Composition for forming release layer and release layer

Abstract

This invention provides a release layer forming composition, which is a release layer forming composition having high heat resistance and moderate peelability, and can impart excellent stability to the release layer after film formation, comprising: (A)(A1) Cellulose or its derivatives containing hydroxyalkyl groups, etc. (B) Acid compounds or their salts, (C) Crosslinking agents selected from compounds having nitrogen atoms substituted with hydroxyalkyl and / or alkoxymethyl groups. (D) Polymer additives containing repeating units represented by formulas (a1), (b) and (c) (E) solvent, and For every 100 parts by mass of component (A), there are 5 to 100 parts by mass of component (D). (R A is a hydrogen atom or a methyl group, R B1 is a branched alkyl group with 3 or 4 carbon atoms, in which at least one hydrogen atom is substituted by a fluorine atom; R C is a hydroxyalkyl group having 1 to 10 carbon atoms, R D is a polycyclic alkyl group with 6 to 20 carbon atoms or an aryl group with 6 to 12 carbon atoms.

Description

[Technical Field]

[0001] This invention relates to a composition for forming a release layer and a release layer. [Previous Technology]

[0002] In recent years, in addition to the characteristics of thinness and lightness, electronic devices also require the ability to be flexible. Therefore, in order to replace the bulky, fragile and inflexible glass substrates of the past, it is necessary to use lightweight flexible plastic substrates.

[0003] In particular, the development of active-matrix full-color TFT display panels using lightweight flexible plastic substrates (hereinafter also referred to as resin substrates) is required in next-generation displays. Furthermore, touch panel displays are developing materials that can accommodate flexibility, such as transparent electrodes or resin substrates used in conjunction with touch panels in display panels. As transparent electrodes, in addition to the previously used ITO, proposals have been made for flexible transparent conductive polymers such as PEDOT, metal nanowires, and their hybrid systems, as well as other transparent electrode materials (Patent Documents 1-4).

[0004] On the other hand, the substrate of the touch panel film has also changed from glass to a sheet made of plastics such as polyethylene terephthalate (PET), polyimide, cycloolefins, and acrylic, and a flexible transparent touch screen panel is being developed (Patent Documents 5-7).

[0005] Generally, flexible touchscreen panels are manufactured by forming a release (adhesive) layer on a support substrate such as a glass substrate, and then peeling it off after fabricating a device thereon (Patent Document 8), in order to ensure stable production and peeling. This release layer cannot be peeled off from the support substrate during the process, and a low peeling force is necessary during peeling. Furthermore, to improve productivity, it is necessary to store the release layer in film form for a long period after it has been formed. Therefore, the release layer must have stability after film formation. [Prior Art Documents] [Patent Documents]

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

[0007] [The problem the invention aims to solve]

[0008] This invention is made in view of the foregoing circumstances, and its object is to provide a release layer forming composition that has high heat resistance and moderate peelability, and can impart excellent stability to the release layer after film formation. [Means for solving the problem]

[0009] As a result of the inventors’ active and repeated review in order to achieve the aforementioned objective, they discovered that the composition for forming a release layer comprising (A) (A1) cellulose or a derivative thereof having hydroxyalkyl groups, (A2) polyester having hydroxyl groups, or (A3) acrylic polymer having primary or secondary hydroxyl groups, (B) an acid compound or a salt thereof, (C) a crosslinking agent selected from a compound having nitrogen atoms substituted with hydroxyalkyl and / or alkoxymethyl groups, (D) a polymeric additive containing specific repeating units, and (E) a solvent, can reproducibly impart a release layer with high heat resistance, excellent adhesion to the matrix, moderate adhesion to the resin substrate, and moderate peelability, thereby completing the present invention.

[0010] That is, the present invention provides 1. a composition for forming a release layer, comprising (A) (A1) a cellulose having a hydroxyalkyl group or a derivative thereof, (A2) a polyester having a hydroxyl group, or (A3) an acrylic polymer having a primary or secondary hydroxyl group and not having a fluorine atom, (B) an acid compound or a salt thereof, and (C) a crosslinking agent selected from a compound having a nitrogen atom substituted with a hydroxyalkyl group and / or an alkoxymethyl group. (D) A polymeric additive comprising repeating units represented by formula (a1), repeating units represented by formula (b), and repeating units represented by formula (c), and (E) a solvent, wherein, relative to 100 parts by mass of the aforementioned component (A), it comprises 5 to 100 parts by mass of the aforementioned polymeric additive (D), (where RA is each independently a hydrogen atom or a methyl group, RB1 is a branched alkyl group with 3 or 4 carbon atoms substituted by at least one hydrogen atom, RC is a hydroxyalkyl group with 1 to 10 carbon atoms, and RD is a polycyclic alkyl group with 6 to 20 carbon atoms or an aryl group with 6 to 12 carbon atoms.) 2. A composition for forming a release layer as described in 1, wherein, in the repeating unit represented by formula (b), RC is a hydroxyalkyl group with 2 to 10 carbon atoms, and wherein the carbon atom bonded to the hydroxyl group is a second-order or third-order carbon atom; 3. As in the composition for forming the release layer of 1, wherein in the repeating unit represented by formula (b) above, RC is a hydroxyalkyl group having 1 to 10 carbon atoms, and the carbon atom bonded by the hydroxyl group is a first-order carbon atom, and the proportion of the repeating unit represented by formula (a1) in the total repeating unit of the polymer additive (D) is 25 mol% or more, 4. As in the composition for forming the release layer of 1, the aforementioned (D) polymeric additive comprises repeating units represented by formula (a2), repeating units represented by formula (b), repeating units represented by formula (c), and repeating units represented by formula (d) (where RA, RC, and RD have the same meaning as described above, RB2 is a branched alkyl group with 3 or 4 carbon atoms substituted by at least one hydrogen atom, but does not contain 2-methyl-1,1,1,3,3,3-hexafluoroisopropyl, RE is a single bond, a polycyclic alkyl group with 6 to 20 carbon atoms, or an aryl group with 6 to 12 carbon atoms, RF is a single bond or an alkyl group with 1 to 10 carbon atoms, and RG is methyl, ethyl, or hydroxyl).5. A release layer forming composition according to any one of claims 1 to 4, wherein the aforementioned component (A1) is at least one selected from the group consisting of hydroxyethyl cellulose and hydroxypropyl cellulose, and derivatives thereof; 6. A release layer forming composition according to any one of claims 1 to 4, wherein the aforementioned component (A2) is a polyester having an aromatic or alicyclic group in the main chain; 7. A release layer forming composition according to any one of claims 1 to 4 and 6, wherein the aforementioned component (A2) is a polyester obtained by reacting a compound having two epoxy sites with a compound having two carboxyl groups; 8. A release layer forming composition according to any one of claims 1 to 4, wherein the aforementioned component (A3) is an acrylic polymer having a polyethylene glycol group or a primary or secondary hydroxyalkyl ester group having 2 to 6 carbon atoms; 9. 10. A composition for forming a release layer as described in any of claims 1 to 4 and 8, wherein the aforementioned component (A3) is an acrylic polymer having a first- or second-order hydroxyalkyl group having 2 to 6 carbon atoms in its side chain; 11. A composition for forming a release layer as described in any of claims 1 to 9, wherein the aforementioned component (B) is a sulfonic acid compound or a salt thereof; 12. A composition for forming a release layer as described in any of claims 1 to 10, wherein the aforementioned crosslinking agent (C) is a compound represented by any of the following formulas (C-1) to (C-5), (where R11 to R26 are each independently an alkyl group having 1 to 6 carbon atoms, and R27 is a hydrogen atom or a methyl group); 13. A composition for forming a release layer as described in any of claims 1 to 11, wherein the content of the aforementioned crosslinking agent (C) is 10 to 100 parts by mass relative to 100 parts by mass of the aforementioned component (A); 14. A release layer obtained from a release layer forming composition as described in any one of claims 1 to 12; 15. A laminate having a resin layer having a light transmittance of 80% or more at a wavelength of 400 nm deposited on a release layer as described in claim 13; 16. A method for manufacturing a resin substrate, comprising: a step of coating a release layer forming composition as described in any one of claims 1 to 12 onto a substrate to form a release layer; a step of forming a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm on the aforementioned release layer; and a step of peeling the aforementioned resin substrate with a peeling force of 0.25 N / 25 mm or less. [Effects of the Invention].

[0011] By using the release layer forming composition of the present invention, a release layer with high heat resistance, excellent adhesion to the substrate, moderate adhesion to the resin substrate, and moderate peelability can be reproducibly obtained. Furthermore, in the manufacturing process of flexible electronic devices, damage to the resin substrate formed on the substrate and the circuitry further disposed thereon can be avoided, and the resin substrate and the circuitry can be separated from the substrate simultaneously. Therefore, the release layer forming composition of the present invention can contribute to the speeding up of the manufacturing process of flexible electronic devices with resin substrates and improve their yield.

Implementation Method

[0012] [Composition for forming the release layer]

[0013] The composition system for forming the release layer of the present invention comprises (A) (A1) cellulose or a derivative thereof having hydroxyalkyl groups, (A2) polyester having hydroxyl groups, or (A3) acrylic polymer having primary or secondary hydroxyl groups and not having fluorine atoms, (B) an acid compound or a salt thereof, (C) a crosslinking agent selected from a compound having nitrogen atoms substituted with hydroxyalkyl and / or alkoxymethyl groups, (D) a polymeric additive containing specific repeating units, and (E) a solvent.

[0014] [(A)(A1) cellulose or a derivative thereof having hydroxyalkyl groups, (A2) polyester having hydroxyl groups, or (A3) acrylic polymer having primary or secondary hydroxyl groups and not having fluorine atoms] [(A1) cellulose or a derivative thereof] (A1) is cellulose or a derivative thereof having hydroxyalkyl groups.

[0015] Examples of component (A1) include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl ethyl cellulose, and their derivatives. In this invention, among these, hydroxyalkyl celluloses and their derivatives are preferred, and hydroxyethyl cellulose and hydroxypropyl cellulose, and their derivatives are even more preferred. (A1) A cellulose having a hydroxyalkyl group or its derivative may be used alone or in combination of two or more.

[0016] (A1) The weight-average molecular weight (Mw) of the component is not particularly limited; however, 1,000 to 500,000 is preferred, 3,000 to 400,000 is more preferred, and 5,000 to 300,000 is even more preferred. Furthermore, the weight-average molecular weight is a polystyrene-converted value determined by gel permeation chromatography (GPC) (the same applies hereinafter).

[0017] [(A2) Polyester with hydroxyl groups] The polyester with hydroxyl groups in (A2) is not particularly limited, however, in this invention, it is preferred to have aromatic or alicyclic groups in the main chain.

[0018] The polyester of such (A2) component is preferably a polyester obtained by reacting a compound having two epoxy sites with a compound having two carboxyl groups.

[0019] (A2) The weight average molecular weight (Mw) of the polyester component is not particularly limited, however, 1,000 to 200,000 is preferred, 3,000 to 100,000 is even more preferred, and 5,000 to 50,000 is even more preferred.

