WO2022186144A1

WO2022186144A1 - Composition for forming release layer, and release layer

Info

Publication number: WO2022186144A1
Application number: PCT/JP2022/008321
Authority: WO
Inventors: 元信松山; 和也進藤; 優樹古川
Original assignee: 日産化学株式会社
Priority date: 2021-03-03
Filing date: 2022-02-28
Publication date: 2022-09-09
Also published as: JPWO2022186144A1; TW202302745A; KR20230154052A

Abstract

As a composition for forming a release layer, which yields a release layer that exhibits high heat resistance and suitable release properties and exhibits excellent stability following film formation, the present invention provides a composition for forming a release layer, which contains: (A) a hydroxyalkyl group-containing cellulose (A1) or a derivative thereof, or the like; (B) an acid compound or a salt thereof; (C) a crosslinking agent selected from among compounds having a nitrogen atom substituted with a hydroxyalkyl group and/or an alkoxymethyl group; (D) a polymer additive containing repeating units represented by formula (a1), formula (b) and formula (c); and (E) a solvent, and in which component (D) is contained at a quantity of 5-100 parts by mass relative to 100 parts by mass of component (A). (R^A is a hydrogen atom or a methyl group, R^B1 is a branched alkyl group which has 3 or 4 carbon atoms and in which at least one hydrogen atom is substituted with a fluorine atom, R^C is a hydroxyalkyl group having 1-10 carbon atoms, and R^D is a polycyclic alkyl group having 6-20 carbon atoms or an aryl group having 6-12 carbon atoms.)

Description

Release layer-forming composition and release layer

The present invention relates to a release layer-forming composition and a release layer.

In recent years, in addition to the characteristics of thinness and weight reduction, electronic devices are required to be given the function of being able to bend. For this reason, it is required to use a lightweight flexible plastic substrate instead of the conventional glass substrate which is heavy, fragile and cannot be bent.

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

On the other hand, the base material of the touch panel film has changed from glass to polyethylene terephthalate (PET), polyimide, cycloolefin, acrylic and other plastic sheets, etc., and transparent flexible touch screen panels with flexibility have been developed. (Patent Documents 5 to 7).

In general, flexible touch screen panels are manufactured by creating a release (adhesive) layer on a support substrate such as a glass substrate, and then releasing the device after fabrication to ensure stable production and release. (Patent Document 8). This release layer must not be peeled off from the support substrate during the process, but requires a low peel force when peeled off. In addition, in order to improve productivity, it is necessary to store the release layer in the form of a film for a long period of time after forming the release layer. Therefore, the release layer is required to have stability after film formation.

WO2012/147235 JP 2009-283410 A Japanese Patent Publication No. 2010-507199 JP 2009-205924 A WO2017/002664 WO2016/160338 JP 2015-166145 A JP 2016-531358 A

The present invention has been made in view of the above circumstances, and provides a composition for forming a release layer which has high heat resistance and appropriate release properties and which can provide a release layer with excellent stability after film formation. for the purpose.

The present inventors have made intensive studies to achieve the above objects, and found that (A) (A1) a cellulose having a hydroxyalkyl group or a derivative thereof, (A2) a polyester having a hydroxy group, or (A3) A cross-linking agent selected from an acrylic polymer having a primary or secondary hydroxy group, (B) an acid compound or a salt thereof, (C) a compound having a nitrogen atom substituted with a hydroxyalkyl group and/or an alkoxymethyl group, (D ) a polymeric additive containing a predetermined repeating unit, and (E) a composition for forming a release layer containing a solvent has high heat resistance, excellent adhesion to a substrate, moderate adhesion to a resin substrate, and moderate adhesion to a resin substrate. The inventors have found that a release layer having excellent release properties can be provided with good reproducibility, and completed the present invention.

That is, the present invention
1. (A) (A1) a cellulose having a hydroxyalkyl group or a derivative thereof, (A2) a polyester having a hydroxy group, or (A3) an acrylic polymer having a primary or secondary hydroxy group and no fluorine atom ,
(B) an acid compound or a salt thereof;
(C) a cross-linking agent selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and/or an alkoxymethyl group;
(D) a polymer additive containing a repeating unit represented by the following formula (a1), a repeating unit represented by the following formula (b) and a repeating unit represented by the following formula (c), and (E) a solvent and the polymer additive (D) is contained in an amount of 5 to 100 parts by mass based on 100 parts by mass of the component (A),

(Wherein, R ^A is 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 substituted with a fluorine atom, R ^C is a hydroxyalkyl group having 1 to 10 carbon atoms, and R ^D is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.)
2. In the repeating unit represented by the formula (b), R ^C is a hydroxyalkyl group having 2 to 10 carbon atoms, and the carbon atom to which the hydroxy group is bonded is a secondary or tertiary carbon atom 1 A composition for forming a release layer of
3. In the repeating unit represented by the formula (b), ^R is a hydroxyalkyl group having 1 to 10 carbon atoms, the carbon atom to which the hydroxy group is bonded is a primary carbon atom, and the formula ( 1. The composition for forming a release layer of 1, wherein the content of the repeating unit represented by a1) is 25 mol% or more of the total repeating units of the polymer additive (D);
4. The (D) polymer additive 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). ) 1 composition for forming a release layer containing a repeating unit represented by

(wherein R ^A , R ^C and R ^D have the same meanings as above, and R ^B2 is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. However, 2-methyl-1,1,1,3,3,3-hexafluoroisopropyl group is not included, and R ^E is a single bond, a polycyclic alkylene group having 6 to 20 carbon atoms, or 6 to 12 carbon atoms. is an arylene group, R ^F is a single bond or an alkylene group having 1 to 10 carbon atoms, and R ^G is a methyl group, an ethyl group or a hydroxy group.)
5. 4. 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 the group consisting of 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 its main chain.
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 and a compound having two carboxy groups;
8. 4. 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;
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 its side chain;
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;
11. 10. The composition for forming a release layer according to any one of 1 to 10, wherein the cross-linking agent (C) is a compound represented by any one of the following formulas (C-1) to (C-5);

(In the formula, R ¹¹ to R ²⁶ are each independently an alkyl group having 1 to 6 carbon atoms, and R ²⁷ is a hydrogen atom or a methyl group.)
12. 11. The composition for forming a release layer according to any one of 1 to 11, wherein the content of the (C) crosslinking agent is 10 to 100 parts by mass with respect to 100 parts by mass of the component (A);
13. a release layer obtained from the release layer-forming composition according to any one of 1 to 12;
14. A laminate in which a resin layer having a light transmittance of 80% or more at a wavelength of 400 nm is laminated on the release layer of 13,
15. A step of applying the release layer-forming composition according to any one of 1 to 12 to a substrate to form a release layer, and a step of forming a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm on the release layer. and a step of peeling the resin substrate with a peeling force of 0.25 N/25 mm or less.

By using the composition for forming a release layer of the present invention, a release layer having high heat resistance, excellent adhesion to a substrate, appropriate adhesion to a resin substrate, and appropriate release properties can be obtained with good reproducibility. can. Further, in the manufacturing process of the flexible electronic device, it is possible to separate the resin substrate from the base together with the circuit etc. without damaging the resin substrate formed on the base and the circuit etc. provided thereon. It becomes possible.
Therefore, the composition for forming a release layer of the present invention can contribute to speeding up the manufacturing process of flexible electronic devices having a resin substrate, improving the yield thereof, and the like.

