Composition for forming release layer, and release layer

Abstract

The present invention provides a composition for forming a release layer, the composition containing: (A) a resin having a hydroxy group or a carboxy group; (B) a photoacid generator; (C) a crosslinking agent which is selected from among compounds having a nitrogen atom that is substituted by a hydroxyalkyl group and / or an alkoxymethyl group; (D) a polymer additive which comprises a repeating unit represented by formula (a), a repeating unit represented by formula (b), and a repeating unit represented by formula (c); and (E) a solvent. With respect to this composition for forming a release layer, the polymer additive (D) is contained in an amount of 5 parts by mass to 100 parts by mass with respect to 100 parts by mass of the resin (A) having a hydroxy group or a carboxy group.

Description

Release layer-forming composition and release layer

[0001] The present invention relates to a composition for forming a release layer and a release layer.

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

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

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

[0005] Generally, flexible touch screen panels are produced stably by forming a release (adhesive) layer on a support substrate such as a glass substrate, and then peeling it off after fabricating a device on the support substrate (Patent Document 8). This flexible touch screen must not be peeled off from the support substrate during the process, but low peeling force is required when peeling. In particular, peeling off from the support substrate during the flexible touch screen panel fabrication process can cause contamination of the production line and a significant decrease in yield. Furthermore, to improve productivity, the release layer must be deposited and then stored in its formed state for a long period of time. For this reason, the release layer must be stable after deposition.

[0006] International Publication No. 2012 / 147235 JP 2009-283410 A JP 2010-507199 A JP 2009-205924 A JP 2017 / 002664 JP 2016 / 160338 JP 2015-166145 A JP 2016-531358 A

[0007] The present invention has been made in consideration of the above circumstances, and aims to provide a composition for forming a release layer that has high heat resistance and appropriate release properties, can suppress unnecessary peeling during processing, and provides a release layer that has excellent stability after film formation.

[0008] As a result of extensive research into achieving the above-mentioned object, the present inventors have found that by using a resin composition containing (A) a resin having a hydroxy group or a carboxy group, (B) a photoacid generator, (C) a crosslinking agent selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and / or an alkoxymethyl group, (D) a polymer additive containing a predetermined repeating unit, and (E) a solvent, a release layer can be formed in a predetermined region by exposure and development steps, and that the release layer has excellent adhesion to a substrate and moderate adhesion and moderate releasability to a resin substrate, and that the resin composition can provide the release layer with good reproducibility, thereby completing the present invention.

[0009] That is, the present invention provides the following release layer-forming composition and release layer: 1. A release layer-forming composition comprising: (A) a resin having a hydroxy group or a carboxy group, (B) a photoacid generator, (C) a crosslinking agent selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and / or an alkoxymethyl group, (D) a polymer additive including a repeating unit represented by the following formula (a), a repeating unit represented by the following formula (b), and a repeating unit represented by the following formula (c), and (E) a solvent, wherein the polymer additive (D) is included in an amount of 5 to 100 parts by mass per 100 parts by mass of the (A) resin having a hydroxy group or a carboxy group. (In the formula, R A are each independently a hydrogen atom or a methyl group; R Bis a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; R C is a hydroxyalkyl group having 2 to 10 carbon atoms, but the carbon atom to which the hydroxy group is bonded is a secondary or tertiary carbon atom; R D is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.) 2. A release layer-forming composition according to 1, wherein (A) the resin having a hydroxy group or a carboxy group is polyurea having a hydroxy group, an acrylic polymer having a hydroxy group or a carboxy group, a polyester having a hydroxy group, or cellulose having a hydroxyalkyl group or a derivative thereof. 3. A release layer-forming composition according to 1 or 2, wherein (B) the acid generated by the photoacid generator is hydrochloric acid or an organic sulfonic acid. 4. A release layer obtained from a release layer-forming composition according to any one of 1 to 3. 5. A laminate in which a resin layer having a transmittance of 80% or more to light with a wavelength of 400 nm is laminated on the release layer according to 4. 6. A method for producing a release layer, comprising the steps of: forming a resin film on a substrate using a release layer-forming composition according to any one of 1 to 3; exposing predetermined regions of the resin film to radiation; and developing the exposed resin film and removing unexposed areas. 7. A method for manufacturing a resin substrate, comprising: a step of forming a resin film on a substrate using a release layer-forming composition according to any one of 1 to 3; a step of exposing a predetermined region of the resin film to radiation; a step of developing the resin film irradiated with radiation with a developer to remove unexposed portions and form a release layer in the predetermined region; a step of forming a resin substrate having a transmittance of 80% or more to light with a wavelength of 400 nm on the surface of the substrate on which the release layer has been formed in the predetermined region, so as to completely cover the release layer; and a step of peeling off the resin substrate formed on the release layer with a peeling force of 1.0 N / 25 mm or less.

[0010] By using the release layer-forming composition of the present invention, it is possible to reproducibly obtain a release layer that has excellent adhesion to the substrate and appropriate releasability from the resin substrate, and that can be formed in a predetermined area by exposure and development processes. Furthermore, in the manufacturing process of a flexible electronic device, unnecessary peeling can be suppressed during manufacturing without damaging the resin substrate formed on the substrate or the circuits and the like formed thereon, making it possible to separate the resin substrate together with the circuits and the like from the substrate when necessary. Therefore, the release layer-forming composition of the present invention can contribute to speeding up the manufacturing process of flexible electronic devices equipped with a resin substrate and improving its yield.

[0011] [Composition for forming a release layer] The composition for forming a release layer of the present invention comprises (A) a resin having a hydroxy group or a carboxy group, (B) a photoacid generator, (C) a crosslinking agent selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and / or an alkoxymethyl group, (D) a polymer additive containing a predetermined repeating unit, and (E) a solvent.

[0012] [(A) Resin Having a Hydroxy Group or a Carboxy Group] The resin having a hydroxy group or a carboxy group of the component (A) is not particularly limited as long as it reacts with the acid generated from the component (B) and the crosslinking agent of the component (C) and hardens. However, polyurea having a hydroxy group, an acrylic polymer having a hydroxy group or a carboxy group, polyester having a hydroxy group, or cellulose having a hydroxyalkyl group or a derivative thereof is preferred.

