as those in the description of the laminate of the present invention.

< Procedure (1) >)

In the step (1), the release layer is formed by, for example, applying a release layer-forming composition and heating the same.

The coating method is not particularly limited, and examples thereof include a casting coating method, a spin coating method, a doctor blade coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, an ink jet method, a printing method (relief, gravure, offset, screen printing, etc.), and the like.

The heating is performed, for example, to evaporate the solvent contained in the composition for forming a release layer.

The heating is performed, for example, to form a crosslinked structure in the release layer.

In addition, for example, when the film-forming component contained in the composition for forming a release layer satisfies the condition (B), heating is performed so that the 2 partial structures react with each other to form a broken structure.

The heating temperature is not particularly limited.

The heating temperature for evaporating the solvent contained in the composition for forming a release layer is, for example, 40 to 100 ℃. The heating time in this case is, for example, 1 minute to 1 hour.

The heating temperature for forming a crosslinked structure in the release layer is, for example, 120 to 200 ℃. The heating time in this case is, for example, 5 minutes to 2 hours.

The temperature and time for heating to react the 2 partial structures with each other to form a cleavage structure can be appropriately selected according to the kind of reaction. The heating at this time may be a combination of heating for evaporating the solvent, heating for forming a crosslinked structure, and the like.

The heating may be performed in stages. For example, the release layer may be formed by heating to 40 ℃ to 100 ℃ in the first stage and then heating to 120 ℃ to 200 ℃ in the second stage.

Examples of the means for heating include a hot plate and an oven.

The heating atmosphere may be under air or inert gas, or under normal pressure or reduced pressure.

In the case where the composition for forming a release layer 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.

< Procedure (2) >)

In the step (2), the resin layer precursor is formed by, for example, applying a resin layer-forming composition and heating the same.

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 examples thereof include 40 to 100 ℃.

The heating time is not particularly limited, and examples thereof include 1 minute to 1 hour.

Examples of the means for heating include a hot plate and an oven.

< Procedure (3) >)

In the step (3), the conversion from the resin layer precursor to the resin layer is performed by heating the resin layer precursor, for example.

The heating temperature is not particularly limited, and examples thereof include 120℃to 200 ℃.

The heating time is not particularly limited, and examples thereof include 5 minutes to 2 hours.

Examples of the means for heating include a hot plate and an oven.

When the resin layer precursor is converted into the resin layer, for example, a reaction between the first reactive group of the release layer and the second reactive group of the resin layer precursor is performed.

(Method for manufacturing electronic device)

The method for manufacturing 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 any one of the resin layers in the laminate of the present invention and the laminate produced by the production method of the laminate of the present invention,

Step (II): a step of irradiating the support body side of the laminate with active energy rays toward the release layer to release the support body from the resin layer,

< Procedure (I) >)

In the step (I), a method for forming at least any 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 a known method is exemplified.

Examples of the photoelectric conversion element include a light-emitting element that converts electric energy into light, and a light-receiving element that converts light into electric energy. Examples of the light emitting element include a light emitting diode and a semiconductor laser. Examples of the light receiving element include a photodiode and a phototransistor.

Examples of the display element include a liquid crystal display element, an inorganic EL (electroluminescence ), and an organic EL.

Examples of the member for a display element include a transparent electrode of a touch panel, a color filter, and the like.

Examples of the electronic circuit include a capacitor and a transistor.

< Procedure (II) >)

In the step (II), the irradiation amount of the active energy ray to be irradiated to the release layer is not particularly limited, and examples thereof include irradiation amounts that do not damage the support and the resin layer and reduce the release force of the release layer to such an extent that the support can be released from the resin layer.

Examples of such an irradiation amount include 500 to 10000mJ/cm ² (converted to 365 nm).

Examples

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

The compounds used in the following synthesis examples, preparations and examples are as follows.

[ Solvent ]

PGME: propylene glycol monomethyl ether

NMP: n-methylpyrrolidone

BCS: ethylene glycol monobutyl ether

THF: tetrahydrofuran (THF)

CHN: cyclohexanone

DMF: n, N-dimethylformamide

DMSO: dimethyl sulfoxide

[ Cross-linking agent ]

PL:1,3,4, 6-tetra (methoxyethyl) glycoluril (Allnex Co., ltd., trade name: POWDERLINK 1174)

TP:1,3, 5-Triglycidyl isocyanurate (trade name: TEPIC (registered trademark) -L, manufactured by Nissan chemical Co., ltd.)