[Composition for forming release layer]
The release layer-forming composition of the present invention includes (A) (A1) a cellulose or derivative thereof having a hydroxyalkyl group, (A2) a polyester having a hydroxy group, or (A3) a primary or secondary hydroxy group. and a cross-linking agent selected from acrylic polymers having no fluorine atoms, (B) an acid compound or a salt thereof, (C) a compound having a nitrogen atom substituted with a hydroxyalkyl group and/or an alkoxymethyl group, (D ) a polymeric additive containing a predetermined repeating unit; and (E) a solvent.

[(A) (A1) a cellulose having a hydroxyalkyl group or a derivative thereof, (A2) a polyester having a hydroxy group, or (A3) an acrylic having a primary or secondary hydroxy group and having no fluorine atom polymer]
[(A1) Cellulose or its derivative]
The (A1) component is cellulose or its derivative having a hydroxyalkyl group.

The (A1) component includes hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose, hydroxyalkylalkylcelluloses such as hydroxyethylmethylcellulose, hydroxypropylmethylcellulose and hydroxyethylethylcellulose, and derivatives thereof. In the present invention, among these, hydroxyalkyl celluloses and derivatives thereof are preferred, and hydroxyethyl cellulose, hydroxypropyl cellulose, and derivatives thereof are more preferred. (A1) The cellulose or derivative thereof having a hydroxyalkyl group may be used alone or in combination of two or more.

The weight average molecular weight (Mw) of component (A1) is not particularly limited, but is preferably 1,000 to 500,000, more preferably 3,000 to 400,000, and 5,000 to 300,000. is even more preferred. In addition, a weight average molecular weight is a polystyrene conversion measured value by a gel permeation chromatography (GPC) (the same applies below).

[(A2) a polyester having a hydroxy group]
The (A2) polyester having a hydroxy group is not particularly limited, but in the present invention, those having an aromatic group or an alicyclic group in the main chain are preferred.

A polyester obtained by reacting a compound having two epoxy moieties and a compound having two carboxyl groups is preferable as such a polyester for component (A2).

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

<Epoxy compound>
Examples of compounds having two epoxy moieties described above include:
Bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone di glycidyl ether, 1,5-dihydroxynaphthalenediglycidyl ether, dihydroxybiphenyldiglycidyl ether, octachloro-4,4'-dihydroxybiphenyldiglycidyl ether, tetramethylbiphenyldiglycidyl ether, 9,9'-bis(4-hydroxyphenyl ) bisphenol diglycidyl ethers such as fluorenediglycidyl ether, 9,9'-bis(4-hydroxyphenyl)fluorenediglycidyl ether, 9,9'-bis(6-hydroxy-2-naphthyl)fluorenediglycidyl ether;
Aliphatic diols such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether diglycidyl ether;
Cyclohexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, dicyclopentadienediol diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol B diglycidyl ether, hydrogenated bisphenol S di Alicyclic diol diglycidyl ethers such as glycidyl ethers;
Aromatic dicarboxylic acid diglycidyl esters such as phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, and terephthalic acid diglycidyl ester;
Alicyclic dicarboxylic acid diglycidyl esters such as bisglycidyl oxalate, bisglycidyl adipate, bisglycidyl pimelate, and bisglycidyl 2-ethyl-3-propyl-1,5-pentanedioate;
Bisphenol A type epoxy resin jER828 (manufactured by Mitsubishi Chemical Corporation, trade name), terephthalate type epoxy resin Denacol EX711 (manufactured by Nagase ChemteX Corporation, trade name), biphenyl type epoxy resin YX4000H (manufactured by Mitsubishi Chemical Corporation, trade name), fluorene-type epoxy resin Ogusol PG-100 (manufactured by Osaka Gas Chemicals Co., Ltd., trade name), fluorene-type epoxy resin Ogsol CG-500 (manufactured by Osaka Gas Chemicals Co., Ltd., trade name:), cyclohexyl epoxy Resins having epoxy groups at both ends, such as resin CEL2021P (manufactured by Daicel Corporation, trade name);
Vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, tetrahydroindene dioxide, Epocalyc (ENEOS Co., Ltd. registered trademark) THI-DE, Epocalyc (ENEOS Co., Ltd. registered trademark) DE-102, Epocalyc (ENEOS ( Alicyclic dioxide such as registered trademark) DE-103;
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2,2-bis(3,4-epoxycyclohexyl)propane, bis(3,4-epoxycyclohexylmethyl) oxalate, bis(3,4-epoxycyclohexyl) adipate 4-epoxycyclohexylmethyl), bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis(3,4-epoxycyclohexylmethyl) pimelate, 2-ethyl-3-propyl-1,5-pentane Examples thereof include compounds having two 3,4-epoxycyclohexyl groups such as bis(3,4-epoxycyclohexylmethyl)dioate.
In addition, these compounds may be used individually by 1 type, or may be used in combination of 2 or more type.

<Carboxy group-containing compound>
Compounds having two carboxy groups include terephthalic acid, isophthalic acid, diphenic acid, 2-methylterephthalic acid, 2-hydroxyterephthalic acid, 2,5-dimethylterephthalic acid, 5-methylisophthalic acid, and 5-hydroxyisophthalic acid. , 2,6-naphthalenedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like. In addition, these compounds may be used individually by 1 type, or may be used in combination of 2 or more type.

The method for obtaining the polyester, which is an example of the component (A2), is not particularly limited. can get. At that time, the solvent to be used is not particularly limited as long as it dissolves each compound, the polymerization initiator, and the like.

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

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

(Wherein, X and Y each independently represent a structure having an aromatic group or an alicyclic group.)

The above X is preferably a group represented by the following formula (X-1).

In the formula, 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 is a single bond, ether represents a bond, carbonyl, sulfonyl, 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; represents 0, 1 or 2.

X ¹ is preferably a cyclic unsaturated hydrocarbon group having 4 to 16 carbon atoms or a saturated cyclic hydrocarbon group having 4 to 16 carbon atoms, and a cyclic unsaturated hydrocarbon group having 4 to 8 carbon atoms or 4 to 4 carbon atoms. 8 cyclic saturated hydrocarbon groups are more preferred. Any hydrogen atoms contained in X ¹ may be independently substituted with an aliphatic group, and a plurality of substituents among these aliphatic groups may be bonded together to form a 4- to 6-membered ring. may be formed.

Specific examples of X include, but are not limited to, groups represented by the following formulas (X-2) to (X-13).

(In the formula, * represents a bond.)

As the X, a structure derived from a resin having epoxy groups at both ends is also preferable.

Examples of Y include, but are not limited to, groups represented by the following formulas (Y-1) to (Y-4).

(In the formula, * represents a bond.)

As the (A2) component polyester, those having a structural unit represented by the following formula [A2-2] are also preferable.

In the formula, Cy is a group derived from the alicyclic dioxide, i.e., a tetravalent organic group containing an aliphatic ring, wherein all four bonding groups to OH and O are derived from the aliphatic ring. and Y has the same definition as Y in formula [A2-1].

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

(In the formula, *1 and *2 each represent a bond, and one of the two *1 and *2 in each structural formula respectively bonds to a hydroxyl group.)

As the (A2) component polyester, those having a structural unit represented by the following formula [A2-3] are also preferable.

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

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

(In the formula, * represents a bond.)

[(A3) acrylic polymer]
The (A3) component acrylic polymer having a primary or secondary hydroxy group and not having a fluorine atom is not particularly limited, but in the present invention, a polyethylene glycol ester group or a Those having a primary or secondary hydroxyalkyl ester group of are preferred, and those having these groups in their side chains are more preferred.
As the acrylic polymer, an acrylic ester homopolymer, a methacrylic ester homopolymer, a copolymer thereof, and a copolymer of these with a monomer having an unsaturated double bond such as styrene can be used. .
The acrylic polymer having a polyethylene glycol ester group or a primary or secondary hydroxyalkyl ester group having 2 to 6 carbon atoms, which is a preferred example of the acrylic polymer of component (A3), may be an acrylic polymer having any of these groups. There are no particular restrictions on the skeleton (other structural units) of the main chain of the polymer that constitutes the acrylic polymer, the types of side chains, and the like.

