Composition for forming a release layer and release layer

Abstract

As a composition for forming a peeling layer that can form a peeling layer having high heat resistance and moderate peeling properties and excellent stability after film formation, the following peeling layer forming composition is provided, which comprises: (A) (A1) cellulose having a hydroxyalkyl group or a derivative thereof, (B) an acid compound or a salt thereof, (C) a crosslinking agent selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and / or an alkoxymethyl group, (D) a polymer additive comprising a repeating unit represented by formula (a1), formula (b) and formula (c), and (E) a solvent, wherein the component (D) is contained in an amount of 5 to 100 parts by mass relative to 100 parts by mass of the component (A). (R A is a hydrogen atom or a methyl group, R B1 is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom, R C is a hydroxyalkyl group having 1 to 10 carbon atoms, R D It is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.

Description

Technical Field

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

[0002] In recent years, electronic devices are being required to be flexible in addition to being thinner and lighter. This has led to a need for lightweight, flexible plastic substrates to replace conventional glass substrates, which are heavy, fragile, and non-flexible.

[0003] In particular, for next-generation displays, there is a need to develop active-matrix full-color TFT display panels using lightweight, flexible plastic substrates (hereinafter also referred to as resin substrates). Furthermore, for touch-panel displays, materials that address flexibility, such as transparent electrodes for touch panels and resin substrates, used in combination with display panels, have been developed. Transparent electrode materials have been proposed, ranging from conventionally used ITO to flexible transparent conductive polymers such as PEDOT, metal nanowires, and hybrids thereof (Patent Documents 1-4).

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

[0005] In general, in order to stably produce and peel off, a peeling (pressure-sensitive adhesive) layer is made on a supporting substrate such as a glass substrate, and a device is made thereon and then peeled off to produce a flexible touch screen panel (patent document 8). The peeling layer must be peeled off from the supporting substrate during the process. On the other hand, a low peeling force is required during peeling. In addition, in order to improve productivity, after the peeling layer is formed into a film, it is necessary to store it for a long time in the form of a film. Therefore, for the peeling layer, stability after film formation is required.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: International Publication No. 2012 / 147235

[0009] Patent Document 2: Japanese Patent Application Laid-Open No. 2009-283410

[0010] Patent Document 3: Japanese Patent Application No. 2010-507199

[0011] Patent Document 4: Japanese Patent Application Laid-Open No. 2009-205924

[0012] Patent Document 5: International Publication No. 2017 / 002664

[0013] Patent Document 6: International Publication No. 2016 / 160338

[0014] Patent Document 7: Japanese Patent Application Laid-Open No. 2015-166145

[0015] Patent Document 8: Japanese Patent Application Laid-Open No. 2016-531358 Summary of the Invention

[0016] Problems to be solved by the invention

[0017] The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a composition for forming a release layer that can form a release layer having high heat resistance and appropriate release properties and excellent stability after film formation.

[0018] Means for solving problems

[0019] The present inventors have conducted intensive studies to achieve the above-mentioned object and, as a result, have discovered that 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, (B) an acid compound or a salt thereof, (C) a crosslinking agent selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and / or an alkoxymethyl group, (D) a polymer additive comprising a predetermined repeating unit, and (E) a solvent can reproducibly form a release layer having high heat resistance, excellent adhesion to a substrate, moderate adhesion to a resin substrate, and moderate releasability, thereby completing the present invention.

[0020] That is, the present invention provides:

[0021] 1. A composition for forming a peeling layer, comprising:

[0022] (A) (A1) 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 having no fluorine atom,

[0023] (B) an acid compound or a salt thereof,

[0024] (C) a crosslinking agent selected from compounds having nitrogen atoms substituted with hydroxyalkyl groups and / or alkoxymethyl groups,

[0025] (D) a polymer additive comprising a repeating unit represented by the following formula (a1), a repeating unit represented by the following formula (b), and a repeating unit represented by the following formula (c), and

[0026] (E) solvent;

[0027] The composition for forming a release layer contains 5 to 100 parts by mass of the polymer additive (D) relative to 100 parts by mass of the component (A).

[0028] [Chemistry 1]

[0029]

[0030] (Where R A are each independently a hydrogen atom or a methyl group, R B1 is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom, R C is a hydroxyalkyl group having 1 to 10 carbon atoms, R D It is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.

[0031] 2. The composition for forming a release layer according to 1, wherein in the repeating unit represented by the above formula (b), R C is a hydroxyalkyl group having 2 to 10 carbon atoms, wherein the carbon atom to which the hydroxyl group is bonded is a secondary or tertiary carbon atom,

[0032] 3. The composition for forming a release layer according to 1, wherein in the repeating unit represented by the above formula (b), R C is a hydroxyalkyl group having 1 to 10 carbon atoms, the carbon atom to which the hydroxyl group is bonded is a primary carbon atom, and the content ratio of the repeating unit represented by formula (a1) is 25 mol% or more of all the repeating units of the polymer additive (D),

[0033] 4. The composition for forming a release layer according to 1, wherein the polymer additive (D) comprises a repeating unit represented by the following formula (a2), a repeating unit represented by the following formula (b), a repeating unit represented by the following formula (c), and a repeating unit represented by the following formula (d).

[0034] [Chemistry 2]

[0035]

[0036] (Where R A 、R C and R D Means the same as above, R B2 is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom, and does not contain 2-methyl-1,1,1,3,3,3-hexafluoroisopropyl, R E is a single bond, a polycyclic alkylene group having 6 to 20 carbon atoms, or an arylene group having 6 to 12 carbon atoms, R F is a single bond or an alkylene group with 1 to 10 carbon atoms, R Gis methyl, ethyl or hydroxy.)

[0037] 5. The composition for forming a release layer according to any one of 1 to 4, wherein the component (A1) is at least one selected from hydroxyethyl cellulose, hydroxypropyl cellulose, and derivatives thereof.

[0038] 6. The composition for forming a release layer according to any one of 1 to 4, wherein the component (A2) is a polyester having an aromatic group or an alicyclic group in the main chain.

[0039] 7. The composition for forming a release layer according to any one of 1 to 4 and 6, wherein the component (A2) is a polyester obtained by reacting a compound having two epoxy moieties with a compound having two carboxyl groups.

[0040] 8. The composition for forming a release layer according to any one of 1 to 4, wherein the component (A3) is an acrylic polymer having a polyethylene glycol ester group or a primary or secondary hydroxyalkyl ester group having 2 to 6 carbon atoms,

[0041] 9. The composition for forming a release layer according to any one of 1 to 4 and 8, wherein the component (A3) is an acrylic polymer having a primary or secondary hydroxyalkyl group having 2 to 6 carbon atoms in a side chain.

[0042] 10. The composition for forming a release layer according to any one of 1 to 9, wherein the component (B) is a sulfonic acid compound or a salt thereof.

[0043] 11. The composition for forming a release layer according to any one of 1 to 10, wherein the crosslinking agent (C) is a compound represented by any one of the following formulas (C-1) to (C-5):

[0044] [Chemistry 3]

[0045]

[0046] (Where R 11 ~R 26 are each independently an alkyl group having 1 to 6 carbon atoms, R 27 is a hydrogen atom or a methyl group.)

[0047] 12. The composition for forming a release layer according to any one of 1 to 11, wherein the content of the crosslinking agent (C) is 10 to 100 parts by mass relative to 100 parts by mass of the component (A).

[0048] 13. A peeling layer obtained from the peeling layer forming composition according to any one of 1 to 12,

[0049] 14. A laminate comprising: a release layer according to 13, and a resin layer having a light transmittance of 80% or more at a wavelength of 400 nm.

[0050] 15. A method for manufacturing a resin substrate, comprising: applying a composition for forming a peeling layer according to any one of 1 to 12 to a substrate to form a peeling layer; forming a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm on the peeling layer; and peeling the resin substrate with a peeling force of 0.25 N / 25 mm or less.

[0051] Effects of the Invention

[0052] By using the release layer-forming composition of the present invention, a release layer having high heat resistance, excellent adhesion to a substrate, moderate adhesion to a resin substrate, and moderate releasability can be obtained with good reproducibility. Furthermore, in the manufacturing process of flexible electronic devices, the resin substrate formed on the substrate and the circuitry provided thereon can be separated from the substrate together with the circuitry, etc., without damaging the resin substrate.

[0053] Therefore, the release layer-forming composition of the present invention can contribute to speeding up the production process of flexible electronic devices including a resin substrate and improving the yield thereof. DETAILED DESCRIPTION

[0054] [Composition for forming a release layer]

[0055] The composition for forming a release layer of the present invention comprises: (A) (A1) 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 no fluorine atom, (B) an acid compound or a salt thereof, (C) a crosslinking agent selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and / or an alkoxymethyl group, (D) a polymer additive containing a predetermined repeating unit, and (E) a solvent.

[0056] [(A) (A1) cellulose having a hydroxyalkyl group or a derivative thereof, (A2) polyester having a hydroxyl group, or (A3) acrylic polymer having a primary or secondary hydroxyl group and no fluorine atom]

[0057] [(A1) Cellulose or its derivatives]

[0058] The component (A1) is cellulose having a hydroxyalkyl group or a derivative thereof.

[0059] Component (A1) includes hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkylalkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl ethyl cellulose, and their derivatives. In the present invention, hydroxyalkyl celluloses and their derivatives are preferred, and hydroxyethyl cellulose and hydroxypropyl cellulose and their derivatives are more preferred. Cellulose (A1) having a hydroxyalkyl group or its derivative may be used alone or in combination of two or more.

[0060] The weight average molecular weight (Mw) of the component (A1) is not particularly limited, but is preferably 1,000 to 500,000, more preferably 3,000 to 400,000, and even more preferably 5,000 to 300,000. The weight average molecular weight is a value measured in terms of polystyrene by gel permeation chromatography (GPC) (the same applies hereinafter).

[0061] [(A2) Polyester having hydroxyl groups]

[0062] The polyester having a hydroxyl group as the component (A2) is not particularly limited. In the present invention, a polyester having an aromatic group or an alicyclic group in the main chain is preferred.

[0063] As such a polyester of the component (A2), a polyester obtained by reacting a compound having two epoxy moieties with a compound having two carboxyl groups is preferred.

[0064] The weight average molecular weight (Mw) of the polyester of the component (A2) is not particularly limited, but is preferably 1,000 to 200,000, more preferably 3,000 to 100,000, and even more preferably 5,000 to 50,000.