[ Curing catalyst ]

PPTS: pyridinium p-toluenesulfonate

SI: ( 4-Acetoxyphenyl) methyl (2-methylbenzyl) sulfonium tetrakis (pentafluorophenyl) borate (trade name, sanxingxiao chemical Co., ltd.: SI-B2A )

The weight average molecular weight (Mw) of the polymer was measured using GPC equipment (column: shodex (registered trademark) KF803L and KF804L (manufactured by Showa Denko Co., ltd.); eluent: THF, flow rate: 1.0 mL/min, column temperature: 40 ℃ C., mw: standard polystyrene conversion value) manufactured by Shimadzu corporation.

Further, ¹ H-NMR was measured using AVANCE III HD manufactured by Bruker, inc., and the frequency was measured: 500MHz, determination solvent: deuterated chloroform manufactured by Kanto chemical Co., ltd., or deuterated DMSO manufactured by Kanto chemical Co., ltd., internal standard: tetramethylsilane (δ=0.00 ppm).

[1] Synthesis of polymers

Synthesis example 1

5.00G (28.87 mmol) of N-phenylmaleimide, 3.34g (32.08 mmol) of styrene, 0.46g (3.21 mmol) of glycidyl methacrylate and 0.21g of azobisisobutyronitrile as a polymerization catalyst were dissolved in 80.0g of THF and reacted at 60℃for 20 hours to thereby obtain a polymer solution. The resulting polymer solution was slowly dropped into 500g of methanol to precipitate a solid. The precipitated solid was filtered off and dried under reduced pressure, whereby a polymer (PA-1) containing no broken structure was obtained. The Mw of the polymer (PA-1) was 21000.

[ Chemical 41]

Synthesis example 2

Methyl methacrylate 4.00g (39.95 mmol), glycidyl methacrylate 1.42g (9.99 mmol), and azobisisobutyronitrile 0.25g as a polymerization catalyst were dissolved in PGME 50.0g and reacted at 80 ℃ for 20 hours, thereby obtaining a polymer solution. The resulting polymer solution was slowly dropped into 400g of hexane to precipitate a solid. The precipitated solid was filtered off and dried under reduced pressure, whereby a polymer (PA-2) containing no broken structure was obtained. The Mw of the polymer (PA-2) was 22000.

[ Chemical 42]

Synthesis example 3

To 4.58g of 2-nitro-4-bromobenzyl alcohol and 3.23g of 4-vinylphenylboronic acid were added 9.9g of potassium carbonate, 28mL of water, 12mL of ethanol and 48mL of toluene, and after stirring under nitrogen, 0.71g of tetrakis (triphenylphosphine) palladium was added and the mixture was reacted at 80℃for 4 hours. After the completion of the reaction, liquid-separated extraction was performed with chloroform, and concentration and drying were performed, whereby 6.35g of a crude product was obtained. Purification by a column gave 4.30g of a monomer having a partial structure capable of forming a cleavage structure. The results of ¹ H-NMR are shown below.

¹H-NMR(500MHz、CDCl₃):

δ8.32(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),

1.18G (4.62 mmol) of the obtained monomer, 2.00g (11.55 mmol) of N-phenylmaleimide, 0.72g (6.93 mmol) of styrene and 0.08g of azobisisobutyronitrile as a polymerization catalyst were dissolved in THF35.8g and reacted at 60℃for 20 hours, thereby obtaining a polymer solution. The resulting polymer solution was slowly dropped into 300g of methanol to precipitate a solid. The precipitated solid was filtered off and dried under reduced pressure, whereby a polymer (PA-3) having a side chain comprising a partial structure capable of reacting with PL to form a cleavage structure was obtained. The Mw of the polymer (PA-3) was 22000.

[ Chemical 43]

Synthesis example 4

3.58G of 2-nitroisophthalic acid was dissolved in 40mL of anhydrous THF, and 102mL of borane-tetrahydrofuran complex (8.5% tetrahydrofuran solution) was slowly added dropwise under ice-cooling. The reaction was carried out under ice-cooling until the foaming disappeared, and the reaction was carried out overnight at room temperature. After the completion of the reaction, ice-cooled and quenched with ice-water. Ethyl acetate was added thereto to conduct liquid-phase extraction, and the mixture was washed with saturated brine. 2.8g of the crude product obtained was purified by a column to obtain 2.40g of 2-nitroisophthaloyl dimethanol. The results of ¹ H-NMR are shown below.

