Composition for forming a release layer and release layer

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). (RA is a hydrogen atom or a methyl group, RB1 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, RC is a hydroxyalkyl group having 1-10 carbon atoms, and RD is a polycyclic alkyl group having 6-20 carbon atoms or an aryl group having 6-12 carbon atoms.)

Description

[Technical Field]

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

[0002] In recent years, electronic devices have been required to be not only thin and lightweight, but also flexible. Therefore, there is a demand for lightweight, flexible plastic substrates to replace conventional glass substrates, which are heavy, fragile, and inflexible.

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

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

[0005] Generally, flexible touchscreen panels are produced by creating a release (adhesive) layer on a support substrate such as a glass substrate, and then fabricating the device on top of it and peeling it off, in order to ensure stable production and peeling (Patent Document 8). This release layer must not be peeled off from the support substrate during the process, but a low peeling force is required when peeling it off. Furthermore, in order to improve productivity, the release layer needs to be stored for a long period of time in film form after film formation. For this reason, stability after film formation is required for the release layer.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Summary of the Invention

Problems to be Solved by the Invention

[0007] The present invention has been made in view of the above circumstances, and an object thereof is to provide a composition for forming a release layer that has high heat resistance and appropriate peelability and can provide a release layer excellent in stability after film formation. ]>

Means for Solving the Problems

[0008] [[ID=?6]] As a result of diligent research to achieve the above objective, the present inventors have found that a composition for forming a release layer comprising (A) (A1) cellulose or a derivative thereof having a hydroxyalkyl group, (A2) polyester having a hydroxyl group, or (A3) an acrylic polymer having a primary or secondary hydroxyl group, (B) an acid compound or a salt thereof, (C) a crosslinking agent selected from a compound having a nitrogen atom substituted with a hydroxyalkyl group and / or an alkoxymethyl group, (D) a polymer additive containing a predetermined repeating unit, and (E) a solvent can reproducibly provide a release layer having high heat resistance, excellent adhesion to the substrate, appropriate adhesion to the resin substrate, and appropriate release properties, and have completed the present invention.

[0009] In other words, the present invention is 1. (A)(A1) Cellulose or derivative thereof having a hydroxyalkyl group, (A2) Polyester having a hydroxyl group, or (A3) Acrylic polymer having a primary or secondary hydroxyl group and not having a fluorine atom. (B) Acid compounds or salts thereof, (C) A crosslinking agent selected from compounds having nitrogen atoms substituted with hydroxyalkyl groups and / or alkoxymethyl groups, (D) Polymer additives containing repeating units represented by the following formula (a1), repeating units represented by the following formula (b), and repeating units represented by the following formula (c), and A composition for forming a release layer, comprising (E) a solvent and (D) a polymer additive in an amount of 5 to 100 parts by mass per 100 parts by mass of component (A), [ka] (In the formula, R A Each is independently either a hydrogen atom or a methyl group, and R B1 R is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, C R is a hydroxyalkyl group having 1 to 10 carbon atoms. D (These are polycyclic alkyl groups with 6 to 20 carbon atoms or aryl groups with 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. A composition for forming a release layer 3. In the repeating unit represented by the formula (b), R C 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 content ratio of the repeating unit represented by the formula (a1) is 25 mol% or more in all the repeating units of the (D) polymer additive. A composition for forming a release layer 4. The (D) polymer additive contains 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). A composition for forming a release layer

Chemical formula

[0010] By using the release layer forming composition of the present invention, a release layer with high heat resistance, excellent adhesion to the substrate, appropriate adhesion to the resin substrate, and appropriate release properties can be reproducibly obtained. Furthermore, in the manufacturing process of flexible electronic devices, it becomes possible to separate the resin substrate from the substrate together with the circuits, etc., without damaging the resin substrate formed on the substrate or the circuits, etc., provided thereon. Therefore, the release layer forming composition of the present invention can contribute to speeding up the manufacturing process of flexible electronic devices equipped with a resin substrate and improving its yield. [Modes for carrying out the invention]

[0011] [Composition for forming a release layer] The release layer forming composition of the present invention comprises (A) (A1) cellulose or a derivative thereof having a hydroxyalkyl group, (A2) polyester having a hydroxyl group, or (A3) an acrylic polymer having a primary or secondary hydroxyl group and not having a fluorine atom, (B) an acid compound or a salt thereof, (C) a crosslinking agent selected from a compound having a nitrogen atom substituted with a hydroxyalkyl group and / or an alkoxymethyl group, (D) a polymer additive containing a predetermined repeating unit, and (E) a solvent.

[0012] [(A)(A1) Cellulose or derivative thereof having a hydroxyalkyl group, (A2) Polyester having a hydroxyl group, or (A3) Acrylic polymer having a primary or secondary hydroxyl group and not having a fluorine atom] [(A1) Cellulose or its derivatives] (A1) Component is cellulose or a derivative thereof having a hydroxyalkyl group.

[0013] (A1) Examples of components include hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose, hydroxyalkylalkylcelluloses such as hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, and hydroxyethylethylcellulose, and derivatives thereof. In the present invention, among these, hydroxyalkylcelluloses and their derivatives are preferred, and hydroxyethylcellulose and hydroxypropylcellulose, and their derivatives are more preferred. (A1) Cellulose having a hydroxyalkyl group or its derivative may be used alone or in combination of two or more.

[0014] 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 even more preferably 5,000 to 300,000. The weight-average molecular weight is measured in polystyrene equivalent by gel permeation chromatography (GPC) (the same applies hereafter).

[0015] [(A2) Polyester containing a hydroxyl group] The polyester having a hydroxyl group in component (A2) is not particularly limited, but in the present invention, it is preferable to have an aromatic group or an alicyclic group in the main chain.

[0016] As such a (A2) component polyester, a polyester obtained by reacting a compound having two epoxy moieties with a compound having two carboxyl groups is preferred.

[0017] The weight-average molecular weight (Mw) of the polyester component (A2) is not particularly limited, but is preferably 1,000 to 200,000, more preferably 3,000 to 100,000, and even more preferably 5,000 to 50,000.

[0018] <Epoxy compounds> Examples of compounds having two of the aforementioned epoxy moieties include: Bisphenol diglycidyl ethers such as bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD ​​diglycidyl ether, bisphenol S diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyl diglycidyl ether, tetramethylbiphenyl diglycidyl ether, 9,9'-bis(4-hydroxyphenyl)flourangorange glycidyl ether, 9,9'-bis(4-hydroxyphenyl)flourangorange glycidyl ether, and 9,9'-bis(6-hydroxy-2-naphthyl)flourangorange glycidyl ether; Aliphatic diol diglycidyl ethers such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and neopentyl glycol diglycidyl ether; Alicyclic diol diglycidyl ethers such as cyclohexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, dicyclopentadienediol diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol B diglycidyl ether, and hydrogenated bisphenol S diglycidyl ether; Diglycidyl esters of aromatic dicarboxylic acids such as diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate; Diglycidyl esters of alicyclic dicarboxylic acids such as bisglycidyl oxalate, bisglycidyl adipicate, bisglycidyl pimelate, and bisglycidyl 2-ethyl-3-propyl-1,5-pentanedioate; Resins having epoxy groups at both ends, such as 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 Chemical Co., Ltd., trade name), fluorene type epoxy resin Ogusol CG-500 (manufactured by Osaka Gas Chemical Co., Ltd., trade name), and cyclohexyl type epoxy resin CEL2021P (manufactured by Daicel Corporation, trade name); Alicyclic dioxides such as vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, tetrahydroindene dioxide, Epocalic (registered trademark of ENEOS Corporation) THI-DE, Epocalic (registered trademark of ENEOS Corporation) DE-102, Epocalic (registered trademark of ENEOS Corporation) DE-103; Examples include compounds having two 3,4-epoxycyclohexyl groups, such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2,2-bis(3,4-epoxycyclohexyl)propane, bis(3,4-epoxycyclohexylmethyl) oxalate, bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis(3,4-epoxycyclohexylmethyl) pimerate, and bis(3,4-epoxycyclohexylmethyl) 2-ethyl-3-propyl-1,5-pentanedioate. These compounds may be used individually or in combination of two or more.

[0019] <Carboxylic group-containing compounds> Compounds having two carboxyl groups include terephthalic acid, isophthalic acid, diphenic acid, 2-methylterephthalic acid, 2-hydroxyterephthalic acid, 2,5-dimethylterephthalic acid, 5-methylisophthalic acid, 5-hydroxyisophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. These compounds may be used individually or in combination of two or more.