[0065] Epoxy compounds

[0066] Examples of the compound having two epoxy moieties include

[0067] Bisphenol diglycidyl ethers such as 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)fluorene diglycidyl ether, 9,9'-bis(4-hydroxyphenyl)fluorene diglycidyl ether, and 9,9'-bis(6-hydroxy-2-naphthyl)fluorene diglycidyl ether;

[0068] Aliphatic glycol 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;

[0069] Alicyclic glycol diglycidyl ethers such as cyclohexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, dicyclopentadiene glycol diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol B diglycidyl ether, and hydrogenated bisphenol S diglycidyl ether;

[0070] Aromatic dicarboxylic acid diglycidyl esters such as diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate;

[0071] Alicyclic diglycidyl dicarboxylate such as diglycidyl oxalate, diglycidyl adipate, diglycidyl trimellitate, and diglycidyl 2-ethyl-3-propyl-1,5-pentanedioate;

[0072] Resins having epoxy groups at both ends, such as bisphenol A-type epoxy resin jER828 (trade name, manufactured by Mitsubishi Chemical Corporation), terephthalate-type epoxy resin Denacole EX711 (trade name, manufactured by Nagasekex Corporation), biphenyl-type epoxy resin YX4000H (trade name, manufactured by Mitsubishi Chemical Corporation), fluorene-type epoxy resin Ogusol PG-100 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.), fluorene-type epoxy resin Ogusol CG-500 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.), and cyclohexyl-type epoxy resin CEL2021P (trade name, manufactured by Daicel Corporation);

[0073] Alicyclic dioxides such as vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, tetrahydroindene dioxide, Epokaric (registered trademark of ENEOS Co., Ltd.) THI-DE, Epokaric (registered trademark of ENEOS Co., Ltd.) DE-102, and Epokaric (registered trademark of ENEOS Co., Ltd.) DE-103;

[0074] Compounds having two 3,4-epoxycyclohexyl groups, such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2,2-bis(3,4-epoxycyclohexyl)propane, bis(3,4-epoxycyclohexylmethyl)oxalate, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, bis(3,4-epoxycyclohexylmethyl)pimelate, and bis(3,4-epoxycyclohexylmethyl)2-ethyl-3-propyl-1,5-pentanedioate.

[0075] These compounds may be used alone or in combination of two or more.

[0076] <Carboxyl group-containing compounds>

[0077] Examples of the compound having two carboxyl groups include terephthalic acid, isophthalic acid, 2-methylterephthalic acid, 2-hydroxyterephthalic acid, 2,5-dimethylterephthalic acid, 5-methylisophthalic acid, 5-hydroxyisophthalic acid, 2,6-naphthalene dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, and 1,4-cyclohexane dicarboxylic acid. These compounds may be used alone or in combination of two or more.

[0078] The method for obtaining the polyester as an example of component (A2) is not particularly limited, and can be obtained, for example, by a polymerization reaction at a temperature of 50 to 150° C. in a solvent in the coexistence of the above-mentioned ester compound, carboxyl group-containing compound, and a catalyst. The solvent used is not particularly limited as long as it dissolves the compounds and the polymerization initiator.

[0079] The polyester of the component (A2) obtained by the above method is usually in the state of a solution dissolved in a solvent.

[0080] The polyester as the component (A2) preferably has a structural unit represented by the following formula [A2-1].

[0081] [Chemistry 4]

[0082]

[0083] (In the formula, X and Y each independently represent a structure having an aromatic group or an alicyclic group.)

[0084] As the above-mentioned X, a group represented by the following formula (X-1) is preferable.

[0085] [Chemistry 5]

[0086]

[0087] Where, L 1 represents an ether bond or an ester bond, X 1 represents an alkylene group having 1 to 10 carbon atoms, a cyclic unsaturated hydrocarbon group or a cyclic saturated hydrocarbon group, R 1 represents a single bond, an ether bond, a carbonyl group, a sulfonyl group, a saturated hydrocarbon group having 1 to 30 carbon atoms, an unsaturated hydrocarbon group having 2 to 30 carbon atoms, or a saturated hydrocarbon group having 1 to 30 carbon atoms substituted with a fluorine atom, and p represents 0, 1 or 2.

[0088] As the above X 1, preferably a cyclic unsaturated hydrocarbon group having 4 to 16 carbon atoms or a cyclic saturated hydrocarbon group having 4 to 16 carbon atoms, more preferably a cyclic unsaturated hydrocarbon group having 4 to 8 carbon atoms or a cyclic saturated hydrocarbon group having 4 to 8 carbon atoms. 1 Any hydrogen atoms contained therein may be independently substituted with an aliphatic group. In addition, a plurality of substituents in these aliphatic groups may be combined with each other to form a 4- to 6-membered ring.

[0089] Specific examples of X include groups represented by the following formulae (X-2) to (X-13), but are not limited thereto.

[0090] [Chemistry 6]

[0091]

[0092] (Where * represents the bonding end.)

[0093] As the above-mentioned X, a structure derived from the above-mentioned resin having epoxy groups at both terminals is also preferable.

[0094] Examples of Y include groups represented by the following formulae (Y-1) to (Y-4), but are not limited thereto.

[0095] [Chemistry 7]

[0096]

[0097] (Where * represents the bonding end.)

[0098] As the polyester of the component (A2), a polyester having a structural unit represented by the following formula [A2-2] is also preferred.

[0099] [Chemistry 8]

[0100]

[0101] In the formula, Cy is a group derived from the above-mentioned alicyclic dioxide, that is, a tetravalent organic group containing an aliphatic ring, and represents a group in which OH and O4 bonding groups are both derived from the aliphatic ring, and Y represents the same definition as Y in formula [A2-1].

[0102] Specific examples of Cy in formula [A2-2] include groups represented by the following formulae (Cy-1) to (Cy-4).

[0103] [Chemistry 9]

[0104]

[0105] (In the formula, *1 and *2 represent bonding ends, respectively. In each structural formula, one of the two *1 and *2 is bonded to a hydroxyl group.)

[0106] As the polyester of the component (A2), a polyester having a structural unit represented by the following formula [A2-3] is also preferred.

[0107] [Chemistry 10]

[0108]

[0109] In the formula, X and Y have the same definitions as X and Y in formula [A2-1].

[0110] Specific examples of X in formula [A2-3] include groups represented by the following formulae (X-Ch-1) to (X-Ch-3).

[0111] [Chemistry 11]

[0112]

[0113] (Where * represents the bonding end.)

[0114] [(A3) Acrylic polymer]

[0115] The acrylic polymer having a primary or secondary hydroxyl group and no fluorine atom as component (A3) is not particularly limited. In the present invention, an acrylic polymer having a polyethylene glycol ester group or a primary or secondary hydroxyalkyl ester group having 2 to 6 carbon atoms is preferred, and an acrylic polymer having these groups in the side chain is more preferred.

[0116] As the acrylic polymer, there can be used a homopolymer of acrylic acid ester, a homopolymer of methacrylic acid ester, a copolymer thereof, and a copolymer of these with a monomer having an unsaturated double bond such as styrene.

[0117] A preferred example of the acrylic polymer as component (A3) is an acrylic polymer having a polyethylene glycol ester group or a primary or secondary hydroxyalkyl ester group having 2 to 6 carbon atoms. Any acrylic polymer having any of these groups is acceptable, and there are no particular limitations on the types of the main chain skeleton (other structural units) and side chains constituting the polymeric structure of the acrylic polymer.

[0118] As the structural unit having a polyethylene glycol ester group or a primary or secondary hydroxyalkyl ester group having 2 to 6 carbon atoms, a structural unit represented by the following formula [A3-1] is preferred.

[0119] [Chemistry 12]

[0120]

[0121] In the above formula [A3-1], R A are each independently a hydrogen atom or a methyl group, Y 1 Represents H-(OCH2CH2) n - group (wherein n is an integer of 2 to 30, preferably an integer of 2 to 10), or a primary or secondary hydroxyalkyl group having 2 to 6 carbon atoms.

[0122] The weight average molecular weight (Mw) of the acrylic polymer of the component (A3) is not particularly limited, but is preferably 1,000 to 200,000, more preferably 3,000 to 100,000, and even more preferably 5,000 to 50,000.

[0123] The acrylic polymer of the component (A3) can be obtained by polymerizing a monomer having at least one of a polyethylene glycol group and a primary or secondary hydroxyalkyl group having 2 to 6 carbon atoms, for example.

[0124] Examples of monomers having a polyethylene glycol ester group include H-(OCH2CH2) n -OH (n represents the same meaning as above). Monoacrylate or monomethacrylate.

[0125] 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, and glycerol monomethacrylate.

[0126] In addition, in this embodiment, when synthesizing the acrylic polymer of component (A3), monomers other than the above-mentioned monomers, specifically, monomers having no polyethylene glycol ester group, no primary or secondary hydroxyl group, and no fluorine atom, can be used in combination unless the effects of the present invention are impaired.

[0127] Examples of such monomers include acrylate compounds such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, and tert-butyl acrylate; methacrylate compounds such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate; maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; acrylamide compounds; acrylonitrile; maleic anhydride; styrene compounds; and vinyl compounds.

[0128] The method for producing the acrylic polymer (component (A3)) (polymerization method) is not particularly limited. For example, a method in which the above-mentioned monomers and other monomers and a polymerization initiator are dissolved in a solvent and subjected to a polymerization reaction at a temperature of 50 to 110°C is exemplified. The solvent used is not particularly limited as long as it can dissolve the monomers and the polymerization initiator.

[0129] Preferred examples of the acrylic polymer as the component (A3) include acrylic polymers having a primary or secondary hydroxyalkyl group in a side chain, such as polymers 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, and glycerol monomethacrylate; or polymers obtained by copolymerizing the primary or secondary hydroxyalkyl ester monomer with a monomer other than these monomers, for example, one or more monomers not having a primary or secondary hydroxyl group.

[0130] The acrylic polymer of the component (A3) obtained by the above method is usually in the form of a solution dissolved in a solvent.

[0131] [(B) Acid compound or its salt]

[0132] The release layer forming composition of the present invention contains an acid compound or a salt thereof as the component (B).

[0133] Specific examples of the acid compound 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.

[0134] Examples of the salts of the acid compounds include pyridinium salts, isopropanolamine salts, and N-methylmorpholine salts of the above-mentioned acids. Specific examples include pyridinium p-toluenesulfonate, pyridinium 1-naphthalenesulfonate, isopropanolamine p-toluenesulfonate, and N-methylmorpholine p-toluenesulfonate.

[0135] The content of component (B) is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of component (A). When the content of component (B) is within this range, a composition capable of forming a release layer having high heat resistance, moderate releasability, and excellent stability after film formation is obtained.

[0136] The (B) acid compound or its salt may be used alone or in combination of two or more.