[0020] <Epoxy Compound> Examples of compounds having two epoxy sites 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)furan diglycidyl ether, 9,9'-bis(4-hydroxyphenyl)furan diglycidyl ether, 9,9'-bis(6-hydroxy-2-naphthyl)furan diglycidyl ether, etc. Aliphatic diol diglycidyl ethers, such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and neopentyl glycol diglycidyl ether; alicyclic diol diglycidyl ethers, such as cyclohexanediol diglycidyl ether, cyclohexanediethanol diglycidyl ether, dicyclopentadienediol diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol B diglycidyl ether, and hydrogenated bisphenol S diglycidyl ether; and aromatic dicarboxylic acid diglycidyl esters, such as diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate. Alicyclic dicarboxylic acid diglycidyl esters such as oxalate diglycidyl ester, adipic acid diglycidyl ester, pimelic acid diglycidyl ester, and 2-ethyl-3-propyl-1,5-pentanediic acid diglycidyl ester; resins with epoxy groups at both ends, such as bisphenol A type epoxy resin jER828 (manufactured by Mitsubishi Chemical Co., Ltd., trade name), terephthalate type epoxy resin Denacol EX711 (manufactured by Nagase ChemteX Co., Ltd., trade name), biphenyl type epoxy resin YX4000H (manufactured by Mitsubishi Chemical Co., Ltd., trade name), fluorene type epoxy resin OGSOL PG-100 (manufactured by Osaka Gas Chemical Co., Ltd., trade name), fluorene type epoxy resin OGSOL CG-500 (manufactured by Osaka Gas Chemical Co., Ltd., trade name), and cyclopentyl type epoxy resin CEL2021P (manufactured by Daicel Co., Ltd., trade name); Alicyclic dioxides of vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, tetrahydroindene dioxide, EPOCHALIC (ENEOS registered trademark) THI-DE, EPOCHALIC (ENEOS registered trademark) DE-102, EPOCHALIC (ENEOS registered trademark) DE-103, etc.Examples of compounds containing two 3,4-epoxycyclopentylmethyl-3,4-epoxycyclohexane carboxylate include 3,4-epoxycyclopentylmethyl-3,4-epoxycyclohexane carboxylate, 2,2-bis(3,4-epoxycyclopentyl)propane, bis(3,4-epoxycyclopentylmethyl)oxalate, bis(3,4-epoxycyclopentylmethyl)adipate, bis(3,4-epoxy-6-methylcyclopentylmethyl)adipate, bis(3,4-epoxycyclopentylmethyl)pimelic acid, and bis(3,4-epoxycyclopentylmethyl)2-ethyl-3-propyl-1,5-pentanedic acid. Furthermore, these compounds can be used alone or in combination of two or more.

[0021] <Compounds containing carboxyl groups> Examples of compounds having two carboxyl groups include terephthalic acid, isophthalic acid, biphenyl 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, and 1,4-cyclohexanedicarboxylic acid. Furthermore, such compounds can be used alone or in combination of two or more.

[0022] The method for obtaining the polyester of the example (A2) composition is not particularly limited. However, for example, it can be obtained by polymerization at a temperature of 50 to 150°C in a solvent in which the above-mentioned ester compound and the carboxyl-containing compound coexist with a catalyst. In this case, the solvent that can be used is not particularly limited if it can dissolve the compounds and the polymerization initiator.

[0023] The polyester of component (A2) obtained by the aforementioned method is usually in a solution dissolved in a solvent.

[0024] The polyester as component (A2) is preferably one that has the structural unit represented by the following formula [A2-1].

[0025] (In the formula, X and Y each independently represent structures having aromatic or alicyclic groups.)

[0026] Preferably, X is represented by the basis of the following formula (X-1).

[0027]

[0028] In the formula, L1 represents ether or ester bond, X1 represents alkyl, cyclic unsaturated hydrocarbon or cyclic saturated hydrocarbon with 1 to 10 carbon atoms, R1 represents single bond, ether bond, carbonyl, sulfonyl, saturated hydrocarbon with 1 to 30 carbon atoms, unsaturated hydrocarbon with 2 to 30 carbon atoms, or saturated hydrocarbon with 1 to 30 carbon atoms substituted with fluorine atoms, and p represents 0, 1 or 2.

[0029] As for the aforementioned X1, a cyclic unsaturated hydrocarbon group having 4 to 16 carbon atoms or a cyclic saturated hydrocarbon group having 4 to 16 carbon atoms is preferred, and a cyclic unsaturated hydrocarbon group having 4 to 8 carbon atoms or a cyclic saturated hydrocarbon group having 4 to 8 carbon atoms is even more preferred. Furthermore, any hydrogen atom contained in X1 can be independently replaced by an aliphatic group, and in addition, multiple substituents in such aliphatic groups can bond with each other to form a 4 to 6-membered ring.

[0030] As a specific example of the aforementioned X, the bases represented by the following formulas (X-2) to (X-13) can be cited, but are not limited to these.

[0031] (In the formula, * represents a bond.)

[0032] Furthermore, as for the aforementioned X, the structure derived from the aforementioned resin having epoxy groups at both ends is also preferred.

[0033] As for the aforementioned Y, the bases represented by the following formulas (Y-1) to (Y-4) can be cited, but are not limited to them.

[0034] (In the formula, * represents a bond.)

[0035] It is also preferable that the polyester as component (A2) has the structural unit represented by the following formula [A2-2].

[0036]

[0037] In the formula, Cy is a group derived from the aforementioned alicyclic dioxide, that is, an organic group containing a tetravalent aliphatic ring. The four bonding groups to OH and O all represent groups derived from aliphatic rings. Y is the same as the Y in formula [A2-1].

[0038] As a specific example of Cy in formula [A2-2], the basis represented by the following formulas (Cy-1)~(Cy-4) can be cited.

[0039] (In the formula, *1 and *2 each represent a bonding bond, and one of the two *1 and *2 in each structural formula is bonded to a hydroxyl group.)

[0040] It is also preferable that the polyester as component (A2) has the structural unit represented by the following formula [A2-3].

[0041]

[0042] In the formula, X and Y have the same definition as X and Y in formula [A2-1].

[0043] As a specific example of X in formula [A2-3], the basis represented by the following formulas (X-Ch-1)~(X-Ch-3) can be cited.

[0044] (In the formula, * represents a bond.)

[0045] [(A3) Acrylic Polymer] The acrylic polymer having primary or secondary hydroxyl groups and not having fluorine atoms in component (A3) is not particularly limited. However, in this invention, it is preferred to have polyethylene glycol groups or primary or secondary hydroxyalkyl ester groups with 2 to 6 carbon atoms, and it is even more preferred to have such groups on the side chains. As acrylic polymer, polymers of acrylate alone, polymers of methacrylate alone, copolymers of such polymers, and copolymers of such polymers with monomers having unsaturated double bonds such as styrene can be used. A preferred example of the acrylic polymer of component (A3) is an acrylic polymer having polyethylene glycol groups or primary or secondary hydroxyalkyl ester groups with 2 to 6 carbon atoms. Any acrylic polymer having any of these groups is acceptable, and the backbone (other building units) constituting the main chain of the acrylic polymer and the type of side chains are not particularly limited.

[0046] The structural unit having a polyethylene glycol ester group or a first- or second-order hydroxyalkyl ester group having 2 to 6 carbon atoms is preferably represented by the following formula [A3-1].

[0047]

[0048] In the aforementioned formula [A3-1], each of the RA series is a hydrogen atom or a methyl group, and the Y1 series represents an H-(OCH2CH2)n- group (where n is an integer from 2 to 30, preferably an integer from 2 to 10), or a first-order or second-order hydroxyalkyl group with 2 to 6 carbon atoms.

[0049] (A3) The weight average molecular weight (Mw) of the acrylic polymer is not particularly limited, however, 1,000 to 200,000 is preferred, 3,000 to 100,000 is more preferred, and 5,000 to 50,000 is even more preferred.

[0050] (A3) The acrylic polymer can be obtained by polymerizing a monomer having a polyethylene glycol group and at least one of a primary or secondary hydroxyalkyl group having 2 to 6 carbon atoms. Examples of monomers having a polyethylene glycol ester group include H-(OCH2CH2)n-OH (where n means as described above). On the other hand, examples of monomers having a primary or secondary 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, glycerol monoacrylate, glycerol monomethacrylate, etc.

[0051] Furthermore, in this embodiment, when synthesizing the acrylic polymer of component (A3), monomers other than those mentioned above may be used without impairing the effects of the present invention. Specifically, monomers that do not have polyethylene glycol ester groups or primary or secondary hydroxyl groups and do not have fluorine atoms may be used. Examples of such monomers include, for example, acrylate compounds such as methacrylates, ethyl acrylates, propyl acrylates, isopropyl acrylates, butyl acrylates, isobutyl acrylates, and t-butyl acrylates; methacrylate compounds such as methyl methacrylates, ethyl methacrylates, propyl methacrylates, isopropyl methacrylates, butyl methacrylates, isobutyl methacrylates, and t-butyl methacrylates; maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclopentylmaleimide; acrylamide compounds; acrylonitrile; maleic anhydride; styrene compounds; and vinyl compounds.

[0052] The method for manufacturing the acrylic polymer of component (A3) is not particularly limited. However, for example, a method in which the polymerization reaction is carried out in a solution containing the above-mentioned monomers and other monomers and polymerization initiators dissolved in a solvent at a temperature of 50 to 110°C is not particularly limited. As for the solvent that can be used, it is not particularly limited if it is a solvent that can dissolve monomers and polymerization initiators.

[0053] A preferred example of an acrylic polymer as component (A3) is a polymer obtained by polymerizing a primary or secondary hydroxyalkyl ester monomer such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, etc., or a polymer obtained by copolymerizing the primary or secondary hydroxyalkyl ester monomer with monomers other than these monomers, such as one or more monomers selected from the group consisting of monomers that do not have primary or secondary hydroxyl groups, etc., which are acrylic polymers having primary or secondary hydroxyalkyl side chains.

[0054] In addition, the acrylic polymer of component (A3) obtained by the aforementioned method is usually in the state of a solution dissolved in a solvent.

[0055] [(B) Acid Compound or Salt thereof] The composition system for forming the release layer of the present invention includes an acid compound or a salt thereof as component (B). Specific examples of acid compounds include sulfonic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate, salicylic acid, camphorsulfonic acid, sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, and pyridinium-1-naphthalenesulfonic acid; and carboxylic acid compounds such as salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, and hydroxybenzoic acid. Furthermore, examples of salts of acid compounds include pyridinium salts, isopropanolamine salts, and N-methylmorpholine salts of the aforementioned acids. Specifically, examples include pyridinium p-toluenesulfonate, pyridinium 1-naphthalenesulfonate, isopropanolamine p-toluenesulfonate, and N-methylmorpholine p-toluenesulfonate.

[0056] The content of component (B) is preferably 0.01 to 15 parts by weight, and more preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of component (A). If the content of component (B) is within this range, a composition that imparts a release layer with high heat resistance, moderate peelability, and excellent stability after film formation can be obtained. In addition, the acid compound (B) or its salt can be used alone or in combination of two or more.