¹H-NMR(500MHz、CDCl₃):

δ7.58(s,3H),4.74(d,4H,J＝6.0Hz),2.18(t,2H,J＝6.0Hz).

2.40G (13.10 mmol) of the obtained 2-nitro-m-xylylene glycol, 2.24g (12.84 mmol) of toluene-2, 4-diisocyanate and 0.01g of dibutyltin dilaurate as a polymerization catalyst were dissolved in 41.8g of THF and reacted under reflux for 20 hours to obtain a polymer solution. The resulting polymer solution was slowly dropped into 300g of methanol to precipitate a solid. The precipitated solid was filtered off and dried under reduced pressure, whereby a polymer (PA-4) having a broken structure in the main chain was obtained. The Mw of the polymer (PA-4) was 18000.

[ 44]

Synthesis example 5

By the same procedures as in Synthesis example 4, 2.40g of 2-nitro-m-xylylene glycol was obtained. 2.31g (12.61 mmol) of the resulting 2-nitro-m-xylylene glycol, 2.51g (12.36 mmol) of m-xylylene chloride and 2.00g (25.22 mmol) of pyridine were dissolved in NMP15.9g and reacted at 60℃for 20 hours, whereby a polymer solution was obtained. The resulting polymer solution was slowly dropped into 300g of methanol to precipitate a solid. The precipitated solid was filtered off and dried under reduced pressure, whereby a polymer (PA-5) having a broken structure in the main chain was obtained. The Mw of the polymer (PA-5) was 3100.

[ 45]

Synthesis example 6

To 12.05g of 1, 4-diacetylbenzene and 12.46g of hydroxylamine hydrochloride were added 60mL of DMF, and the mixture was reacted at 80℃for 3 hours. After the completion of the reaction, 200mL of water was added to collect a solid, which was washed 3 times with water and dried to obtain 14.07g of diol. The results of ¹ H-NMR are shown below.

¹H-NMR(500MHz、DMSO-d₆):δ11.26(s,2H),7.67(s,4H),2.17(s,6H).

1.70G (8.84 mmol) of the obtained diol, 2.17g (8.67 mmol) of methylene diphenyl 4,4' -diisocyanate and 0.01g of dibutyltin dilaurate as a polymerization catalyst were dissolved in NMP34.9g and reacted at 60℃for 20 hours, thereby obtaining a polymer solution. The resulting polymer solution was slowly dropped into 300g of methanol to precipitate a solid. The precipitated solid was filtered off and dried under reduced pressure, whereby a polymer (PA-6) having a broken structure in the main chain was obtained.

[ Chemical 46]

Synthesis example 7

4.00G (28.97 mmol) of terephthalyl alcohol, 4.54g (26.08 mmol) of toluene-2, 4-diisocyanate and 0.02g of dibutyltin dilaurate as a polymerization catalyst were dissolved in 34.2g of THF and reacted under reflux with heating for 20 hours to thereby obtain a polymer solution. The resulting polymer solution was slowly dropped into 300g of methanol to precipitate a solid. The precipitated solid was filtered off and dried under reduced pressure, whereby a polymer (PA-7) containing no broken structure was obtained. The Mw of the polymer (PA-7) was 21000.

[ 47]

[2] Synthesis of crosslinker

Synthesis example 8

To 10.11g of 1,3, 5-triacetoxybenzene and 12.45g of hydroxylamine hydrochloride were added 60mL of DMAc, and the mixture was reacted at 80℃for 5 hours. After the completion of the reaction, 200mL of water was added to collect a solid, which was washed with water for 3 times and dried to obtain 11.96g of 1,3, 5-triacetyl-phenyloxime. To 1.81g of the obtained 1,3, 5-triacetoxybenzoxime and 2.93g of 2-allyloxypropionic acid were added 40mL of THF and stirred, 5.43g of 1- (dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 4.46g of 1-hydroxybenzotriazole, and the mixture was reacted overnight at room temperature. After the completion of the reaction, the mixture was extracted with ethyl acetate, washed with sodium hydrogencarbonate water, and then concentrated and dried to obtain 4.12g of a crude product. The crude product obtained was purified by column to obtain 3.78g of 1,3, 5-triacetoxybenzoxime 2-allyloxypropionate. To 3.78g of the obtained 1,3, 5-triacetoxybenzoxime 2-allyloxypropionate was added 60mL of chloroform, and after stirring under ice-cooling, 6.28g of m-chloroperoxybenzoic acid was added to the mixture to react overnight. After the completion of the reaction, the mixture was extracted with chloroform, washed 3 times with sodium hydrogencarbonate water, and then concentrated and dried to obtain 5.8g of a crude product. The crude product obtained was purified by means of a column to obtain 2.0g of a crosslinking agent (B-1) having a cleavage structure. The results of ¹ H-NMR are shown below.