[0020] The method for obtaining polyester, which is an example of component (A2), is not particularly limited, but for example, it can be obtained by a polymerization reaction at a temperature of 50 to 150°C in a solvent containing the ester compound, carboxyl group-containing compound, and catalyst described above. The solvent used in this case is not particularly limited as long as it dissolves each compound and polymerization initiator.

[0021] The polyester of component (A2) obtained by the above method is usually in the form of a solution dissolved in a solvent.

[0022] (A2) The polyester component is preferably one having a structural unit represented by the following formula [A2-1].

[0023] [ka] (In the formula, X and Y each independently represent a structure having an aromatic group or an alicyclic group.)

[0024] The X is preferably a group represented by the following formula (X-1).

[0025] [ka]

[0026] In the formula, L 1 X represents an ether bond or an ester bond. 1R represents an alkylene group, a cyclic unsaturated hydrocarbon group, or a cyclic saturated hydrocarbon group having 1 to 10 carbon atoms. 1 The symbol represents a single bond, an ether bond, a carbonyl group, a sulfonyl group, a saturated hydrocarbon group with 1 to 30 carbon atoms, an unsaturated hydrocarbon group with 2 to 30 carbon atoms, or a saturated hydrocarbon group with 1 to 30 carbon atoms substituted with a fluorine atom, and p represents 0, 1, or 2.

[0027] The aforementioned X 1 Preferably, the carbon atoms are cyclic unsaturated hydrocarbon groups having 4 to 16 carbon atoms or cyclic saturated hydrocarbon groups having 4 to 16 carbon atoms, and more preferably, cyclic unsaturated hydrocarbon groups having 4 to 8 carbon atoms or cyclic saturated hydrocarbon groups having 4 to 8 carbon atoms. Also, X 1 Any hydrogen atom contained in may be independently substituted with an aliphatic group, and multiple substituents among these aliphatic groups may bond to each other to form a 4-6 membered ring.

[0028] Specific examples of X include, but are not limited to, the groups represented by the following formulas (X-2) to (X-13).

[0029] [ka] (In the formula, * represents a bond.)

[0030] As X, a structure derived from a resin having epoxy groups at both ends is also preferred.

[0031] The aforementioned Y may include, but is not limited to, the groups represented by the following formulas (Y-1) to (Y-4).

[0032] [ka] (In the formula, * represents a bond.)

[0033] (A2) The polyester component may also have a structural unit represented by the following formula [A2-2].

[0034] [ka]

[0035] In the formula, Cy represents a group derived from the alicyclic dioxide, that is, a tetravalent organic group containing an aliphatic ring, in which all four bonding groups to OH and O originate from the aliphatic ring, and Y represents the same definition as Y in formula [A2-1].

[0036] Specific examples of Cy in equation [A2-2] include the groups represented by the following equations (Cy-1) to (Cy-4).

[0037] [ka] (In the formula, *1 and *2 represent bond sites, and one of the two *1 and *2 sites in each structural formula is bonded to a hydroxyl group.)

[0038] (A2) The polyester component may also have a structural unit represented by the following formula [A2-3].

[0039] [ka]

[0040] In the formula, X and Y have the same definitions as X and Y in formula [A2-1].

[0041] Specific examples of X in equation [A2-3] include the group represented by the following equations (X-Ch-1) to (X-Ch-3).

[0042] [ka] (In the formula, * represents a bond.)

[0043] [(A3) Acrylic Polymer] (A3) The acrylic polymer having a primary or secondary hydroxyl group and no fluorine atom is not particularly limited, but in the present invention, it is preferable to have a polyethylene glycol ester group or a primary or secondary hydroxyalkyl ester group having 2 to 6 carbon atoms, and it is more preferable to have these groups in the side chain. As acrylic polymers, homopolymers of acrylic acid esters, homopolymers of methacrylic acid esters, copolymers thereof, and copolymers thereof with monomers having unsaturated double bonds such as styrene can be used. A preferred example of the acrylic polymer of component (A3) is an acrylic polymer having a polyethylene glycol ester group or a primary or secondary hydroxyalkyl ester group having 2 to 6 carbon atoms. Any acrylic polymer having either of these groups is acceptable, and there are no particular limitations on the backbone (other structural units) of the main chain and the type of side chains of the polymer constituting the acrylic polymer.

[0044] A preferred structural unit having a polyethylene glycol ester group or a primary or secondary hydroxyalkyl ester group having 2 to 6 carbon atoms is one represented by the following formula [A3-1].

[0045] [ka]

[0046] In the above formula [A3-1], R A Each is independently either a hydrogen atom or a methyl group, Y 1 H-(OCH2CH2) n - Represents a group (where n is an integer from 2 to 30, preferably from 2 to 10), or a primary or secondary hydroxyalkyl group having 2 to 6 carbon atoms.

[0047] The weight-average molecular weight (Mw) of the acrylic polymer component (A3) is not particularly limited, but is preferably 1,000 to 200,000, more preferably 3,000 to 100,000, and even more preferably 5,000 to 50,000.

[0048] The acrylic polymer of component (A3) 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. Examples of monomers having a polyethylene glycol ester group include H-(OCH2CH2) n Examples include monoacrylates or monomethacrylates of -OH (where n has the same meaning as above). On the other hand, examples of monomers having a primary or secondary hydroxyalkyl group with 2 to 6 carbon atoms include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, glycerin monoacrylate, and glycerin monomethacrylate.

[0049] Furthermore, in this embodiment, when synthesizing the acrylic polymer of component (A3), monomers other than those described above, specifically monomers that do not have polyethylene glycol ester groups or primary or secondary hydroxyl groups and do not have fluorine atoms, can be used in combination, as long as the effects of the present invention are not impaired. Examples of such monomers include acrylic acid ester compounds such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, and t-butyl acrylate; methacrylic acid ester compounds such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate; maleimide compounds such as maleimide, N-methyl maleimide, N-phenyl maleimide, and N-cyclohexyl maleimide; acrylamide compounds; acrylonitrile; maleic anhydride; styrene compounds and vinyl compounds, etc.

[0050] The method for producing the acrylic polymer of component (A3) is not particularly limited, but one example is to carry out a polymerization reaction at a temperature of 50 to 110°C in a solution in which the above-mentioned monomer, other monomers, and polymerization initiator are dissolved in a solvent. The solvent used is not particularly limited as long as it can dissolve the monomer and polymerization initiator.

[0051] (A3) Examples of acrylic polymers of component (A3) include polymers obtained by polymerizing primary or secondary hydroxyalkyl ester monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, glycerin monoacrylate, and glycerin monomethacrylate, or acrylic polymers having primary or secondary hydroxyalkyl groups in their side chains, such as polymers obtained by copolymerizing the primary or secondary hydroxyalkyl ester monomer with one or more monomers selected from the group consisting of monomers other than these monomers, for example, monomers that do not have primary or secondary hydroxyl groups.

[0052] The acrylic polymer of component (A3) obtained by the above method is usually in the form of a solution dissolved in a solvent.

[0053] [(B) Acid compounds or salts thereof] The release layer forming composition of the present invention contains an acid compound or a salt thereof as component (B). Specific examples of acid compounds include sulfonic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate, salicylic acid, camphorsulfonic acid, sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, and pyridinium-1-naphthalenesulfonic acid; and carboxylic acid compounds such as salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, and hydroxybenzoic acid. Furthermore, examples of salts of acid compounds include pyridinium salts, isopropanolamine salts, and N-methylmorpholine salts of the aforementioned acids. Specifically, examples include pyridinium p-toluenesulfonate, pyridinium 1-naphthalenesulfonate, isopropanolamine p-toluenesulfonate, and N-methylmorpholine p-toluenesulfonate.

[0054] The content of component (B) is preferably 0.01 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass, per 100 parts by mass of component (A). When the content of component (B) is within this range, a composition can be obtained that provides a release layer with high heat resistance, moderate release properties, and excellent stability after film formation. Furthermore, (B) the acid compound or its salt may be used alone or in combination of two or more types.

[0055] [(C) Crosslinking agent] The release layer forming composition of the present invention comprises a crosslinking agent selected as component (C) from compounds having nitrogen atoms substituted with hydroxyalkyl groups and / or alkoxymethyl groups. The crosslinking agent is preferably a compound represented by any of the following formulas (C-1) to (C-5).

[0056] [ka]

[0057] In each of the above formulas, R 11 ~R 26 Each of these is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, but an alkyl group having 1 to 6 carbon atoms is preferred. 27 This is either a hydrogen atom or a methyl group.

[0058] Specific examples of crosslinking agents include nitrogen-containing compounds such as hexamethylolmelamine, tetramethylolbenzoguanamine, 1,3,4,6-tetramethylol glycoluryl, hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluryl, 1,3,4,6-tetrakis(butoxymethyl)glycoluryl, and 1,3,4,6-tetrakis(hydroxymethyl)glycoluryl.