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

In the above formula [A3-1], R ^A is each independently a hydrogen atom or a methyl group, Y ¹ is an H—(OCH ₂ CH ₂ ) _n — group (where n is 2 to 30 is an integer, preferably an integer of 2 to 10.), or a primary or secondary hydroxyalkyl group having 2 to 6 carbon atoms.

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

The (A3) component acrylic polymer can be obtained, for example, 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.
Monomers having a polyethylene glycol ester group include monoacrylates and monomethacrylates of H--(OCH ₂ CH ₂ ) _n --OH (where n has the same meaning as above).
On the other hand, examples of monomers having a primary or secondary hydroxyalkyl group having 2 to 6 carbon atoms include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 4- Hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, glycerin monoacrylate, glycerin monomethacrylate and the like.

Further, in the present embodiment, when synthesizing the acrylic polymer of the component (A3), as long as the effects of the present invention are not impaired, monomers other than the above-described monomers, specifically, polyethylene glycol ester groups, primary or A monomer having no secondary hydroxy group and no fluorine atom can be used in combination.
Examples of such monomers include acrylic ester compounds such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, Methacrylic acid ester compounds such as butyl methacrylate, isobutyl methacrylate and t-butyl methacrylate; maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide; acrylamide compounds; acrylonitrile; maleic anhydride; and vinyl compounds.

The production method (polymerization method) of the (A3) component acrylic polymer is not particularly limited. A method of polymerization reaction is mentioned. The solvent to be used is not particularly limited as long as it dissolves the monomer, the polymerization initiator, and the like.

Preferable examples of the (A3) component acrylic polymer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, and glycerin. Monoacrylate, a polymer obtained by polymerizing a primary or secondary hydroxyalkyl ester monomer such as glycerin monomethacrylate, or the primary or secondary hydroxyalkyl ester monomer and a monomer other than these monomers, such as a primary or secondary hydroxy Examples include acrylic polymers having primary or secondary hydroxyalkyl groups in side chains, such as polymers obtained by copolymerizing one or more monomers selected from the group consisting of monomers having no groups.

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

[(B) acid compound or salt thereof]
The release layer-forming composition of the present invention contains an acid compound or a salt thereof as the component (B).
Specific examples of acid compounds include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate, salicylic acid, camphorsulfonic acid, sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, and benzenedisulfone. acid, sulfonic acid compounds such as 1-naphthalenesulfonic acid and pyridinium-1-naphthalenesulfonic acid; carboxylic acid compounds such as salicylic acid, sulfosalicylic acid, citric acid, benzoic acid and hydroxybenzoic acid;
Examples of the salt of the acid compound include pyridinium salts, isopropanolamine salts, N-methylmorpholine salts, etc. of each of the acids mentioned above. Specifically, pyridinium p-toluenesulfonate, pyridinium 1-naphthalenesulfonate, isopropanol amine p-toluenesulfonate, N-methylmorpholine p-toluenesulfonate and the like.

The content of component (B) is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of component (A). If the content of the component (B) is within this range, a composition having high heat resistance and suitable peelability and capable of providing a peeling layer with excellent stability after film formation can be obtained.
In addition, (B) an acid compound or its salt may be used individually by 1 type, or may be used in combination of 2 or more type.

[(C) Crosslinking agent]
The release layer-forming composition of the present invention contains, as component (C), a crosslinking agent selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and/or an alkoxymethyl group.
As the cross-linking agent, a compound represented by any one of the following formulas (C-1) to (C-5) is preferable.

In the above formulas, R ¹¹ to R ²⁶ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. ^R27 is a hydrogen atom or a methyl group.

Specific examples of cross-linking agents include hexamethylolmelamine, tetramethylolbenzoguanamine, 1,3,4,6-tetramethylolglycoluril, hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxy nitrogen-containing compounds such as methyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, and 1,3,4,6-tetrakis(hydroxymethyl)glycoluril;

In addition, a commercially available cross-linking agent can also be used in the present invention. Methyl-type melamine compound (trade name Mycoat (registered trademark) 506, Mycoat 508), glycoluril compound (trade name Cymel 1170, POWDERLINK 1174), methylated urea resin (trade name UFR65), butylated urea resin (trade name Nitrogen-containing compounds such as UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea/formaldehyde-based resins manufactured by DIC Corporation (trade names: Beccamin (registered trademark) J-300S, Beccamin P-955, Beccamin N) is mentioned.

Furthermore, as a cross-linking agent, a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide Polymers made using (meth)acrylamide compounds substituted with can also be used.
Specific examples of such polymers include poly(N-butoxymethyl(meth)acrylamide), copolymers of N-butoxymethyl(meth)acrylamide and styrene, N-hydroxymethyl(meth)acrylamide and methyl (meth)acrylamide). ) copolymer with acrylate, copolymer of N-ethoxymethyl methacrylamide and benzyl methacrylate, copolymer of N-butoxymethyl (meth)acrylamide, benzyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate etc.

Among these crosslinkers, hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril (POWDERLINK 1174), 1,3,4,6-tetrakis(butoxymethyl) It is preferred to use glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril.

The above-mentioned cross-linking agent can cause a cross-linking reaction by self-condensation, and can also cause a cross-linking reaction with the hydroxy groups in the acrylic polymer of component (A). Due to these cross-linking reactions, the formed peeling layer becomes stronger and less soluble in organic solvents.

The content of component (C) is preferably 10 to 100 parts by mass, more preferably 20 to 50 parts by mass, per 100 parts by mass of component (A). If the content of the component (C) is within this range, a composition having high heat resistance and appropriate peelability and capable of providing a peeling layer with excellent stability after film formation can be obtained.
In addition, (C) crosslinking agent may be used individually by 1 type, or may be used in combination of 2 or more type.

[(D) polymer additive]
In the release layer-forming composition of the present invention, the component (D) is 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). Contains polymeric additives containing repeating units.

In each of the above formulas, ^RA is each independently a hydrogen atom or a methyl group, and ^RB1 is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. , R ^C is a hydroxyalkyl group having 1 to 10 carbon atoms, and R ^D is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.

Specific examples of branched alkyl groups having 3 or 4 carbon atoms for R ^B1 include isopropyl, isobutyl, sec-butyl and tert-butyl groups.
R ^B1 is a group in which at least one hydrogen atom of these branched alkyl groups is substituted with a fluorine atom, and specific examples thereof include 1,1,1-trifluoroisopropyl, 1,1,1,3 , 3,3-hexafluoroisopropyl and nonafluorotert-butyl groups.

Specific examples of hydroxyalkyl groups having 1 to 10 carbon atoms for R ^C include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl and 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-methylbutyl, 4-hydroxy-2 - hydroxyalkyl groups having 1 to 10 carbon atoms such as methylbutyl and 4-hydroxy-3-methylbutyl groups, wherein the carbon atom to which the hydroxy group is bonded is a primary carbon atom; 1-hydroxyethyl, 1- hydroxypropyl, 2-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 1-hydroxyhexyl, 2-hydroxyhexyl, 1-hydroxyoctyl, 2-hydroxyoctyl, 1-hydroxydecyl, 2-hydroxydecyl, 1- hydroxyalkyl groups having 2 to 10 carbon atoms such as hydroxy-1-methylethyl and 2-hydroxy-2-methylpropyl groups, wherein the carbon atom to which the hydroxy group is bonded is a secondary or tertiary carbon atom; things are mentioned.