[0137] [(C) Cross-linking agent]

[0138] The release layer-forming composition of the present invention contains, as the component (C), a crosslinking agent selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and / or an alkoxymethyl group.

[0139] As the cross-linking agent, a compound represented by any one of the following formulas (C-1) to (C-5) is preferred.

[0140] [Chemistry 13]

[0141]

[0142] In the above formulas, R 11 ~R 26 Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. 27 is a hydrogen atom or a methyl group.

[0143] Specific examples of the crosslinking agent include nitrogen-containing compounds such as hexamethylolmelamine, tetramethylolbenzoguanamine, 1,3,4,6-tetramethylolglycoluril, hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, and 1,3,4,6-tetrakis(hydroxymethyl)glycoluril.

[0144] In addition, commercially available crosslinking agents can also be used in the present invention. Specific examples thereof include methoxymethyl-type melamine compounds (trade names: Smel (registered trademark) 300, Smel 301, Smel 303, Smel 350), butoxymethyl-type melamine compounds (trade names: MyCool (registered trademark) 506, MyCool 508), glycoluril compounds (trade names: Smel 1170, POWDERLINK) manufactured by Ornex Corporation. 1174), methylated urea-formaldehyde resin (trade name UFR65), butylated urea-formaldehyde resin (trade names UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin manufactured by DIC Corporation (trade names Beckamin (registered trademark) J-300S, Beckamin P-955, Beckamin N) and other nitrogen-containing compounds.

[0145] Furthermore, as the crosslinking agent, a polymer produced from a (meth)acrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, or N-butoxymethyl (meth)acrylamide, can also be used.

[0146] 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 methyl(meth)acrylate, copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, and copolymers of N-butoxymethyl(meth)acrylamide, benzyl(meth)acrylate, and 2-hydroxypropyl(meth)acrylate.

[0147] Among these crosslinking agents, hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril (POWDERLINK 1174), 1,3,4,6-tetrakis(butoxymethyl)glycoluril, and 1,3,4,6-tetrakis(hydroxymethyl)glycoluril are preferably used.

[0148] Furthermore, the crosslinking agent can cause a crosslinking reaction by self-condensation and can also crosslink with the hydroxyl groups in the acrylic polymer of component (A). These crosslinking reactions strengthen the formed release layer and reduce its solubility in organic solvents.

[0149] The content of component (C) is preferably 10 to 100 parts by mass, more preferably 20 to 50 parts by mass, relative to 100 parts by mass of component (A). When the content of component (C) is within this range, a composition capable of forming a release layer having high heat resistance, moderate releasability, and excellent stability after film formation is obtained.

[0150] Furthermore, the cross-linking agent (C) may be used alone or in combination of two or more.

[0151] [(D) Polymer additives]

[0152] The release layer forming composition of the present invention contains a polymer additive as component (D), and the polymer additive contains a repeating unit represented by the following formula (a1), a repeating unit represented by the following formula (b), and a repeating unit represented by the following formula (c).

[0153] [Chemistry 14]

[0154]

[0155] In the above formulas, R A are each independently a hydrogen atom or a methyl group, R B1 is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom, R C is a hydroxyalkyl group having 1 to 10 carbon atoms, R D It is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.

[0156] As R B1 Specific examples of the branched alkyl group having 3 or 4 carbon atoms include isopropyl, isobutyl, sec-butyl and tert-butyl.

[0157] R B1 These branched alkyl groups are groups in which at least one hydrogen atom is substituted with a fluorine atom. Specific examples thereof include 1,1,1-trifluoroisopropyl, 1,1,1,3,3,3-hexafluoroisopropyl, and nonafluoro-tert-butyl.

[0158] As R C Specific examples of the hydroxyalkyl group having 1 to 10 carbon atoms include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 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- Hydroxyalkyl groups having 1 to 10 carbon atoms, i.e., groups in which the carbon atom to which the hydroxyl group is bonded is a primary carbon atom, such as methylbutyl, 4-hydroxy-2-methylbutyl, and 4-hydroxy-3-methylbutyl; and hydroxyalkyl groups having 2 to 10 carbon atoms, i.e., groups in which the carbon atom to which the hydroxyl group is bonded is a secondary or tertiary carbon atom, such as 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 1-hydroxyhexyl, 2-hydroxyhexyl, 1-hydroxyoctyl, 2-hydroxyoctyl, 1-hydroxydecyl, 2-hydroxydecyl, 1-hydroxy-1-methylethyl, and 2-hydroxy-2-methylpropyl.

[0159] As R D Specific examples of the polycyclic alkyl group having 6 to 20 carbon atoms include 1-adamantyl, 2-adamantyl, isobornyl, norbornyl, etc., and specific examples of the aryl group having 6 to 12 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-biphenylyl, 2-biphenylyl, etc.

[0160] In addition, the polymer additive (D) may include a repeating unit represented by the following formula (a2), a repeating unit represented by the following formula (b), a repeating unit represented by the following formula (c), and a repeating unit represented by the following formula (d).

[0161] [Chemistry 15]

[0162]

[0163] (Where R A 、R C and R DMeanings the same as above.)

[0164] R B2 A branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is substituted by a fluorine atom (excluding 2-methyl-1,1,1,3,3,3-hexafluoroisopropyl). Examples of the fluorinated alkyl group include the same groups as exemplified above.

[0165] R E is a single bond, a polycyclic alkylene group having 6 to 20 carbon atoms, or an arylene group having 6 to 12 carbon atoms, R F is a single bond or an alkylene group with 1 to 10 carbon atoms, R G is methyl, ethyl or hydroxy.

[0166] As R E The polycyclic alkylene group having 6 to 20 carbon atoms includes groups obtained by removing one hydrogen atom from the above-mentioned specific examples of the polycyclic alkyl group having 6 to 20 carbon atoms, for example, adamantylene, isobornylene, norbornylene, etc.

[0167] As R E Examples of the arylene group having 6 to 12 carbon atoms include groups obtained by removing one hydrogen atom from the above-mentioned specific examples of the aryl group having 6 to 12 carbon atoms, such as phenylene, naphthylene, and biphenylene.

[0168] As R F Specific examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, etc. Among these, alkylene groups having 1 to 5 carbon atoms are preferred, methylene and ethylene are more preferred, and methylene is further preferred.

[0169] Examples of the repeating unit represented by formula (a1) or (a2) include, but are not limited to, the repeating units represented by the following formulae (a-1) to (a-3). A It has the same meaning as above (same below).

[0170] [Chemistry 16]

[0171]

[0172] Examples of the repeating unit represented by formula (b) include repeating units represented by the following formulae (b-1) to (b-16), but the repeating unit is not limited thereto.

[0173] [Chemistry 17]

[0174]

[0175] Examples of the repeating unit represented by formula (c) include repeating units represented by the following formulae (c-1) to (c-13), but the repeating unit is not limited thereto.

[0176] [Chemistry 18]

[0177]

[0178] Examples of the repeating unit represented by formula (d) include repeating units represented by the following formulae (d-1) to (d-8), but the repeating unit is not limited thereto.

[0179] [Chemistry 19]

[0180]

[0181] In the present invention, when the polymer additive (D) comprises a repeating unit represented by formula (a1), a repeating unit represented by formula (b) and a repeating unit represented by formula (c), and the carbon atom to which the hydroxyl group in the hydroxyalkyl group in the repeating unit represented by formula (b) is bound is a secondary or tertiary carbon atom (hereinafter such a polymer additive will be referred to as polymer additive D1), the content of the repeating unit represented by formula (a1) is preferably 30 to 60 mol%, more preferably 35 to 50 mol%, in all the repeating units, the content of the repeating unit represented by formula (b) is preferably 10 to 35 mol%, more preferably 15 to 30 mol%, and the content of the repeating unit represented by formula (c) is preferably 5 to 60 mol%, more preferably 20 to 50 mol%, in all the repeating units.

[0182] On the other hand, when the polymer additive (D) comprises a repeating unit represented by formula (a1), a repeating unit represented by formula (b) and a repeating unit represented by formula (c), and the carbon atom to which the hydroxyl group in the hydroxyalkyl group in the repeating unit represented by formula (b) is bound is a primary carbon atom (hereinafter such a polymer additive is referred to as polymer additive D2), the content of the repeating unit represented by formula (a1) is preferably 15 to 60 mol%, more preferably 25 to 60 mol%, further preferably 30 to 60 mol%, and further preferably 35 to 50 mol% in all the repeating units; the content of the repeating unit represented by formula (b) is preferably 8 to 38 mol%, more preferably 10 to 38 mol%, further preferably 10 to 35 mol%, and further preferably 15 to 30 mol% in all the repeating units; and the content of the repeating unit represented by formula (c) is preferably 2 to 77 mol%, more preferably 2 to 65 mol%, further preferably 5 to 60 mol%, and further preferably 20 to 50 mol% in all the repeating units.

[0183] When the polymer additive (D) contains a repeating unit represented by formula (a2), a repeating unit represented by formula (b), a repeating unit represented by formula (c), and a repeating unit represented by formula (d) (hereinafter, such a polymer additive is referred to as polymer additive D3), the content of the repeating unit represented by formula (a2) is preferably 2 to 45 mol%, more preferably 5 to 35 mol%, in the total repeating units, the content of the repeating unit represented by formula (b) is preferably 20 to 35 mol%, more preferably 25 to 35 mol%, in the total repeating units, the content of the repeating unit represented by formula (c) is preferably 30 to 45 mol%, more preferably 35 to 45 mol%, in the total repeating units, and the content of the repeating unit represented by formula (d) is preferably 5 to 18 mol%, more preferably 5 to 15 mol%, in the total repeating units.

[0184] The weight average molecular weight (Mw) of the polymer additive (D) is preferably 2000 to 10000, more preferably 3000 to 6000. The Mw / Mn ratio is preferably 1.0 to 2.1, more preferably 1.0 to 1.9 (Mn is the number average molecular weight).

[0185] The content of the polymer additive (D) is 5 to 100 parts by mass per 100 parts by mass of the component (A). If the content of the polymer additive is less than 5 parts by mass, the peeling force may be increased, while if it exceeds 100 parts by mass, repellency may occur during film formation.

[0186] Particularly, when the (D) polymer additive is the polymer additive D1, its content is preferably 10 to 100 parts by mass, more preferably 20 to 100 parts by mass, and even more preferably 30 to 100 parts by mass relative to 100 parts by mass of the (A) component.

[0187] When the polymer additive (D) is other than the polymer additive D1, the content thereof is preferably 5 to 80 parts by mass, more preferably 5 to 50 parts by mass, relative to 100 parts by mass of the component (A).

[0188] The (D) polymer additive may be used alone or in combination of two or more.

[0189] [(E) Solvent]

[0190] The release layer forming composition of the present invention contains a solvent as the component (E).