[0059] Furthermore, the present invention can also utilize commercially available crosslinking agents. Specific examples include nitrogen-containing compounds such as methoxymethyl type melamine compounds (product names Cymel® 300, Cymel 301, Cymel 303, Cymel 350) manufactured by Ornex Corporation, butoxymethyl type melamine compounds (product names Mycoat® 506, Mycoat 508), glycoluryl compounds (product names Cymel 1170, POWDERLINK 1174), methylated urea resin (product name UFR65), butylated urea resin (product names UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea / formaldehyde resins manufactured by DIC Corporation (product names Beccamine® J-300S, Beccamine P-955, Beccamine N).

[0060] Furthermore, polymers produced using (meth)acrylamide compounds substituted with hydroxymethyl or alkoxymethyl groups, such as N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, and N-butoxymethyl(meth)acrylamide, can also be used as crosslinking agents. Specific examples of such polymers include poly(N-butoxymethyl(meth)acrylamide), copolymers of N-butoxymethyl(meth)acrylamide and styrene, copolymers of N-hydroxymethyl(meth)acrylamide and methyl(meth)acrylate, copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, and copolymers of N-butoxymethyl(meth)acrylamide, benzyl(meth)acrylate and 2-hydroxypropyl(meth)acrylate.

[0061] Among these crosslinking agents, it is preferable to use hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluryl (POWDERLINK 1174), 1,3,4,6-tetrakis(butoxymethyl)glycoluryl, or 1,3,4,6-tetrakis(hydroxymethyl)glycoluryl.

[0062] Furthermore, the aforementioned crosslinking agent can undergo a crosslinking reaction by self-condensation, and can also undergo a crosslinking reaction with the hydroxyl groups in the acrylic polymer of component (A). These crosslinking reactions result in a stronger release layer and reduced solubility in organic solvents.

[0063] The content of component (C) is preferably 10 to 100 parts by mass, and more preferably 20 to 50 parts by mass, per 100 parts by mass of component (A). When the content of component (C) is within this range, a composition can be obtained that provides a release layer with high heat resistance, moderate release properties, and excellent stability after film formation. Furthermore, (C) crosslinking agents may be used individually or in combination of two or more types.

[0064] [(D) Polymer additives] The release layer forming composition of the present invention includes a polymer additive as component (D) that comprises 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).

[0065] [ka]

[0066] In each of the above formulas, R A Each is independently either a hydrogen atom or a methyl group, and R B1 R is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, C R is a hydroxyalkyl group having 1 to 10 carbon atoms. D This is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.

[0067] R B1 Specific examples of branched alkyl groups having 3 or 4 carbon atoms include isopropyl, isobutyl, sec-butyl, and tert-butyl groups. R B1 These are groups in which at least one hydrogen atom of these branched alkyl groups is substituted with a fluorine atom. Specific examples include 1,1,1-trifluoroisopropyl, 1,1,1,3,3,3-hexafluoroisopropyl, and nonafluorotert-butyl groups.

[0068] R CSpecific examples of hydroxyalkyl groups with 1 to 10 carbon atoms include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 7-hydroxyheptyl, 8-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 2-hydroxy-1-methylethyl, 2-hydroxy-1,1-dimethylethyl, 3-hydroxy-1-methylpropyl, 3-hydroxy-2-methylpropyl, 3-hydroxy-1,1-dimethylpropyl, 3-hydroxy-1,2-dimethylpropyl, 3-hydroxy-2,2-dimethylpropyl, 4-hydroxy-1-methylbutyl, 4-hydroxy-2- Examples include hydroxyalkyl groups having 1 to 10 carbon atoms, such as methylbutyl and 4-hydroxy-3-methylbutyl, where the carbon atom to which the hydroxyl group is bonded is a primary carbon atom; and hydroxyalkyl groups having 2 to 10 carbon atoms, such as 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 1-hydroxyhexyl, 2-hydroxyhexyl, 1-hydroxyoctyl, 2-hydroxyoctyl, 1-hydroxydecyl, 2-hydroxydecyl, 1-hydroxy-1-methylethyl, and 2-hydroxy-2-methylpropyl, where the carbon atom to which the hydroxyl group is bonded is a secondary or tertiary carbon atom.

[0069] R D Specific examples of polycyclic alkyl groups having 6 to 20 carbon atoms include 1-adamantyl, 2-adamantyl, isobornyl, norbornyl groups, while specific examples of aryl groups having 6 to 12 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-biphenylyl, and 2-biphenylyl groups.

[0070] Furthermore, the polymer additive (D) may include repeating units represented by the following formula (a2), repeating units represented by the following formula (b), repeating units represented by the following formula (c), and repeating units represented by the following formula (d).

[0071] [ka] (In the formula, R A , R C and R D (This expresses the same meaning as above.)

[0072] R B2 This is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom (excluding the 2-methyl-1,1,1,3,3,3-hexafluoroisopropyl group), and examples of this fluorine-containing alkyl group are the same as those exemplified above. R E R is a single bond, a polycyclic alkylene group having 6 to 20 carbon atoms, or an arylene group having 6 to 12 carbon atoms. F R is a single bond or an alkylene group having 1 to 10 carbon atoms. G This is a methyl group, an ethyl group, or a hydroxyl group.

[0073] R E Examples of polycyclic alkylene groups having 6 to 20 carbon atoms include those obtained by removing one hydrogen atom from the aforementioned specific examples of polycyclic alkyl groups having 6 to 20 carbon atoms, such as adamantylene, isobornylene, and norbornylene groups. R E Examples of arylene groups having 6 to 12 carbon atoms include those obtained by removing one hydrogen atom from the aforementioned specific examples of aryl groups having 6 to 12 carbon atoms, such as phenylene, naphthylene, and biphenylene groups.

[0074] R F Specific examples of alkylene groups having 1 to 10 carbon atoms include methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene groups. Among these, alkylene groups having 1 to 5 carbon atoms are preferred, methylene groups and ethylene groups are more preferred, and methylene groups are even more preferred.

[0075] The repeating units represented by formula (a1) or (a2) include, but are not limited to, those represented by the following formulas (a-1) to (a-3). Note that in the following formulas, R A This expresses the same meaning as above (and so on).

[0076] [ka]

[0077] Examples of repeating units represented by equation (b) include, but are not limited to, those represented by equations (b-1) to (b-16) below.

[0078] [ka]

[0079] Examples of repeating units represented by formula (c) include, but are not limited to, those represented by formulas (c-1) to (c-13) below.

[0080] [ka]

[0081] Examples of repeating units represented by equation (d) include, but are not limited to, those represented by equations (d-1) to (d-8) below.

[0082] [ka]

[0083] In the present invention, (D) polymer additive comprises a repeating unit represented by formula (a1), a repeating unit represented by formula (b), and a repeating unit represented by formula (c), wherein the carbon atom to which the hydroxyl group is bonded in the hydroxyalkyl group in the repeating unit represented by formula (b) is a secondary or tertiary carbon atom (hereinafter, such polymer additive is referred to as polymer additive D1). In this case, the content of the repeating unit represented by 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 formula (b) is preferably 10 to 35 mol%, more preferably 15 to 30 mol%, of the total repeating units; and the content of the repeating unit represented by formula (c) is preferably 5 to 60 mol%, more preferably 20 to 50 mol%, of the total repeating units.

[0084] On the other hand, if the polymer additive (D) contains repeating units represented by formula (a1), repeating units represented by formula (b), and repeating units represented by formula (c), and the carbon atom to which the hydroxyl 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 will be referred to as polymer additive D2), then 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 still more preferably 35 to 50 mol%, of the total repeating units; the content of the repeating unit represented by formula (b) is preferably 8 to 38 mol%, more preferably 10 to 38 mol%, even more preferably 10 to 35 mol%, and still more preferably 15 to 30 mol%, of the total repeating units; and the content of the repeating unit represented by formula (c) is preferably 2 to 77 mol%, more preferably 2 to 65 mol%, even more preferably 5 to 60 mol%, and still more preferably 20 to 50 mol%.

[0085] (D) When the polymer additive contains repeating units represented by formula (a2), formula (b), formula (c), and formula (d) (hereinafter referred to as polymer additive D3), the content of the repeating unit represented by formula (a2) is preferably 2 to 45 mol%, more preferably 5 to 35 mol%, of the total repeating units; the content of the repeating unit represented by formula (b) is preferably 20 to 35 mol%, more preferably 25 to 35 mol%, of the total repeating units; the content of the repeating unit represented by formula (c) is preferably 30 to 45 mol%, more preferably 35 to 45 mol%, of the total repeating units; and the content of the repeating unit represented by formula (d) is preferably 5 to 18 mol%, more preferably 5 to 15 mol%, of the total repeating units.