Specific examples of polycyclic alkyl groups having 6 to 20 carbon atoms for R ^D include 1-adamantyl, 2-adamantyl, isobornyl and norbornyl groups, and specific examples of aryl groups having 6 to 12 carbon atoms are , phenyl, 1-naphthyl, 2-naphthyl, 1-biphenylyl, 2-biphenylyl groups and the like.

Further, (D) the polymer additive includes 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 the following formula ( It may contain a repeating unit represented by d).

(In the formula, R ^A , R ^C and R ^D have the same meanings as above.)

R ^B2 is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom (with the proviso that 2-methyl-1,1,1,3,3,3-hexafluoro isopropyl group), and examples of the fluorine-containing alkyl group include the same groups as those exemplified above.
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 having 1 to 10 carbon atoms ^; is a methyl group, an ethyl group or a hydroxy group.

Examples of the polycyclic alkylene group having 6 to 20 carbon atoms of R ^E include groups obtained by removing one hydrogen atom from the above-mentioned polycyclic alkyl groups having 6 to 20 carbon atoms, such as adamantylene. , isobornylene, and norbornylene groups.
Examples of the arylene group having 6 to 12 carbon atoms of R ^E include groups obtained by removing one hydrogen atom from the specific examples of the aryl group having 6 to 12 carbon atoms described above, and examples thereof include phenylene, naphthylene, biphenylylene groups, and the like. mentioned.

Specific examples of the C 1-10 alkylene group for R ^F include methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene and decamethylene groups. Among these, an alkylene group having 1 to 5 carbon atoms is preferred, a methylene group and an ethylene group are more preferred, and a methylene group is even more preferred.

Examples of repeating units represented by formula (a1) or (a2) include, but are not limited to, those represented by formulas (a-1) to (a-3) below. In the formula below, ^RA has the same meaning as above (the same applies hereinafter).

The repeating unit represented by formula (b) includes, but is not limited to, those represented by formulas (b-1) to (b-16) below.

The repeating unit represented by formula (c) includes, but is not limited to, those represented by formulas (c-1) to (c-13) below.

The repeating unit represented by formula (d) includes, but is not limited to, those represented by formulas (d-1) to (d-8) below.

In the present invention, 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). In the case where the carbon atom to which the hydroxy group is bonded in the hydroxyalkyl group in the repeating unit represented by formula (b) is a secondary or tertiary carbon atom (hereinafter, such a polymer additive is referred to as a high The content of the repeating unit represented by the formula (a1) is preferably 30 to 60 mol%, more preferably 35 to 50 mol%, of the total repeating units. The content of the repeating unit represented by the total repeating units is preferably 10 to 35 mol%, more preferably 15 to 30 mol%, and the content of the repeating unit represented by formula (c) is the total repeating units. Among them, 5 to 60 mol % is preferable, and 20 to 50 mol % is more preferable.

On the other hand, the polymer additive (D) contains a repeating unit represented by formula (a1), a repeating unit represented by formula (b), and a repeating unit represented by formula (c), When the carbon atom to which the hydroxy group is bonded in the hydroxyalkyl group in the repeating unit represented by formula (b) 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%, even more preferably 30 to 60 mol%, and 35 More preferably to 50 mol%, the content of the repeating unit represented by the formula (b) is preferably 8 to 38 mol%, more preferably 10 to 38 mol%, more preferably 10 to 35 mol% of the total repeating units. is more preferably 15 to 30 mol%, and the content of the repeating unit represented by formula (c) is preferably 2 to 77 mol%, more preferably 2 to 65 mol%, of all repeating units. , 5 to 60 mol % is more preferred, and 20 to 50 mol % is even more preferred.

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

(D) The weight average molecular weight (Mw) of the polymeric additive is preferably 2,000 to 10,000, more preferably 3,000 to 6,000. Also, the Mw/Mn is preferably 1.0 to 2.1, more preferably 1.0 to 1.9 (Mn is the number average molecular weight).

The content of the polymeric additive of component (D) is 5 to 100 parts by mass with respect to 100 parts by mass of component (A). If the polymer additive content is less than 5 parts by mass, the peeling force may increase, and if it exceeds 100 parts by mass, repelling may occur during film formation.

In particular, when the polymer additive (D) is polymer additive D1, the content thereof is preferably 10 to 100 parts by mass, more preferably 20 to 100 parts by mass, relative to 100 parts by mass of component (A). Preferably, 30 to 100 parts by mass is more preferable.
When the polymer additive (D) is other than polymer additive D1, the content thereof is preferably 5 to 80 parts by mass, more preferably 5 to 50 parts by mass, per 100 parts by mass of component (A). part is more preferred.
In addition, (D) polymeric additive may be used individually by 1 type, or may be used in combination of 2 or more type.

[(E) solvent]
The release layer-forming composition of the present invention contains a solvent as component (E).
Preferred solvents are glycol ether solvents with 3 to 20 carbon atoms, ester solvents with 3 to 20 carbon atoms, ketone solvents with 3 to 20 carbon atoms, and amide solvents with 3 to 20 carbon atoms.

Specific examples of glycol ether solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether, and propylene glycol monopropyl ether.
Specific examples of ester solvents include ethyl lactate, γ-butyrolactone, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate.
Specific examples of ketone solvents include methyl ethyl ketone, cyclopentanone, cyclohexanone, and benzophenone.
Amide solvents include N-methylpyrrolidone, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropanamide and the like.

The content of (E) the solvent is not particularly limited, but is preferably an amount such that the solid content concentration in the release layer-forming composition of the present invention is 0.1 to 40% by mass, and 0.5 An amount of ∼20% by weight is more preferred, and an amount of 0.5 to 10% by weight is even more preferred. The solid content means all components of the release layer-forming composition other than the solvent, and the solid content is the total amount thereof.
In addition, (E) a solvent may be used individually by 1 type, or may be used in mixture of 2 or more types.

[Other additives]
The release layer-forming composition of the present invention may contain a surfactant, if necessary. By adding a surfactant, it is possible to improve the coatability of the release layer forming composition on the substrate.
As the surfactant, known surfactants such as nonionic surfactants, fluorine-based surfactants, and silicone-based surfactants can be used.

Specific examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether; Polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenyl ether; Polyoxyethylene-polyoxypropylene block copolymers; Sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate , sorbitan tristearate and other sorbitan fatty acid esters; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate and polyoxyethylene sorbitan fatty acid esters such as

Specific examples of fluorosurfactants include Ftop (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac (registered trademark) F171, F173, F554, F559, F563, R -30, R-40, R-40-LM, DS-21 (manufactured by DIC Corporation), FLUORAD (registered trademark) FC430, FC431 (manufactured by 3M), Asahiguard (registered trademark) AG710, Surflon (registered trademark) ) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC) and the like.
Specific examples of silicone-based surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

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, preferably 0.001 to 0.5 part by mass, per 100 parts by mass of component (A). part is more preferred.
In addition, surfactant may be used individually by 1 type, or may be used in combination of 2 or more type.

[Preparation of release layer forming composition]
The method for preparing the release layer-forming composition of the present invention is not particularly limited. (E) A method of mixing the component and the like in a predetermined ratio to form a uniform solution can be mentioned. The solvent for dissolving component (A) may be the same as or different from component (E).
Moreover, when other additives are used, they may be added and mixed at any stage of the preparation of the composition.