[0057] [(C) Crosslinking Agent] The composition for forming the release layer of the present invention comprises a crosslinking agent selected from a nitrogen-containing compound substituted with hydroxyalkyl and / or alkoxymethyl groups as component (C). Preferably, the crosslinking agent is a compound represented by any one of the following formulas (C-1) to (C-5).

[0058]

[0059] In the foregoing formulas, R11 to R26 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, but preferably an alkyl group having 1 to 6 carbon atoms. R27 is a hydrogen atom or a methyl group.

[0060] Specific examples of crosslinking agents include nitrogen-containing compounds such as hexamethylolmelamine, tetramethylolguanidine, 1,3,4,6-tetramethylolglycolurea, hexamethoxymethylmelamine, tetramethoxymethylguanidine, 1,3,4,6-tetra(methoxymethyl)glycolurea, 1,3,4,6-tetra(butoxymethyl)glycolurea, and 1,3,4,6-tetra(hydroxymethyl)glycolurea.

[0061] Furthermore, commercially available crosslinking agents can also be used in this invention. Specific examples include nitrogen-containing compounds such as those manufactured by Allnex (trade names CYMEL 300, CYMEL 301, CYMEL 303, CYMEL 350), butoxymethyl melamine compounds (trade names MYCOAT 506, MYCOAT 508), glycourea compounds (trade names CYMEL 1170, POWDERLINK 1174), methylated urea resin (trade name UFR65), butylated urea resin (trade names UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea / formaldehyde resins manufactured by DIC (stocks) (trade names BECKAMINE J-300S, BECKAMINE P-955, BECKAMINE N).

[0062] Furthermore, as a crosslinking agent, polymers manufactured from (meth)acrylamide compounds such as N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, and N-butoxymethyl (meth)acrylamide, which are substituted with hydroxymethyl or alkoxymethyl groups, can also be used. Specific 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 meth (meth)acrylate, copolymers of N-ethoxymethyl (meth)acrylamide and benzyl methacrylate, and copolymers of N-butoxymethyl (meth)acrylamide, benzyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate.

[0063] Among these crosslinking agents, hexamethoxymethyl melamine, tetramethoxymethyl guanidine, 1,3,4,6-tetra(methoxymethyl)glycourea (POWDERLINK 1174), 1,3,4,6-tetra(butoxymethyl)glycourea, and 1,3,4,6-tetra(hydroxymethyl)glycourea are preferred.

[0064] Furthermore, the aforementioned crosslinking agent can initiate a crosslinking reaction by self-condensation, and can also cause a crosslinking reaction with the hydroxyl groups in the acrylic polymer of component (A). Through these crosslinking reactions, the resulting release layer becomes strong while its solubility in organic solvents decreases.

[0065] The content of component (C) is preferably 10 to 100 parts by weight, and more preferably 20 to 50 parts by weight, relative to 100 parts by weight of component (A). If the content of component (C) is within this range, a composition that imparts a release layer with high heat resistance, moderate peelability, and excellent stability after film formation can be obtained. In addition, crosslinking agent (C) can be used alone or in combination of two or more.

[0066] [(D) Polymer Additive] The composition system for forming the release layer of the present invention comprises a polymer additive containing repeating units represented by the following formula (a1), repeating units represented by the following formula (b) and repeating units represented by the following formula (c) as component (D).

[0067]

[0068] In the foregoing formulas, each of the RA series is a hydrogen atom or a methyl group, RB1 is a branched alkyl group with 3 or 4 carbon atoms that has at least 1 hydrogen atom replaced by a fluorine atom, RC is a hydroxyalkyl group with 1 to 10 carbon atoms, and RD is a polycyclic alkyl group with 6 to 20 carbon atoms or an aryl group with 6 to 12 carbon atoms.

[0069] Specific examples of branched alkyl groups having 3 or 4 carbon atoms in RB1 include isopropyl, isobutyl, sec-butyl, and tert-butyl. RB1 is a group in which at least one hydrogen atom of such branched alkyl groups is substituted with a fluorine atom, and specific examples include 1,1,1-trifluoroisopropyl, 1,1,1,3,3,3-hexafluoroisopropyl, and nonafluorotert-butyl.

[0070] Specific examples of hydroxyalkyl groups having 1 to 10 carbon atoms in RC include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxypentyl, 7-hydroxyheptyl, 8-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 2-hydroxy-1-methylethyl, 2-hydroxy-1,1-dimethylethyl, 3-hydroxy-1-methylpropyl, 3-hydroxy-2-methylpropyl, 3-hydroxy-1,1-dimethylpropyl, 3-hydroxy-1,2-dimethylpropyl, 3-hydroxy-2,2-dimethylpropyl, 4-hydroxy-1 1-methylbutyl, 4-hydroxy-2-methylbutyl, 4-hydroxy-3-methylbutyl, etc., hydroxyalkyl groups having 1 to 10 carbon atoms, wherein the carbon atom bonded to the hydroxyl group is a first-order carbon atom; 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 1-hydroxypentyl, 2-hydroxypentyl, 1-hydroxyoctyl, 2-hydroxyoctyl, 1-hydroxydecyl, 2-hydroxydecyl, 1-hydroxy-1-methylethyl, 2-hydroxy-2-methylpropyl, etc., hydroxyalkyl groups having 2 to 10 carbon atoms, wherein the carbon atom bonded to the hydroxyl group is a second-order or third-order carbon atom.

[0071] Specific examples of polycyclic alkyl groups having 6 to 20 carbon atoms in RD include 1-adamantyl, 2-adamantyl, isocamphenyl, norbornyl, etc. Specific examples of aryl groups having 6 to 12 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-biphenyl, 2-biphenyl, etc.

[0072] Furthermore, (D) the polymer additive may also be a repeating unit represented by formula (a2), formula (b), formula (c) and formula (d).

[0073] (In the formula, the meanings of RA, RC and RD are as described above.)

[0074] RB2 is a branched alkyl group with 3 or 4 carbon atoms that has at least one hydrogen atom substituted with a fluorine atom (except for 2-methyl-1,1,1,3,3,3-hexafluoroisopropyl). Examples of such fluorinated alkyl groups are those similar to those exemplified above. RE is a single bond, a polycyclic alkyl group with 6 to 20 carbon atoms, or an aryl group with 6 to 12 carbon atoms; RF is a single bond or an alkyl group with 1 to 10 carbon atoms; and RG is methyl, ethyl, or hydroxyl.

[0075] As a polycyclic alkyl group having 6 to 20 carbon atoms in the RE, examples can be made by removing one hydrogen atom from the aforementioned polycyclic alkyl group having 6 to 20 carbon atoms, such as adamantyl, isobornyl, and norbornyl. As an aryl group having 6 to 12 carbon atoms in the RE, examples can be made by removing one hydrogen atom from the aforementioned aryl group having 6 to 12 carbon atoms, such as phenyl, naphthyl, and biphenyl.

[0076] Specific examples of alkyl groups having 1 to 10 carbon atoms in RF include methylene, ethyl, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene. Among these, alkyl groups having 1 to 5 carbon atoms are preferred, methylene and ethyl groups are even better, and methylene groups are even better.

[0077] As a repeating unit represented by formula (a1) or (a2), examples can be given by formulas (a-1) to (a-3) below, but are not limited to these. In addition, in the following formulas, RA has the same meaning as before (the same applies below).

[0078]

[0079] As the repeating unit represented by equation (b), examples can be given by equations (b-1) to (b-16), but are not limited to these.

[0080]

[0081] As the repeating unit represented by equation (c), examples can be given by equations (c-1) to (c-13), but are not limited to these.

[0082]

[0083] As the repeating unit represented by equation (d), examples can be given by equations (d-1) to (d-8), but are not limited to these.

[0084]

[0085] In this invention, (D) polymeric additive comprises repeating units represented by formula (a1), repeating units represented by formula (b), and repeating units represented by formula (c). In the repeating unit represented by formula (b), the carbon atom bonded to the hydroxyl group in the repeating unit is a second-order or third-order carbon atom (hereinafter, such polymeric additive is referred to as polymeric additive D1). The content of repeating units represented by formula (a1) in the total repeating units is preferably 30-60 mol%, more preferably 35-50 mol%. The content of repeating units represented by formula (b) in the total repeating units is preferably 10-35 mol%, more preferably 15-30 mol%. The content of repeating units represented by formula (c) in the total repeating units is preferably 5-60 mol%, more preferably 20-50 mol%.

[0086] On the other hand, (D) the polymer additive includes the repeating unit represented by formula (a1), the repeating unit represented by formula (b), and the repeating unit represented by formula (c), wherein, in the repeating unit represented by formula (b), the carbon atom bonded to the hydroxyl group in the hydroxyalkyl group is a first-order carbon atom (hereinafter, such polymer additive is referred to as polymer additive D2). The content of the repeating unit represented by formula (a1) in the total repeating unit is preferably 15 to 60 mol%, and 25 to 60 mol% is preferred. The percentage of repeating units represented by formula (b) is preferably 8-38 mol%, preferably 10-38 mol%, preferably 10-35 mol%, preferably 15-30 mol%, and the percentage of repeating units represented by formula (c) is preferably 2-77 mol%, preferably 2-65 mol%, preferably 5-60 mol%, and preferably 20-50 mol%.

[0087] (D) The polymeric additive includes the repeating unit represented by formula (a2), the repeating unit represented by formula (b), the repeating unit represented by formula (c), and the repeating unit represented by formula (d) (hereinafter, such polymeric additive is referred to as polymeric additive D3). The content of the repeating unit represented by formula (a2) in the total repeating unit is preferably 2 to 45 mol%, more preferably 5 to 35 mol%, the content of the repeating unit represented by formula (b) in the total repeating unit is preferably 20 to 35 mol%, more preferably 25 to 35 mol%, the content of the repeating unit represented by formula (c) in the total repeating unit is preferably 30 to 45 mol%, more preferably 35 to 45 mol%, and the content of the repeating unit represented by formula (d) in the total repeating unit is preferably 5 to 18 mol%, more preferably 5 to 15 mol%.

[0088] (D) The weight average molecular weight (Mw) of the polymer additive is preferably in the range of 2,000 to 10,000, and more preferably in the range of 3,000 to 6,000. Furthermore, its Mw / Mn ratio is preferably in the range of 1.0 to 2.1, and more preferably in the range of 1.0 to 1.9 (Mn is the number average molecular weight).

[0089] The content of the polymer additive in component (D) is 5 to 100 parts by mass relative to 100 parts by mass of component (A). If the content of the polymer additive is less than 5 parts by mass, the peel strength will increase; if it exceeds 100 parts by mass, shrinkage will occur during film formation.

[0090] In particular, when (D) is polymeric additive D1, its content is preferably 10-100 parts by weight, more preferably 20-100 parts by weight, and even more preferably 30-100 parts by weight, relative to 100 parts by weight of component (A). Furthermore, when (D) is a polymeric additive other than D1, its content is preferably 5-80 parts by weight, more preferably 5-50 parts by weight, relative to 100 parts by weight of component (A). In addition, (D) can be used alone or in combination with two or more other polymeric additives.