[0191] As the solvent, glycol ether solvents having 3 to 20 carbon atoms, ester solvents having 3 to 20 carbon atoms, ketone solvents having 3 to 20 carbon atoms, and amide solvents having 3 to 20 carbon atoms are preferred.

[0192] Specific examples of the glycol ether-based solvent include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether, and propylene glycol monopropyl ether.

[0193] Specific examples of the ester solvent include ethyl lactate, γ-butyrolactone, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate.

[0194] Specific examples of the ketone solvent include methyl ethyl ketone, cyclopentanone, cyclohexanone, and benzophenone.

[0195] Examples of the amide solvent include N-methylpyrrolidone, N,N-dimethylacetamide, and 3-methoxy-N,N-dimethylpropionamide.

[0196] The content of the solvent (E) is not particularly limited. However, the solids concentration in the release layer-forming composition of the present invention is preferably 0.1 to 40% by mass, more preferably 0.5 to 20% by mass, and even more preferably 0.5 to 10% by mass. The term "solids" refers to all components of the release layer-forming composition excluding the solvent, and the solids content refers to the total amount of these components.

[0197] The (E) solvent may be used alone or in combination of two or more.

[0198] [Other additives]

[0199] The composition for forming a release layer of the present invention may contain a surfactant as needed. By adding a surfactant, the coating properties of the composition for forming a release layer on a substrate can be improved.

[0200] As the surfactant, known surfactants such as nonionic surfactants, fluorine-based surfactants, and silicone-based surfactants can be used.

[0201] Specific examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate.

[0202] Specific examples of fluorine-based surfactants include EFTOP (registered trademark) EF301, EF303, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), MEGAFAC (registered trademark) F171, F173, F554, F559, F563, R-30, R-40, R-40-LM, and DS-21 (manufactured by DIC Corporation), FLUORAD (registered trademark) FC430 and FC431 (manufactured by 3M Co., Ltd.), ASAHI GUARD (registered trademark) AG710, and SURFLON (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by AGC Corporation).

[0203] Specific examples of the silicone-based surfactant include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0204] When the release layer forming composition of the present invention contains a surfactant, the content thereof is preferably 0.0001 to 1 part by mass, more preferably 0.001 to 0.5 part by mass, relative to 100 parts by mass of the component (A).

[0205] The surfactant may be used alone or in combination of two or more.

[0206] [Preparation of Composition for Forming Release Layer]

[0207] The method for preparing the release layer-forming composition of the present invention is not particularly limited. For example, a method can be used in which components (B), (C), (D), and (E) are mixed at predetermined ratios in a solution of component (A) dissolved in a solvent to form a uniform solution. The solvent in which component (A) is dissolved may be the same solvent as component (E) or a different solvent.

[0208] Furthermore, when other additives are used, they may be added and mixed at any stage of the composition preparation.

[0209] In preparing the release layer-forming composition of the present invention, a solution of a polymer obtained by a polymerization reaction in a solvent can be used directly. For example, component (B), component (C), component (D), component (E), etc. can be added to the solution obtained after the polymerization reaction to produce component (A) to form a uniform solution. In this case, a solvent may be further added for the purpose of concentration adjustment; this solvent may be the same as or different from the solvent used in the production of component (A).

[0210] The prepared solution of the composition for forming a release layer is preferably filtered using a filter having a pore size of about 0.2 μm before use.

[0211] The viscosity of the release layer-forming composition of the present invention is appropriately set in consideration of the thickness of the release layer to be produced, but particularly when the goal is to obtain a film having a thickness of approximately 0.01 to 5 μm with good reproducibility, the viscosity is preferably approximately 1 to 5000 mPa·s at 25°C, and more preferably approximately 1 to 2000 mPa·s.

[0212] The viscosity in the present invention can be measured using a commercially available viscometer for measuring the viscosity of liquids, for example, in accordance with the procedure described in JIS K7117-2, at a temperature of 25°C for the composition. A cone-plate type (cone-plate type) rotational viscometer is preferably used as the viscometer. It is also preferable to use a viscometer of the same type, using a 1°34' x R24 standard conical rotor, and measuring the composition at a temperature of 25°C. An example of such a rotational viscometer is the TVE-25L manufactured by Toki Sangyo Co., Ltd.

[0213] [Peeling layer]

[0214] The peeling layer forming composition of the present invention is applied to a substrate and then fired at 180 to 250° C. to obtain a peeling layer having excellent adhesion to the substrate and moderate adhesion to a resin substrate.

[0215] In this case, the heating time during firing varies depending on the heating temperature and therefore cannot be uniformly specified, but is generally 1 minute to 5 hours. In addition, as long as the maximum temperature during firing falls within the above range, a firing step at a temperature below the maximum temperature may be included.

[0216] A preferred example of the heating method in the present invention includes heating at 50-150°C for 1 minute to 1 hour, then increasing the heating temperature to 180-250°C for 5 minutes to 4 hours. A more preferred example of the heating method includes heating at 50-150°C for 1 minute to 1 hour, and then heating at 200-250°C for 5 minutes to 2 hours. Another more preferred example of the heating method includes heating at 50-150°C for 1 minute to 30 minutes, followed by heating at 200-250°C for 5 minutes to 1 hour.

[0217] When forming the release layer of the present invention on a substrate, the release layer may be formed on a portion of the substrate surface or on the entire surface. Options for forming the release layer on a portion of the substrate surface include forming the release layer only within a predetermined area of ​​the substrate surface, or forming the release layer in a pattern such as a dot pattern, a line pattern, and a space pattern over the entire substrate surface. In the present invention, the term "substrate" refers to an object on whose surface the release layer-forming composition of the present invention is applied, and refers to an object used in the manufacture of flexible electronic devices, etc.

[0218] Examples of the substrate include glass, metal (such as a silicon wafer), and stone. Glass is particularly preferred because the release layer obtained from the release layer forming composition of the present invention has sufficient adhesion thereto.

[0219] Furthermore, the substrate surface may be composed of a single material or of two or more materials. Examples of substrate surfaces composed of two or more materials include a substrate surface in which a certain area is composed of a certain material and the remainder of the surface is composed of another material, or a substrate surface in which a material is present in a pattern such as a dot pattern, a line and space pattern, etc., within another material.

[0220] There is no particular limitation on the coating method of the composition for forming the release layer, and examples thereof include cast coating, spin coating, blade coating, dip coating, roll coating, rod coating, die coating, inkjet coating, and printing methods (such as relief printing, gravure printing, lithography, and screen printing).

[0221] Examples of the apparatus for heating include a hot plate and an oven. The heating atmosphere may be air or an inert gas, and may be normal pressure or reduced pressure.

[0222] The thickness of the release layer is usually about 0.01 to 50 μm, preferably about 0.01 to 20 μm, more preferably about 0.01 to 5 μm from the viewpoint of productivity. The thickness of the coating film before heating is adjusted to achieve a desired thickness.

[0223] The release layer of the present invention exhibits excellent adhesion to a substrate, particularly a glass substrate, and moderate adhesion and release properties from a resin substrate. Therefore, during the manufacturing process of a flexible electronic device, the release layer of the present invention does not damage the resin substrate of the device and is suitable for peeling the resin substrate, along with the circuitry formed thereon, from the substrate.

[0224] [Method for manufacturing resin substrate]

[0225] An example of a method for producing a flexible electronic device using the release layer of the present invention will be described.

[0226] First, a release layer is formed on a glass substrate using the release layer-forming composition of the present invention using the aforementioned method. A resin substrate-forming solution for forming a resin substrate is applied to the release layer, and the resulting coating is fired to form a resin substrate fixed to the glass substrate via the release layer of the present invention.

[0227] The firing temperature of the coating film is appropriately set depending on the type of resin, etc. In the present invention, the maximum firing temperature is preferably 200-250°C, more preferably 210-250°C, and even more preferably 220-240°C. By setting the maximum firing temperature within this range during the production of the resin substrate, the adhesion between the peeling layer serving as the base and the substrate, as well as the appropriate adhesion and peelability between the peeling layer and the resin substrate, can be further improved. In this case, as long as the maximum temperature is within the above range, a firing step at a temperature below this range may be included.

[0228] The resin substrate is preferably formed to have an area larger than that of the release layer so as to entirely cover the release layer.

[0229] Examples of the resin substrate include a resin substrate composed of an acrylic polymer and a resin substrate composed of a cycloolefin polymer. A resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm is preferred.

[0230] The resin substrate can be formed by a conventional method.

[0231] Next, a desired circuit is formed as needed on the resin substrate fixed to the base via the release layer of the present invention. The resin substrate is then cut, for example, along the release layer, and the resin substrate and the circuit are peeled off from the release layer to separate the resin substrate from the base. In this case, a portion of the base may be cut together with the release layer.

[0232] When the release layer of the present invention is used, a resin substrate can be peeled from the release layer with a peeling force of 0.25 N / 25 mm or less. In particular, when the polymeric additive (D) is polymeric additive D2 or polymeric additive D3, the resin substrate can be peeled from the release layer with a peeling force of 0.15 N / 25 mm or less. Furthermore, when the polymeric additive (D) is polymeric additive D1, the resin substrate can be peeled from the release layer with a peeling force of 0.1 N / 25 mm or less.

[0233] Example

[0234] The present invention will be described in more detail below with reference to Synthesis Examples, Preparation Examples, Examples, and Comparative Examples. However, the present invention is not limited to the following Examples.

[0235] (I) Composition for forming a release layer comprising (A1) cellulose having a hydroxyalkyl group or a derivative thereof

[0236] The compounds used in the following examples are as follows.

[0237] PGME: Propylene glycol monomethyl ether

[0238] PGMEA: Propylene glycol monomethyl ether acetate

[0239] HPC-SSL: Hydroxypropyl cellulose, Mw 40,000

[0240] HPC-SL: Hydroxypropyl cellulose, Mw 100000

[0241] HPC-L: Hydroxypropyl cellulose, Mw 140000

[0242] CAB: Cellulose acetate butyrate, Mw 155800

[0243] CAP: Cellulose acetate propionate, Mw 71300

[0244] PL-LI: 1,3,4,6-tetrakis(methoxyethyl)glycyluril (manufactured by Kosu Co., Ltd., trade name: POWDERLINK 1174)

[0245] PPTS: Pyridinium p-toluenesulfonate

[0246] HPMA: 2-Hydroxypropyl Methacrylate

[0247] ADMA: 2-adamantyl methacrylate

[0248] HFiPMA: 1,1,1,3,3,3-hexafluoroisopropyl methacrylate

[0249] AIBN: Azobisisobutyronitrile

[0250] DDT: Dodecanethiol

[0251] The weight-average molecular weight (Mw) of the polymer was measured using a GPC apparatus manufactured by Shimadzu Corporation (columns: Shodex (registered trademark) KF803L and KF804L (manufactured by Showa Denko K.K.); eluent: THF; flow rate: 1.0 mL / min; column temperature: 40°C; Mw: standard polystyrene conversion value).