In the preparation of the release layer-forming composition of the present invention, the polymer solution obtained by the polymerization reaction in the solvent may be used as it is. For example, component (B), component (C), component (D), component (E), etc. may be added to the solution after the polymerization reaction to produce component (A) to obtain a uniform solution. At this time, a solvent may be added for the purpose of adjusting the concentration, and this solvent may be the same as or different from the solvent used in the preparation of component (A).

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.

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, etc. In particular, it is desirable to obtain a film having a thickness of about 0.01 to 5 μm with good reproducibility. is preferably about 1 to 5,000 mPa·s at 25° C., more preferably about 1 to 2,000 mPa·s.
The viscosity in the present invention can be measured using a commercially available liquid viscosity measuring viscometer, for example, with reference to the procedure described in JIS K7117-2, at a composition temperature of 25°C. . As a viscometer, it is preferable to use a cone-plate type (cone plate type) rotational viscometer. It is preferable to measure under the condition of °C. Examples of such a rotational viscometer include TVE-25L manufactured by Toki Sangyo Co., Ltd.

[Release layer]
The composition for forming a release layer of the present invention is coated on a substrate and then baked at 180 to 250° C. in a baking method, whereby excellent adhesion to the substrate and appropriate adhesion to the resin substrate are obtained. A release layer having appropriate release properties can be obtained.
In this case, the heating time for firing varies depending on the heating temperature and cannot be generally defined, but is usually 1 minute to 5 hours. Moreover, the temperature at the time of firing may include a step of firing at a temperature lower than the maximum temperature, as long as the maximum temperature falls within the above range.

A preferred example of the heating mode in the present invention includes heating at 50 to 150°C for 1 minute to 1 hour and then increasing the heating temperature as it is to heat at 180 to 250°C for 5 minutes to 4 hours. In particular, a more preferable heating mode is heating at 50 to 150° C. for 1 minute to 1 hour and heating at 200 to 250° C. for 5 minutes to 2 hours. Furthermore, another more preferable example of the heating mode includes heating at 50 to 150° C. for 1 to 30 minutes and then heating at 200 to 250° C. for 5 minutes to 1 hour.

When the release layer of the present invention is formed on the substrate, the release layer may be formed on a part of the surface of the substrate, or may be formed on the entire surface. Examples of forming the release layer on a part of the surface of the substrate include forming the release layer only on a predetermined area of the surface of the substrate, and forming the release layer on the entire surface of the substrate in a pattern such as a dot pattern or a line and space pattern. There is an aspect of forming. In the present invention, the term "substrate" means a substrate whose surface is coated with the release layer-forming composition of the present invention, and which is used in the production of flexible electronic devices and the like.

Examples of the substrate (substrate) include glass, metal (silicon wafer, etc.), slate, and the like. Glass is preferred because it has
The substrate surface may be composed of a single material, or may be composed of two or more materials. Examples of embodiments in which the surface of the substrate is composed of two or more materials include an embodiment in which a certain area of the surface of the substrate is composed of a certain material and the rest of the surface is composed of another material; , a patterned material such as a line-and-space pattern exists in another material.

The method of applying the composition for forming a release layer is not particularly limited. (letterpress, intaglio, lithography, screen printing, etc.) and the like.

Equipment used for heating includes, for example, hot plates and ovens. The heating atmosphere may be under air or under an inert gas, and may be under normal pressure or under reduced pressure.

The thickness of the release layer is usually about 0.01 to 50 μm, but from the viewpoint of productivity, it is preferably about 0.01 to 20 μm, more preferably about 0.01 to 5 μm. thickness to achieve the desired thickness.

The release layer of the present invention has excellent adhesion to substrates, particularly glass substrates, and moderate adhesion and moderate releasability to resin substrates. Therefore, the release layer of the present invention can be used to separate the resin substrate of the device from the substrate together with the circuit or the like formed on the resin substrate without damaging the resin substrate of the device in the manufacturing process of the flexible electronic device. It can be suitably used to allow

[Method for manufacturing resin substrate]
An example of a method for manufacturing a flexible electronic device using the release layer of the present invention will be described.
First, using the composition for forming a release layer of the present invention, a release layer is formed on a glass substrate by the method described above. A resin substrate-forming solution for forming a resin substrate is applied onto the release layer, and the resulting coating film is baked to obtain a resin fixed to the glass substrate via the release layer of the present invention. forming a substrate;

The baking temperature of the coating film is appropriately set according to the type of resin, etc., but in the present invention, the maximum temperature during baking is preferably 200 to 250 ° C., and 210 to 250 ° C. is more preferable, and 220 to 240° C. is even more preferable. By setting the maximum temperature during baking in the production of the resin substrate within this range, the adhesiveness between the base release layer and the substrate, and the appropriate adhesion and releasability between the release layer and the resin substrate are further improved. be able to. Also in this case, as long as the maximum temperature falls within the above range, a step of firing at a temperature lower than that may be included.

It is preferable that the resin substrate is formed with an area larger than the area of the peeling layer so as to cover the entire peeling layer.
Examples of the resin substrate include resin substrates made of acrylic polymer and resin substrates made of cycloolefin polymer, and those having a light transmittance of 80% or more at a wavelength of 400 nm are preferable.
Incidentally, the method of forming the resin substrate may follow a conventional method.

Next, on the resin substrate fixed to the substrate via the release layer of the present invention, a desired circuit is formed as necessary, and then, for example, the resin substrate is cut along the release layer to form the circuit. At the same time, the resin substrate is separated from the release layer to separate the resin substrate and the base. At this time, part of the substrate may be cut together with the release layer.
By using the release layer of the present invention, the resin substrate can be separated from the release layer with a release force of 0.25 N/25 mm or less. In particular, when the polymer additive (D) is polymer additive D2 or polymer additive D3, the resin substrate can be separated from the release layer with a release force of 0.15 N/25 mm or less. Further, when the polymer additive (D) is polymer additive D1, the resin substrate can be separated from the release layer with a release force of 0.1 N/25 mm or less.

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

(I) (A1) Composition for Forming a Release Layer Containing Cellulose Having a Hydroxyalkyl Group or a Derivative thereof Compounds used in the following examples are as follows.
PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl ether acetate HPC-SSL: hydroxypropyl cellulose, Mw 40,000
HPC-SL: Hydroxypropyl cellulose, Mw 100,000
HPC-L: Hydroxypropyl cellulose, Mw 140,000
CAB: cellulose acetate butyrate, Mw 155,800
CAP: cellulose acetate propionate, Mw 71,300
PL-LI: 1,3,4,6-tetrakis(methoxyethyl) glycoluril (manufactured by Ornex, trade name: POWDERLINK 1174)
PPTS: pyridinium p-toluenesulfonate HPMA: 2-hydroxypropyl methacrylate ADMA: 2-adamantyl methacrylate HFiPMA: 1,1,1,3,3,3-hexafluoroisopropyl methacrylate AIBN: azobisisobutyronitrile DDT: dodecanethiol

In addition, the weight average molecular weight (Mw) of the polymer was measured using a GPC apparatus manufactured by Shimadzu Corporation (column: Shodex (registered trademark) KF803L and KF804L (manufactured by Showa Denko Co., Ltd.); eluent: THF; flow rate: 1 0 mL/min; column temperature: 40° C.; Mw: standard polystyrene conversion value).

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

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

[2] Preparation of Resin Substrate-Forming Composition [Preparation Example 1] Preparation of Resin Substrate-Forming Composition F1 In an eggplant flask containing 100 g of carbon tetrachloride, Zeonor (registered trademark) 1020R (manufactured by Nippon Zeon Co., Ltd.) olefin polymer) and 3 g of Epolead (registered trademark) GT401 (manufactured by Daicel Corporation) were added. This solution was dissolved by stirring for 24 hours in a nitrogen atmosphere to prepare a resin substrate-forming composition F1.