[0086] (D) The weight-average molecular weight (Mw) of the polymer additive is preferably 2,000 to 10,000, and more preferably 3,000 to 6,000. Furthermore, the Mw / Mn ratio is preferably 1.0 to 2.1, and more preferably 1.0 to 1.9 (where Mn is the number-average molecular weight).

[0087] The content of the polymer additive in component (D) is 5 to 100 parts by mass per 100 parts by mass of component (A). If the content of the polymer additive is less than 5 parts by mass, the peeling force may increase, and if it exceeds 100 parts by mass, repulsion may occur during film formation.

[0088] In particular, when (D) polymer additive is polymer additive D1, its content is preferably 10 to 100 parts by mass, more preferably 20 to 100 parts by mass, and even more preferably 30 to 100 parts by mass, per 100 parts by mass of component (A). Furthermore, if the polymer additive (D) is something other than polymer additive D1, its content is preferably 5 to 80 parts by mass, and more preferably 5 to 50 parts by mass, per 100 parts by mass of component (A). Furthermore, (D) polymer additives may be used individually or in combination of two or more types.

[0089] [(E) Solvent] The release layer forming composition of the present invention contains a solvent as component (E). Preferred solvents include glycol ether solvents having 3 to 20 carbon atoms, ester solvents having 3 to 20 carbon atoms, ketone solvents having 3 to 20 carbon atoms, and amide solvents having 3 to 20 carbon atoms.

[0090] 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-based 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. Examples of amide solvents include N-methylpyrrolidone, N,N-dimethylacetamide, and 3-methoxy-N,N-dimethylpropanamide.

[0091] (E) The solvent content is not particularly limited, but it is preferably such that the solid content concentration in the release layer forming composition of the present invention is 0.1 to 40% by mass, more preferably 0.5 to 20% by mass, and even more preferably 0.5 to 10% by mass. The solid content refers to all components of the release layer forming composition other than the solvent, and the amount of solid content is the total amount of these components. Furthermore, (E) solvent may be used alone or as a mixture of two or more types.

[0092] [Other additives] The release layer forming composition of the present invention may optionally contain a surfactant. By adding a surfactant, the coatability of the release layer forming composition on the substrate can be improved. As the surfactant, known surfactants such as nonionic surfactants, fluorinated surfactants, and silicone surfactants can be used.

[0093] 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 alkylaryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate.

[0094] Specific examples of fluorine-based surfactants include F-Top® EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac® F171, F173, F554, F559, F563, R-30, R-40, R-40-LM, DS-21 (manufactured by DIC Corporation), FLUORAD® FC430, FC431 (manufactured by 3M Company), Asahiguard® AG710, Surflon® S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Inc.), and others. Specific examples of silicone-based surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0095] If the release layer forming composition of the present invention contains a surfactant, its content is preferably 0.0001 to 1 part by mass, and more preferably 0.001 to 0.5 parts by mass, per 100 parts by mass of component (A). Furthermore, surfactants may be used individually or in combination of two or more types.

[0096] [Preparation of composition for forming a release layer] The method for preparing the release layer-forming composition of the present invention is not particularly limited, and for example, one method is to mix components (B), (C), (D), and (E) in predetermined proportions into a solution of component (A) dissolved in a solvent to obtain a homogeneous solution. The solvent used to dissolve component (A) may be the same solvent as that used for component (E) or a different solvent. Furthermore, if other additives are used, they can be added and mixed at any stage of composition preparation.

[0097] In preparing the release layer-forming composition of the present invention, the solution of the polymer obtained by the polymerization reaction in the solvent may be used as is. For example, component (B), and further components (C), (D), (E), etc., can be added to the polymerization reaction solution used to produce component (A) to obtain a homogeneous solution. In this case, a solvent may be added to adjust the concentration, and this solvent may be the same as the solvent used to produce component (A) or a different solvent.

[0098] Furthermore, it is preferable to filter the prepared release layer-forming composition solution using a filter with a pore size of approximately 0.2 μm before use.

[0099] The viscosity of the release layer forming composition of the present invention is set appropriately considering the thickness of the release layer to be produced, etc., but when the aim is to obtain a film with a thickness of about 0.01 to 5 μm with good reproducibility, a viscosity of about 1 to 5,000 mPa·s at 25°C is preferred, and a viscosity of about 1 to 2,000 mPa·s is more preferred. The viscosity in this invention can be measured using a commercially available viscometer for measuring the viscosity of liquids, for example, by referring to the procedure described in JIS K7117-2, under conditions where the composition is at a temperature of 25°C. Preferably, a cone-plate type rotational viscometer is used, and it is also preferable to use a standard cone rotor of 1°34'×R24 with the same type of viscometer, and to measure under conditions where the composition is at a temperature of 25°C. An example of such a rotational viscometer is the TVE-25L manufactured by Toki Sangyo Co., Ltd.

[0100] [Exfoliation layer] By applying the release layer-forming composition of the present invention onto a substrate and then firing it at 180 to 250°C, a release layer having excellent adhesion to the substrate and appropriate adhesion and release properties to the resin substrate can be obtained. In this case, the heating time during firing cannot be specified in general terms as it varies depending on the heating temperature, but it is usually between 1 minute and 5 hours. Furthermore, the firing temperature may include a process at a temperature lower than the above range, as long as the maximum temperature remains within that range.

[0101] A preferred example of the heating method in the present invention is to heat at 50-150°C for 1 minute to 1 hour, and then continue to increase the heating temperature to 180-250°C for 5 minutes to 4 hours. A particularly preferred example of the heating method is to heat at 50-150°C for 1 minute to 1 hour, and then heat at 200-250°C for 5 minutes to 2 hours. Furthermore, another example of a more preferred heating method is to heat at 50-150°C for 1 to 30 minutes, and then heat at 200-250°C for 5 minutes to 1 hour.

[0102] When forming the release layer of the present invention on a substrate, the release layer may be formed on a part of the substrate's surface or on the entire surface. Examples of forming the release layer on a part of the substrate's surface include forming the release layer only in a predetermined area of ​​the substrate's surface, and forming the release layer in a pattern such as a dot pattern or a line-and-space pattern on the entire substrate surface. In this invention, "substrate" refers to a material on which the release layer-forming composition of the present invention is applied, and which is used in the manufacture of flexible electronic devices and the like.

[0103] Examples of substrates include glass, metal (such as silicon wafers), and slate, but glass is particularly preferred because the release layer obtained from the release layer forming composition of the present invention has sufficient adhesion to it. The substrate surface may be composed of a single material or of two or more materials. Examples of the substrate surface being composed of two or more materials include a configuration in which a certain area of ​​the substrate surface is composed of one material and the remaining surface is composed of other materials, and a configuration in which a patterned material such as a dot pattern or a line and space pattern is present in the other materials across the entire substrate surface.

[0104] The method for applying the release layer-forming composition is not particularly limited, but examples include cast coating, spin coating, blade coating, dip coating, roll coating, bar coating, die coating, inkjet, and printing methods (relief printing, intaglio printing, planographic printing, screen printing, etc.).

[0105] Examples of heating equipment include hot plates and ovens. The heating atmosphere may be in the presence of air or an inert gas, and may be under normal pressure or reduced pressure.

[0106] The thickness of the release layer is usually about 0.01 to 50 μm, but from the viewpoint of productivity, it is preferably about 0.01 to 20 μm, more preferably about 0.01 to 5 μm, and the desired thickness is achieved by adjusting the thickness of the coating film before heating.

[0107] The release layer of the present invention has excellent adhesion to a substrate, particularly a glass substrate, as well as appropriate adhesion and release properties to a resin substrate. For this reason, the release layer of the present invention can be suitably used in the manufacturing process of flexible electronic devices to release the resin substrate from the substrate, along with circuits and other elements formed on the resin substrate, without damaging the resin substrate of the device.

[0108] [Method for manufacturing resin substrates] An example of a method for manufacturing a flexible electronic device using the release layer of the present invention will be described. First, a release layer is formed on a glass substrate using the release layer forming composition of the present invention by the method described above. A resin substrate forming solution for forming a resin substrate is applied onto this release layer, and the resulting coating is fired to form a resin substrate fixed to the glass substrate via the release layer of the present invention.

[0109] The firing temperature of the coating film is set appropriately according to the type of resin, etc., but in the present invention, it is preferable to set the maximum firing temperature to 200 to 250°C, more preferably to 210 to 250°C, and even more preferably to 220 to 240°C. By setting the maximum firing temperature during resin substrate production within this range, the adhesion between the release layer (which is the base material) and the substrate, as well as the appropriate adhesion and release properties between the release layer and the resin substrate, can be further improved. In this case as well, as long as the maximum temperature falls within the above range, a firing step at a lower temperature may be included.