[0091] [(E) Solvent] The composition system for forming the release layer of the present invention includes a solvent as component (E). Preferably, the solvent is a glycol ether solvent with 3 to 20 carbon atoms, an ester solvent with 3 to 20 carbon atoms, a ketone solvent with 3 to 20 carbon atoms, or a amide solvent with 3 to 20 carbon atoms.

[0092] Specific examples of glycol ether solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether, and propylene glycol monopropyl ether. Specific examples of ester solvents include ethyl lactate, γ-butyrolactone, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate. Specific examples of ketone solvents include methyl ethyl ketone, cyclopentanone, cyclohexanone, and benzophenone. Specific examples of acetylamine solvents include N-methylpyrrolidone, N,N-dimethylacetylamine, and 3-methoxy-N,N-dimethylpropionic acid.

[0093] (E) The solvent content is not particularly limited; however, it is preferable that the concentration of solid components in the composition for forming the release layer 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. Furthermore, the term "solid component" refers to substances other than the solvent in the total composition of the composition for forming the release layer, and the amount of solid component is the total amount of such substances. Furthermore, (E) a single solvent may be used, or two or more solvents may be used in combination.

[0094] [Other Additives] The release layer forming composition of the present invention may also include a surfactant as needed. By adding a surfactant, the coatability of the aforementioned release layer forming composition to the substrate can be improved. As a surfactant, known surfactants such as nonionic surfactants, fluorinated surfactants, and polysiloxane surfactants can be used.

[0095] Specific examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearate ether, polyoxyethylene hexadecyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl 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.

[0096] Specific examples of fluorinated surfactants include EFtop (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronics Chemicals, Inc.), Megafac (registered trademark) F171, F173, F554, F559, F563, R-30, R-40, 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). Specific examples of polysiloxane surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.).

[0097] In the case where the composition for forming the release layer of the present invention includes a surfactant, the content of the surfactant is preferably 0.0001 to 1 part by weight relative to 100 parts by weight of component (A), and more preferably 0.001 to 0.5 parts by weight. In addition, a single surfactant may be used alone, or two or more surfactants may be used in combination.

[0098] [Preparation of the composition for release layer formation] The method for preparing the composition for release layer formation of the present invention is not particularly limited. For example, it can be a method of mixing components (B), (C), (D), and (E) in a specific ratio to form a homogeneous solution in a solution of component (A) dissolved in a solvent. Furthermore, the solvent in which component (A) is dissolved can be the same solvent as component (E) or a different solvent. Also, in the case of using other additives, these can be added and mixed at any stage of composition preparation.

[0099] In the preparation of the composition for forming the release layer of the present invention, a solution of the polymer obtained in the polymerization reaction in a solvent can also be used directly. For example, component (B), and further components (C), (D), and (E) can be added to the solution after the polymerization reaction of component (A) to form a homogeneous solution. At this time, a solvent can be further added to adjust the concentration to the desired effect. This solvent can be the same as or different from the solvent used in the manufacture of component (A).

[0100] Furthermore, the solution of the composition for forming the release layer is preferably filtered after being filtered using a filter with a pore size of about 0.2 μm.

[0101] The viscosity of the composition for forming the release layer of the present invention is appropriately set by considering the desired thickness of the release layer. However, especially when the aim is to obtain a film with a thickness of about 0.01 to 5 μm with good reproducibility, a viscosity of about 1 to 5,000 mPa·s at 25°C is preferred, and about 1 to 2,000 mPa·s is even more preferred. The viscosity in the present invention is measured using a commercially available viscometer for measuring the viscosity of liquids. For example, the measurement can be performed at a temperature of 25°C of the composition, following the sequence described in JIS K7117-2. As a viscometer, a conical plate type (cone plate type) rotational viscometer is preferred. Furthermore, it is preferable to use a viscometer of the same type with a 1°34'×R24 standard conical rotor, and the measurement is performed at a temperature of 25°C of the composition. For example, the TVE-25L manufactured by Toki Sangyo Co., Ltd. can be cited as such a rotational viscometer.

[0102] [Release Layer] By a sintering method comprising the steps of applying the release layer forming composition of the present invention onto a substrate and then sintering at 180~250°C, a release layer having excellent adhesion to the substrate and moderate adhesion and release properties to the resin substrate can be obtained. In this case, since the heating time during sintering varies depending on the heating temperature, it cannot be uniformly specified, but it is usually 1 minute to 5 hours. Furthermore, if the highest temperature during sintering is within the aforementioned range, a step of sintering at a temperature below that temperature may also be included.

[0103] As a preferred example of the heating state in this invention, an example of heating at 50-150°C for 1 minute to 1 hour, followed by directly raising the heating temperature to 180-250°C for 5 minutes to 4 hours, can be given. More particularly, as a more preferred example of the heating state, an example of heating at 50-150°C for 1 minute to 1 hour, followed by heating at 200-250°C for 5 minutes to 2 hours, can be given. Furthermore, as another more preferred example of the heating state, an example of heating at 50-150°C for 1 to 30 minutes, followed by heating at 200-250°C for 5 minutes to 1 hour, can be given.

[0104] Furthermore, in the case where the release layer of the present invention is formed on a substrate, the release layer may be formed on a portion of the surface of the substrate or it may be formed all over the substrate. As for the form of forming the release layer on a portion of the surface of the substrate, there are forms where the release layer is formed only in a specific area of ​​the substrate surface, and forms the release layer all over the substrate surface in the form of a pattern such as a dot pattern, a line pattern, and a gap pattern. Furthermore, in the present invention, the term "substrate" refers to a material on which the release layer forming composition of the present invention is coated, and is used in the manufacture of flexible electronic devices, etc.

[0105] Examples of substrates include glass, metal (silicon wafers, etc.), and stone slabs. However, glass is preferred because the release layer obtained by the release layer forming composition of the present invention has sufficient adhesion to it. Furthermore, the substrate surface can be made of a single material or of two or more materials. As for the state in which the substrate surface is made of two or more materials, there are states in which certain areas of the substrate surface are made of certain materials and the rest of the surface is made of other materials, and there are states in which the materials present in the pattern of dots, lines and gaps, etc., of the entire substrate surface are also present in other materials.

[0106] The coating method for the composition used to form the release layer is not particularly limited. For example, casting coating, spin coating, doctor blade coating, dip coating, roller coating, bar coating, mold coating, inkjet coating, and printing methods (letterpress, gravure, offset, screen printing, etc.) can be cited.

[0107] As a heating appliance, examples include hot plates and ovens. The heating environment can be in air or inert gas, and can be at normal pressure or under reduced pressure.

[0108] The thickness of the release layer is usually around 0.01~50μm, but from a production point of view, it is better to be around 0.01~20μm, and even better to be around 0.01~5μm. The desired thickness is achieved by adjusting the thickness of the coating before heating.

[0109] The release layer of the present invention has excellent adhesion to the substrate, especially to a glass substrate, and moderate adhesion and moderate peelability to the resin substrate. Therefore, the release layer of the present invention will not cause damage to the resin substrate of the flexible electronic device during the manufacturing process, and can be used appropriately when the resin substrate and the circuits formed on the resin substrate are simultaneously peeled off from the substrate.

[0110] [Manufacturing Method of Resin Substrate] An example of a manufacturing method for a flexible electronic device using the release layer of the present invention will be described. First, a release layer is formed on a glass substrate using the release layer forming composition of the present invention and the aforementioned method. A resin substrate forming solution for forming a resin substrate is coated on this release layer, and a resin substrate fixed to the glass substrate is formed by sintering the obtained coating film, thereby separating the release layer of the present invention.

[0111] Although the sintering temperature of the coating is appropriately set according to the type of resin, etc., in this invention, it is preferable to set the maximum sintering temperature to 200~250°C, more preferably 210~250°C, and even more preferably 220~240°C. By setting the maximum sintering temperature during the fabrication of the resin substrate within this range, the adhesion between the release layer and the substrate, or the appropriate adhesion and release properties between the release layer and the resin substrate, can be further improved. In this case, as long as the maximum temperature is within the aforementioned range, a step of sintering at a temperature lower than that temperature may also be included.

[0112] Preferably, the resin substrate is formed with an area larger than that of the release layer, covering the entire release layer. Examples of resin substrates include those made of acrylic polymers or cyclic olefin polymers, with a transmittance of 80% or more at a wavelength of 400 nm being preferred. Furthermore, the resin substrate can be formed using conventional methods.

[0113] Next, on the resin substrate fixed to the substrate by the release layer of the present invention, the desired circuit is formed as needed. Then, for example, the resin substrate is cut along the release layer, and the resin substrate is peeled off from the release layer simultaneously with the circuit, separating the resin substrate from the substrate. At this time, a portion of the substrate can also be cut simultaneously with the release layer. If the release layer of the present invention is used, the resin substrate can be peeled off from the release layer with a peeling force of 0.25 N / 25 mm or less. In particular, when (D) the polymer additive is polymer additive D2 or polymer additive D3, the resin substrate can be peeled off from the release layer with a peeling force of 0.15 N / 25 mm or less. Also, when (D) the polymer additive is polymer additive D1, the resin substrate can be peeled off from the release layer with a peeling force of 0.1 N / 25 mm or less. [Example]

[0114] Hereinafter, the present invention will be described in more detail by way of examples of synthesis, modulation, embodiments and comparative examples. However, the present invention is not limited to the following embodiments.

[0115] (I)(A1) A composition for forming a release layer of cellulose or a derivative thereof containing hydroxyalkyl groups. The compounds used in the following examples are as follows. PGME: Propylene glycol monomethyl ether; PGMEA: Propylene glycol monomethyl ether acetate; HPC-SSL: Hydroxypropyl cellulose, Mw 40,000; HPC-SL: Hydroxypropyl cellulose, Mw 100,000; HPC-L: Hydroxypropyl cellulose, Mw 140,000; CAB: Cellulose acetate butyrate, Mw 155,800; CAP: Cellulose acetate propionate, Mw 71,300; PL-LI: 1,3,4,6-Tetra(methoxyethyl)glycourea (Allnex, trade name: POWDERLINK 1174); PPTS: Pyridinium p-toluenesulfonate; HPMA: 2-Hydroxypropyl methacrylate; ADMA: 2-Adamantane methacrylate; HFiPMA: 1,1,1,3,3,3-Hexafluoroisopropyl methacrylate; AIBN: Azobisisobutyronitrile; DDT: Dodecanethiol.

[0116] Furthermore, the weight average molecular weight (Mw) of the polymer was determined using a GPC apparatus manufactured by Shimadzu Corporation (column: Shodex KF803L and KF804L (Showa Denko Corporation); dissolution solution: THF; flow rate: 1.0 mL / min; column temperature: 40°C; Mw: standard polystyrene conversion value).