[0013] The polyurea having a hydroxy group preferably contains a repeating unit represented by the following formula (1):

[0014] In formula (1), A 1 , A 2 , A 3 , A 4 , A 5 and A 6 are each independently a hydrogen atom, a methyl group, or an ethyl group. From the viewpoint of releasability and productivity, A 1 ~A 6 are preferably all hydrogen atoms.

[0015] In formula (1), X 1 is a group represented by the following formula (X1), (X2), (X3) or (X4). (In the formula, * represents a bond to the carbonyl group in the formula, and ** represents a bond to the nitrogen atom in the formula.)

[0016] In formulas (X1) and (X2), R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group. The phenyl group may be substituted with at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 6 carbon atoms. 1 and R 2 may be bonded to each other to form a ring having 3 to 6 carbon atoms together with the carbon atoms to which they are attached.

[0017] In formula (X3), R 3 is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group. The phenyl group may be substituted with at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 6 carbon atoms.

[0018] In formula (1), Q 1 is a group represented by the following formula (Q1) or (Q2): (In the formula, * represents a bond.)

[0019] In formula (Q1), X 2 is a group represented by formula (X1), formula (X2) or formula (X4). 2 is a group represented by formula (X2), its structure is represented by formula (Q1-1) below. (In the formula, R 1 and R 2 is the same as above. * is a bond.)

[0020] In formula (Q2), Q2 is an alkylene group having 1 to 10 carbon atoms, a phenylene group, a naphthylene group, or an anthrylene group. The phenylene group, naphthylene group, and anthrylene group may be substituted with at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 6 carbon atoms. 2 When n is a phenylene group, naphthylene group, or anthrylene group, the bonding positions thereof are not particularly limited. That is, for example, the phenylene group may be bonded at the 1st and 2nd positions, the 1st and 3rd positions, or the 1st and 4th positions, the naphthylene group may be bonded at the 1st and 2nd positions, the 1st and 4th positions, the 1st and 5th positions, or the 2nd and 3rd positions, and the anthrylene group may be bonded at the 1st and 2nd positions, the 1st and 4th positions, or the 9th and 10th positions, and any of these may be acceptable. 1 and n 2 are each independently 0 or 1.

[0021] The alkyl group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a cyclohexyl group, etc. The alkenyl group having 3 to 6 carbon atoms may be linear, branched, or cyclic, and examples thereof include a 2-propenyl group, a 3-butenyl group, etc.

[0022] The alkoxy group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include a methoxy group, an ethoxy group, an isopropoxy group, an n-pentyloxy group, and a cyclohexyloxy group. The alkylthio group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and specific 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. In addition, R 1 and R 2Examples of the ring having 3 to 6 carbon atoms formed by bonding include a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring.

[0023] The alkylene group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include a methylene group, an ethylene group, a propylene group, a pentamethylene group, a cyclohexylene group, and a 2-methylpropylene group.

[0024] In addition, in formula (1), X 1 When X is a group represented by formula (X2), the structure is represented by formula (1A) below. 1 is a group represented by formula (X3), its structure is represented by formula (1B) below. 3 However, it is preferably a 2-propenyl group. (In the formula, A 1 ~A 6 , R 1 ~R 3 and Q 1 is the same as above.)

[0025] In formula (1), Q 1 Preferably, Q contains a cyclic structure from the viewpoint of the heat resistance of the polyurea of ​​the component (A). 1 is a group represented by formula (Q1) or a group represented by formula (Q2), 2 is preferably a cyclic alkylene group, a phenylene group, a naphthylene group or an anthrylene group, and more preferably a group represented by formula (Q1).

[0026] The repeating unit represented by formula (1) is preferably one represented by the following formulas (1-1) to (1-19): In the following formulas, Me is a methyl group, and Et is an ethyl group.

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033] The polyurea can be synthesized, for example, by referring to International Publication No. 2005 / 098542.

[0034] Examples of the acrylic polymer having a hydroxy group or a carboxy group include a homopolymer of an acrylic acid ester, a homopolymer of a methacrylic acid ester, a copolymer thereof, and a copolymer of these with a monomer having an unsaturated double bond such as styrene.

[0035] A preferred example of the acrylic polymer is an acrylic polymer having a polyethylene glycol ester group or a hydroxyalkyl ester group having 2 to 6 carbon atoms. Such an acrylic polymer may be an acrylic polymer having any of these groups, and there are no particular limitations on the main chain skeleton (other repeating units) and the type of side chain that constitutes the acrylic polymer.

[0036] The acrylic polymer having a polyethylene glycol ester group or a hydroxyalkyl ester group having 2 to 6 carbon atoms preferably contains a repeating unit represented by the following formula (2):

[0037] In formula (2), R 11 is a hydrogen atom or a methyl group. 12 is -(CH2CH2O) n It is a —H group or a hydroxyalkyl group having 2 to 6 carbon atoms, and n is an integer of 2 to 30, preferably an integer of 2 to 10.

[0038] Examples of the hydroxyalkyl group having 2 to 6 carbon atoms include a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, a 4-hydroxybutyl group, and a 2,3-dihydroxypropyl group.

[0039] Furthermore, the acrylic polymer may contain a repeating unit other than the repeating unit represented by formula (2), specifically, a repeating unit derived from a monomer that does not have a polyethylene glycol ester group or a hydroxyalkyl ester group having 2 to 6 carbon atoms, as long as the effects of the present invention are not impaired.

[0040] The method for producing the acrylic polymer is not particularly limited, but examples thereof include a method in which a monomer having at least one of a polyethylene glycol group and a hydroxyalkyl group having 2 to 6 carbon atoms, and, if necessary, a monomer not having a polyethylene glycol ester group or a hydroxyalkyl ester group having 2 to 6 carbon atoms, are polymerized in a solution obtained by dissolving a polymerization initiator in a solvent at a temperature of 50 to 110° C. The solvent used is not particularly limited as long as it dissolves the monomer, polymerization initiator, etc.

[0041] The monomer having a polyethylene glycol ester group is H—(OCH2CH2) n Examples of the monomer having a hydroxyalkyl group having 2 to 6 carbon atoms include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, glycerin monoacrylate, and glycerin monomethacrylate.

[0042] Examples of the monomer that does not have a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 6 carbon atoms include carboxylic acid compounds such as acrylic acid and methacrylic acid; acrylic acid ester compounds such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate, phenyl acrylate, and 4-hydroxyphenyl acrylate; methacrylic acid ester compounds such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, phenyl methacrylate, and 4-hydroxyphenyl methacrylate; maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide, N-(4-hydroxyphenyl)maleimide, and N-cyclohexylmaleimide; acrylamide compounds; methacrylamide compounds; acrylonitrile, maleic anhydride, styrene compounds; and vinyl compounds.