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

[Example 1-2] Preparation of release layer-forming composition 2 Release layer-forming composition 1-2 was prepared in the same manner as in Example 1-1, except that PL-LI was changed to 0.50 g. prepared.

[Example 1-3] Preparation of release layer-forming composition 3 Release layer-forming composition 1-3 was prepared in the same manner as in Example 1-1, except that PL-LI was changed to 0.25 g. prepared.

[Example 1-4] Preparation of release layer forming composition 4 Release layer forming composition 1- was prepared in the same manner as in Example 1-1 except that HPC-SL was used instead of HPC-SSL. 4 was prepared.

[Example 1-5] Preparation of release layer-forming composition 5 Release layer-forming composition 1- was prepared in the same manner as in Example 1-1 except that HPC-L was used instead of HPC-SSL. 5 was prepared.

[Example 1-6] Preparation of release layer-forming composition 6 Release layer-forming composition 1 was prepared in the same manner as in Example 1-1, except that the acrylic polymer (S1) solution was changed to 0.50 g. -6 was prepared.

[Example 1-7] Preparation of release layer-forming composition 7 Release layer-forming composition 1 was prepared in the same manner as in Example 1-1, except that the acrylic polymer (S1) solution was changed to 0.38 g. -7 was prepared.

[Example 1-8] Preparation of release layer forming composition 8 A release layer 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. Forming compositions 1-8 were prepared.

[Comparative Example 1-1] Preparation of Release Layer-Forming Composition 9 A release layer-forming composition 1-9 was prepared in the same manner as in Example 1-1, except that CAB was used instead of HPC-SSL. prepared.

[Comparative Example 1-2] Preparation of Release Layer-Forming Composition 10 A release layer-forming composition 1-10 was prepared in the same manner as in Example 1-1, except that CAP was used instead of HPC-SSL. prepared.

[4] Production of release layer and resin substrate [Example 2-1]
Using a spin coater (conditions: 1,000 rpm for about 30 seconds), the release layer-forming composition 1-1 was applied onto a glass substrate (100 mm×100 mm, hereinafter the same). The resulting coating film was heated at 100° C. for 2 minutes using a hot plate and then heated at 230° C. for 10 minutes using a hot plate to form a release layer having a thickness of about 0.1 μm on the glass substrate. , a glass substrate with a release layer was obtained.
Immediately thereafter, a spin coater (conditions: 200 rpm for about 15 seconds) was used to apply the resin substrate-forming composition F1 onto the release layer (resin thin film) on the glass substrate. The resulting coating film is heated using a hot plate at 80° C. for 2 minutes, and then heated at 230° C. for 30 minutes using a hot plate to form a resin substrate having a thickness of about 3 μm on the release layer, A glass substrate with a resin substrate and a release layer was obtained. After that, the light transmittance was measured using an ultraviolet-visible spectrophotometer (UV-2600 manufactured by Shimadzu Corporation), and the resin substrate exhibited a transmittance of 90% or more at 400 nm.

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

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

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

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

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

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

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

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

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

[5] Evaluation of peelability The glass substrates with peeling layers and the resin substrates and the glass substrates with peeling layers obtained in Examples 2-1 to 2-8 and Comparative Examples 2-1 and 2-2 were subjected to the following method. to confirm the peelability. In addition, the following test was performed with the same glass substrate.

(1) Evaluation of releasability between release layer and glass substrate 2 mm intervals, the same applies hereinafter), and 25 Muscats were performed. That is, 25 squares of 2 mm square were formed by this cross-cutting.
An adhesive tape was attached to the 25 muscat portion, the tape was peeled off, and the degree of peeling was evaluated according to the following criteria. Table 1 shows the results.
<Judgment Criteria>
5B: 0% peeling (no peeling)
4B: Less than 5% peeling 3B: 5% or more and less than 15% peeling 2B: 15% or more and less than 35% peeling 1B: 35% or more and less than 65% peeling 0B: 65% or more and less than 80% peeling B: 80 % or more and less than 95% peeling A: 95% or more and less than 100% peeling AA: 100% peeling (all peeling)

(2) Evaluation of peeling force between peeling layer and resin substrate I made a strip of paper. Furthermore, after applying Cellotape (registered trademark) (CT-24 manufactured by Nichiban Co., Ltd.), Autograph AGS-X500N (manufactured by Shimadzu Corporation) was used at a peeling angle of 90 ° and a peeling speed of 300 mm / min. It was peeled off and the peel force was measured. In addition, what could not be peeled was made into non-peelable. Table 1 shows the results.

From the results shown in Table 1, it was confirmed that the release layers of Examples had excellent adhesion to the glass substrate and were easily separated from the resin film. On the other hand, it was confirmed that the release layers of Comparative Examples 2-1 and 2-2 had excellent adhesion to the glass substrate, but were difficult to separate from the resin substrate.

(II) (A2) Release Layer-Forming Composition Containing Polyester Having Hydroxy Group Compounds used in the following examples are as follows.
PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl ether acetate PL-LI: 1,3,4,6-tetrakis(methoxyethyl) glycoluril (manufactured by Allnex, trade name: POWDERLINK 1174)
PPTS: pyridinium p-toluenesulfonate HPMA: 2-hydroxypropyl methacrylate ADMA: 2-adamantyl methacrylate HFiPMA: 1,1,1,3,3,3-hexafluoroisopropyl methacrylate AIBN: azobisisobutyronitrile DDT: Dodecanethiol EP1: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: jER828)
EP2: terephthalate type epoxy resin (manufactured by Nagase ChemteX Corporation, trade name: Denacol EX711)
EP3: Biphenyl-type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: YX4000H)
EP4: Fluorene type epoxy resin (manufactured by Osaka Gas Chemicals Co., Ltd., trade name: Ogusol PG-100)
EP5: Fluorene type epoxy resin (manufactured by Osaka Gas Chemicals Co., Ltd., trade name: Ogusol CG-500)
EP6: Cyclohexyl type epoxy resin (manufactured by Daicel Corporation, trade name: CEL2021P)
TPhA: terephthalic acid IPhA: isophthalic acid 5HIPhA: 5-hydroxyisophthalic acid 14CHA: 1,4-cyclohexyldicarboxylic acid BTEAC: benzyltriethylammonium chloride ETPPB: ethyltriphenylphosphonium bromide

Also, the weight average molecular weight (Mw) of the polymer was measured by the same method as described in (I) above.

[1] Synthesis of Polymer [Synthesis Example 2-1] Synthesis of Polyester (A2-1) 10.0 g of EP1, 5.4 g of TPhA and 0.25 g of BTEAC are dissolved in 36.4 g of PGME, reacted at 120° C. for 20 hours, A polyester (A2-1) solution (solid concentration: 30% by mass) was obtained. As a result of GPC analysis, Mw of the obtained polyester (A2-1) was 13,200 and Mw/Mn was 3.9.

[Synthesis Example 2-2] Synthesis of polyester (A2-2) 10.0 g of EP3, 5.2 g of TPhA and 0.24 g of BTEAC were dissolved in 36.0 g of PGME and reacted at 120° C. for 20 hours to give polyester (A2-2). A solution (solid concentration: 30% by mass) was obtained. As a result of GPC analysis, the resulting polyester (A2-2) had an Mw of 21,000 and an Mw/Mn of 3.2.