[0117] [1] Synthesis of Polymer [Synthesis Example 1-1] Synthesis of Acrylic Polymer (S1) 6.43 g of HFiPMA, 3.93 g of HPMA, 8.00 g of ADMA, 0.74 g of AIBN and 0.92 g of DDT were dissolved in 80.1 g of PGME and reacted at 70 °C for 20 hours to obtain an acrylic polymer (S1) solution (solid component concentration 20% by mass). The composition ratio of each unit was HFiPMA:HPMA:ADMA = 30:30:40. According to GPC analysis, the Mw of the obtained acrylic polymer (S1) was 5,310 and the Mw / Mn ratio was 1.8.

[0118] [Synthesis Example 1-2] Synthesis of Acrylic Polymer (S2): 8.57 g of HFiPMA, 2.62 g of HPMA, 8.00 g of ADMA, 0.74 g of AIBN, and 0.92 g of DDT were dissolved in 83.4 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (S2) solution (solid component concentration 20% by mass). The composition ratio of each unit was HFiPMA:HPMA:ADMA = 40:20:40. GPC analysis showed that the obtained acrylic polymer (S2) had a Mw of 5,500 and an Mw / Mn ratio of 1.8.

[0119] [2] Preparation of composition for resin substrate formation [Preparation Example 1] The composition F1 for resin substrate formation was prepared by adding 10g of ZEONOR 1020R (a cyclic olefin polymer manufactured by ZEON Corporation, Japan) and 3g of Epolead GT401 (manufactured by Daicel Corporation) to a flask containing 100g of carbon tetrachloride. The solution was stirred and dissolved under nitrogen for 24 hours to prepare composition F1 for resin substrate formation.

[0120] [3] Preparation of composition for release layer formation [Example 1-1] Preparation of composition 1 for release layer formation: 0.32g of PL-LI, 0.05g of PPTS, 0.84g of acrylic polymer (S1) solution and PGMEA were added to HPC-SSL 1.00g and diluted with PGME to make the solid component concentration 5% by mass and the PGMEA concentration 30% by mass, so as to prepare composition 1-1 for release layer formation.

[0121] [Examples 1-2] The composition 2 for forming the release layer was prepared by the same method as in Example 1-1, except that PL-LI was changed to 0.50g.

[0122] [Examples 1-3] The release layer forming composition 3 was prepared by the same method as in Example 1-1, except that PL-LI was changed to 0.25g.

[0123] [Examples 1-4] The release layer forming composition 4 was modulated by the same method as in Examples 1-1, except that HPC-SL was used instead of HPC-SSL.

[0124] [Examples 1-5] The release layer forming composition 5 was modulated by the same method as in Examples 1-1, except that HPC-L was used instead of HPC-SSL.

[0125] [Examples 1-6] The release layer forming composition 6 was prepared by the same method as in Examples 1-1, except that the acrylic polymer (S1) solution was changed to 0.50g.

[0126] [Examples 1-7] The release layer forming composition 7 was prepared by the same method as in Examples 1-1, except that the acrylic polymer (S1) solution was changed to 0.38g.

[0127] [Examples 1-8] The release layer forming composition 8 was prepared by means of the same method as in Examples 1-1, except that an acrylic polymer (S2) solution was used instead of an acrylic polymer (S1) solution.

[0128] [Comparative Example 1-1] The release layer forming composition 9 was modulated by the same method as in Example 1-1, except that CAB was used instead of HPC-SSL.

[0129] [Comparative Examples 1-2] The release layer forming composition 10 was modulated by the same method as in Examples 1-1, except that CAP was used instead of HPC-SSL.

[0130] [4] Fabrication of release layer and resin substrate [Example 2-1] Using a spin coater (conditions: approximately 30 seconds at 1,000 rpm), release layer forming composition 1-1 was applied to a glass substrate (100 mm × 100 mm, the same applies below). The obtained coating was heated at 100°C for 2 minutes using a hot plate, and then heated at 230°C for 10 minutes using a hot plate to form a release layer with a thickness of approximately 0.1 μm on the glass substrate, thus obtaining a glass substrate with a release layer. Immediately afterwards, using a spin coater (conditions: approximately 15 seconds at 200 rpm), resin substrate forming composition F1 was applied to the release layer (resin film) on the aforementioned glass substrate. The obtained 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 with a thickness of approximately 3 μm on the release layer, thus obtaining a glass substrate with a resin substrate and release layer. Subsequently, the light transmittance was measured using a UV-2600 UV-Vis spectrophotometer (manufactured by Shimadzu Corporation). The results showed that the resin substrate exhibited a transmittance of over 90% at 400 nm.

[0131] [Example 2-2] Except that the release layer forming composition 1-2 is used instead of the release layer forming composition 1-1, the release layer and the resin substrate are made by the same method as in Example 2-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0132] [Example 2-3] Except that the release layer forming composition 1-3 is used instead of the release layer forming composition 1-1, the release layer and the resin substrate are made by the same method as in Example 2-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0133] [Examples 2-4] Except that the release layer forming composition 1-4 is used instead of the release layer forming composition 1-1, the release layer and the resin substrate are made by the same method as in Example 2-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0134] [Examples 2-5] Except that the release layer forming composition 1-5 is used instead of the release layer forming composition 1-1, the release layer and the resin substrate are prepared by the same method as in Example 2-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0135] [Examples 2-6] Except that the release layer forming composition 1-6 is used instead of the release layer forming composition 1-1, the release layer and the resin substrate are made by the same method as in Example 2-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0136] [Examples 2-7] Except that the release layer forming composition 1-7 is used instead of the release layer forming composition 1-1, the release layer and the resin substrate are made by the same method as in Example 2-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0137] [Examples 2-8] Except that the release layer forming composition 1-8 is used instead of the release layer forming composition 1-1, the release layer and the resin substrate are made by the same method as in Example 2-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0138] [Comparative Example 2-1] Except that the release layer forming composition 1-9 is used instead of the release layer forming composition 1-1, the release layer and the resin substrate are prepared by the same method as in Example 2-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0139] [Comparative Example 2-2] Except that the release layer forming composition 1-10 is used instead of the release layer forming composition 1-1, the release layer and the resin substrate are prepared by the same method as in Example 2-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0140] [5] The peelability was evaluated for the glass substrates with release layers and glass substrates with resin substrates and release layers obtained in Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-2. The peelability was confirmed by the following method. In addition, the following tests were performed on the same glass substrate.

[0141] (1) Evaluation of the peelability of the release layer to the glass substrate The release layers on the glass substrates with release layers obtained in Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-2 were cross-cut (with 2mm intervals in length and width, the same below) to cut out 25 pieces. That is, 25 square grids of 2mm were formed by this cross-cut. Adhesive tape was applied to these 25 cut portions, the tape was peeled off, and the degree of peeling was evaluated based on the following criteria. The results are shown in Table 1. <Judgment Criteria> 5B: 0% peeling (no peeling) 4B: Less than 5% peeling 3B: 5% or more, less than 15% peeling 2B: 15% or more, less than 35% peeling 1B: 35% or more, less than 65% peeling 0B: 65% or more, less than 80% peeling B: 80% or more, less than 95% peeling A: 95% or more, less than 100% peeling AA: 100% peeling (complete peeling)

[0142] (2) Evaluation of the peel force between the release layer and the resin substrate: A strip of 25mm × 50mm was fabricated from the glass substrates with resin substrates and release layers obtained in Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-2. Cellotape (registered trademark) (NICHIBAN CT-24) was then applied, and peeling was performed using an automatic stereoscopic plotter AGS-X500N (manufactured by Shimadzu Corporation) at a peel angle of 90° and a peel speed of 300mm / min to measure the peel force. Furthermore, those that could not be peeled were defined as non-peelable. The results are shown in Table 1.

[0143]

[0144] As shown in Table 1, it can be confirmed that the release layer of the embodiment has excellent adhesion to the glass substrate and can be easily peeled off from the resin film system. On the other hand, it was confirmed that although the release layer of Comparative Examples 2-1 to 2-2 has excellent adhesion to the glass substrate, it is difficult to peel off from the resin substrate.

[0145] (II)(A2) The composition for forming a release layer of a polyester containing hydroxyl groups is the same as described below. PGME: Propylene glycol monomethyl ether; PGMEA: Propylene glycol monomethyl ether acetate; PL-LI: 1,3,4,6-Tetra(methoxyethyl)glycourea (Allnex, trade name: POWDERLINK 1174); PPTS: Pyridinium p-toluenesulfonate; HPMA: 2-Hydroxypropyl methacrylate; ADMA: 2-Adamantane methacrylate; HFiPMA: 1,1,1,3,3,3-Hexafluoroisopropyl methacrylate; AIBN: Azobisisobutyronitrile; DDT: Dodecanethiol; EP1: Bisphenol A type epoxy resin (Mitsubishi Chemical, trade name: jER828); EP2: Terephthalate type epoxy resin (Nagase ChemteX, trade name: Denacol EX711); EP3: Biphenyl type epoxy resin (Mitsubishi Chemical, trade name: YX4000H). EP4: Fluorene-type epoxy resin (manufactured by Osaka Gas Chemical Co., Ltd., trade name: OGSOL PG-100) EP5: Fluorene-type epoxy resin (manufactured by Osaka Gas Chemical Co., Ltd., trade name: OGSOL CG-500) EP6: Cyclopentyl-type epoxy resin (manufactured by CEL2021P, trade name: CEL2021P) TPhA: Terephthalic acid IPhA: Isophthalic acid 5HIPhA: 5-Hydroxyisophthalic acid 14CHA: 1,4-Cyclopentyl dicarboxylic acid BTEAC: Benzyl triethylammonium chloride ETPPB: Ethyl triphenylphosphine bromide

[0146] Furthermore, the determination of the weight average molecular weight (Mw) of the polymer is performed by the same method as described in (I) above.

[0147] [1] Synthesis of Polymers [Synthesis Example 2-1] Synthesis of Polyester (A2-1) 10.0 g of EP1, 5.4 g of TPhA 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 (A2-1) solution (solid component concentration 30% by mass). According to GPC analysis, the obtained polyester (A2-1) had a Mw of 13,200 and a Mw / Mn of 3.9.

[0148] [Synthesis Example 2-2] Synthesis of Polyester (A2-2) 10.0 g of EP3, 5.2 g of TPhA and 0.24 g of BTEAC were dissolved in 36.0 g of PGME and reacted at 120 °C for 20 hours to obtain a polyester (A2-2) solution (solid component concentration 30% by mass). GPC analysis showed that the obtained polyester (A2-2) had a Mw of 21,000 and an Mw / Mn ratio of 3.2.

[0149] [Synthesis Example 2-3] Synthesis of Polyester (A2-3) 10.0 g of EP1, 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 (A2-3) solution (solid component concentration 30% by mass). GPC analysis showed that the obtained polyester (A2-3) had a Mw of 6,600 and an Mw / Mn ratio of 2.1.

[0150] [Synthesis Example 2-4] Synthesis of Polyester (A2-4) 10.0 g of EP2, 6.8 g of IPhA and 0.31 g of BTEAC were dissolved in 39.9 g of PGME and reacted at 120 °C for 20 hours to obtain a polyester (A2-4) solution (solid component concentration 30% by mass). GPC analysis showed that the obtained polyester (A2-4) had a Mw of 5,400 and an Mw / Mn ratio of 4.1.