¹H-NMR(500MHz、CDCl₃):

δ8.17(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).

[ 48]

[3] Preparation of composition for Forming resin substrate

PREPARATION EXAMPLE 1 preparation of composition F1 for Forming resin substrate

To an eggplant-shaped flask containing 100g of carbon tetrachloride, 10g of ZEONOR (registered trademark) 1020R (a cyclic olefin polymer manufactured by rayleigh Weng Zhushi, japan) and 3g of EPOLEAD (registered trademark) GT401 (manufactured by cellophane corporation) were added. The solution was stirred under nitrogen atmosphere for 24 hours to dissolve the solution, thereby preparing a resin substrate-forming composition F1.

[4] Preparation of composition for Forming Release layer

Examples 1 to 1

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 were mixed to obtain a mixture. CHN was added to the obtained mixture as a solvent to prepare a composition (A-1) for forming a release layer having a solid content concentration of 5.0% by mass.

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 respective components were as described in table 1.

TABLE 1

[5] Production of release layer and evaluation thereof

Examples 2 to 1

The release layer-forming composition (A-1) was applied onto a glass substrate (EAGLE XG, 100 mm. Times.100 mm. Times.0.7 mm manufactured by Corning Co., ltd.) as a base using a spin coater (condition: rotation speed 800rpm for about 30 seconds). The obtained coating film was heated at 80℃for 2 minutes using a hot plate, followed by heating at 150℃for 10 minutes using a hot plate, to form a peeling layer having a thickness of about 0.1. Mu.m on a glass substrate. Then, a spin coater (condition: rotation speed 500rpm for about 30 seconds) was used to apply the resin substrate-forming composition F1 to the entire surface of the glass substrate on which the release layer was formed. The obtained coating film was heated at 80℃for 2 minutes using a hot plate to form a resin precursor, and then heated at 150℃for 30 minutes using a hot plate to form a resin substrate (resin layer) having a thickness of about 3 μm on the release layer, to obtain a glass substrate with a resin substrate/release layer.

Examples 2-2 to 2-7, comparative examples 2-1 and 2-2

Resin substrate-peeled glass substrates of examples 2-2 to 2-7 and comparative examples 2-1 and 2-2 were obtained in the same manner as in example 2-1 except that the compositions (A-2) to (A-9) for forming a peeling layer were used in place of the composition (A-1) for forming a peeling layer and the heating temperature using a hot plate was changed to the temperature described in "heating temperature" in Table 2.

Comparative examples 2 to 3

The resin substrate-forming composition F1 was applied onto a glass substrate (EAGLE XG, 100 mm. Times.100 mm. Times.0.7 mm, manufactured by Corning Co., ltd.) as a base using a spin coater (condition: rotation speed 500rpm for about 30 seconds). The obtained coating film was heated at 80℃for 2 minutes using a hot plate, and then heated at 150℃for 30 minutes using a hot plate, to form a resin substrate having a thickness of about 3 μm on a glass substrate, thereby obtaining a glass substrate with a resin substrate.