[0043] The acrylic polymer obtained by the above method is usually in the form of a solution dissolved in a solvent.

[0044] Suitable examples of the acrylic polymer include polymers obtained by polymerizing hydroxyalkyl ester monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, glycerin monoacrylate, and glycerin monomethacrylate; and acrylic polymers having a hydroxyalkyl group in the side chain, such as polymers obtained by copolymerizing the hydroxyalkyl ester monomers with monomers other than these monomers, for example, one or more monomers selected from the group consisting of monomers having no polyethylene glycol ester group and no hydroxyalkyl ester group having 2 to 6 carbon atoms.

[0045] The polyester having a hydroxy group is not particularly limited, but is preferably one having an aromatic group or an alicyclic group in the main chain, and is preferably a polyester obtained by reacting a compound having two or more epoxy moieties with a compound having two carboxy groups.

[0046] Examples of the compound having two or more epoxy moieties include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD ​​diglycidyl ether, bisphenol S diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyl diglycidyl ether, tetramethylbiphenyl diglycidyl ether, 9,9'-bis(4-hydroxyphenyl)furodienyl glycidyl ether, 9,9'-bis(4-hydroxyphenyl)furodienyl glycidyl ether, and 9,9'-bis(6-hydroxy-2-naphthyl)furodienyl glycidyl ether; ethylene glycol diglycidyl ether, and propylene glycol diglycidyl ether. aliphatic diol diglycidyl ethers such as glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and neopentyl glycol diglycidyl ether; cyclohexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, dicyclopentadiene diol diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, and hydrogenated bisphenol A diglycidyl ether; alicyclic diol diglycidyl ethers such as bisphenol B diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, and the like; aromatic diglycidyl esters of dicarboxylic acids such as phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, and terephthalic acid diglycidyl ester; alicyclic diglycidyl esters of dicarboxylic acids such as bisglycidyl oxalate, bisglycidyl adipate, bisglycidyl pimelate, and bisglycidyl 2-ethyl-3-propyl-1,5-pentanedioate;Alicyclic dicarboxylic acid diester diepoxides such as bis(3,4-epoxycyclohexylmethyl) oxalate, bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis(3,4-epoxycyclohexylmethyl) pimelic acid, and bis(3,4-epoxycyclohexylmethyl) 2-ethyl-3-propyl-1,5-pentanedioate; and alicyclic dioxides such as vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, Epocalic (registered trademark) THI-DE, DE-102, DE-103 (manufactured by ENEOS Corporation), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2,2-bis(3,4-epoxycyclohexyl)propane. These compounds may be used alone or in combination of two or more.

[0047] Examples of compounds having two carboxy groups include terephthalic acid, isophthalic acid, diphenic acid, 2-methylterephthalic acid, 2-hydroxyterephthalic acid, 2,5-dimethylterephthalic acid, 5-methylisophthalic acid, 5-hydroxyisophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc. These compounds may be used alone or in combination of two or more.

[0048] The method for synthesizing the polyester is not particularly limited, but examples thereof include a method in which the ester compound, the carboxyl group-containing compound, and the catalyst are polymerized in a solvent at a temperature of 50 to 150°C. The solvent used is not particularly limited as long as it dissolves the compounds, the polymerization initiator, and the like. The polyester obtained by the method is usually in the form of a solution dissolved in the solvent.

[0049] The polyester preferably contains a repeating unit represented by the following formula (3):

[0050] In formula (3), Y1 and Z 1 are each independently a divalent group having an aromatic ring or an alicyclic ring.

[0051] Y 1 As the group, a group represented by the following formula (Y1-1) is preferred. (In the formula, * represents a bond.)

[0052] In formula (Y1-1), L 1 are each independently an ether bond or an ester bond. 2 are each independently a divalent cyclic unsaturated hydrocarbon group having 3 to 10 carbon atoms or a divalent cyclic saturated hydrocarbon group having 3 to 10 carbon atoms. 21 represents a single bond, an ether bond, a carbonyl group, a sulfonyl group, a divalent saturated hydrocarbon group having 1 to 30 carbon atoms, a divalent unsaturated hydrocarbon group having 2 to 30 carbon atoms, or a divalent saturated hydrocarbon group having 1 to 30 carbon atoms substituted with a fluorine atom. p is 0, 1, or 2.

[0053] Y 2 is preferably a divalent cyclic unsaturated hydrocarbon group having 4 to 16 carbon atoms or a divalent cyclic saturated hydrocarbon group having 4 to 16 carbon atoms, more preferably a divalent cyclic unsaturated hydrocarbon group having 4 to 8 carbon atoms or a divalent cyclic saturated hydrocarbon group having 4 to 8 carbon atoms. 2 Some or all of the hydrogen atoms contained in may be substituted with an aliphatic group, and a plurality of such substituents may be bonded to each other to form a 4- to 6-membered ring.

[0054] Y 2 Specific examples of the group include, but are not limited to, groups represented by the following formulae (Y2-1) to (Y2-12). (In the formula, * represents a bond.)

[0055] Z 1 is preferably an arylene group having 6 to 20 carbon atoms or a divalent cyclic saturated hydrocarbon group having 3 to 20 carbon atoms. The arylene group or the divalent cyclic saturated hydrocarbon group may be substituted with a hydroxy group, a methyl group, or the like.

[0056] Z 1 Specific examples of the group include, but are not limited to, groups represented by the following formulae (Z1-1) to (Z1-4). (In the formula, * represents a bond.)

[0057] The polyester preferably has a repeating unit represented by the following formula (4):

[0058] In formula (4), Z 1 The ring Cy is a tetravalent cyclic saturated hydrocarbon group having 4 to 20 carbon atoms or a tetravalent group represented by the following formula (Cy-1):

[0059] In formula (Cy-1), Cy′ is a trivalent cyclic saturated hydrocarbon group having 4 to 20 carbon atoms. 31 is a divalent saturated hydrocarbon group having 1 to 20 carbon atoms or a divalent unsaturated hydrocarbon group having 2 to 20 carbon atoms, which may contain an ester bond, etc. *1 and *2 are bonds, and one of the two *1 and *2 is bonded to a hydroxy group.