[0151] [Synthesis Example 2-5] Synthesis of Polyester (A2-5) 10.0 g of EP3, 5.2 g of IPhA and 0.24 g of BTEAC were dissolved in 36.0 g of PGME and reacted at 120 °C for 20 hours to obtain a polyester (A2-5) solution (solid component concentration 30% by mass). GPC analysis showed that the obtained polyester (A2-5) had a Mw of 5,400 and an Mw / Mn ratio of 3.3.

[0152] [Synthesis Example 2-6] Synthesis of Polyester (A2-6) 10.0 g of EP4, 4.0 g of IPhA and 0.18 g of BTEAC were dissolved in 56.5 g of PGME and reacted at 120 °C for 20 hours to obtain a polyester (A2-6) solution (solid component concentration 20% by mass). GPC analysis showed that the obtained polyester (A2-6) had a Mw of 8,100 and an Mw / Mn ratio of 3.3.

[0153] [Synthesis Example 2-7] Synthesis of Polyester (A2-7) 10.0 g of EP5, 3.4 g of IPhA and 0.15 g of BTEAC were dissolved in 54.2 g of PGME and reacted at 120 °C for 20 hours to obtain a polyester (A2-7) solution (solid component concentration 20% by mass). GPC analysis showed that the obtained polyester (A2-7) had a Mw of 6,600 and an Mw / Mn ratio of 2.0.

[0154] [Synthesis Example 2-8] Synthesis of Polyester (A2-8) 10.0 g of EP4, 4.3 g of 5HIPhA and 0.18 g of BTEAC were dissolved in 58.1 g of PGME and reacted at 120 °C for 20 hours to obtain a polyester (A2-8) solution (solid component concentration 20% by mass). GPC analysis showed that the obtained polyester (A2-8) had a Mw of 6,200 and an Mw / Mn ratio of 2.4.

[0155] [Synthesis Example 2-9] Synthesis of Polyester (A2-9): 10.0 g of EP5, 3.7 g of 5HIPhA and 0.15 g of BTEAC were dissolved in 5.5 g of PGME and reacted at 120 °C for 20 hours to obtain a polyester (A2-9) solution (solid component concentration 20% by mass). GPC analysis showed that the obtained polyester (A2-9) had a Mw of 7,600 and an Mw / Mn ratio of 2.2.

[0156] [Synthesis Example 2-10] Synthesis of Polyester (A2-10) 10.0 g of EP6, 6.6 g of TPhA and 0.59 g of ETPPB were dissolved in 40.1 g of PGME and reacted at 120 °C for 20 hours to obtain a polyester (A2-10) solution (solid component concentration 20% by mass). GPC analysis showed that the obtained polyester (A2-10) had a Mw of 9,200 and an Mw / Mn ratio of 2.1.

[0157] [Synthesis Example 2-11] Synthesis of Polyester (A2-11) 10.0 g of EP6, 6.8 g of 14CHA and 0.59 g of ETPPB were dissolved in 40.7 g of PGME and reacted at 120 °C for 20 hours to obtain a polyester (A2-11) solution (solid component concentration 20% by mass). GPC analysis showed that the obtained polyester (A2-11) had a Mw of 5,800 and an Mw / Mn ratio of 1.7.

[0158] [Synthesis Example 2-12] Synthesis of acrylic polymer (S1): 6.43 g of HFiPMA, 3.93 g of HPMA, 8.00 g of ADMA, 0.74 g of AIBN, and 0.92 g of DDT were dissolved in 80.1 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (S1) solution (solid component concentration 20% by mass). The composition ratio of each unit was HFiPMA:HPMA:ADMA = 30:30:40. GPC analysis showed that the obtained acrylic polymer (S1) had a Mw of 5,310 and an Mw / Mn ratio of 1.8.

[0159] [2] Preparation of composition for resin substrate formation [Preparation Example 1] The composition F1 for resin substrate formation was prepared by adding 10g of ZEONOR 1020R (a cyclic olefin polymer manufactured by ZEON Corporation of Japan) and 3g of Epolead GT401 (manufactured by Daicel Corporation) to a flask containing 100g of carbon tetrachloride. The solution was stirred and dissolved under nitrogen for 24 hours to prepare composition F1 for resin substrate formation.

[0160] [3] Preparation of composition for release layer formation [Example 3-1] Preparation of composition 1 for release layer formation: 1 g of polyester (A2-1) solution obtained in Synthesis Example 1 was mixed with 0.06 g of PL-LI, 0.01 g of PPTS, 0.17 g of acrylic polymer (S1) solution and PGMEA, and diluted with PGME to make the solid component concentration 5% by mass and the PGMEA concentration 30% by mass to prepare composition 2-1 for release layer formation.

[0161] [Example 3-2] The release layer forming composition 2 was prepared by means of the same method as in Example 3-1, except that a polyester (A2-2) solution was used instead of a polyester (A2-1) solution.

[0162] [Example 3-3] The release layer forming composition 3 was prepared by means of the same method as in Example 3-1, except that a polyester (A2-3) solution was used instead of a polyester (A2-1) solution.

[0163] [Examples 3-4] The release layer forming composition 4 was prepared by means of the same method as in Example 3-1, except that a polyester (A2-4) solution was used instead of a polyester (A2-1) solution.

[0164] [Examples 3-5] The release layer forming composition 5 was prepared by means of the same method as in Example 3-1, except that a polyester (A2-5) solution was used instead of a polyester (A2-1) solution.

[0165] [Examples 3-6] The release layer forming composition 6 was prepared by means of the same method as in Example 3-1, except that a polyester (A2-6) solution was used instead of a polyester (A2-1) solution.

[0166] [Examples 3-7] The release layer forming composition 7 was prepared by means of the same method as in Example 3-1, except that a polyester (A2-7) solution was used instead of a polyester (A2-1) solution.

[0167] [Examples 3-8] The release layer forming composition 8 was prepared by means of the same method as in Example 3-1, except that a polyester (A2-8) solution was used instead of a polyester (A2-1) solution.

[0168] [Examples 3-9] The release layer forming composition 9 was prepared by means of the same method as in Example 3-1, except that a polyester (A2-9) solution was used instead of a polyester (A2-1) solution.

[0169] [Example 3-10] The release layer forming composition 2-10 was prepared by the same method as in Example 3-1, except that a polyester (A2-10) solution was used instead of a polyester (A2-1) solution.

[0170] [Example 3-11] The release layer forming composition 2-11 was prepared by means of the same method as in Example 3-1, except that a polyester (A2-11) solution was used instead of a polyester (A2-1) solution.

[0171] [4] Fabrication of release layer and resin substrate [Example 4-1] Using a spin coater (conditions: approximately 30 seconds at 1,000 rpm), release layer forming composition 2-1 was applied to a glass substrate (100 mm × 100 mm, the same applies below). The obtained coating was heated at 100°C for 2 minutes using a hot plate, and then heated at 230°C for 10 minutes using a hot plate to form a release layer with a thickness of approximately 0.1 μm on the glass substrate, thus obtaining a glass substrate with a release layer. Immediately afterwards, using a spin coater (conditions: approximately 15 seconds at 200 rpm), resin substrate forming composition F1 was applied to the release layer (resin film) on the aforementioned glass substrate. The obtained 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 with a thickness of approximately 3 μm on the release layer, thus obtaining a glass substrate with a resin substrate and release layer. Subsequently, the light transmittance was measured using a UV-2600 UV-Vis spectrophotometer (manufactured by Shimadzu Corporation). The results showed that the resin substrate exhibited a transmittance of over 90% at 400 nm.

[0172] [Example 4-2] Except that the release layer forming composition 2-2 is used instead of the release layer forming composition 2-1, the release layer and the resin substrate are made by the same method as in Example 4-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0173] [Example 4-3] Except that the release layer forming composition 2-3 is used instead of the release layer forming composition 2-1, the release layer and the resin substrate are made by the same method as in Example 4-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0174] [Example 4-4] Except that the release layer forming composition 2-4 is used instead of the release layer forming composition 2-1, the release layer and the resin substrate are made by the same method as in Example 4-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0175] [Examples 4-5] Except that the release layer forming composition 2-5 is used instead of the release layer forming composition 2-1, the release layer and the resin substrate are prepared by the same method as in Example 4-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0176] [Examples 4-6] Except that the release layer forming composition 2-6 is used instead of the release layer forming composition 2-1, the release layer and the resin substrate are prepared by the same method as in Example 4-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0177] [Examples 4-7] Except that the release layer forming composition 2-7 is used instead of the release layer forming composition 2-1, the release layer and the resin substrate are made by the same method as in Example 4-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0178] [Examples 4-8] Except that the release layer forming composition 2-8 is used instead of the release layer forming composition 2-1, the release layer and the resin substrate are made by the same method as in Example 4-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0179] [Examples 4-9] Except that the release layer forming composition 2-9 is used instead of the release layer forming composition 2-1, the release layer and the resin substrate are made by the same method as in Example 4-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0180] [Example 4-10] Except that the release layer forming composition 2-10 is used instead of the release layer forming composition 2-1, the release layer and the resin substrate are made by the same method as in Example 4-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0181] [Example 4-11] Except that the release layer forming composition 2-11 is used instead of the release layer forming composition 2-1, the release layer and the resin substrate are made by the same method as in Example 4-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0182] [5] Evaluation of peelability The peelability of the glass substrates with peelable layers and the glass substrates with resin substrates and peelable layers obtained in Examples 4-1 to 4-11 above was confirmed by the same method as described in [4] of (I) above. The results are shown in Table 2.

[0183]

[0184] The results shown in Table 2 confirm that the release layer of the embodiment has excellent adhesion to the glass substrate and can be easily peeled off from the resin film system.

[0185] (III)(A3) A composition for forming a release layer of an acrylic polymer having primary or secondary hydroxyl groups and not having fluorine atoms. The compounds used in the following examples are as follows: PGME: Propylene glycol monomethyl ether; PGMEA: Propylene glycol monomethyl ether acetate; CHN: Cyclohexanone; PL-LI: 1,3,4,6-Tetra(methoxyethyl)glycourea (Allnex, trade name: POWDERLINK 1174); PPTS: Pyridinium p-toluenesulfonate; MMA: Methyl methacrylate; HPMA: 2-hydroxypropyl methacrylate; HEMA: 2-hydroxyethyl methacrylate; 4HBA: 4-hydroxybutyl acrylate; HADM: 3-hydroxy-1-adamantane methacrylate; ADMA: 2-adamantane methacrylate; HFiPMA: 1,1,1,3,3,3-hexafluoroisopropyl methacrylate; AIBN: Azobisisobutyronitrile; DDT: Dodecanethiol.

[0186] Furthermore, the weight average molecular weight (Mw) of the polymer was determined by the same method as described in (I) above.