[ Evaluation of peeling force ]

The resin substrate/release layer-carrying glass substrates obtained in examples 2-1 to 2-7, comparative examples 2-1 and 2-2, and the resin substrate-carrying glass substrate obtained in comparative example 2-3 were irradiated with ultraviolet rays of 2000mJ/cm ² (in terms of 365 nm) through a cut-off filter absorbing light having a wavelength of 300nm or less by using a high-pressure mercury lamp in a half area of the surface on which the resin substrate was formed. Then, a scribe was formed in a long shape of 25mm×50mm on each of the exposed portion and the unexposed portion by using a dicing blade. Further, SELLOTAPE (registered trademark) (CT-24 manufactured by NICHIBAN Co., ltd.) was adhered to the resin substrate, and then peeled off at a peeling angle of 90℃at a peeling rate of 300 mm/min using an Autograph AGS-X500N (manufactured by Shimadzu corporation), and the peeling force was measured. The sample of the resin substrate which was not peeled off from the glass substrate was evaluated as "unable to peel (> 8.0)", since peeling occurred at the interface between the resin substrate and SELLOTAPE (registered trademark) at this time, the peeling force was about 8.0N/25 mm. The evaluation results were defined as "peeling force", and the results of the exposed portion and the unexposed portion are shown in Table 2.

TABLE 2

According to the results shown in table 2, in the examples, the resin substrate could not be peeled off before exposure, or exhibited a high peeling force. On the other hand, the resin substrate can be peeled off after exposure, showing a low peeling force.

On the other hand, in the comparative example, the resin substrate could not be peeled off regardless of the presence or absence of exposure.

Claims

1. A laminate, characterized in that the laminate has: a support having a transmission of active energy rays, a release layer on the support, and a resin layer on the release layer,

The resin layer is formed from a resin layer precursor,

The film forming component has a first reactive group,

2. The laminate according to claim 1, wherein the laminate satisfies at least any one of the following conditions (A) and (B),

Condition (a): the film forming component has the fracture structure;

3. The laminate according to claim 1, wherein the cleavage structure comprises at least any one selected from an oxime ester structure, an oxime ether structure, an o-nitrobenzyl structure, an acetophenone structure, an alkylbenzene ketone structure, a pyrenylmethyl structure, a coumarin ylmethyl structure, an aminoalkyl ketone structure, and a benzyl ketal structure.

4. The laminate according to claim 3, wherein the cleavage structure comprises at least any one selected from the group consisting of the oxime ester structure, the oxime ether structure, the o-nitrobenzyl structure and the acetophenone structure,

The o-nitrobenzyl structure is shown in the following formula (2),

The acetophenone structure is shown in the following formula (3),

In the 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 heterocyclic group having 2 to 30 carbon atoms, or a group in which 1 or not adjacent 2 or more of the hydrocarbon group or the methylene group in the heterocyclic group are substituted with a 2-valent group selected from the group consisting of:

Group I is-O-, -C (=o) O-, -N (-R ³)-、-N(-R³)C(＝O)-、-S-、-C(＝S)-、-SO₂ -, -SC (=o) -and-OC (=s) -, 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 and is preferably selected from the group consisting of,

In the 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 heterocyclic group having 2 to 30 carbon atoms, or a group in which 1 or not adjacent 2 or more of the hydrocarbon group or the methylene group in the heterocyclic group are substituted with a 2-valent group selected from the group consisting of:

R ¹² represents a halogen atom, a cyano group, a hydrocarbon group having 1 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms;

n11 represents 0 or 1;

n12 represents an integer of 0 to 3, R ¹² is the same or different when n12 is 2 or 3,

In the 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 are the same or different;

n22 represents 0 or 1 and is preferably selected from the group consisting of,

In the formulas (1) to (3), the bonding bond is represented.

5. The laminate according to claim 2, wherein the laminate satisfies the condition (A),

The film forming component comprises a polymer and a cross-linking agent,

The crosslinker has the first reactive group and the cleavage structure.

6. The laminate according to claim 2, wherein the laminate satisfies the condition (A),

The film forming component comprises a polymer and a cross-linking agent,

The polymer has the above-mentioned broken structure,

The crosslinker has the first reactive group.

7. The laminate according to claim 2, wherein the laminate satisfies the condition (B),

The film forming component comprises a polymer and a cross-linking agent,

The crosslinker has the first reactive group.

8. The laminate of claim 1, wherein the first reactive group and the second reactive group are the same reactive group.

9. A method for producing a laminate, comprising the steps of:

a step of forming a release layer on a support having transparency to active energy rays;

forming a resin layer precursor on the release layer; and

A step of converting the resin layer precursor into a resin layer,

The film forming component has a first reactive group,

10. The method for producing a laminate according to claim 9, wherein the method for producing a laminate satisfies at least any one of the following conditions (A) and (B),

Condition (a): the film forming component has the fracture structure;

11. The method for producing a laminate according to claim 9, wherein the cleavage structure comprises at least any one selected from an oxime ester structure, an oxime ether structure, an o-nitrobenzyl structure, an acetophenone structure, an alkylbenzene ketone structure, a pyrenylmethyl structure, a coumarin ylmethyl structure, an aminoalkyl ketone structure, and a benzyl ketal structure.