[Synthesis Example 2-3] Synthesis of polyester (A2-3) 10.0 g of EP1, 5.4 g of IPhA and 0.25 g of BTEAC were dissolved in 36.4 g of PGME and reacted at 120° C. for 20 hours to give polyester (A2-3). A solution (solid concentration: 30% by mass) was obtained. As a result of GPC analysis, the resulting polyester (A2-3) had an Mw of 6,600 and an Mw/Mn of 2.1.

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

[Synthesis Example 2-5] Synthesis of polyester (A2-5) 10.0 g of EP3, 5.2 g of IPhA and 0.24 g of BTEAC were dissolved in 36.0 g of PGME and reacted at 120° C. for 20 hours to give polyester (A2-5). A solution (solid concentration: 30% by mass) was obtained. As a result of GPC analysis, Mw of the obtained polyester (A2-5) was 5,400 and Mw/Mn was 3.3.

[Synthesis Example 2-6] Synthesis of polyester (A2-6) EP4 10.0 g, IPhA 4.0 g and BTEAC 0.18 g were dissolved in PGME 56.5 g, reacted at 120 ° C. for 20 hours, polyester (A2-6) A solution (solid concentration: 20% by mass) was obtained. As a result of GPC analysis, the resulting polyester (A2-6) had an Mw of 8,100 and an Mw/Mn of 3.3.

[Synthesis Example 2-7] Synthesis of polyester (A2-7) 10.0 g of EP5, 3.4 g of IPhA and 0.15 g of BTEAC were dissolved in 54.2 g of PGME, reacted at 120 ° C. for 20 hours, and polyester (A2-7) A solution (solid concentration: 20% by mass) was obtained. As a result of GPC analysis, the resulting polyester (A2-7) had an Mw of 6,600 and an Mw/Mn of 2.0.

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

[Synthesis Example 2-9] Synthesis of polyester (A2-9) 10.0 g of EP5, 3.7 g of 5HIPhA and 0.15 g of BTEAC were dissolved in 55.5 g of PGME, reacted at 120 ° C. for 20 hours, and polyester (A2-9) A solution (solid concentration: 20% by mass) was obtained. As a result of GPC analysis, the resulting polyester (A2-9) had an Mw of 7,600 and an Mw/Mn of 2.2.

[Synthesis Example 2-10] Synthesis of polyester (A2-10) 10.0 g of EP6, 6.6 g of TPhA and 0.59 g of ETPPB were dissolved in 40.1 g of PGME and reacted at 120° C. for 20 hours to give polyester (A2-10). A solution (solid concentration: 20% by mass) was obtained. As a result of GPC analysis, the resulting polyester (A2-10) had an Mw of 9,200 and an Mw/Mn of 2.1.

[Synthesis Example 2-11] Synthesis of polyester (A2-11) 10.0 g of EP6, 6.8 g of 14CHA and 0.59 g of ETPPB were dissolved in 40.7 g of PGME and reacted at 120° C. for 20 hours to give polyester (A2-11). A solution (solid concentration: 20% by mass) was obtained. As a result of GPC analysis, Mw of the obtained polyester (A2-11) was 5,800 and Mw/Mn was 1.7.

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

[3] Preparation of release layer forming composition [Example 3-1] Preparation of release layer forming composition 1 To 1 g of the polyester (A2-1) solution obtained in Synthesis Example 1, 0.06 g of PL-LI, Add 0.01 g of PPTS, 0.17 g of acrylic polymer (S1) solution, and PGMEA, and dilute with PGME so that the solid content concentration is 5% by mass and the PGMEA concentration is 30% by mass, to prepare a release layer forming composition 2- 1 was prepared.

[Example 3-2] Preparation of release layer-forming composition 2 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, A release layer forming composition 2-2 was prepared.

[Example 3-3] Preparation of release layer-forming composition 3 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, A release layer forming composition 2-3 was prepared.

[Example 3-4] Preparation of release layer-forming composition 4 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, A release layer forming composition 2-4 was prepared.

[Example 3-5] Preparation of release layer forming composition 5 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, A release layer forming composition 2-5 was prepared.

[Example 3-6] Preparation of release layer-forming composition 6 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, A release layer forming composition 2-6 was prepared.

[Example 3-7] Preparation of release layer-forming composition 7 A release layer forming composition 2-7 was prepared.

[Example 3-8] Preparation of release layer forming composition 8 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, A release layer forming composition 2-8 was prepared.

[Example 3-9] Preparation of release layer-forming composition 9 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, A release layer forming composition 2-9 was prepared

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

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

[4] Preparation of release layer and resin substrate [Example 4-1]
Using a spin coater (conditions: 1,000 rpm for about 30 seconds), the release layer-forming composition 2-1 was applied onto a glass substrate (100 mm×100 mm, hereinafter the same). The resulting coating film was heated at 100° C. for 2 minutes using a hot plate and then heated at 230° C. for 10 minutes using a hot plate to form a release layer having a thickness of about 0.1 μm on the glass substrate. , a glass substrate with a release layer was obtained.
Immediately thereafter, a spin coater (conditions: 200 rpm for about 15 seconds) was used to apply the resin substrate-forming composition F1 onto the release layer (resin thin film) on the glass substrate. The resulting coating film is heated using a hot plate at 80° C. for 2 minutes, and then heated at 230° C. for 30 minutes using a hot plate to form a resin substrate having a thickness of about 3 μm on the release layer, A glass substrate with a resin substrate and a release layer was obtained. After that, the light transmittance was measured using an ultraviolet-visible spectrophotometer (UV-2600 manufactured by Shimadzu Corporation), and the resin substrate exhibited a transmittance of 90% or more at 400 nm.

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

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

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

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

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

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

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

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

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

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

[5] Evaluation of peelability The glass substrate with a peeling layer and the resin substrate/glass substrate with a peeling layer obtained in Examples 4-1 to 4-11 were subjected to the method described in [4] of (I) above. The peelability was confirmed by the same method. Table 2 shows the results.

From the results shown in Table 2, it was confirmed that the release layers of Examples had excellent adhesion to the glass substrate and were easily separated from the resin film.

(III) (A3) Composition for Forming a Release Layer Containing an Acrylic Polymer Having a Primary or Secondary Hydroxy Group and Not Having a Fluorine Atom Compounds used in the following examples are as follows.
PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl ether acetate CHN: cyclohexanone PL-LI: 1,3,4,6-tetrakis(methoxyethyl) glycoluril (manufactured by Allnex, trade name: POWDERLINK 1174)
PPTS: pyridinium p-toluenesulfonate MMA: methyl methacrylate HPMA: 2-hydroxypropyl methacrylate HEMA: 2-hydroxyethyl methacrylate 4HBA: 4-hydroxybutyl acrylate HADM: 3-hydroxy-1-adamantyl methacrylate ADMA: 2-adamantyl methacrylate HFiPMA: 1,1,1,3,3,3-hexafluoroisopropyl methacrylate AIBN: azobisisobutyronitrile DDT: dodecanethiol

[1] Synthesis of polymer [Synthesis Example 3-1] Synthesis of acrylic polymer (A3-1) 20.0 g of HEMA, 1.26 g of AIBN and 1.56 g of DDT are dissolved in 92 g of PGME and reacted at 70°C for 20 hours to give an acrylic polymer. (A3-1) A solution (solid concentration: 20% by mass) was obtained. As a result of GPC analysis, the obtained acrylic polymer (A3-1) had an Mw of 5,400 and an Mw/Mn of 1.7.

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

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

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

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

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

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

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

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

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

[Synthesis Example 3-11] Synthesis of acrylic polymer (A3-11) 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 give an acrylic polymer. (A11) A solution (solid concentration: 20% by mass) was obtained. The composition ratio of each unit was MMA:HADM=70:30. As a result of GPC analysis, the obtained acrylic polymer (A3-11) had an Mw of 6,600 and an Mw/Mn of 1.6.