[0060] The tetravalent cyclic saturated hydrocarbon group and the trivalent cyclic saturated hydrocarbon group may be monocyclic or polycyclic, and in the case of a polycyclic ring, it may be any of a fused ring, a bridged ring, a spiro ring, or a ring containing a plurality of these ring structures.

[0061] Specific examples of the group represented by Cy include groups represented by the following formulae (Cy-2) to (Cy-8). (In the formula, *1 and *2 are bonds, and one of the two *1 and *2 in each structural formula is bonded to a hydroxy group.)

[0062] Examples of the cellulose or derivatives thereof having a hydroxyalkyl group include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkyl alkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl ethyl cellulose, and derivatives thereof. Among these, hydroxyalkyl celluloses and derivatives thereof are preferred, and hydroxyethyl cellulose, hydroxypropyl cellulose, and derivatives thereof are more preferred. The cellulose or derivatives thereof having a hydroxyalkyl group may be used alone or in combination of two or more.

[0063] The weight average molecular weight (Mw) of component (A) is not particularly limited, but is preferably 1,000 to 500,000, more preferably 3,000 to 400,000, and even more preferably 5,000 to 300,000. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) relative to polystyrene standards.

[0064] [(B) Photoacid Generator] The release layer-forming composition of the present invention contains a photoacid generator as component (B). The photoacid generator for component (B) is not particularly limited as long as it is a compound that is photodecomposed by irradiation with radiation to generate an acid.

[0065] Examples of the acid generated upon photolysis of the photoacid generator include hydrochloric acid; and organic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H,1H,2H,2H-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, and dodecylbenzenesulfonic acid.

[0066] Examples of the photoacid generator include bis(tosyloxy)ethane, bis(tosyloxy)propane, bis(tosyloxy)butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3-phenylene tris(methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p-toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, N-ethyl-p-toluenesulfonamide, and compounds represented by the following formulae (PAG-1) to (PAG-41).

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074] Commercially available products can be used as the photoacid generator, and specific examples thereof include Irgacure (registered trademark) PAG103, PAG121, and PAG203 (all manufactured by BASF Japan Ltd.), ADEKA ARCURES (registered trademark) SP-056, SP-066, SP-140, SP-141, SP-082, SP-601, SP-606, SP-701, SP-150, SP-170, and SP-171 (all manufactured by ADEKA Corporation), and CPI (registered trademark) 110P, -110B, -310B, -210S, -100P, -101A, -200K (all manufactured by San-Apro Ltd.), PAI-01, PAI-101, DPI-105, DPI-106, DPI-109, DPI-201, BI-105, MPI-105, MPI-106, MPI-109, BBI-102, BBI-103, BBI- 105, BBI-106, BBI-109, BBI-110, BBI-200, BBI-201, BBI-300, BBI-301, TPS-102, TPS-103, TPS-105, TPS-106, TPS-109, TPS-200, TPS-300, TPS-1000, HDS-109, MDS-103, MDS-105, MDS -205, MDS-209, BDS-109, MNPS-109, DTS-102, DTS-103, DTS-105, DTS-200, NDS-103, NDS-105, NDS-155, NDS-165, SI-105, NDI-105, NDI-109, NAI-105, and NAI-109 (all manufactured by Midori Chemical Co., Ltd.).

[0075] In the release layer-forming composition of the present invention, the content of the photoacid generator (B) is preferably 0.01 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the resin (A). When the content of the photoacid generator (B) is within the above range, the release layer-forming composition has high heat resistance and appropriate release properties, is capable of forming a release layer in a predetermined region on a substrate, and exhibits excellent stability after film formation. The photoacid generator (B) may be used alone or in combination of two or more types.

[0076] [Crosslinking Agent (C)] The release layer-forming composition of the present invention contains a crosslinking agent as component (C). The crosslinking agent is selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and / or an alkoxymethyl group.

[0077] The crosslinking agent is preferably a compound represented by any one of the following formulas (C-1) to (C-5).

[0078] In formulas (C-1) to (C-5), R 101 ~R 116 are each independently an alkyl group having 1 to 6 carbon atoms. B is a hydrogen atom or a methyl group.

[0079] Specific examples of the crosslinking agent include nitrogen-containing compounds such as hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, and 1,3,4,6-tetrakis(hydroxymethyl)glycoluril.

[0080] Other examples of commercially available nitrogen-containing compounds include methoxymethyl-type melamine compounds (trade names: Cymel (registered trademark) 300, Cymel 301, Cymel 303, Cymel 350), butoxymethyl-type melamine compounds (trade names: Mycoat (registered trademark) 506, Mycoat 508), glycoluril compounds (trade names: Cymel 1170, POWDERLINK 1174), methylated urea resins (trade names: UFR65), butylated urea resins (trade names: UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea / formaldehyde resins (trade names: Beckamine (registered trademark) J-300S, Beckamine P-955, Beckamine N), all manufactured by Allnex Corporation.

[0081] Also usable as a crosslinking agent are polymers produced using (meth)acrylamide compounds substituted with hydroxymethyl or alkoxymethyl groups, such as N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, and N-butoxymethyl(meth)acrylamide. Examples of such polymers include poly(N-butoxymethyl(meth)acrylamide), copolymers of N-butoxymethyl(meth)acrylamide and styrene, copolymers of N-hydroxymethyl(meth)acrylamide and methyl(meth)acrylate, copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, and copolymers of N-butoxymethyl(meth)acrylamide, benzyl(meth)acrylate, and 2-hydroxypropyl(meth)acrylate.

[0082] More preferred examples of the crosslinking agent include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril (POWDERLINK 1174), 1,3,4,6-tetrakis(butoxymethyl)glycoluril, and 1,3,4,6-tetrakis(hydroxymethyl)glycoluril.

[0083] These crosslinking agents can undergo a crosslinking reaction by self-condensation. They can also undergo a crosslinking reaction with the hydroxyl or carboxyl groups in the resin of component (A). This crosslinking reaction strengthens the release layer that is formed, resulting in a release layer with low solubility in organic solvents.

[0084] In the release layer-forming composition of the present invention, the content of the crosslinking agent (component (C)) is preferably 10 to 100 parts by mass, more preferably 20 to 50 parts by mass, per 100 parts by mass of the resin (component (A)). When the content of the crosslinking agent (C) is within the above range, a release layer resin composition can be obtained that has high heat resistance, appropriate release properties, and excellent stability after film formation. The crosslinking agent (C) may be used alone or in combination of two or more types.