[0252] [1] Synthesis of polymers

[0253] [Synthesis Example 1-1] Synthesis of acrylic polymer (S1)

[0254] 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 (solids concentration 20% by mass). The unit composition ratio was HFiPMA:HPMA:ADMA = 30:30:40. GPC analysis showed that the obtained acrylic polymer (S1) had an Mw of 5310 and an Mw / Mn ratio of 1.8.

[0255] [Synthesis Example 1-2] Synthesis of acrylic polymer (S2)

[0256] 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 (solids concentration 20% by mass). The unit composition ratio was HFiPMA:HPMA:ADMA = 40:20:40. GPC analysis showed that the obtained acrylic polymer (S2) had an Mw of 5500 and an Mw / Mn ratio of 1.8.

[0257] [2] Preparation of a composition for forming a resin substrate

[0258] [Preparation Example 1] Preparation of Composition F1 for Forming a Resin Substrate

[0259] To an eggplant-shaped flask containing 100 g of carbon tetrachloride, 10 g of Zeonoa (registered trademark) 1020R (a cycloolefin polymer manufactured by Zeon Co., Ltd.) and 3 g of Eporedo (registered trademark) GT401 (manufactured by Daicel Corporation) were added. The solution was stirred for 24 hours under a nitrogen atmosphere to dissolve the mixture, thereby preparing composition F1 for forming a resin substrate.

[0260] [3] Preparation of a composition for forming a peeling layer

[0261] [Example 1-1] Preparation of Composition 1 for Forming a Release Layer

[0262] 0.32 g of PL-LI, 0.05 g of PPTS, 0.84 g of an acrylic polymer (S1) solution, and PGMEA were added to 1.00 g of HPC-SSL, and the mixture was diluted with PGME to a solid content concentration of 5% by mass and a PGMEA concentration of 30% by mass to prepare a release layer-forming composition 1-1.

[0263] [Example 1-2] Preparation of Composition 2 for Forming a Release Layer

[0264] Composition 1-2 for forming a release layer was prepared in the same manner as in Example 1-1 except that the amount of PL-LI was changed to 0.50 g.

[0265] [Examples 1-3] Preparation of Composition 3 for Forming a Peeling Layer

[0266] Composition 1-3 for forming a release layer was prepared in the same manner as in Example 1-1 except that the amount of PL-LI was changed to 0.25 g.

[0267] [Examples 1-4] Preparation of Composition 4 for Forming a Peeling Layer

[0268] Composition 1-4 for forming a release layer was prepared in the same manner as in Example 1-1, except that HPC-SL was used instead of HPC-SSL.

[0269] [Examples 1-5] Preparation of Composition 5 for Forming a Release Layer

[0270] Composition 1-5 for forming a release layer was prepared in the same manner as in Example 1-1, except that HPC-L was used instead of HPC-SSL.

[0271] [Examples 1-6] Preparation of Composition 6 for Forming a Peeling Layer

[0272] Composition 1-6 for forming a release layer was prepared in the same manner as in Example 1-1 except that the amount of the acrylic polymer (S1) solution was changed to 0.50 g.

[0273] [Example 1-7] Preparation of Composition 7 for Forming a Release Layer

[0274] Composition 1-7 for forming a release layer was prepared in the same manner as in Example 1-1 except that the amount of the acrylic polymer (S1) solution was changed to 0.38 g.

[0275] [Example 1-8] Preparation of Composition 8 for Forming a Release Layer

[0276] A release layer-forming composition 1-8 was prepared in the same manner as in Example 1-1, except that the acrylic polymer (S2) solution was used instead of the acrylic polymer (S1) solution.

[0277] [Comparative Example 1-1] Preparation of Composition 9 for Forming a Release Layer

[0278] Composition 1-9 for forming a release layer was prepared in the same manner as in Example 1-1, except that CAB was used instead of HPC-SSL.

[0279] [Comparative Example 1-2] Preparation of Composition 10 for Forming a Release Layer

[0280] Composition 1-10 for forming a release layer was prepared in the same manner as in Example 1-1, except that CAP was used instead of HPC-SSL.

[0281] [4] Preparation of peeling layer and resin substrate

[0282] [Example 2-1]

[0283] Composition 1-1 for forming a release layer was applied to a glass substrate (100 mm × 100 mm, the same below) using a spin coater (conditions: rotation speed 1000 rpm, approximately 30 seconds). The resulting coating was heated at 100°C for 2 minutes using a hot plate, and then at 230°C for 10 minutes using a hot plate, forming a release layer having a thickness of approximately 0.1 μm on the glass substrate. This yielded a glass substrate with a release layer.

[0284] Immediately thereafter, the resin substrate-forming composition F1 was applied onto the release layer (resin film) on the glass substrate using a spin coater (conditions: rotation speed 200 rpm, approximately 15 seconds). The resulting coating was heated at 80°C for 2 minutes on a hot plate, and then at 230°C for 30 minutes on a hot plate to form a resin substrate having a thickness of approximately 3 μm on the release layer, resulting in a glass substrate with a resin substrate-release layer. The transmittance of the resin substrate was then measured using an ultraviolet-visible spectrophotometer (UV-2600, manufactured by Shimadzu Corporation). The results showed that the transmittance of the resin substrate at 400 nm was 90% or higher.

[0285] [Example 2-2]

[0286] A peeling layer and a resin substrate were prepared in the same manner as in Example 2-1, except that the peeling layer-forming composition 1-2 was used instead of the peeling layer-forming composition 1-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0287] [Examples 2-3]

[0288] A peeling layer and a resin substrate were prepared in the same manner as in Example 2-1, except that peeling layer-forming composition 1-3 was used instead of peeling layer-forming composition 1-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0289] [Examples 2-4]

[0290] A peeling layer and a resin substrate were prepared in the same manner as in Example 2-1, except that peeling layer-forming composition 1-4 was used instead of peeling layer-forming composition 1-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0291] [Examples 2-5]

[0292] A peeling layer and a resin substrate were prepared in the same manner as in Example 2-1, except that peeling layer-forming composition 1-5 was used instead of peeling layer-forming composition 1-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0293] [Examples 2-6]

[0294] A peeling layer and a resin substrate were prepared in the same manner as in Example 2-1, except that peeling layer-forming composition 1-6 was used instead of peeling layer-forming composition 1-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0295] [Example 2-7]

[0296] A peeling layer and a resin substrate were prepared in the same manner as in Example 2-1, except that peeling layer-forming composition 1-7 was used instead of peeling layer-forming composition 1-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0297] [Example 2-8]

[0298] A peeling layer and a resin substrate were prepared in the same manner as in Example 2-1, except that peeling layer-forming composition 1-8 was used instead of peeling layer-forming composition 1-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0299] [Comparative Example 2-1]

[0300] A peeling layer and a resin substrate were prepared in the same manner as in Example 2-1, except that peeling layer-forming composition 1-9 was used instead of peeling layer-forming composition 1-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0301] [Comparative Example 2-2]

[0302] A peeling layer and a resin substrate were prepared in the same manner as in Example 2-1, except that peeling layer-forming composition 1-10 was used instead of peeling layer-forming composition 1-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0303] [5] Evaluation of peelability

[0304] The peelability of the glass substrates with peeling layers and the glass substrates with resin substrates and peeling layers obtained in Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-2 was confirmed by the following method.

[0305] (1) Evaluation of the peeling properties between the peeling layer and the glass substrate

[0306] The release layer on the glass substrate with release layer obtained in Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-2 was cut horizontally (2 mm intervals vertically and horizontally, the same applies below) to form 25 grids of 2 mm squares.

[0307] Adhesive tape was attached to the 25 grid-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.

[0308] <Judgment Criteria>

[0309] 5B: 0% peeling (not peeling)

[0310] 4B: Less than 5% peeling

[0311] 3B: 5% or more and less than 15% peeling

[0312] 2B: 15% or more and less than 35% peeling

[0313] 1B: 35% or more and less than 65% peeling

[0314] 0B: 65% or more and less than 80% peeling

[0315] B: 80% or more and less than 95% peeling

[0316] A: 95% or more but less than 100% peeling

[0317] AA: 100% peeling (full peeling)

[0318] (2) Evaluation of the peeling force between the peeling layer and the resin substrate

[0319] The glass substrates with the resin substrate-peeling layer obtained in Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-2 were fabricated into rectangular pieces measuring 25 mm x 50 mm. A Cellotop (registered trademark) (CT-24 manufactured by Nichiban Co., Ltd.) was then attached to the glass substrates. The peeling force was measured using an Autograph AGS-X500N (manufactured by Shimadzu Corporation) at a peel angle of 90° and a peel speed of 300 mm / min. Cases in which the glass substrates could not be peeled off were marked as "unpeelable." The results are shown in Table 1.

[0320] [Table 1]

[0321]

[0322] The results shown in Table 1 confirm that the peeling layers of Examples have excellent adhesion to the glass substrate and are easily peeled from the resin film. On the other hand, the peeling layers of Comparative Examples 2-1 and 2-2 have excellent adhesion to the glass substrate and are not easily peeled from the resin substrate.

[0323] (II) Release Layer-Forming Composition Containing (A2) Hydroxyl-Having Polyester The compounds used in the following examples are as follows.

[0324] PGME: Propylene glycol monomethyl ether

[0325] PGMEA: Propylene glycol monomethyl ether acetate

[0326] PL-LI: 1,3,4,6-tetrakis(methoxyethyl)glycyluril (manufactured by Kosu Co., Ltd., trade name: POWDERLINK 1174)

[0327] PPTS: Pyridinium p-toluenesulfonate

[0328] HPMA: 2-Hydroxypropyl Methacrylate

[0329] ADMA: 2-adamantyl methacrylate

[0330] HFiPMA: 1,1,1,3,3,3-hexafluoroisopropyl methacrylate

[0331] AIBN: Azobisisobutyronitrile

[0332] DDT: Dodecanethiol

[0333] EP1: Bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: jER828)

[0334] EP2: Terephthalate-type epoxy resin (manufactured by Nagakushu Co., Ltd., trade name: Tetraphthalate EX711)

[0335] EP3: Biphenyl epoxy resin (Mitsubishi Chemical Corporation, trade name: YX4000H)

[0336] EP4: Fluorene-type epoxy resin (manufactured by Osaka Gas Chemical Co., Ltd., trade name: Ogusol PG-100)

[0337] EP5: Fluorene-based epoxy resin (manufactured by Osaka Gas Chemical Co., Ltd., trade name: Ogusol CG-500)

[0338] EP6: Cyclohexyl epoxy resin (manufactured by Daicel Corporation, trade name: CEL2021P)

[0339] TPhA: terephthalic acid

[0340] IPhA: Isophthalic acid

[0341] 5HIPhA: 5-hydroxyisophthalic acid

[0342] 14CHA: 1,4-cyclohexanedicarboxylic acid

[0343] BTEAC: benzyltriethylammonium chloride

[0344] ETPPB: Ethyltriphenylphosphonium bromide

[0345] The weight average molecular weight (Mw) of the polymer was measured by the same method as described in the above (I).