[0110] It is preferable that the resin substrate be formed with an area larger than the area of ​​the release layer, so as to completely cover the release layer. Examples of resin substrates include those made of acrylic polymer and those made of cycloolefin polymer, with a light transmittance of 80% or more at a wavelength of 400 nm being preferred. The method for forming the resin substrate can be the standard method.

[0111] Next, a desired circuit is formed on the resin substrate fixed to the substrate via the release layer of the present invention, and then, for example, the resin substrate is cut along the release layer, and the resin substrate is peeled off from the release layer together with the circuit, thereby separating the resin substrate from the substrate. At this time, a part of the substrate may be cut together with the release layer. Using the release layer of the present invention, a resin substrate can be peeled from the release layer with a peeling force of 0.25 N / 25 mm or less. In particular, when (D) polymer additive is polymer additive D2 or polymer additive D3, the resin substrate can be peeled from the release layer with a peeling force of 0.15 N / 25 mm or less. Furthermore, when (D) polymer additive is polymer additive D1, the resin substrate can be peeled from the release layer with a peeling force of 0.1 N / 25 mm or less. [Examples]

[0112] 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.

[0113] (I)(A1) Composition for forming a release layer comprising cellulose or a derivative thereof having a hydroxyalkyl group The compounds used in the following example are as follows: PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate HPC-SSL: Hydroxypropylcellulose, Mw 40,000 HPC-SL: Hydroxypropylcellulose, Mw 100,000 HPC-L: Hydroxypropylcellulose, 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) glycoluryl (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

[0114] Furthermore, the weight-average molecular weight (Mw) of the polymer was measured using a GPC instrument manufactured by Shimadzu Corporation (columns: Shodex® KF803L and KF804L (manufactured by Showa Denko K.K.); eluent: THF; flow rate: 1.0 mL / min; column temperature: 40°C; Mw: value equivalent to standard polystyrene).

[0115] [1] Polymer synthesis [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 0.1 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (S1) solution (solid content concentration 20% by mass). The composition ratio of each unit was HFiPMA:HPMA:ADMA = 30:30:40. GPC analysis revealed that the obtained acrylic polymer (S1) had a Mw of 5,310 and an Mw / Mn ratio of 1.8.

[0116] [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 3.4 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (S2) solution (solid content concentration 20% by mass). The composition ratio of each unit was HFiPMA:HPMA:ADMA = 40:20:40. GPC analysis revealed that the obtained acrylic polymer (S2) had a Mw of 5,500 and an Mw / Mn ratio of 1.8.

[0117] [2] Preparation of compositions for forming resin substrates [Preparation Example 1] Preparation of resin substrate forming composition F1 10 g of Zeonor® 1020R (cycloolefin polymer manufactured by Nippon Zeon Co., Ltd.) and 3 g of Epolid® GT401 (manufactured by Daicel Corporation) were added to a round-bottom flask containing 100 g of carbon tetrachloride. This solution was stirred under a nitrogen atmosphere for 24 hours to dissolve and prepare resin substrate formation composition F1.

[0118] [3] Preparation of composition for forming a release layer [Example 1-1] Preparation of composition 1 for forming a release layer Composition 1-1 for forming a release layer was prepared by adding 0.32 g of PL-LI, 0.05 g of PPTS, 0.84 g of acrylic polymer (S1) solution, and PGMEA to 1.00 g of HPC-SSL, and diluting with PGME to a solid content concentration of 5% by mass and a PGMEA concentration of 30% by mass.

[0119] [Examples 1-2] Preparation of Composition 2 for Forming a Release Layer Composition 1-2 for forming the release layer was prepared in the same manner as in Example 1-1, except that PL-LI was changed to 0.50 g.

[0120] [Examples 1-3] Preparation of Composition 3 for Forming a Peeling Layer Composition 1-3 for forming the release layer was prepared in the same manner as in Example 1-1, except that PL-LI was changed to 0.25 g.

[0121] [Examples 1-4] Preparation of release layer forming composition 4 Composition 1-4 for forming the release layer was prepared in the same manner as in Example 1-1, except that HPC-SL was used instead of HPC-SSL.

[0122] [Examples 1-5] Preparation of release layer forming composition 5 Composition 1-5 for forming the release layer was prepared in the same manner as in Example 1-1, except that HPC-L was used instead of HPC-SSL.

[0123] [Examples 1-6] Preparation of release layer forming composition 6 Composition 1-6 for forming a release layer was prepared in the same manner as in Example 1-1, except that the acrylic polymer (S1) solution was changed to 0.50 g.

[0124] [Examples 1-7] Preparation of release layer forming composition 7 Composition 1-7 for forming a release layer was prepared in the same manner as in Example 1-1, except that the acrylic polymer (S1) solution was changed to 0.38 g.

[0125] [Examples 1-8] Preparation of release layer forming composition 8 Composition 1-8 for forming a release layer was prepared in the same manner as in Example 1-1, except that an acrylic polymer (S2) solution was used instead of an acrylic polymer (S1) solution.

[0126] [Comparative Example 1-1] Preparation of Composition 9 for Forming a Release Layer Composition 1-9 for forming the release layer was prepared in the same manner as in Example 1-1, except that CAB was used instead of HPC-SSL.

[0127] [Comparative Example 1-2] Preparation of Composition 10 for Forming a Peeling Layer Composition 1-10 for forming the release layer was prepared in the same manner as in Example 1-1, except that CAP was used instead of HPC-SSL.

[0128] [4] Fabrication of the release layer and resin substrate [Example 2-1] Composition 1-1 for forming the release layer was applied to a glass substrate (100 mm × 100 mm, hereafter the same) using a spin coater (conditions: rotation speed 1,000 rpm for approximately 30 seconds). The resulting coating was heated on a hot plate at 100°C for 2 minutes, and then heated on a hot plate at 230°C for 10 minutes to form a release layer approximately 0.1 μm thick on the glass substrate, obtaining a glass substrate with a release layer. Subsequently, the resin substrate forming composition F1 was immediately applied to the release layer (resin thin film) on the glass substrate using a spin coater (conditions: rotation speed 200 rpm for approximately 15 seconds). The resulting coating was heated on a hot plate at 80°C for 2 minutes, and then heated on a hot plate at 230°C for 30 minutes to form a resin substrate with a thickness of approximately 3 μm on the release layer, obtaining a glass substrate with a resin substrate and release layer. After that, the light transmittance was measured using a UV-Vis spectrophotometer (Shimadzu Corporation UV-2600), and the resin substrate showed a transmittance of 90% or more at 400 nm.

[0129] [Example 2-2] Except for using release layer forming composition 1-2 instead of release layer forming composition 1-1, a release layer and a resin substrate were prepared in the same manner as in Example 2-1, and a glass substrate with a release layer and a resin substrate / glass substrate with a release layer were obtained.

[0130] [Examples 2-3] Except for using release layer forming composition 1-3 instead of release layer forming composition 1-1, a release layer and a resin substrate were prepared in the same manner as in Example 2-1, and a glass substrate with a release layer and a resin substrate / glass substrate with a release layer were obtained.

[0131] [Examples 2-4] Except for using release layer forming composition 1-4 instead of release layer forming composition 1-1, a release layer and a resin substrate were prepared in the same manner as in Example 2-1, and a glass substrate with a release layer and a resin substrate / glass substrate with a release layer were obtained.

[0132] [Examples 2-5] Except for using release layer forming composition 1-5 instead of release layer forming composition 1-1, a release layer and a resin substrate were prepared in the same manner as in Example 2-1, and a glass substrate with a release layer and a resin substrate / glass substrate with a release layer were obtained.

[0133] [Examples 2-6] Except for using release layer forming composition 1-6 instead of release layer forming composition 1-1, a release layer and a resin substrate were prepared in the same manner as in Example 2-1, and a glass substrate with a release layer and a resin substrate / glass substrate with a release layer were obtained.

[0134] [Examples 2-7] Except for using release layer forming composition 1-7 instead of release layer forming composition 1-1, a release layer and a resin substrate were prepared in the same manner as in Example 2-1 to obtain a glass substrate with a release layer and a resin substrate / glass substrate with a release layer.

[0135] [Examples 2-8] Except for using release layer forming composition 1-8 instead of release layer forming composition 1-1, a release layer and a resin substrate were prepared in the same manner as in Example 2-1 to obtain a glass substrate with a release layer and a resin substrate / glass substrate with a release layer.