[0085] [(D) Polymer Additive] The release layer-forming composition of the present invention contains, as component (D), a polymer additive including a repeating unit represented by the following formula (a), a repeating unit represented by the following formula (b), and a repeating unit represented by the following formula (c).

[0086] In formulas (a) to (c), R A are each independently a hydrogen atom or a methyl group. B is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. C is a hydroxyalkyl group having 2 to 10 carbon atoms, but the carbon atom to which the hydroxy group is bonded is a secondary or tertiary carbon atom. D is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.

[0087] Examples of the branched alkyl group having 3 or 4 carbon atoms include an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. B As the branched alkyl group, those in which at least one hydrogen atom has been substituted with a fluorine atom are preferred, and specific examples include a 1,1,1-trifluoroisopropyl group, a 1,1,1,3,3,3-hexafluoroisopropyl group, and a nonafluoro-tert-butyl group.

[0088] Examples of the hydroxyalkyl group having 2 to 10 carbon atoms include a 1-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 2-hydroxybutyl group, a 2-hydroxyhexyl group, a 2-hydroxyoctyl group, a 2-hydroxydecyl group, a 1-hydroxy-1-methylethyl group, and a 2-hydroxy-2-methylpropyl group.

[0089] Examples of the polycyclic alkyl group having 6 to 20 carbon atoms include a 1-adamantyl group, a 2-adamantyl group, an isobornyl group, a norbornyl group, etc. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-biphenyl group, a 2-biphenyl group, etc.

[0090] Examples of the repeating unit represented by formula (a) include, but are not limited to, those represented by the following formulae (a-1) to (a-3). A is the same as above.

[0091] Examples of the repeating unit represented by formula (b) include, but are not limited to, those represented by the following formulae (b-1) to (b-4). A is the same as above.

[0092] Examples of the repeating unit represented by formula (c) include, but are not limited to, those represented by the following formulas (c-1) to (c-13). A is the same as above.

[0093] In the polymer additive (D), the content of the repeating unit represented by formula (a) is preferably 30 to 60 mol %, more preferably 35 to 50 mol %, of all repeating units. The content of the repeating unit represented by formula (b) is preferably 10 to 35 mol %, more preferably 15 to 30 mol %, of all repeating units. The content of the repeating unit represented by formula (c) is preferably 5 to 60 mol %, more preferably 20 to 50 mol %, of all repeating units.

[0094] The Mw of the polymer additive (D) is preferably 2,000 to 10,000, more preferably 3,000 to 6,000, and the Mw / Mn is preferably 1.0 to 2.1, more preferably 1.0 to 1.9.

[0095] In the release layer-forming composition of the present invention, the content of the polymer additive (D) is 5 to 100 parts by mass, preferably 5 to 90 parts by mass, and more preferably 5 to 80 parts by mass, per 100 parts by mass of the resin (A). If the content of the polymer additive (D) is less than 5 parts by mass, the peel force may be too strong, and if it exceeds 100 parts by mass, repelling may occur during film formation. The polymer additive (D) may be used alone or in combination of two or more types.

[0096] [(E) Solvent] The release layer-forming composition of the present invention contains a solvent as component (E). The solvent is preferably a glycol ether-based solvent having 3 to 20 carbon atoms, an ester-based solvent having 3 to 20 carbon atoms, a ketone-based solvent having 3 to 20 carbon atoms, or a cyclic compound-based solvent having 3 to 20 carbon atoms.

[0097] Examples of the glycol ether solvents include 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 solvents include methyl ethyl ketone, cyclohexanone, cyclopentanone, and benzophenone. Examples of the cyclic compound solvents include N-methylpyrrolidone and γ-butyrolactone.

[0098] The content of the solvent (E) in the release layer-forming composition of the present invention is preferably an amount such that the solids concentration in the release layer-forming composition of the present invention is 0.1 to 40% by mass, more preferably 0.5 to 20% by mass, and even more preferably 0.5 to 10% by mass. The solids are a collective term for all components of the release layer-forming composition other than the solvent. The solvent (E) may be used alone or in combination of two or more.

[0099] [Other Additives] The release layer-forming composition of the present invention may contain a surfactant as needed. By adding a surfactant, the coatability of the release layer-forming composition to the substrate can be improved. As the surfactant, known surfactants such as nonionic surfactants, fluorine-based surfactants, and silicone-based surfactants can be used.

[0100] Specific 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 octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate.

[0101] Examples of the fluorine-based surfactants include FTOP (registered trademark) EF301, EF303, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), MEGAFAC (registered trademark) F171, F173, F554, F559, F563, R-30, R-40, R-40-LM, and DS-21 (manufactured by DIC Corporation), FLUORAD (registered trademark) FC430 and FC431 (manufactured by 3M), Asahiguard (registered trademark) AG710, Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd.).

[0102] Furthermore, examples of silicone surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0103] When the release layer-forming composition contains a surfactant, the content thereof is preferably 0.0001 to 1 part by mass, and more preferably 0.001 to 0.5 parts by mass, relative to 100 parts by mass of the resin (A). The surfactant may be used alone or in combination of two or more types.

[0104] [Method for preparing a composition for forming a release layer] The method for preparing the composition for forming a release layer of the present invention is not particularly limited, but examples include a method in which a solution of component (A) dissolved in a solvent is mixed with components (B), (C), (D), and (E), etc., in a predetermined ratio to obtain a homogeneous solution, and a method in which other additives are further added and mixed as necessary at an appropriate stage of the preparation method.

[0105] In preparing the composition for forming release layer of the present invention, the polymer solution obtained by polymerization reaction in solvent can be used as it is.In this case, for example, in the solution of component (A), as described above, component (B), further component (C), component (D), component (E) etc. are added to make a uniform solution.At this time, for the purpose of adjusting concentration, solvent can be added additionally.At this time, the solvent used in the process of producing component (A) and the solvent used for adjusting the concentration of composition for forming release layer can be the same or different.

[0106] The prepared solution of the composition for forming the release layer is preferably used after being filtered using a filter having a pore size of about 0.2 to 1.0 μm.

[0107] The viscosity of the release layer-forming composition of the present invention is appropriately set taking into consideration the coating method used, the thickness of the release layer to be produced, etc., but when the aim is to reproducibly obtain a film having a thickness of about 0.01 to 5 μm, the viscosity is usually about 1 to 5,000 mPa·s at 25°C, and preferably about 1 to 2,000 mPa·s.