12. The method for producing a laminate according to claim 11, wherein the cleavage structure comprises at least any one selected from the group consisting of the oxime ester structure, the oxime ether structure, the o-nitrobenzyl structure and the acetophenone structure,

The o-nitrobenzyl structure is shown in the following formula (2),

The acetophenone structure is shown in the following formula (3),

n1 represents 0 or 1;

n2 represents 0 or 1 and is preferably selected from the group consisting of,

n11 represents 0 or 1;

n22 represents 0 or 1 and is preferably selected from the group consisting of,

In the formulas (1) to (3), the bonding bond is represented.

13. The method for producing a laminate according to claim 10, wherein the laminate satisfies the condition (A),

The film forming component comprises a polymer and a cross-linking agent,

The crosslinker has the first reactive group and the cleavage structure.

14. The method for producing a laminate according to claim 10, wherein the laminate satisfies the condition (A),

The film forming component comprises a polymer and a cross-linking agent,

The polymer has the above-mentioned broken structure,

The crosslinker has the first reactive group.

15. The method for producing a laminate according to claim 10, wherein the laminate satisfies the condition (B),

The film forming component comprises a polymer and a cross-linking agent,

The crosslinker has the first reactive group.

16. The method for producing a laminate according to claim 9, wherein the first reactive group and the second reactive group are the same reactive group.

17. The method for producing a laminate according to claim 9, 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.

18. A method for manufacturing an electronic device, comprising:

A step of forming at least one selected from a photoelectric conversion element, a display element, a member for a display element, and an electronic circuit on the resin layer of any one of the laminated body according to any one of claims 1 to 8 and the laminated body produced by the method for producing a laminated body according to any one of claims 9 to 17; and

And a step of irradiating the release layer with the active energy rays from the support side of the laminate to release the support from the resin layer.

19. A composition for forming a release layer, which is used for any one of the production of the laminate according to claim 2 and the production method of the laminate according to claim 10,

The composition for forming a release layer contains a film-forming component and a solvent,

The composition for forming a release layer satisfies at least one of the following conditions (A) and (B),

Condition (a): the film forming component has the fracture structure;

Condition (B): the film-forming component has 2 partial structures capable of reacting with each other to form the cleavage structure,

The film forming component has a first reactive group.

20. The composition for forming a release layer according to claim 19, wherein the cleavage structure comprises at least any one selected from an oxime ester structure, an oxime ether structure, an o-nitrobenzyl structure, an acetophenone structure, an alkylbenzene ketone structure, a pyrenylmethyl structure, a coumarin ylmethyl structure, an aminoalkyl ketone structure, and a benzyl ketal structure.

21. The composition for forming a release layer according to claim 20, wherein the cleavage structure contains at least any one selected from the group consisting of the oxime ester structure, the oxime ether structure, the o-nitrobenzyl structure, and the acetophenone structure,

The o-nitrobenzyl structure is shown in the following formula (2),

The acetophenone structure is shown in the following formula (3),

n1 represents 0 or 1;

n2 represents 0 or 1 and is preferably selected from the group consisting of,

n11 represents 0 or 1;

n22 represents 0 or 1 and is preferably selected from the group consisting of,

In the formulas (1) to (3), the bonding bond is represented.

22. The composition for forming a release layer according to claim 19, wherein the composition for forming a release layer satisfies the condition (a),

The film forming component comprises a polymer and a cross-linking agent,

The crosslinker has the first reactive group and the cleavage structure.

23. The composition for forming a release layer according to claim 19, wherein the composition for forming a release layer satisfies the condition (a),

The film forming component comprises a polymer and a cross-linking agent,

The polymer has the above-mentioned broken structure,

The crosslinker has the first reactive group.

24. The composition for forming a release layer according to claim 19, wherein the composition for forming a release layer satisfies the condition (B),

The film forming component comprises a polymer and a cross-linking agent,

The crosslinker has the first reactive group.

25. The composition for forming a release layer according to claim 19, wherein the first reactive group and the second reactive group of the resin layer precursor are the same reactive group.