[0136] [Comparative Example 2-1] Except for using release layer forming composition 1-9 instead of release layer forming composition 1-1, a release layer and a resin substrate were prepared in the same manner as in Example 2-1 to obtain a glass substrate with a release layer and a resin substrate / glass substrate with a release layer.

[0137] [Comparative Example 2-2] Except for using release layer forming composition 1-10 instead of release layer forming composition 1-1, a release layer and a resin substrate were prepared in the same manner as in Example 2-1, and a glass substrate with a release layer and a resin substrate / glass substrate with a release layer were obtained.

[0138] [5] Evaluation of peelability The peelability of the glass substrates with release layers and the resin substrates with release layers obtained in Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-2 was confirmed by the following method. The following tests were performed on the same glass substrate.

[0139] (1) Evaluation of the peelability between the release layer and the glass substrate The release layer on the glass substrate with the release layer obtained in Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-2 was cross-cut (at 2 mm intervals vertically and horizontally, the same applies hereafter) to form 25 grids. That is, this cross-cutting created 25 grids of 2 mm squares. Adhesive tape was applied to the 25 Muscat grape section, and the tape was removed. The degree of peeling was evaluated based on the following criteria. The results are shown in Table 1. <Judgment criteria> 5B: 0% peeling (no peeling) 4B: Less than 5% peeling 3B: Peeling of 5% to less than 15% 2B: Peeling of 15% to less than 35% 1B: Peeling of 35% to less than 65% 0B: Peeling of 65% to less than 80% B: Peeling of 80% to less than 95% A: Peeling of 95% or more but less than 100% AA: 100% peeling (complete peeling)

[0140] (2) Evaluation of peeling force between the release layer and the resin substrate Strips measuring 25 mm x 50 mm were prepared from the resin substrates and glass substrates with release layers obtained in Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-2. Furthermore, after applying cellophane tape (registered trademark) (CT-24, manufactured by Nichiban Co., Ltd.), the strips were peeled using an Autograph AGS-X500N (manufactured by Shimadzu Corporation) at a peeling angle of 90° and a peeling speed of 300 mm / min, and the peeling force was measured. Strips that could not be peeled were classified as unpeeled. The results are shown in Table 1.

[0141] [Table 1]

[0142] As shown in Table 1, the release layer of the example demonstrated excellent adhesion to the glass substrate and was easily peeled away from the resin film. On the other hand, the release layers of Comparative Examples 2-1 to 2-2 demonstrated excellent adhesion to the glass substrate, but were difficult to peel away from the resin substrate.

[0143] (II)(A2) Composition for forming a release layer containing a polyester having a hydroxyl group The compounds used in the following example are as follows: PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate PL-LI: 1,3,4,6-tetrakis(methoxyethyl) glycoluryl (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 EP1: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name: jER828) EP2: Terephthalate-type epoxy resin (manufactured by Nagase ChemteX Co., Ltd., product name: Denacol EX711) EP3: Biphenyl-type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name: YX4000H) EP4: Fluorene-type epoxy resin (manufactured by Osaka Gas Chemical Co., Ltd., product name: Ogusol PG-100) EP5: Fluorene-type epoxy resin (manufactured by Osaka Gas Chemical Co., Ltd., product name: Ogusol CG-500) EP6: Cyclohexyl epoxy resin (manufactured by Daicel Corporation, product name: CEL2021P) TPhA: Terephthalic acid IPhA: Isophthalic acid 5HIPhA: 5-hydroxyisophthalic acid 14CHA:1,4-Cyclohexyldicarboxylic acid BTEAC: Benzyltriethylammonium chloride ETPPB: Ethyltriphenylphosphonium bromide

[0144] Furthermore, the weight-average molecular weight (Mw) of the polymer was measured using the same method as described in (I) above.

[0145] [1] Polymer synthesis [Synthesis Example 2-1] Synthesis of Polyester (A2-1) 10.0 g of EP1, 5.4 g of TPhA, and 0.25 g of BTEAC were dissolved in 36.4 g of PGME and reacted at 120°C for 20 hours to obtain a polyester (A2-1) solution (solid content concentration 30% by mass). GPC analysis revealed that the obtained polyester (A2-1) had a Mw of 13,200 and an Mw / Mn ratio of 3.9.

[0146] [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 6.0 g of PGME and reacted at 120°C for 20 hours to obtain a polyester (A2-2) solution (solid content concentration 30% by mass). GPC analysis revealed that the obtained polyester (A2-2) had a Mw of 21,000 and an Mw / Mn ratio of 3.2.

[0147] [Synthesis Example 2-3] Synthesis of Polyester (A2-3) 10.0 g of EP1, 5.4 g of IPhA, and 0.25 g of BTEAC were dissolved in 36.4 g of PGME and reacted at 120°C for 20 hours to obtain a polyester (A2-3) solution (solid content concentration 30% by mass). GPC analysis revealed that the obtained polyester (A2-3) had a Mw of 6,600 and an Mw / Mn ratio of 2.1.

[0148] [Synthesis Example 2-4] Synthesis of Polyester (A2-4) 10.0 g of EP2, 6.8 g of IPhA, and 0.31 g of BTEAC were dissolved in 39.9 g of PGME and reacted at 120°C for 20 hours to obtain a polyester (A2-4) solution (solid content concentration 30% by mass). GPC analysis revealed that the obtained polyester (A2-4) had a Mw of 5,400 and an Mw / Mn ratio of 4.1.

[0149] [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 6.0 g of PGME and reacted at 120°C for 20 hours to obtain a polyester (A2-5) solution (solid content concentration 30% by mass). GPC analysis revealed that the obtained polyester (A2-5) had a Mw of 5,400 and an Mw / Mn ratio of 3.3.

[0150] [Synthesis Example 2-6] Synthesis of Polyester (A2-6) 10.0 g of EP4, 4.0 g of IPhA, and 0.18 g of BTEAC were dissolved in 56.5 g of PGME and reacted at 120°C for 20 hours to obtain a polyester (A2-6) solution (solid content concentration 20% by mass). GPC analysis revealed that the obtained polyester (A2-6) had a Mw of 8,100 and an Mw / Mn ratio of 3.3.

[0151] [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 4.2 g of PGME5 and reacted at 120°C for 20 hours to obtain a polyester (A2-7) solution (solid content concentration 20% by mass). GPC analysis revealed that the obtained polyester (A2-7) had a Mw of 6,600 and an Mw / Mn ratio of 2.0.

[0152] [Synthesis Example 2-8] Synthesis of Polyester (A2-8) 10.0 g of EP4, 4.3 g of 5HIPhA, and 0.18 g of BTEAC were dissolved in 58.1 g of PGME and reacted at 120°C for 20 hours to obtain a polyester (A2-8) solution (solid content concentration 20% by mass). GPC analysis revealed that the obtained polyester (A2-8) had a Mw of 6,200 and an Mw / Mn ratio of 2.4.

[0153] [Synthesis Example 2-9] Synthesis of Polyester (A2-9) 10.0 g of EP5, 3.7 g of 5HIPhA, and 0.15 g of BTEAC were dissolved in 5.5 g of PGME and reacted at 120°C for 20 hours to obtain a polyester (A2-9) solution (solid content concentration 20% by mass). GPC analysis revealed that the obtained polyester (A2-9) had a Mw of 7,600 and an Mw / Mn ratio of 2.2.

[0154] [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 4 g of PGME and reacted at 120°C for 20 hours to obtain a polyester (A2-10) solution (solid content concentration 20% by mass). GPC analysis revealed that the obtained polyester (A2-10) had a Mw of 9,200 and an Mw / Mn ratio of 2.1.

[0155] [Synthesis Example 2-11] Synthesis of Polyester (A2-11) 10.0 g of EP6, 6.8 g of 14CHA, and 0.59 g of ETPPB were dissolved in 40.7 g of PGME and reacted at 120°C for 20 hours to obtain a polyester (A2-11) solution (solid content concentration 20% by mass). GPC analysis revealed that the obtained polyester (A2-11) had a Mw of 5,800 and an Mw / Mn ratio of 1.7.

[0156] [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 0.1 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (S1) solution (solid content concentration 20% by mass). The composition ratio of each unit was HFiPMA:HPMA:ADMA = 30:30:40. GPC analysis revealed that the obtained acrylic polymer (S1) had a Mw of 5,310 and an Mw / Mn ratio of 1.8.

[0157] [2] Preparation of compositions for forming resin substrates [Preparation Example 1] Preparation of resin substrate forming composition F1 10 g of Zeonor® 1020R (cycloolefin polymer manufactured by Nippon Zeon Co., Ltd.) and 3 g of Epolid® GT401 (manufactured by Daicel Corporation) were added to a round-bottom flask containing 100 g of carbon tetrachloride. This solution was stirred under a nitrogen atmosphere for 24 hours to dissolve and prepare resin substrate formation composition F1.