[0108] The viscosity can be measured using a commercially available viscometer for measuring the viscosity of liquids, for example, by referring to the method described in JIS K7117-2, at a composition temperature of 25°C. Preferably, a cone-plate type rotational viscometer is used as the viscometer, and preferably the same type of viscometer is used with a standard cone rotor of 1°34' x R24, and the viscosity can be measured at a composition temperature of 25°C. An example of such a rotational viscometer is the TVE-25L manufactured by Toki Sangyo Co., Ltd.

[0109] [Release Layer] The release layer of the present invention can be produced by a method including the steps of forming a resin film on a substrate using the release layer-forming composition (resin film forming step), exposing predetermined areas of the resin film to radiation (exposure step), and developing the irradiated resin film with a developer to remove unexposed areas (development step).

[0110] In the resin film forming step, a method for forming the resin film includes applying the release layer forming composition to a substrate and then heating the applied composition. A pre-drying step of volatilizing the solvent before heating may also be included. In the present invention, the substrate refers to a substrate on whose surface the release layer forming composition of the present invention is applied, and is used in the manufacture of flexible electronic devices, etc.

[0111] Examples of the substrate include glass, metal (such as silicon wafer), slate, etc., but glass is particularly preferred because the release layer obtained from the release layer-forming composition of the present invention has sufficient adhesion thereto.The substrate surface may be composed of a single material, or may be composed of two or more materials.The substrate surface may be composed of two or more materials in the form of a substrate surface in which a certain area of ​​the substrate surface is composed of one material, and the remaining surface is composed of other materials, or in which a material in a pattern such as a dot pattern or a line and space pattern is present in the other material on the entire substrate surface.

[0112] The coating method is not particularly limited, and examples thereof include slit coating, cast coating, spin coating, blade coating, dip coating, roll coating, bar coating, die coating, inkjet printing, and printing methods (relief printing, intaglio printing, planographic printing, screen printing, etc.).

[0113] Examples of pre-drying methods include a method in which a substrate coated with a release layer-forming composition is enclosed in a predetermined container and the solvent is evaporated by reducing the pressure. The method of reducing the pressure is not particularly limited, but examples include a method in which the pressure inside a pressure-resistant container is reduced to a predetermined reduced pressure using a vacuum pump. The reduced pressure is usually 20 to 200 Pa, but preferably 40 to 100 Pa. The reduced pressure time cannot be generally specified because it varies depending on the performance of the vacuum pump and the size of the pressure-resistant container, but is usually 10 to 60 seconds, and preferably 15 to 30 seconds.

[0114] Examples of heating equipment include a hot plate, an oven, etc. The heating atmosphere may be air or an inert gas, and may be atmospheric pressure or reduced pressure.

[0115] The heating temperature is usually 50 to 250° C., preferably 50 to 150° C. The heating time cannot be generally specified because it varies depending on the heating temperature, but is usually 1 minute to 5 hours, preferably 1 minute to 1 hour.

[0116] In the exposure step, radiation is applied to a predetermined region of the resin film to harden the exposed portion. One example of a method for irradiating the predetermined region with radiation is a method of irradiating through a mask having a predetermined pattern. When irradiating through a mask, a release layer having a pattern such as a dot pattern or a line and space pattern is obtained.

[0117] The radiation is not particularly limited as long as it has a wavelength that can be absorbed by the photoacid generator, and examples thereof include ultraviolet rays or visible light having a wavelength of 150 to 800 nm. Preferably, ultraviolet rays have a wavelength of 200 to 400 nm, and specific examples thereof include i-rays (365 nm). The irradiation dose is sufficient to completely cure the exposed area, and is 100 to 2,000 mJ / cm. 2 is preferred, and 300 to 1,000 mJ / cm 2 is more preferred.

[0118] The radiation irradiation direction is not particularly limited, and may be perpendicular to the substrate surface, oblique, or a combination of these. Preferably, radiation is irradiated from an angle close to the perpendicular to the substrate surface.

[0119] The light source to be used is not particularly limited as long as it can irradiate light in the above-mentioned wavelength range, and examples thereof include a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, an excimer lamp, an electrodeless lamp, etc. Radiation in the above-mentioned preferred wavelength range can be obtained by using the above-mentioned light source in combination with a filter or the like.

[0120] After exposure, a post-exposure bake (PEB) may be performed. The heating temperature for the PEB is usually 50 to 250° C., preferably 80 to 200° C. The heating time cannot be generally specified because it varies depending on the heating temperature, but is usually 30 seconds to 30 minutes, preferably 1 to 20 minutes.

[0121] The developer used in the developing step may be any that can dissolve and remove unexposed areas, and may be appropriately selected depending on the resin of component (A). Examples of the developer include glycol ether organic solvents such as propylene glycol monomethyl ether, aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and alkaline aqueous solutions such as aqueous amine solutions such as ethanolamine, propylamine, and ethylenediamine. A surfactant or the like may be added to these developers.

[0122] The developing method may be any of the puddle method, dipping method, and swing immersion method, etc. The developing time is usually 15 to 300 seconds.

[0123] After development, the release layer is washed with running water for, for example, 20 to 120 seconds, and then air-dried using compressed air or compressed nitrogen, or by spinning, to remove water from the substrate and obtain a patterned film.

[0124] After development, a heat treatment may be carried out. The heating temperature is usually 50 to 300° C., preferably 80 to 250° C. The heating time cannot be generally specified because it varies depending on the heating temperature, but it is usually 30 seconds to 30 minutes, preferably 1 to 20 minutes.

[0125] Furthermore, the desired effect can also be achieved by removing only the component (D) present on the surface of the release layer by development.

[0126] The thickness of the release layer is usually about 0.01 to 50 μm, but from the viewpoint of productivity, it is preferably about 0.01 to 20 μm, more preferably about 0.01 to 5 μm, and the desired thickness can be achieved by adjusting the thickness of the coating film before heating.

[0127] The release layer of the present invention has excellent adhesion to a substrate, particularly a glass substrate, and also has adequate adhesion to and adequate release properties with a resin substrate. Therefore, the release layer of the present invention can be suitably used in the manufacturing process of a flexible electronic device to release a resin substrate of the device together with circuits and the like formed on the resin substrate from the substrate without damaging the resin substrate.