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

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

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

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

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

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

[Example 5-4] Preparation of release layer-forming composition 4 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. A release layer forming composition 3-4 was prepared.

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

[Example 5-6] Preparation of release layer forming composition 6 The same method as in Example 5-1 except that the acrylic polymer (A3-6) solution was used instead of the acrylic polymer (A3-1) solution. A release layer-forming composition 3-6 was prepared.

[Example 5-7] Preparation of release layer forming composition 7 The acrylic polymer (A3-6) solution was used instead of the acrylic polymer (A3-1) solution, and the acrylic polymer (S1) was changed to 0.17 g. A release layer-forming composition 3-7 was prepared in the same manner as in Example 5-1, except for the above.

[Example 5-8] Preparation of release layer forming composition 8 The same method as in Example 5-1 except that the acrylic polymer (A3-7) solution was used instead of the acrylic polymer (A3-1) solution. A release layer forming composition 3-8 was prepared.

[Example 5-9] Preparation of release layer forming composition 9 Acrylic polymer (A3-7) solution was used instead of acrylic polymer (A3-1) solution, and acrylic polymer (S1) was changed to 0.17 g. A release layer-forming composition 3-9 was prepared in the same manner as in Example 1-1, except for the above.

[Example 5-10] Preparation of release layer-forming composition 10 Acrylic polymer (A3-7) solution was used instead of acrylic polymer (A3-1) solution, and acrylic polymer (S1) solution was replaced with acrylic polymer (A3-7) solution. S2) A release layer-forming composition 3-10 was prepared in the same manner as in Example 5-1, except that the solution was used.

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

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

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

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

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

[4] Preparation of release layer and resin substrate [Example 6-1]
Using a spin coater (conditions: 1,000 rpm for about 30 seconds), the release layer-forming composition 3-1 was applied onto a glass substrate (100 mm×100 mm, hereinafter the same). The resulting coating film was heated at 100° C. for 2 minutes using a hot plate and then heated at 230° C. for 10 minutes using a hot plate to form a release layer having a thickness of about 0.1 μm on the glass substrate. , a glass substrate with a release layer was obtained.
Immediately thereafter, a spin coater (conditions: 200 rpm for about 15 seconds) was used to apply the resin substrate-forming composition F1 onto the formed release layer (resin thin film) on the glass substrate. The resulting coating film is heated using a hot plate at 80° C. for 2 minutes, and then heated at 230° C. for 30 minutes using a hot plate to form a resin substrate having a thickness of about 3 μm on the release layer, A glass substrate with a resin substrate and a release layer was obtained. After that, the light transmittance was measured using an ultraviolet-visible spectrophotometer (UV-2600 manufactured by Shimadzu Corporation), and the resin substrate exhibited a transmittance of 90% or more at 400 nm.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[5] Evaluation of peelability For the glass substrates with peeling layers and resin substrates/glass substrates with peeling layers obtained in Examples 6-1 to 6-12 and Comparative Examples 4-1 to 4-3, the above (I) The peelability was confirmed by the same method as described in [4]. Table 3 shows the results.

[6] Curability Evaluation The glass substrates with release layers obtained in Examples 6-1 to 6-12 and Comparative Examples 4-1 to 4-3 were immersed in EDM at room temperature for 5 minutes. After that, it was dried by heating at 100° C. for 2 minutes using a hot plate. The film thickness before and after immersion in PGME was measured, the residual film ratio was calculated by the following formula, and the degree of curing was evaluated based on the following criteria. Table 3 shows the results.
<Remaining film rate calculation formula>
{(film thickness after immersion)/(film thickness before immersion)}×100
<Judgment Criteria>
◎: Remaining film rate ≥ 95%
○: Remaining film rate 70 to 94%
△: Remaining film rate 50 to 69%
×: Remaining film rate <50%

As shown in Table 3, it was confirmed that the release layers of Examples had excellent adhesion to the glass substrate and were easily separated from the resin film. On the other hand, it was confirmed that the release layers of Comparative Examples 4-1 to 4-3 had excellent adhesion to the glass substrate, but were difficult to separate from the resin substrate.

Claims

(A) (A1) a cellulose having a hydroxyalkyl group or a derivative thereof, (A2) a polyester having a hydroxy group, or (A3) an acrylic polymer having a primary or secondary hydroxy group and no fluorine atom ,
(B) an acid compound or a salt thereof;
(C) a cross-linking agent selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and/or an alkoxymethyl group;
(D) a polymer additive containing a repeating unit represented by the following formula (a1), a repeating unit represented by the following formula (b) and a repeating unit represented by the following formula (c), and (E) a solvent and 5 to 100 parts by mass of the polymer additive (D) per 100 parts by mass of the component (A).

(Wherein, R A is 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 substituted with a fluorine atom, R C is a hydroxyalkyl group having 1 to 10 carbon atoms, and R D is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.)
wherein in the repeating unit represented by the formula (b), R is a hydroxyalkyl group having 2 to 10 carbon atoms, and the carbon atom to which the hydroxy group is bonded is a secondary or tertiary carbon atom; Item 1. The composition for forming a release layer according to item 1.
In the repeating unit represented by the formula (b), R is a hydroxyalkyl group having 1 to 10 carbon atoms, the carbon atom to which the hydroxy group is bonded is a primary carbon atom, and the formula ( 2. The composition for forming a release layer according to claim 1, wherein the content of the repeating unit represented by a1) is 25 mol % or more of all the repeating units of the polymer additive (D).
The (D) polymer additive 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). 2. The composition for forming a release layer according to claim 1, comprising a repeating unit represented by ).

(wherein R A , R C and R D have the same meanings as above, and R B2 is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. However, 2-methyl-1,1,1,3,3,3-hexafluoroisopropyl group is not included, and R E is a single bond, a polycyclic alkylene group having 6 to 20 carbon atoms, or 6 to 12 carbon atoms. is an arylene group, R F is a single bond or an alkylene group having 1 to 10 carbon atoms, and R G is a methyl group, an ethyl group or a hydroxy group.)
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 the group consisting of hydroxyethyl cellulose, hydroxypropyl cellulose, and derivatives thereof.
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 its main chain.
The release layer-forming according to any one of claims 1 to 4 and 6, wherein the component (A2) is a polyester obtained by reacting a compound having two epoxy moieties and a compound having two carboxy groups. composition.
The composition for forming a release layer according to any one of claims 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. thing.
9. The composition for forming a release layer according to any one of claims 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 its side chain. .
The composition for forming a release layer according to any one of claims 1 to 9, wherein the component (B) is a sulfonic acid compound or a salt thereof.
The composition for forming a release layer according to any one of claims 1 to 10, wherein the (C) crosslinking agent is a compound represented by any one of the following formulas (C-1) to (C-5).

(In the formula, R 11 to R 26 are each independently an alkyl group having 1 to 6 carbon atoms, and R 27 is a hydrogen atom or a methyl group.)
The composition for forming a release layer according to any one of claims 1 to 11, wherein the content of the (C) crosslinking agent is 10 to 100 parts by mass with respect to 100 parts by mass of the component (A).
A release layer obtained from the release layer-forming composition according to any one of claims 1 to 12.
A laminate in which a resin layer having a light transmittance of 80% or more at a wavelength of 400 nm is laminated on the release layer according to claim 13.
a step of applying the composition for forming a release layer according to any one of claims 1 to 12 to a substrate to form a release layer;
Manufacture of a resin substrate, comprising the steps of: 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. Method.