[0158] [3] Preparation of composition for forming a release layer [Example 3-1] Preparation of composition 1 for forming a release layer To 1 g of the polyester (A2-1) solution obtained in Synthesis Example 1, 0.06 g of PL-LI, 0.01 g of PPTS, 0.17 g of acrylic polymer (S1) solution, and PGMEA were added, and the mixture was diluted with PGME to a solid content concentration of 5% by mass and a PGMEA concentration of 30% by mass to prepare composition 2-1 for forming the release layer.

[0159] [Example 3-2] Preparation of Composition 2 for Forming a Release Layer Composition 2-2 for forming a release layer was prepared in the same manner as in Example 3-1, except that a polyester (A2-2) solution was used instead of a polyester (A2-1) solution.

[0160] [Example 3-3] Preparation of composition 3 for forming a release layer Composition 2-3 for forming a release layer was prepared in the same manner as in Example 3-1, except that a polyester (A2-3) solution was used instead of a polyester (A2-1) solution.

[0161] [Examples 3-4] Preparation of Composition 4 for Forming a Peeling Layer Composition 2-4 for forming a release layer was prepared in the same manner as in Example 3-1, except that a polyester (A2-4) solution was used instead of a polyester (A2-1) solution.

[0162] [Examples 3-5] Preparation of release layer forming composition 5 Composition 2-5 for forming a release layer was prepared in the same manner as in Example 3-1, except that a polyester (A2-5) solution was used instead of a polyester (A2-1) solution.

[0163] [Examples 3-6] Preparation of release layer forming composition 6 Composition 2-6 for forming a release layer was prepared in the same manner as in Example 3-1, except that a polyester (A2-6) solution was used instead of a polyester (A2-1) solution.

[0164] [Examples 3-7] Preparation of release layer forming composition 7 Composition 2-7 for forming a release layer was prepared in the same manner as in Example 3-1, except that a polyester (A2-7) solution was used instead of a polyester (A2-1) solution.

[0165] [Examples 3-8] Preparation of composition 8 for forming a release layer Composition 2-8 for forming a release layer was prepared in the same manner as in Example 3-1, except that a polyester (A2-8) solution was used instead of a polyester (A2-1) solution.

[0166] [Examples 3-9] Preparation of composition 9 for forming a release layer Composition 2-9 for forming a release layer was prepared in the same manner as in Example 3-1, except that polyester (A2-9) solution was used instead of polyester (A2-1) solution.

[0167] [Examples 3-10] Preparation of composition 10 for forming a release layer Composition 2-10 for forming a release layer was prepared in the same manner as in Example 3-1, except that a polyester (A2-10) solution was used instead of a polyester (A2-1) solution.

[0168] [Example 3-11] Preparation of composition 11 for forming a release layer Composition 2-11 for forming a release layer was prepared in the same manner as in Example 3-1, except that a polyester (A2-11) solution was used instead of a polyester (A2-1) solution.

[0169] [4] Fabrication of the release layer and resin substrate [Example 4-1] Composition 2-1 for forming the release layer was applied to a glass substrate (100 mm × 100 mm, hereafter the same) using a spin coater (conditions: rotation speed 1,000 rpm for approximately 30 seconds). The resulting coating was heated on a hot plate at 100°C for 2 minutes, and then heated on a hot plate at 230°C for 10 minutes to form a release layer approximately 0.1 μm thick on the glass substrate, obtaining a glass substrate with a release layer. Subsequently, the resin substrate forming composition F1 was immediately applied to the release layer (resin thin film) on the glass substrate using a spin coater (conditions: rotation speed 200 rpm for approximately 15 seconds). The resulting coating was heated on a hot plate at 80°C for 2 minutes, and then heated on a hot plate at 230°C for 30 minutes to form a resin substrate with a thickness of approximately 3 μm on the release layer, obtaining a glass substrate with a resin substrate and release layer. After that, the light transmittance was measured using a UV-Vis spectrophotometer (Shimadzu Corporation UV-2600), and the resin substrate showed a transmittance of 90% or more at 400 nm.

[0170] [Example 4-2] Except for using release layer formation composition 2-2 instead of release layer formation composition 2-1, a release layer and a resin substrate were prepared in the same manner as in Example 4-1, and a glass substrate with a release layer and a resin substrate / glass substrate with a release layer were obtained.

[0171] [Example 4-3] Except for using release layer formation composition 2-3 instead of release layer formation composition 2-1, a release layer and a resin substrate were prepared in the same manner as in Example 4-1, and a glass substrate with a release layer and a resin substrate / glass substrate with a release layer were obtained.

[0172] [Example 4-4] Except for using release layer formation composition 2-4 instead of release layer formation composition 2-1, a release layer and a resin substrate were prepared in the same manner as in Example 4-1 to obtain a glass substrate with a release layer and a resin substrate / glass substrate with a release layer.

[0173] [Examples 4-5] Except for using release layer formation composition 2-5 instead of release layer formation composition 2-1, a release layer and a resin substrate were prepared in the same manner as in Example 4-1, and a glass substrate with a release layer and a resin substrate / glass substrate with a release layer were obtained.

[0174] [Examples 4-6] Except for using release layer formation composition 2-6 instead of release layer formation composition 2-1, a release layer and a resin substrate were prepared in the same manner as in Example 4-1, and a glass substrate with a release layer and a resin substrate / glass substrate with a release layer were obtained.

[0175] [Examples 4-7] Except for using release layer formation composition 2-7 instead of release layer formation composition 2-1, a release layer and a resin substrate were prepared in the same manner as in Example 4-1, and a glass substrate with a release layer and a resin substrate / glass substrate with a release layer were obtained.

[0176] [Examples 4-8] Except for using release layer formation composition 2-8 instead of release layer formation composition 2-1, a release layer and a resin substrate were prepared in the same manner as in Example 4-1 to obtain a glass substrate with a release layer and a resin substrate / glass substrate with a release layer.

[0177] [Examples 4-9] Except for using release layer formation composition 2-9 instead of release layer formation composition 2-1, a release layer and a resin substrate were prepared in the same manner as in Example 4-1, and a glass substrate with a release layer and a resin substrate / glass substrate with a release layer were obtained.

[0178] [Examples 4-10] Except for using release layer formation composition 2-10 instead of release layer formation composition 2-1, a release layer and a resin substrate were prepared in the same manner as in Example 4-1 to obtain a glass substrate with a release layer and a resin substrate / glass substrate with a release layer.

[0179] [Examples 4-11] A release layer and a resin substrate were produced in the same manner as in Example 4-1, except that the composition for forming a release layer 2-11 was used instead of the composition for forming a release layer 2-1. A glass substrate with a release layer and a resin substrate / glass substrate with a release layer were obtained.

[0180] [5] Evaluation of peelability With respect to the glass substrates with release layers and the resin substrate / glass substrates with release layers obtained in Examples 4-1 to 4-11, the peelability was confirmed in the same manner as the method described in [4] of (I). The results are shown in Table 2.

[0181]

Table 2

[0182] From the results shown in Table 2, it was confirmed that the release layer of the example was excellent in adhesion to the glass substrate and easily peeled off from the resin film.

[0183] (III) (A3) A composition for forming a release layer containing an acrylic polymer having a primary or secondary hydroxy group and no fluorine atom The compounds used in the following examples are as follows. PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate CHN: Cyclohexanone PL-LI: 1,3,4,6-Tetrakis(methoxyethyl) glycoluril (manufactured by Ornex Co., Ltd., 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

[0184] Furthermore, the weight-average molecular weight (Mw) of the polymer was measured using the same method as described in (I) above.

[0185] [1] Polymer synthesis [Synthesis Example 3-1] Synthesis of Acrylic Polymer (A3-1) 20.0 g of HEMA, 1.26 g of AIBN, and 1.56 g of DDT were dissolved in 92 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (A3-1) solution (solid content concentration 20% by mass). GPC analysis revealed that the obtained acrylic polymer (A3-1) had a Mw of 5,400 and an Mw / Mn ratio of 1.7.

[0186] [Synthesis Example 3-2] Synthesis of Acrylic Polymer (A3-2) 20.0 g of HEMA and 1.26 g of AIBN were dissolved in 85 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (A3-2) solution (solid content concentration 20% by mass). GPC analysis revealed that the obtained acrylic polymer (A3-2) had a Mw of 13,300 and an Mw / Mn ratio of 2.5.

[0187] [Synthesis Example 3-3] Synthesis of Acrylic Polymer (A3-3) 20.0 g of HPMA, 1.14 g of AIBN, and 1.40 g of DDT were dissolved in 90.2 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (A3-3) solution (solid content concentration 20% by mass). GPC analysis revealed that the obtained acrylic polymer (A3-3) had a Mw of 6,300 and an Mw / Mn ratio of 1.5.