[0346] [1] Synthesis of polymers

[0347] [Synthesis Example 2-1] Synthesis of Polyester (A2-1)

[0348] 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 (solids concentration: 30% by mass). GPC analysis showed that the obtained polyester (A2-1) had an Mw of 13,200 and an Mw / Mn of 3.9.

[0349] [Synthesis Example 2-2] Synthesis of Polyester (A2-2)

[0350] 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 (solids concentration: 30% by mass). GPC analysis showed that the obtained polyester (A2-2) had an Mw of 21,000 and an Mw / Mn of 3.2.

[0351] [Synthesis Example 2-3] Synthesis of Polyester (A2-3)

[0352] 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 (solids concentration: 30% by mass). GPC analysis showed that the obtained polyester (A2-3) had an Mw of 6600 and an Mw / Mn ratio of 2.1.

[0353] [Synthesis Example 2-4] Synthesis of Polyester (A2-4)

[0354] 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 (solids concentration: 30% by mass). GPC analysis showed that the obtained polyester (A2-4) had an Mw of 5400 and an Mw / Mn ratio of 4.1.

[0355] [Synthesis Example 2-5] Synthesis of Polyester (A2-5)

[0356] 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 (solids concentration: 30% by mass). GPC analysis showed that the obtained polyester (A2-5) had an Mw of 5400 and an Mw / Mn of 3.3.

[0357] [Synthesis Example 2-6] Synthesis of Polyester (A2-6)

[0358] 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 (solids concentration: 20% by mass). GPC analysis showed that the obtained polyester (A2-6) had an Mw of 8100 and an Mw / Mn ratio of 3.3.

[0359] [Synthesis Example 2-7] Synthesis of Polyester (A2-7)

[0360] 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 (solids concentration 20% by mass). GPC analysis showed that the obtained polyester (A2-7) had an Mw of 6600 and an Mw / Mn of 2.0.

[0361] [Synthesis Example 2-8] Synthesis of Polyester (A2-8)

[0362] 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 (solids concentration: 20% by mass). GPC analysis showed that the obtained polyester (A2-8) had an Mw of 6200 and an Mw / Mn ratio of 2.4.

[0363] [Synthesis Example 2-9] Synthesis of Polyester (A2-9)

[0364] 10.0 g of EP5, 3.7 g of 5HIPhA, and 0.15 g of BTEAC were dissolved in 55.5 g of PGME and reacted at 120°C for 20 hours to obtain a polyester (A2-9) solution (solids concentration: 20% by mass). GPC analysis showed that the obtained polyester (A2-9) had an Mw of 7600 and an Mw / Mn ratio of 2.2.

[0365] [Synthesis Example 2-10] Synthesis of Polyester (A2-10)

[0366] 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 (solids concentration: 20% by mass). GPC analysis showed that the obtained polyester (A2-10) had an Mw of 9200 and an Mw / Mn of 2.1.

[0367] [Synthesis Example 2-11] Synthesis of Polyester (A2-11)

[0368] 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 (solids concentration: 20% by mass). GPC analysis showed that the obtained polyester (A2-11) had an Mw of 5800 and an Mw / Mn ratio of 1.7.

[0369] [Synthesis Example 2-12] Synthesis of acrylic polymer (S1)

[0370] 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 (solids concentration 20% by mass). The composition ratio of the units was HFiPMA:HPMA:ADMA = 30:30:40. GPC analysis showed that the obtained acrylic polymer (S1) had an Mw of 5310 and an Mw / Mn ratio of 1.8.

[0371] [2] Preparation of a composition for forming a resin substrate

[0372] [Preparation Example 1] Preparation of Composition F1 for Forming a Resin Substrate

[0373] To an eggplant-shaped flask containing 100 g of carbon tetrachloride, 10 g of Zeonoa (registered trademark) 1020R (a cycloolefin polymer manufactured by Zeon Co., Ltd.) and 3 g of Epolide (registered trademark) GT401 (manufactured by Daicel Corporation) were added. The solution was stirred for 24 hours under a nitrogen atmosphere to dissolve the mixture, thereby preparing composition F1 for forming a resin substrate.

[0374] [3] Preparation of a composition for forming a peeling layer

[0375] [Example 3-1] Preparation of Composition 1 for Forming a Release Layer

[0376] 0.06 g of PL-LI, 0.01 g of PPTS, 0.17 g of an acrylic polymer (S1) solution, and PGMEA were added to 1 g of the polyester (A2-1) solution obtained in Synthesis Example 1, and the solution was diluted with PGME so that the solid content concentration became 5% by mass and the PGMEA concentration became 30% by mass to prepare a composition 2-1 for forming a peeling layer.

[0377] [Example 3-2] Preparation of Composition 2 for Forming a Release Layer

[0378] A release layer-forming composition 2-2 was prepared in the same manner as in Example 3-1, except that the polyester (A2-2) solution was used instead of the polyester (A2-1) solution.

[0379] [Example 3-3] Preparation of Composition 3 for Forming a Release Layer

[0380] A release layer-forming composition 2-3 was prepared in the same manner as in Example 3-1, except that the polyester (A2-3) solution was used instead of the polyester (A2-1) solution.

[0381] [Example 3-4] Preparation of Composition 4 for Forming a Release Layer

[0382] A release layer-forming composition 2-4 was prepared in the same manner as in Example 3-1, except that the polyester (A2-4) solution was used instead of the polyester (A2-1) solution.

[0383] [Examples 3-5] Preparation of Composition 5 for Forming a Release Layer

[0384] A release layer-forming composition 2-5 was prepared in the same manner as in Example 3-1, except that the polyester (A2-5) solution was used instead of the polyester (A2-1) solution.

[0385] [Examples 3-6] Preparation of Composition 6 for Forming a Peeling Layer

[0386] Composition 2-6 for forming a release layer was prepared in the same manner as in Example 3-1, except that the polyester (A2-6) solution was used instead of the polyester (A2-1) solution.

[0387] [Example 3-7] Preparation of Composition 7 for Forming a Release Layer

[0388] Composition 2-7 for forming a release layer was prepared in the same manner as in Example 3-1, except that the polyester (A2-7) solution was used instead of the polyester (A2-1) solution.

[0389] [Example 3-8] Preparation of Composition 8 for Forming a Release Layer

[0390] Composition 2-8 for forming a release layer was prepared in the same manner as in Example 3-1, except that the polyester (A2-8) solution was used instead of the polyester (A2-1) solution.

[0391] [Example 3-9] Preparation of Composition 9 for Forming a Release Layer

[0392] Composition 2-9 for forming a release layer was prepared in the same manner as in Example 3-1, except that the polyester (A2-9) solution was used instead of the polyester (A2-1) solution.

[0393] [Example 3-10] Preparation of Composition 10 for Forming a Peeling Layer

[0394] A release layer-forming composition 2-10 was prepared in the same manner as in Example 3-1, except that the polyester (A2-10) solution was used instead of the polyester (A2-1) solution.

[0395] [Example 3-11] Preparation of Composition 11 for Forming a Peeling Layer

[0396] A release layer-forming composition 2-11 was prepared in the same manner as in Example 3-1, except that the polyester (A2-11) solution was used instead of the polyester (A2-1) solution.

[0397] [4] Preparation of peeling layer and resin substrate

[0398] [Example 4-1]

[0399] Composition 2-1 for forming a release layer was applied to a glass substrate (100 mm × 100 mm, the same below) using a spin coater (conditions: rotation speed 1000 rpm, approximately 30 seconds). The resulting coating was heated at 100°C for 2 minutes on a hot plate, and then at 230°C for 10 minutes on a hot plate to form a release layer having a thickness of approximately 0.1 μm on the glass substrate, thereby obtaining a glass substrate with a release layer.

[0400] Immediately thereafter, the resin substrate-forming composition F1 was applied onto the release layer (resin film) on the glass substrate using a spin coater (conditions: rotation speed 200 rpm, approximately 15 seconds). The resulting coating was heated at 80°C for 2 minutes on a hot plate, and then at 230°C for 30 minutes on a hot plate to form a resin substrate having a thickness of approximately 3 μm on the release layer, resulting in a glass substrate with a resin substrate-release layer. The transmittance of the resin substrate was then measured using an ultraviolet-visible spectrophotometer (UV-2600, manufactured by Shimadzu Corporation). The results showed that the resin substrate exhibited a transmittance of 90% or greater at 400 nm.

[0401] [Example 4-2]

[0402] A peeling layer and a resin substrate were prepared in the same manner as in Example 4-1, except that the peeling layer-forming composition 2-2 was used instead of the peeling layer-forming composition 2-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0403] [Example 4-3]

[0404] A peeling layer and a resin substrate were prepared in the same manner as in Example 4-1, except that the peeling layer-forming composition 2-3 was used instead of the peeling layer-forming composition 2-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0405] [Example 4-4]

[0406] A peeling layer and a resin substrate were prepared in the same manner as in Example 4-1, except that the peeling layer-forming composition 2-4 was used instead of the peeling layer-forming composition 2-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0407] [Examples 4-5]

[0408] A peeling layer and a resin substrate were prepared in the same manner as in Example 4-1, except that the peeling layer-forming composition 2-5 was used instead of the peeling layer-forming composition 2-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0409] [Examples 4-6]

[0410] A peeling layer and a resin substrate were prepared in the same manner as in Example 4-1, except that the peeling layer-forming composition 2-6 was used instead of the peeling layer-forming composition 2-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0411] [Examples 4-7]

[0412] A peeling layer and a resin substrate were prepared in the same manner as in Example 4-1, except that the peeling layer-forming composition 2-7 was used instead of the peeling layer-forming composition 2-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0413] [Examples 4-8]

[0414] A peeling layer and a resin substrate were prepared in the same manner as in Example 4-1, except that the peeling layer-forming composition 2-8 was used instead of the peeling layer-forming composition 2-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0415] [Examples 4-9]

[0416] A peeling layer and a resin substrate were prepared in the same manner as in Example 4-1, except that the peeling layer-forming composition 2-9 was used instead of the peeling layer-forming composition 2-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0417] [Examples 4-10]

[0418] A peeling layer and a resin substrate were prepared in the same manner as in Example 4-1, except that the peeling layer-forming composition 2-10 was used instead of the peeling layer-forming composition 2-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0419] [Example 4-11]

[0420] A peeling layer and a resin substrate were prepared in the same manner as in Example 4-1, except that the peeling layer-forming composition 2-11 was used instead of the peeling layer-forming composition 2-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0421] [5] Evaluation of peelability

[0422] The glass substrates with release layers and the glass substrates with resin substrates and release layers obtained in Examples 4-1 to 4-11 were tested for releasability by the same method as described in [4] of (I) above. The results are shown in Table 2.