[0187] [1] Synthesis of Polymers [Synthesis Example 3-1] Synthesis of Acrylic Polymer (A3-1) 20.0 g of HEMA, 1.26 g of AIBN and 1.56 g of DDT were dissolved in 92 g of PGME and reacted at 70 °C for 20 hours to obtain an acrylic polymer (A3-1) solution (solid component concentration 20% by mass). According to GPC analysis, the Mw of the obtained acrylic polymer (A3-1) was 5,400 and the Mw / Mn ratio was 1.7.

[0188] [Synthesis Example 3-2] Synthesis of acrylic polymer (A3-2): 20.0 g of HEMA and 1.26 g of AIBN were dissolved in 85 g of PGME and reacted at 70 °C for 20 hours to obtain an acrylic polymer (A3-2) solution (solid content concentration 20% by mass). GPC analysis showed that the obtained acrylic polymer (A3-2) had a Mw of 13,300 and an Mw / Mn ratio of 2.5.

[0189] [Synthesis Example 3-3] Synthesis of acrylic polymer (A3-3): 20.0 g of HPMA, 1.14 g of AIBN, and 1.40 g of DDT were dissolved in 90.2 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (A3-3) solution (solid content concentration 20% by mass). GPC analysis showed that the obtained acrylic polymer (A3-3) had a Mw of 6,300 and an Mw / Mn ratio of 1.5.

[0190] [Synthesis Examples 3-4] Synthesis of acrylic polymer (A3-4): 20.0 g of HPMA and 1.14 g of AIBN were dissolved in 84.5 g of PGME and reacted at 70 °C for 20 hours to obtain an acrylic polymer (A3-4) solution (solid content concentration 20% by mass). GPC analysis showed that the obtained acrylic polymer (A3-4) had a Mw of 13,000 and an Mw / Mn ratio of 2.5.

[0191] [Synthesis Example 3-5] Synthesis of acrylic polymer (A3-5): 20.0 g of 4HBA, 1.14 g of AIBN, and 1.40 g of DDT were dissolved in 90.2 g of PGME and reacted at 70 °C for 20 hours to obtain an acrylic polymer (A3-5) solution (solid content concentration 20% by mass). GPC analysis showed that the obtained acrylic polymer (A3-5) had a Mw of 4,200 and an Mw / Mn ratio of 1.3.

[0192] [Synthesis Example 3-6] Synthesis of acrylic polymer (A3-6): 10.0 g of MMA, 13.0 g of HEMA, 1.64 g of AIBN, and 1.21 g of DDT were dissolved in 103.4 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (A3-6) solution (solid component concentration 20% by mass). The composition ratio of each unit was MMA:HEMA = 50:50. GPC analysis showed that the obtained acrylic polymer (A3-6) had a Mw of 6,600 and an Mw / Mn ratio of 1.9.

[0193] [Synthesis Example 3-7] Synthesis of acrylic polymer (A3-7): 10.0 g of MMA, 14.3 g of HPMA, 1.64 g of AIBN, and 1.21 g of DDT were dissolved in 109.0 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (A3-7) solution (solid component concentration 20% by mass). The composition ratio of each unit was MMA:HPMA = 50:50. GPC analysis showed that the obtained acrylic polymer (A3-7) had a Mw of 6,400 and an Mw / Mn ratio of 2.3.

[0194] [Synthesis Example 3-8] Synthesis of acrylic polymer (A3-8): 15.0 g of MMA, 8.36 g of HEMA, 1.74 g of AIBN, and 1.30 g of DDT were dissolved in 105.7 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (A3-8) solution (solid component concentration 20% by mass). The composition ratio of each unit was MMA:HEMA = 70:30. GPC analysis showed that the obtained acrylic polymer (A3-8) had a Mw of 5,500 and an Mw / Mn ratio of 2.0.

[0195] [Synthesis Example 3-9] Synthesis of acrylic polymer (A3-9): 15.0 g of MMA, 9.26 g of HPMA, 1.74 g of AIBN, and 1.30 g of DDT were dissolved in 109.3 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (A3-9) solution (solid component concentration 20% by mass). The composition ratio of each unit was MMA:HPMA = 70:30. GPC analysis showed that the obtained acrylic polymer (A3-9) had a Mw of 6,000 and an Mw / Mn ratio of 2.0.

[0196] [Synthesis Example 3-10] Synthesis of acrylic polymer (A3-10): 20.0 g of HADM, 0.69 g of AIBN, and 0.86 g of DDT were dissolved in 86.2 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (A3-10) solution (solid content concentration 20% by mass). GPC analysis showed that the obtained acrylic polymer (A3-10) had a Mw of 5,100 and an Mw / Mn ratio of 1.5.

[0197] [Synthesis Example 3-11] Synthesis of acrylic polymer (A3-11): MMA 10.0 g, HADM 10.12 g, AIBN 1.17 g and DDT 0.87 g were dissolved in PGME 88.6 g and reacted at 70 °C for 20 hours to obtain an acrylic polymer (A11) solution (solid component concentration 20% by mass). The composition ratio of each unit was MMA:HADM = 70:30. GPC analysis showed that the obtained acrylic polymer (A3-11) had a Mw of 6,600 and an Mw / Mn ratio of 1.6.

[0198] [Synthesis Example 3-12] Synthesis of acrylic polymer (A3-12): 10.0 g of MMA, 0.82 g of AIBN, and 0.61 g of DDT were dissolved in 45.7 g of PGME and reacted at 70 °C for 20 hours to obtain an acrylic polymer (A3-12) solution (solid content concentration 20% by mass). GPC analysis showed that the obtained acrylic polymer (A3-12) had a Mw of 5,200 and an Mw / Mn ratio of 1.7.

[0199] [Synthesis Example 3-13] Synthesis of acrylic polymer (S1): 6.43 g of HFiPMA, 3.93 g of HPMA, 8.00 g of ADMA, 0.74 g of AIBN, and 0.92 g of DDT were dissolved in 80.1 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (S1) solution (solid component concentration 20% by mass). The composition ratio of each unit was HFiPMA:HPMA:ADMA = 30:30:40. GPC analysis showed that the obtained acrylic polymer (S1) had a Mw of 5,310 and an Mw / Mn ratio of 1.8.

[0200] [Synthesis Example 3-14] Synthesis of Acrylic Polymer (S2): 8.57 g of HFiPMA, 2.62 g of HPMA, 8.00 g of ADMA, 0.74 g of AIBN, and 0.92 g of DDT were dissolved in 83.4 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (S2) solution (solid content concentration 20% by mass). The composition ratio of each unit was HFiPMA:HPMA:ADMA = 40:20:40. GPC analysis showed that the obtained acrylic polymer (S2) had a Mw of 5,500 and an Mw / Mn ratio of 1.8.

[0201] [2] Preparation of composition for resin substrate formation [Preparation Example 1] The composition F1 for resin substrate formation was prepared by adding 10g of ZEONOR 1020R (a cyclic olefin polymer manufactured by ZEON Corporation, Japan) and 3g of Epolead GT401 (manufactured by Daicel Corporation) to a flask containing 100g of carbon tetrachloride. The solution was stirred and dissolved under nitrogen for 24 hours to prepare composition F1 for resin substrate formation.

[0202] [3] Preparation of composition for release layer formation [Example 5-1] Preparation of composition 1 for release layer formation: 1 g of acrylic polymer (A3-1) solution obtained in Synthesis Example 1 was mixed with 0.06 g of PL-LI, 0.01 g of PPTS, 0.08 g of acrylic polymer (S1) solution and PGMEA, and diluted with PGMEA to make the solid component concentration 5% by mass and the PGMEA concentration 30% by mass to prepare composition 3-1 for release layer formation.

[0203] [Example 5-2] The composition 2 for forming the release layer was prepared by means of the same method as in Example 5-1, except that an acrylic polymer (A3-2) solution was used instead of an acrylic polymer (A3-1) solution.

[0204] [Example 5-3] The release layer forming composition 3 was prepared by the same method as in Example 5-1, except that an acrylic polymer (A3-3) solution was used instead of an acrylic polymer (A3-1) solution.

[0205] [Example 5-4] The composition 4 for forming the release layer was prepared by means of the same method as in Example 5-1, except that an acrylic polymer (A3-4) solution was used instead of an acrylic polymer (A3-1) solution.

[0206] [Example 5-5] The release layer forming composition 5 was prepared by means of the same method as in Example 5-1, except that an acrylic polymer (A3-5) solution was used instead of an acrylic polymer (A3-1) solution.

[0207] [Examples 5-6] The release layer forming composition 6 was prepared by means of the same method as in Example 5-1, except that an acrylic polymer (A3-6) solution was used instead of an acrylic polymer (A3-1) solution.

[0208] [Examples 5-7] The release layer forming composition 7 was prepared by means of the same method as in Example 5-1, except that an acrylic polymer (A3-6) solution was used instead of an acrylic polymer (A3-1) solution and the acrylic polymer (S1) was changed to 0.17g.

[0209] [Examples 5-8] The release layer forming composition 8 was prepared by means of the same method as in Example 5-1, except that an acrylic polymer (A3-7) solution was used instead of an acrylic polymer (A3-1) solution.

[0210] [Examples 5-9] The release layer forming composition 9 was prepared by means of the same method as in Examples 1-1, except that an acrylic polymer (A3-7) solution was used instead of an acrylic polymer (A3-1) solution and the acrylic polymer (S1) was changed to 0.17g.

[0211] [Examples 5-10] The release layer forming composition 10 was prepared by means of the same method as in Example 5-1, except that an acrylic polymer (A3-7) solution was used instead of an acrylic polymer (A3-1) solution and an acrylic polymer (S2) solution was used instead of an acrylic polymer (S1) solution.

[0212] [Examples 5-11] The release layer forming composition 11 was prepared by means of the same method as in Example 5-1, except that an acrylic polymer (A3-8) solution was used instead of an acrylic polymer (A3-1) solution.

[0213] [Examples 5-12] The release layer forming composition 12 was prepared by means of the same method as in Example 5-1, except that an acrylic polymer (A3-9) solution was used instead of an acrylic polymer (A3-1) solution.

[0214] [Comparative Example 3-1] The composition 13 for forming the release layer was prepared by the same method as in Example 5-1, except that an acrylic polymer (A3-10) solution was used instead of an acrylic polymer (A3-1) solution and the solvent was changed to CHN.

[0215] [Comparative Example 3-2] The release layer forming composition 14 was prepared by means of the same method as in Example 5-1, except that an acrylic polymer (A3-11) solution was used instead of an acrylic polymer (A3-1) solution.

[0216] [Comparative Example 3-3] The release layer forming composition 15 was prepared by means of the same method as in Example 5-1, except that an acrylic polymer (A3-12) solution was used instead of an acrylic polymer (A3-1) solution.

[0217] [4] Fabrication of release layer and resin substrate [Example 6-1] Using a spin coater (conditions: approximately 30 seconds at 1,000 rpm), release layer forming composition 3-1 was applied to a glass substrate (100 mm × 100 mm, the same applies below). The obtained coating was heated at 100°C for 2 minutes using a hot plate, and then heated at 230°C for 10 minutes using a hot plate to form a release layer with a thickness of approximately 0.1 μm on the glass substrate, thus obtaining a glass substrate with a release layer. Immediately afterwards, using a spin coater (conditions: approximately 15 seconds at 200 rpm), resin substrate forming composition F1 was applied to the release layer (resin film) formed on the glass substrate. The obtained 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 with a thickness of approximately 3 μm on the release layer, thus obtaining a glass substrate with a resin substrate and release layer. Subsequently, the light transmittance was measured using a UV-Vis spectrophotometer (Shimadzu Corporation UV-2600). The resin substrate showed a transmittance of over 90% at 400 nm.