[0128] [Manufacturing Method of Resin Substrate] An example of a manufacturing method of a flexible electronic device using the release layer of the present invention will be described. First, a release layer is formed in a predetermined region on a substrate by the above-mentioned method using the release layer-forming composition of the present invention. A resin substrate-forming solution for forming a resin substrate is applied to the surface of the substrate on which this release layer has been formed in the predetermined region so as to cover the entire release layer, and the resulting coating is baked to form a resin substrate fixed to the substrate via the release layer of the present invention.

[0129] The baking temperature of the coating film is set appropriately depending on the type of resin, etc., but the maximum temperature during baking is preferably 200 to 250°C, more preferably 210 to 250°C, and even more preferably 220 to 240°C. By setting the maximum temperature during baking in this range when producing a resin substrate, it is possible to further improve the adhesion between the underlying release layer and the base, as well as the appropriate adhesion and releasability between the release layer and the resin substrate. In this case, too, as long as the maximum temperature is within the above range, a step of baking at a temperature lower than that may be included.

[0130] The resin substrate is preferably formed to have an area larger than the area of ​​the region where the release layer is formed. Examples of the resin substrate include a resin substrate made of an acrylic polymer and a resin substrate made of a cycloolefin polymer. The resin substrate may be formed by a conventional method. Furthermore, the resin substrate preferably has a transmittance of 80% or more for light with a wavelength of 400 nm.

[0131] Next, a desired circuit is formed as needed on the resin substrate fixed to the base via the release layer of the present invention, and then the resin substrate is cut, for example, along the release layer, and the resin substrate together with the circuit is peeled off from the release layer to separate the resin substrate from the base. At this time, a portion of the base may be cut together with the release layer. By using the release layer of the present invention, the resin substrate can be peeled off from the release layer with a peel force of 1.0 N / 25 mm or less.

[0132] The present invention will be explained in more detail below by way of synthesis examples, preparation examples, working examples and comparative examples, but the present invention is not limited to the following examples.

[0133] The compounds used in the following examples are as follows: PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl ether acetate PL-LI: 1,3,4,6-tetrakis(methoxyethyl)glycoluril (manufactured by Allnex Corporation, trade name: POWDERLINK 1174) PPTS: pyridinium p-toluenesulfonate PAG103: Irgacure PAG103 manufactured by BASF (compound represented by formula (PAG-4) above) PAG121: Irgacure PAG121 manufactured by BASF (compound represented by formula (PAG-2) above) PAI101: PAI-101 manufactured by Midori Chemical Industry Co., Ltd. (compound represented by formula (PAG-26) above) MAA: methacrylic acid MMA: methyl methacrylate HPMA: 2-hydroxypropyl methacrylate HEMA: 2-hydroxyethyl methacrylate ADMA: 2-adamantyl methacrylate CHMI: N-cyclohexylmaleimide PQMA: 4-hydroxyphenyl methacrylate HFiPMA: 1,1,1,3,3,3-hexafluoroisopropyl methacrylate AIBN: azobisisobutyronitrile EP: bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: jER828) IPhA: isophthalic acid BTEAC: benzyltriethylammonium chloride HPC: hydroxypropyl cellulose KOH: potassium hydroxide

[0134] The weight average molecular weight (Mw) of the polymer was measured using a GPC apparatus manufactured by Shimadzu Corporation (column: Shodex (registered trademark) KF803L and KF804L (manufactured by Showa Denko K.K.) ; eluent: THF; flow rate: 1.0 mL / min; column temperature: 40°C; Mw: value converted into standard polystyrene).

[0135] [1] Polymer Synthesis [Synthesis Example 1] Synthesis of Polyurea (L1) 100 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemicals Corporation), 66.4 g of 5,5-diethylbarbituric acid, and 4.1 g of benzyltriethylammonium chloride were dissolved in 682 g of PGME, and the mixture was reacted at 130°C for 24 hours to obtain a solution containing Polyurea (L1). GPC analysis showed that the Mw of the obtained Polyurea (L1) was 8,000 and the Mw / Mn was 1.5.

[0136] [Synthesis Example 2] Synthesis of acrylic polymer (L2) 1.00 g of MAA, 3.13 g of HEMA, 2.75 g of MMA, 0.63 g of PQMA, 5.00 g of CHMI, and 0.78 g of AIBN were dissolved in 29.8 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (L2) solution (solids concentration 31% by mass). As a result of GPC analysis, the Mw of the obtained acrylic polymer (L2) was 7,000, and the Mw / Mn was 1.6.

[0137] Synthesis Example 3 Synthesis of Polyester (L3) 10.0 g of EP, 5.4 g of IPhA, and 0.25 g of BTEAC were dissolved in 36.4 g of PGME and reacted at 120° C. for 20 hours to obtain a polyester (L3) solution (solids concentration: 30% by mass). GPC analysis showed that the Mw of the obtained polyester (L3) was 13,200 and the Mw / Mn was 3.9.

[0138] Synthesis Example 4 Synthesis of Acrylic Polymer (S1) 1.00 g of HFiPMA, 0.61 g of HPMA, 1.24 g of ADMA, and 0.12 g of AIBN were dissolved in 11.9 g of PGME and reacted at 70° C. for 20 hours to obtain an acrylic polymer (S1) solution (solid content concentration 20% by mass). As a result of GPC analysis, the Mw of the obtained acrylic polymer (S1) was 4,470, and the Mw / Mn was 1.8.

[0139] [Preparation Example] Preparation of composition F1 for forming resin substrate To a recovery flask containing 100 g of carbon tetrachloride, 10 g of Zeonor (registered trademark) 1020R (a cycloolefin polymer manufactured by Zeon Corporation) and 3 g of Epolead (registered trademark) GT401 (manufactured by Daicel Corporation) were added. The solution was stirred under a nitrogen atmosphere for 24 hours to dissolve the components, thereby preparing composition F1 for forming resin substrate.

[0140] [2] Preparation of release layer-forming composition [Example 1-1] Preparation of release layer-forming composition 1 100 parts by mass of the polyurea (L1) obtained in Synthesis Example 1 as the component (A), 3 parts by mass of PAG121 as the component (B), 7.5 parts by mass of PL-LI as the component (C), 7.5 parts by mass of acrylic polymer (S2) as the component (D), and PGMEA were added, and diluted with PGME to a solids concentration of 5% by mass and a PGMEA concentration of 30% by mass to prepare release layer-forming composition A-1.