[0423] [Table 2]

[0424]

[0425] From the results shown in Table 2, it was confirmed that the peeling layer of the example had excellent adhesion to the glass substrate and was easily peeled from the resin film.

[0426] (III) Composition for forming a release layer comprising (A3) an acrylic polymer having a primary or secondary hydroxyl group and no fluorine atom

[0427] The compounds used in the following examples are as follows.

[0428] PGME: Propylene glycol monomethyl ether

[0429] PGMEA: Propylene glycol monomethyl ether acetate

[0430] CHN: Cyclohexanone

[0431] PL-LI: 1,3,4,6-tetrakis(methoxyethyl)glycyluril (manufactured by Kosu Co., Ltd., trade name: POWDERLINK 1174)

[0432] PPTS: Pyridinium p-toluenesulfonate

[0433] MMA: Methyl Methacrylate

[0434] HPMA: 2-Hydroxypropyl Methacrylate

[0435] HEMA: 2-Hydroxyethyl Methacrylate

[0436] 4HBA: 4-Hydroxybutyl acrylate

[0437] HADM: 3-hydroxy-1-adamantyl methacrylate

[0438] ADMA: 2-adamantyl methacrylate

[0439] HFiPMA: 1,1,1,3,3,3-hexafluoroisopropyl methacrylate

[0440] AIBN: Azobisisobutyronitrile

[0441] DDT: Dodecanethiol

[0442] The weight average molecular weight (Mw) of the polymer was measured by the same method as described in the above (I).

[0443] [1] Synthesis of polymers

[0444] [Synthesis Example 3-1] Synthesis of acrylic polymer (A3-1)

[0445] 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 (solids concentration: 20% by mass). GPC analysis showed that the obtained acrylic polymer (A3-1) had an Mw of 5400 and an Mw / Mn ratio of 1.7.

[0446] [Synthesis Example 3-2] Synthesis of acrylic polymer (A3-2)

[0447] 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 (solids concentration 20% by mass). GPC analysis showed that the obtained acrylic polymer (A3-2) had an Mw of 13,300 and an Mw / Mn of 2.5.

[0448] [Synthesis Example 3-3] Synthesis of acrylic polymer (A3-3)

[0449] 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 (solids concentration 20% by mass). GPC analysis showed that the obtained acrylic polymer (A3-3) had an Mw of 6300 and an Mw / Mn of 1.5.

[0450] [Synthesis Example 3-4] Synthesis of acrylic polymer (A3-4)

[0451] 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 (solids concentration 20% by mass). GPC analysis showed that the obtained acrylic polymer (A3-4) had an Mw of 13,000 and an Mw / Mn of 2.5.

[0452] [Synthesis Example 3-5] Synthesis of acrylic polymer (A3-5)

[0453] 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 (solids concentration: 20% by mass). GPC analysis showed that the obtained acrylic polymer (A3-5) had an Mw of 4200 and an Mw / Mn ratio of 1.3.

[0454] [Synthesis Example 3-6] Synthesis of acrylic polymer (A3-6)

[0455] 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 (solids concentration 20% by mass). The unit composition ratio was MMA:HEMA = 50:50. GPC analysis showed that the obtained acrylic polymer (A3-6) had an Mw of 6600 and an Mw / Mn ratio of 1.9.

[0456] [Synthesis Example 3-7] Synthesis of acrylic polymer (A3-7)

[0457] 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 (solids concentration 20% by mass). The unit composition ratio was MMA:HPMA = 50:50. GPC analysis showed that the obtained acrylic polymer (A3-7) had an Mw of 6400 and an Mw / Mn ratio of 2.3.

[0458] [Synthesis Example 3-8] Synthesis of acrylic polymer (A3-8)

[0459] 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 (solids concentration 20% by mass). The unit composition ratio was MMA:HEMA = 70:30. GPC analysis showed that the obtained acrylic polymer (A3-8) had an Mw of 5500 and an Mw / Mn ratio of 2.0.

[0460] [Synthesis Example 3-9] Synthesis of acrylic polymer (A3-9)

[0461] 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 (solids concentration 20% by mass). The unit composition ratio was MMA:HPMA = 70:30. GPC analysis showed that the obtained acrylic polymer (A3-9) had an Mw of 6000 and an Mw / Mn ratio of 2.0.

[0462] [Synthesis Example 3-10] Synthesis of acrylic polymer (A3-10)

[0463] 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 (solids concentration: 20% by mass). GPC analysis showed that the obtained acrylic polymer (A3-10) had an Mw of 5100 and an Mw / Mn ratio of 1.5.

[0464] [Synthesis Example 3-11] Synthesis of acrylic polymer (A3-11)

[0465] 10.0 g of MMA, 10.12 g of HADM, 1.17 g of AIBN, and 0.87 g of DDT were dissolved in 88.6 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (A11) solution (solids concentration 20% by mass). The unit composition ratio was MMA:HADM = 70:30. GPC analysis showed that the obtained acrylic polymer (A3-11) had an Mw of 6600 and an Mw / Mn ratio of 1.6.

[0466] [Synthesis Example 3-12] Synthesis of acrylic polymer (A3-12)

[0467] 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 (solids concentration: 20% by mass). GPC analysis showed that the obtained acrylic polymer (A3-12) had an Mw of 5200 and an Mw / Mn ratio of 1.7.

[0468] [Synthesis Example 3-13] Synthesis of acrylic polymer (S1)

[0469] 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 (solids concentration 20% by mass). The composition ratio of the units was HFiPMA:HPMA:ADMA = 30:30:40. GPC analysis showed that the obtained acrylic polymer (S1) had an Mw of 5310 and an Mw / Mn ratio of 1.8.

[0470] [Synthesis Example 3-14] Synthesis of acrylic polymer (S2)

[0471] 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 (solids concentration 20% by mass). The unit composition ratio was HFiPMA:HPMA:ADMA = 40:20:40. GPC analysis showed that the obtained acrylic polymer (S2) had an Mw of 5500 and an Mw / Mn ratio of 1.8.

[0472] [2] Preparation of a composition for forming a resin substrate

[0473] [Preparation Example 1] Preparation of Composition F1 for Forming a Resin Substrate

[0474] To an eggplant-shaped flask containing 100 g of carbon tetrachloride, 10 g of Zeonoa (registered trademark) 1020R (a cycloolefin polymer manufactured by Zeon Co., Ltd.) and 3 g of Epolide (registered trademark) GT401 (manufactured by Daicel Corporation) were added. The solution was stirred for 24 hours under a nitrogen atmosphere to dissolve the mixture, thereby preparing composition F1 for forming a resin substrate.

[0475] [3] Preparation of a composition for forming a peeling layer

[0476] [Example 5-1] Preparation of Composition 1 for Forming a Release Layer

[0477] 0.06 g of PL-LI, 0.01 g of PPTS, 0.08 g of the acrylic polymer (S1) solution, and PGMEA were added to 1 g of the acrylic polymer (A3-1) solution obtained in Synthesis Example 1, and the mixture was diluted with PGME so that the solid content concentration became 5% by mass and the PGMEA concentration became 30% by mass to prepare a composition 3-1 for forming a peeling layer.

[0478] [Example 5-2] Preparation of Composition 2 for Forming a Release Layer

[0479] A release layer-forming composition 3-2 was prepared in the same manner as in Example 5-1, except that the acrylic polymer (A3-2) solution was used instead of the acrylic polymer (A3-1) solution.

[0480] [Example 5-3] Preparation of Composition 3 for Forming a Release Layer

[0481] Composition 3-3 for forming a release layer was prepared in the same manner as in Example 5-1, except that the acrylic polymer (A3-3) solution was used instead of the acrylic polymer (A3-1) solution.

[0482] [Example 5-4] Preparation of Composition 4 for Forming a Release Layer

[0483] Composition 3-4 for forming a release layer was prepared by the same method as in Example 5-1, except that the acrylic polymer (A3-4) solution was used instead of the acrylic polymer (A3-1) solution.

[0484] [Example 5-5] Preparation of Composition 5 for Forming a Release Layer

[0485] Composition 3-5 for forming a release layer was prepared in the same manner as in Example 5-1, except that the acrylic polymer (A3-5) solution was used instead of the acrylic polymer (A3-1) solution.

[0486] [Examples 5-6] Preparation of Composition 6 for Forming a Peeling Layer

[0487] Composition 3-6 for forming a release layer was prepared in the same manner as in Example 5-1, except that the acrylic polymer (A3-6) solution was used instead of the acrylic polymer (A3-1) solution.

[0488] [Examples 5-7] Preparation of Composition 7 for Forming a Release Layer

[0489] Composition 3-7 for forming a release layer was prepared in the same manner as in Example 5-1, except that an acrylic polymer (A3-6) solution was used instead of the acrylic polymer (A3-1) solution and the amount of acrylic polymer (S1) was changed to 0.17 g.

[0490] [Examples 5-8] Preparation of Composition 8 for Forming a Peeling Layer

[0491] Composition 3-8 for forming a release layer was prepared in the same manner as in Example 5-1, except that the acrylic polymer (A3-7) solution was used instead of the acrylic polymer (A3-1) solution.

[0492] [Examples 5-9] Preparation of Composition 9 for Forming a Release Layer

[0493] Composition 3-9 for forming a release layer was prepared in the same manner as in Example 1-1, except that an acrylic polymer (A3-7) solution was used instead of the acrylic polymer (A3-1) solution and the amount of acrylic polymer (S1) was changed to 0.17 g.

[0494] [Examples 5-10] Preparation of Composition 10 for Forming a Peeling Layer

[0495] Composition 3-10 for forming a release layer was prepared in the same manner as in Example 5-1, except that an acrylic polymer (A3-7) solution was used instead of the acrylic polymer (A3-1) solution, and an acrylic polymer (S2) solution was used instead of the acrylic polymer (S1) solution.