[0218] [Example 6-2] Except that the release layer forming composition 3-2 is used instead of the release layer forming composition 3-1, the release layer and the resin substrate are made by the same method as in Example 6-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0219] [Example 6-3] Except that the release layer forming composition 3-3 is used instead of the release layer forming composition 3-1, the release layer and the resin substrate are made by the same method as in Example 6-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0220] [Example 6-4] Except that the release layer forming composition 3-4 is used instead of the release layer forming composition 3-1, the release layer and the resin substrate are made by the same method as in Example 6-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0221] [Example 6-5] Except that the release layer forming composition 3-5 is used instead of the release layer forming composition 3-1, the release layer and the resin substrate are made by the same method as in Example 6-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0222] [Example 6-6] Except that the release layer forming composition 3-6 is used instead of the release layer forming composition 3-1, the release layer and the resin substrate are made by the same method as in Example 6-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0223] [Examples 6-7] Except that the release layer forming composition 3-7 is used instead of the release layer forming composition 3-1, the release layer and the resin substrate are made by the same method as in Example 6-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0224] [Examples 6-8] Except that the release layer forming composition 3-8 is used instead of the release layer forming composition 3-1, the release layer and the resin substrate are made by the same method as in Example 6-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0225] [Examples 6-9] Except that the release layer forming composition 3-9 is used instead of the release layer forming composition 3-1, the release layer and the resin substrate are made by the same method as in Example 6-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0226] [Examples 6-10] Except that the release layer forming composition 3-10 is used instead of the release layer forming composition 3-1, the release layer and the resin substrate are made by the same method as in Example 6-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0227] [Example 6-11] Except that the release layer forming composition 3-11 is used instead of the release layer forming composition 3-1, the release layer and the resin substrate are made by the same method as in Example 6-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0228] [Example 6-12] Except that the release layer forming composition 3-12 is used instead of the release layer forming composition 3-1, the release layer and the resin substrate are made by the same method as in Example 6-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer are obtained.

[0229] [Comparative Example 4-1] Except that the release layer forming composition 3-13 was used instead of the release layer forming composition 3-1, the release layer and the resin substrate were prepared by the same method as in Example 6-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer were obtained.

[0230] [Comparative Example 4-2] Except that the release layer forming composition 3-14 was used instead of the release layer forming composition 3-14, the release layer and the resin substrate were prepared by the same method as in Example 6-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer were obtained.

[0231] [Comparative Example 4-3] Except that the release layer forming composition 3-15 was used instead of the release layer forming composition 3-15, the release layer and the resin substrate were prepared by the same method as in Example 6-1, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer were obtained.

[0232] [5] Evaluation of peelability The peelability of the glass substrates with release layer and the glass substrates with resin substrate and release layer obtained in Examples 6-1 to 6-12 and Comparative Examples 4-1 to 4-3 was confirmed by the same method as described in [4] of (I) above. The results are shown in Table 3.

[0233] [6] Hardening Evaluation The glass substrates with release layers obtained in Examples 6-1 to 6-12 and Comparative Examples 4-1 to 4-3 were immersed in EDM at room temperature for 5 minutes. Afterwards, they were dried by heating at 100°C for 2 minutes using a hot plate. The film thickness before and after PGME immersion was measured, and the residual film rate was calculated by the following formula. The degree of hardening was evaluated based on the following criteria. The results are shown in Table 3. <Residual Film Rate Calculation Formula> {(Film thickness after immersion) / (Film thickness before immersion)}×100 <Judgment Criteria> ◎: Residual film rate ≥95% ○: Residual film rate 70~94% △: Residual film rate 50~69% ×: Residual film rate <50%

[0234]

[0235] As shown in Table 3, it was confirmed that the release layer of the embodiment had excellent adhesion to the glass substrate, and could be easily peeled off from the resin film. On the other hand, it was confirmed that the release layer of Comparative Examples 4-1 to 4-3 had excellent adhesion to the glass substrate, but was difficult to peel off from the resin substrate.

Claims

1. A composition for forming a release layer, comprising (A) (A1) cellulose or a derivative thereof having a hydroxyalkyl group, or (A3) an acrylic polymer having a primary or secondary hydroxyl group and without a fluorine atom, (B) an acid compound or a salt thereof, (C) a crosslinking agent selected from a compound having a nitrogen atom substituted with a hydroxyalkyl group and / or an alkoxymethyl group, (D) a polymeric additive comprising repeating units represented by formula (a1), repeating units represented by formula (b), and repeating units represented by formula (c), and (E) a solvent, wherein the polymeric additive comprises 5 to 100 parts by mass of the aforementioned polymeric additive (D) relative to 100 parts by mass of component (A), wherein component (B) is a sulfonic acid compound or a salt thereof, wherein the content of component (B) is 0.01 to 15 parts by mass relative to 100 parts by mass of component (A), and wherein the content of the crosslinking agent (C) is 10 to 100 parts by mass relative to 100 parts by mass of component (A). (In the formula, RA is a hydrogen atom or methyl group, RB1 is a branched alkyl group with 3 or 4 carbon atoms that has at least 1 hydrogen atom replaced by a fluorine atom, RC is a hydroxyalkyl group with 1 to 10 carbon atoms, and RD is a polycyclic alkyl group with 6 to 20 carbon atoms or an aryl group with 6 to 12 carbon atoms).

2. A composition for forming a release layer, comprising (A2) a polyester having a structural unit represented by formula [A2-1], a structural unit represented by formula [A2-2], or a structural unit represented by formula [A2-3], (B) an acid compound or a salt thereof, (C) a crosslinking agent selected from a compound having a nitrogen atom substituted with hydroxyalkyl and / or alkoxymethyl groups, (D) a polymeric additive comprising a repeating unit represented by formula (a1), a repeating unit represented by formula (b), and a repeating unit represented by formula (c), and (E) a solvent, wherein, relative to 100 parts by mass of component (A), it comprises 5 to 100 parts by mass of the aforementioned polymeric additive (D), wherein component (B) is a sulfonic acid compound or a salt thereof, and the content of component (B) is 0.01 to 15 parts by mass relative to 100 parts by mass of component (A). The content of the aforementioned (C) crosslinking agent is 10 to 100 parts by mass relative to 100 parts by mass of the aforementioned (A) component. (In the formula, X is the group X represented by the following formula (X-1), and Y represents a structure having an aromatic group or an alicyclic group.) (In the formula, L1 represents an ether bond or an ester bond, X1 represents an alkyl group, a cyclic unsaturated hydrocarbon group or a cyclic saturated hydrocarbon group with 1 to 10 carbon atoms, R1 represents a single bond, an ether bond, a carbonyl group, a sulfonyl group, a saturated hydrocarbon group with 1 to 30 carbon atoms, an unsaturated hydrocarbon group with 2 to 30 carbon atoms, or a saturated hydrocarbon group with 1 to 30 carbon atoms substituted with a fluorine atom, and p represents 0, 1 or 2.) (In the formula, Cy is a tetravalent organic group containing an aliphatic ring, wherein the two OH groups and the two O atoms are bonded to the aliphatic ring, and Y represents the same definition as Y in formula [A2-1].) (In the formula, X and Y have the same definition as X and Y in formula [A2-1]) (In the formula, RA is each independently a hydrogen atom or a methyl group, RB1 is a branched alkyl group with 3 or 4 carbon atoms that has at least 1 hydrogen atom replaced by a fluorine atom, RC is a hydroxyalkyl group with 1 to 10 carbon atoms, and RD is a polycyclic alkyl group with 6 to 20 carbon atoms or an aryl group with 6 to 12 carbon atoms).

3. The composition for forming the release layer as described in claim 1 or 2, wherein, In the repeating unit represented by the aforementioned formula (b), RC is a hydroxyalkyl group with 2 to 10 carbon atoms, and the carbon atom bonded to the hydroxyl group is a second-order or third-order carbon atom.

4. The composition for forming the release layer as described in claim 1 or 2, wherein, In the repeating unit represented by formula (b) above, RC is a hydroxyalkyl group with 1 to 10 carbon atoms, and the carbon atom bonded by the hydroxyl group is a first-order carbon atom. Furthermore, the proportion of the repeating unit represented by formula (a1) in the fully repeating unit of the polymer additive (D) is 25 mol% or more.

5. The composition for forming a release layer as described in claim 1 or 2, wherein, The aforementioned (D) polymer additive comprises repeating units represented by formula (a2), formula (b), formula (c), and formula (d) (where RA, RC, and RD have the same meaning as described above, RB2 is a branched alkyl group with 3 or 4 carbon atoms that has at least one hydrogen atom replaced by a fluorine atom, but does not contain 2-methyl-1,1,1,3,3,3-hexafluoroisopropyl, RE is a single bond, a polycyclic alkyl group with 6 to 20 carbon atoms, or an aryl group with 6 to 12 carbon atoms, RF is a single bond or an alkyl group with 1 to 10 carbon atoms, and RG is methyl, ethyl, or hydroxyl).

6. The composition for forming a release layer as described in claim 1, wherein, The aforementioned (A1) component is at least one selected from the group consisting of hydroxyethyl cellulose and hydroxypropyl cellulose, and derivatives thereof.

7. The composition for forming a release layer as described in claim 2, wherein, The aforementioned component (A2) is a polyester obtained by reacting a compound having two epoxy sites with a compound having two carboxyl groups.

8. The composition for forming a release layer as described in claim 1, wherein, The aforementioned component (A3) is an acrylic polymer having polyethylene glycol ester groups or first- or second-order hydroxyalkyl ester groups with 2 to 6 carbon atoms.

9. The composition for forming a release layer as described in claim 1, wherein, The aforementioned component (A3) is an acrylic polymer having a first or second order hydroxyalkyl group having 2 to 6 carbon atoms in its side chain.

10. The composition for forming a release layer as described in claim 1 or 2, wherein, The aforementioned (C) crosslinking agent is a compound represented by any one of the following formulas (C-1) to (C-5) (where R11 to R26 are each an alkyl group having 1 to 6 carbon atoms, and R27 is a hydrogen atom or a methyl group).

11. A release layer obtained from a release layer forming composition as described in any one of claims 1 to 10.

12. A laminate attached to a release layer as described in claim 11, the laminate having a resin layer with a light transmittance of 80% or more at a wavelength of 400 nm.

13. A method for manufacturing a resin substrate, comprising the steps of coating a release layer forming composition as described in any one of claims 1 to 10 onto a substrate to form a release layer, forming a resin substrate on the aforementioned release layer with a light transmittance of 80% or more at a wavelength of 400 nm, and peeling the aforementioned resin substrate with a peeling force of 0.25 N / 25 mm or less.