[0141] [Examples 1-2 to 1-6, Comparative Examples 1-1 and 1-2] Compositions A-2 to A-8 for forming a release layer were prepared in the same manner as in Example 1-1, except that the types and amounts of each component were as shown in Table 1.

[0142]

[0143] [3] Preparation of release layer and resin substrate [Example 2-1] Using a spin coater (conditions: rotation speed 800 rpm for approximately 30 seconds), release layer-forming composition A-1 was applied onto a glass substrate (Corning Eagle XG, 100 mm x 100 mm x 0.5 mm, the same applies below) as a base. The resulting coating film was heated at 100°C for 2 minutes using a hot plate. A part of this coating film was irradiated with ultraviolet light using a Canon Inc. PLA-600FA ultraviolet irradiation device at a light intensity of 3.5 mW / cm. 2 UV light with a wavelength of 365 nm is emitted at 500 mJ / cm 2 The glass substrate was irradiated with light, then heated at 180°C for 10 minutes as a post-exposure bake (PEB) to harden the release layer. The substrate was then immersed in PGME for 5 minutes and developed. The unexposed areas were then washed with running ultrapure water for 20 seconds and heated at 230°C for 10 minutes to remove the unexposed areas, forming a release layer approximately 0.1 μm thick in a predetermined area on the glass substrate. Then, using a spin coater (conditions: rotation speed 200 rpm for approximately 15 seconds), resin substrate-forming composition F1 was applied to the entire surface of the glass substrate on which the release layer was formed in the predetermined area. The resulting coating was heated at 80°C for 2 minutes using a hot plate, and then heated at 230°C for 30 minutes using a hot plate to form a resin substrate approximately 3 μm thick on the release layer, resulting in a resin substrate / glass substrate with a release layer.

[0144] [Examples 2-2 to 2-6, Comparative Examples 2-1 and 2-2] A resin substrate and a glass substrate with a release layer were obtained in the same manner as in Example 2-1, except that the release layer-forming composition, PEB temperature, and developer were each as shown in Table 2.

[0145]

[0146] [4] Evaluation of Release Layer [Examples 3-1 to 3-6, Comparative Examples 3-1 and 3-2] [Evaluation of Release Force] 25 mm x 50 mm strips were cut using a cutter into the release layer of the resin substrates and glass substrates with release layers obtained in Examples 2-1 to 2-6 and Comparative Examples 2-1 and 2-2. Furthermore, Cellotape (registered trademark) (CT-24, manufactured by Nichiban Co., Ltd.) was applied, and then the tape was peeled off at a peel angle of 90° and a peel speed of 300 mm / min using an autograph AGS-X500N (manufactured by Shimadzu Corporation), and the release force was measured. Those that could not be peeled were deemed unpeelable. The evaluation results were recorded as "release force," and the results are summarized in Table 3.

[0147] [Evaluation of peeling interface] After the evaluation of the peeling force, the film thickness of the peeling layer remaining on the glass substrate was measured using a stylus film thickness meter. The film thickness was compared with the film thickness at the time of peeling layer formation to determine the peeling interface. The evaluation result was recorded as the "peeling interface," and a remaining film ratio (remaining film ratio (%) = peeling layer film thickness after peeling / peeling layer film thickness at the time of peeling layer formation × 100) of 90% or more was recorded as the peeling layer / resin interface, a remaining film ratio of 10% or more but less than 90% was recorded as cohesive failure of the peeling layer, and a remaining film ratio of less than 10% was recorded as the glass substrate / peeling layer interface. The evaluation results are summarized in Table 3.

[0148]

[0149] From the results shown in Table 3, it was confirmed that the release layer of the example peeled off the resin substrate only in the exposed area. On the other hand, it was confirmed that in Comparative Example 3-1, the unexposed area could not be removed by development, and the resin substrate peeled off regardless of whether exposure was performed, and in Comparative Example 3-2, the resin substrate did not peel off regardless of whether exposure was performed.

Claims

1. A composition for forming a release layer, comprising: (A) a resin having a hydroxy group or a carboxy group, (B) a photoacid generator, (C) a crosslinking agent selected from a compound having a nitrogen atom substituted with a hydroxyalkyl group and / or an alkoxymethyl group, (D) a polymer additive containing a repeating unit represented by the following formula (a), a repeating unit represented by the following formula (b), and a repeating unit represented by the following formula (c), and (E) a solvent, wherein the (D) polymer additive is contained in an amount of 5 to 100 parts by mass with respect to 100 parts by mass of the (A) resin having a hydroxy group or a carboxy group. (In the formula, R A is independently a hydrogen atom or a methyl group; R B is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; R C is a hydroxyalkyl group having 2 to 10 carbon atoms, provided that the carbon atom to which the hydroxy group is bonded is a secondary or tertiary carbon atom; R D is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.) 2. The composition for forming a release layer according to claim 1, wherein the (A) resin having a hydroxy group or a carboxy group is a polyurea having a hydroxy group, an acrylic polymer having a hydroxy group or a carboxy group, a polyester having a hydroxy group, or a cellulose having a hydroxyalkyl group or a derivative thereof.

3. The composition for forming a release layer according to claim 1 or 2, wherein the acid generated by the (B) photoacid generator is hydrochloric acid or an organic sulfonic acid.

4. A release layer obtained from the composition for forming a release layer according to any one of claims 1 to 3.

5. A laminate in which a resin layer having a light transmittance of 80% or more at a wavelength of 400 nm is laminated on the release layer according to claim 4.

6. A method for manufacturing a release layer, comprising: a step of forming a resin film on a substrate using the composition for forming a release layer according to any one of claims 1 to 3; a step of exposing a predetermined region of the resin film to radiation; and a step of developing the exposed resin film to remove the unexposed portion.

7. A step of forming a resin film on a substrate using the composition for forming a release layer according to any one of claims 1 to 3, a step of exposing a predetermined region of the resin film to radiation, a step of developing the resin film irradiated with the radiation with a developer to remove the unexposed portion and form a release layer in a predetermined region, a step of forming a resin substrate having a light transmittance of 80% or more for light with a wavelength of 400 nm so as to entirely cover the release layer on the surface of the substrate on which the release layer is formed in the predetermined region, and a step of peeling the resin substrate formed on the release layer with a peeling force of 1.0 N / 25 mm or less. A method for manufacturing a resin substrate including these steps.