[0496] [Example 5-11] Preparation of Composition 11 for Forming a Peeling Layer

[0497] A release layer-forming composition 3-11 was prepared in the same manner as in Example 5-1, except that the acrylic polymer (A3-8) solution was used instead of the acrylic polymer (A3-1) solution.

[0498] [Example 5-12] Preparation of Composition 12 for Forming a Peeling Layer

[0499] A release layer-forming composition 3-12 was prepared in the same manner as in Example 5-1, except that the acrylic polymer (A3-9) solution was used instead of the acrylic polymer (A3-1) solution.

[0500] [Comparative Example 3-1] Preparation of Composition 13 for Forming a Release Layer

[0501] A release layer-forming composition 3-13 was prepared in the same manner as in Example 5-1, except that an acrylic polymer (A3-10) solution was used instead of the acrylic polymer (A3-1) solution and the solvent was changed to CHN.

[0502] [Comparative Example 3-2] Preparation of Composition 14 for Forming a Release Layer

[0503] A release layer-forming composition 3-14 was prepared in the same manner as in Example 5-1, except that the acrylic polymer (A3-11) solution was used instead of the acrylic polymer (A3-1) solution.

[0504] [Comparative Example 3-3] Preparation of Composition 15 for Forming a Release Layer

[0505] A release layer-forming composition 3-15 was prepared in the same manner as in Example 5-1, except that the acrylic polymer (A3-12) solution was used instead of the acrylic polymer (A3-1) solution.

[0506] [4] Preparation of peeling layer and resin substrate

[0507] [Example 6-1]

[0508] Composition 3-1 for forming a release layer was applied to a glass substrate (100 mm × 100 mm, the same below) using a spin coater (conditions: rotation speed 1000 rpm, approximately 30 seconds). The resulting coating was heated at 100°C for 2 minutes on a hot plate, and then at 230°C for 10 minutes on a hot plate to form a release layer having a thickness of approximately 0.1 μm on the glass substrate, resulting in a glass substrate with a release layer.

[0509] Immediately thereafter, the resin substrate-forming composition F1 was applied onto the release layer (resin film) formed on the glass substrate using a spin coater (conditions: rotation speed 200 rpm, approximately 15 seconds). The resulting coating was heated at 80°C for 2 minutes on a hot plate, and then at 230°C for 30 minutes on a hot plate to form a resin substrate having a thickness of approximately 3 μm on the release layer, resulting in a glass substrate with a resin substrate-release layer. The transmittance of the resin substrate was then measured using an ultraviolet-visible spectrophotometer (UV-2600, manufactured by Shimadzu Corporation). The results showed that the resin substrate exhibited a transmittance of 90% or greater at 400 nm.

[0510] [Example 6-2]

[0511] A peeling layer and a resin substrate were prepared in the same manner as in Example 6-1, except that the peeling layer-forming composition 3-2 was used instead of the peeling layer-forming composition 3-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0512] [Example 6-3]

[0513] A peeling layer and a resin substrate were prepared in the same manner as in Example 6-1, except that the peeling layer-forming composition 3-3 was used instead of the peeling layer-forming composition 3-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0514] [Example 6-4]

[0515] A peeling layer and a resin substrate were prepared in the same manner as in Example 6-1, except that the peeling layer-forming composition 3-4 was used instead of the peeling layer-forming composition 3-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0516] [Example 6-5]

[0517] A peeling layer and a resin substrate were prepared in the same manner as in Example 6-1, except that the peeling layer-forming composition 3-5 was used instead of the peeling layer-forming composition 3-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0518] [Example 6-6]

[0519] A peeling layer and a resin substrate were prepared in the same manner as in Example 6-1, except that the peeling layer-forming composition 3-6 was used instead of the peeling layer-forming composition 3-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0520] [Examples 6-7]

[0521] A peeling layer and a resin substrate were prepared in the same manner as in Example 6-1, except that the peeling layer-forming composition 3-7 was used instead of the peeling layer-forming composition 3-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0522] [Examples 6-8]

[0523] A peeling layer and a resin substrate were prepared in the same manner as in Example 6-1, except that the peeling layer-forming composition 3-8 was used instead of the peeling layer-forming composition 3-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0524] [Examples 6-9]

[0525] A peeling layer and a resin substrate were prepared in the same manner as in Example 6-1, except that the peeling layer-forming composition 3-9 was used instead of the peeling layer-forming composition 3-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0526] [Examples 6-10]

[0527] A peeling layer and a resin substrate were prepared in the same manner as in Example 6-1, except that the peeling layer-forming composition 3-10 was used instead of the peeling layer-forming composition 3-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0528] [Examples 6-11]

[0529] A peeling layer and a resin substrate were prepared in the same manner as in Example 6-1, except that the peeling layer-forming composition 3-11 was used instead of the peeling layer-forming composition 3-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0530] [Examples 6-12]

[0531] A peeling layer and a resin substrate were prepared in the same manner as in Example 6-1, except that the peeling layer-forming composition 3-12 was used instead of the peeling layer-forming composition 3-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0532] [Comparative Example 4-1]

[0533] A peeling layer and a resin substrate were prepared in the same manner as in Example 6-1, except that the peeling layer-forming composition 3-13 was used instead of the peeling layer-forming composition 3-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0534] [Comparative Example 4-2]

[0535] A peeling layer and a resin substrate were prepared in the same manner as in Example 6-1, except that the peeling layer-forming composition 3-14 was used instead of the peeling layer-forming composition 3-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0536] [Comparative Example 4-3]

[0537] A peeling layer and a resin substrate were prepared in the same manner as in Example 6-1, except that the peeling layer-forming composition 3-15 was used instead of the peeling layer-forming composition 3-1, thereby obtaining a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[0538] [5] Evaluation of peelability

[0539] The peeling properties of the glass substrates with peeling layers and the glass substrates with resin substrates and peeling layers obtained in Examples 6-1 to 6-12 and Comparative Examples 4-1 to 4-3 were confirmed by the same method as described in [4] of (I) above. The results are shown in Table 3.

[0540] [6] Curing evaluation

[0541] 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 an EDM at room temperature for 5 minutes. They were then heated on a hot plate at 100°C for 2 minutes and dried. The film thicknesses before and after PGME immersion were measured, and the residual film rate was calculated using the following formula. The degree of curing was evaluated based on the following criteria. The results are shown in Table 3.

[0542] <Residual film rate calculation formula>

[0543] {(film thickness after immersion) / (film thickness before immersion)}×100

[0544] <Evaluation Criteria>

[0545] ◎: Residual film rate ≧95%

[0546] ○: Residual film rate 70 to 94%

[0547] △: Residual film rate 50~69%

[0548] ×: Residual film rate <50%

[0549] [Table 3]

[0550]

[0551] As shown in Table 3, the peeling layers of Examples were found to have excellent adhesion to the glass substrate and to be easily peeled off from the resin film. On the other hand, the peeling layers of Comparative Examples 4-1 to 4-3 were found to have excellent adhesion to the glass substrate but were not easily peeled off from the resin substrate.

Claims

1. A composition for forming a peeling layer, comprising: (A) (A1) cellulose or a derivative thereof having a hydroxyalkyl group, (A2) a polyester having a hydroxyl group, or (A3) an acrylic polymer having a primary or secondary hydroxyl group and having no fluorine atoms and having a primary or secondary hydroxyalkyl group having 2 to 6 carbon atoms in a side chain, (B) a sulfonic acid compound or a salt thereof, (C) a crosslinking agent selected from compounds represented by any one of the following formulae (C-1) to (C-5) having a nitrogen atom substituted with a hydroxyalkyl group and / or an alkoxymethyl group, (D) a polymer additive comprising a repeating unit represented by the following formula (a1), a repeating unit represented by the following formula (b), and a repeating unit represented by the following formula (c), and (E) solvent; The composition for forming a release layer contains 5 to 100 parts by mass of the polymer additive (D) relative to 100 parts by mass of the component (A). In formulas (C-1) to (C-5), R 11 ~R 26 are each independently an alkyl group having 1 to 6 carbon atoms, R 27 is a hydrogen atom or a methyl group, Where R A are each independently a hydrogen atom or a methyl group, R B1 is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom, R C is a hydroxyalkyl group having 1 to 10 carbon atoms, R D It is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.

2. The composition for forming a release layer according to claim 1, wherein In the repeating unit represented by the above formula (b), R C It is a hydroxyalkyl group having 2 to 10 carbon atoms, wherein the carbon atom to which the hydroxy group is bonded is a secondary or tertiary carbon atom.

3. The composition for forming a release layer according to claim 1, wherein In the repeating unit represented by the above formula (b), R C The hydroxyalkyl group has 1 to 10 carbon atoms, the carbon atom to which the hydroxyl group is bonded is a primary carbon atom, and the content of the repeating unit represented by formula (a1) is 25 mol % or more of all the repeating units of the polymer additive (D).

4. The composition for forming a release layer according to claim 1, wherein The polymer additive (D) comprises a repeating unit represented by the following formula (a2), a repeating unit represented by the following formula (b), a repeating unit represented by the following formula (c), and a repeating unit represented by the following formula (d). Where R A 、R C and R D Means the same as above, R B2 is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom, and does not contain 2-methyl-1,1,1,3,3,3-hexafluoroisopropyl, R E is a single bond, a polycyclic alkylene group having 6 to 20 carbon atoms, or an arylene group having 6 to 12 carbon atoms, R F is a single bond or an alkylene group with 1 to 10 carbon atoms, R G is methyl, ethyl or hydroxy.

5. The composition for forming a release layer according to any one of claims 1 to 4, wherein The component (A1) is at least one selected from hydroxyethyl cellulose, hydroxypropyl cellulose, and derivatives thereof.

6. The composition for forming a release layer according to any one of claims 1 to 4, wherein The component (A2) is a polyester having an aromatic group or an alicyclic group in the main chain.

7. The composition for forming a release layer according to any one of claims 1 to 4, wherein The component (A2) is a polyester obtained by reacting a compound having two epoxy moieties with a compound having two carboxyl groups.

8. The composition for forming a release layer according to any one of claims 1 to 4, wherein The content of the cross-linking agent (C) is 10 to 100 parts by mass based on 100 parts by mass of the component (A). 9 . A release layer obtained from the release layer forming composition according to claim 1 . 10 . A laminate comprising the release layer according to claim 9 and a resin layer having a light transmittance of 80% or more at a wavelength of 400 nm.

11. A method for manufacturing a resin substrate, comprising: The process of applying the composition for forming a peeling layer according to any one of claims 1 to 8 to a substrate to form a peeling layer; forming a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm on the peeling layer; and peeling the resin substrate with a peeling force of 0.25 N / 25 mm or less.

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