[0188] [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 content concentration 20% by mass). GPC analysis revealed that the obtained acrylic polymer (A3-4) had a Mw of 13,000 and an Mw / Mn ratio of 2.5.

[0189] [Synthesis Example 3-5] Synthesis of Acrylic Polymer (A3-5) 20.0 g of 4HBA, 1.14 g of AIBN, and 1.40 g of DDT were dissolved in 90.2 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (A3-5) solution (solid content concentration 20% by mass). GPC analysis revealed that the obtained acrylic polymer (A3-5) had a Mw of 4,200 and an Mw / Mn ratio of 1.3.

[0190] [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 3.4 g of PGME10 and reacted at 70°C for 20 hours to obtain an acrylic polymer (A3-6) solution (solid content concentration 20% by mass). The composition ratio of each unit was MMA:HEMA = 50:50. GPC analysis revealed that the obtained acrylic polymer (A3-6) had a Mw of 6,600 and an Mw / Mn ratio of 1.9.

[0191] [Synthesis Example 3-7] Synthesis of Acrylic Polymer (A3-7) 10.0 g of MMA, 14.3 g of HPMA, 1.64 g of AIBN, and 1.21 g of DDT were dissolved in 9.0 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (A3-7) solution (solid content concentration 20% by mass). The composition ratio of each unit was MMA:HPMA = 50:50. GPC analysis revealed that the obtained acrylic polymer (A3-7) had a Mw of 6,400 and an Mw / Mn ratio of 2.3.

[0192] [Synthesis Example 3-8] Synthesis of Acrylic Polymer (A3-8) 15.0 g of MMA, 8.36 g of HEMA, 1.74 g of AIBN and 1.30 g of DDT were dissolved in 105.7 g of PGME and reacted at 70 °C for 20 hours to obtain an acrylic polymer (A3-8) solution (solid content concentration: 20% by mass). The composition ratio of each unit was MMA:HEMA = 70:30. As a result of GPC analysis, the Mw of the obtained acrylic polymer (A3-8) was 5,500 and the Mw / Mn was 2.0.

[0193] [Synthesis Example 3-9] Synthesis of Acrylic Polymer (A3-9) 15.0 g of MMA, 9.26 g of HPMA, 1.74 g of AIBN and 1.30 g of DDT were dissolved in 109.3 g of PGME and reacted at 70 °C for 20 hours to obtain an acrylic polymer (A3-9) solution (solid content concentration: 20% by mass). The composition ratio of each unit was MMA:HPMA = 70:30. As a result of GPC analysis, the Mw of the obtained acrylic polymer (A3-9) was 6,000 and the Mw / Mn was 2.0.

[0194] [Synthesis Example 3-10] Synthesis of Acrylic Polymer (A3-10) 20.0 g of HADM, 0.69 g of AIBN and 0.86 g of DDT were dissolved in 86.2 g of PGME and reacted at 70 °C for 20 hours to obtain an acrylic polymer (A3-10) solution (solid content concentration: 20% by mass). As a result of GPC analysis, the Mw of the obtained acrylic polymer (A3-10) was 5,100 and the Mw / Mn was 1.5.

[0195] [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 obtain an acrylic polymer (A11) solution (solid content concentration: 20% by mass). The composition ratio of each unit was MMA:HADM = 70:30. As a result of GPC analysis, the Mw of the obtained acrylic polymer (A3-11) was 6,600 and the Mw / Mn was 1.6.

[0196] [Synthesis Example 3-12] Synthesis of Acrylic Polymer (A3-12) 10.0 g of MMA, 0.82 g of AIBN, and 0.61 g of DDT were dissolved in 45.7 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (A3-12) solution (solid content concentration 20% by mass). GPC analysis revealed that the obtained acrylic polymer (A3-12) had a Mw of 5,200 and an Mw / Mn ratio of 1.7.

[0197] [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 0.1 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (S1) solution (solid content concentration 20% by mass). The composition ratio of each unit was HFiPMA:HPMA:ADMA = 30:30:40. GPC analysis revealed that the obtained acrylic polymer (S1) had a Mw of 5,310 and an Mw / Mn ratio of 1.8.

[0198] [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 3.4 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (S2) solution (solid content concentration 20% by mass). The composition ratio of each unit was HFiPMA:HPMA:ADMA = 40:20:40. GPC analysis revealed that the obtained acrylic polymer (S2) had a Mw of 5,500 and an Mw / Mn ratio of 1.8.

[0199] [2] Preparation of compositions for forming resin substrates [Preparation Example 1] Preparation of resin substrate forming composition F1 10 g of Zeonor® 1020R (cycloolefin polymer manufactured by Nippon Zeon Co., Ltd.) and 3 g of Epolid® GT401 (manufactured by Daicel Corporation) were added to a round-bottom flask containing 100 g of carbon tetrachloride. This solution was stirred under a nitrogen atmosphere for 24 hours to dissolve and prepare resin substrate formation composition F1.

[0200] [3] Preparation of composition for forming a release layer [Example 5-1] Preparation of composition 1 for forming a release layer To 1 g of the acrylic polymer (A3-1) solution obtained in Synthesis Example 1, 0.06 g of PL-LI, 0.01 g of PPTS, 0.08 g of acrylic polymer (S1) solution, and PGMEA were added, and the mixture was diluted with PGME to a solid content concentration of 5% by mass and a PGMEA concentration of 30% by mass to prepare composition 3-1 for forming the release layer.

[0201] [Example 5-2] Preparation of release layer forming composition 2 Composition 3-2 for forming a release layer was prepared in the same manner as in Example 5-1, except that an acrylic polymer (A3-2) solution was used instead of an acrylic polymer (A3-1) solution.

[0202] [Example 5-3] Preparation of Composition 3 for Forming a Release Layer Composition 3-3 for forming a release layer was prepared in the same manner as in Example 5-1, except that an acrylic polymer (A3-3) solution was used instead of an acrylic polymer (A3-1) solution.

[0203] [Example 5-4] Preparation of release layer forming composition 4 Composition 3-4 for forming a release layer was prepared in the same manner as in Example 5-1, except that an acrylic polymer (A3-4) solution was used instead of an acrylic polymer (A3-1) solution.

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

[0205] [Examples 5-6] Preparation of release layer forming composition 6 Composition 3-6 for forming a release layer was prepared in the same manner as in Example 5-1, except that an acrylic polymer (A3-6) solution was used instead of an acrylic polymer (A3-1) solution.

[0206] [Examples 5-7] Preparation of release layer forming composition 7 Composition 3-7 for forming a release layer was prepared in the same manner as in Example 5-1, except that acrylic polymer (A3-6) solution was used instead of acrylic polymer (A3-1) solution, and acrylic polymer (S1) was changed to 0.17 g.

[0207] [Examples 5-8] Preparation of release layer forming composition 8 Composition 3-8 for forming a release layer was prepared in the same manner as in Example 5-1, except that an acrylic polymer (A3-7) solution was used instead of an acrylic polymer (A3-1) solution.

[0208] [Examples 5-9] Preparation of release layer forming composition 9 Composition 3-9 for forming a release layer was prepared in the same manner as in Example 1-1, except that acrylic polymer (A3-7) solution was used instead of acrylic polymer (A3-1) solution, and acrylic polymer (S1) was changed to 0.17 g.

[0209] [Examples 5-10] Preparation of release layer forming composition 10 Composition 3-10 for forming a release layer was prepared in the same manner as in Example 5-1, except that acrylic polymer (A3-7) solution was used instead of acrylic polymer (A3-1) solution, and acrylic polymer (S2) solution was used instead of acrylic polymer (S1) solution.

[0210] [Examples 5-11] Preparation of release layer forming composition 11 Composition 3-11 for forming a release layer was prepared in the same manner as in Example 5-1, except that an acrylic polymer (A3-8) solution was used instead of an acrylic polymer (A3-1) solution.

[0211] [Examples 5-12] Preparation of release layer forming composition 12 Composition 3-12 for forming a release layer was prepared in the same manner as in Example 5-1, except that an acrylic polymer (A3-9) solution was used instead of an acrylic polymer (A3-1) solution.

[0212] [Comparative Example 3-1] Preparation of Composition 13 for Forming a Peeling Layer Composition 3-13 for forming a release layer was prepared in the same manner as in Example 5-1, except that an acrylic polymer (A3-10) solution was used instead of an acrylic polymer (A3-1) solution and the solvent was changed to CHN.

[0213] [Comparative Example 3-2] Preparation of Composition 14 for Forming a Peeling Layer Composition 3-14 for forming a release layer was prepared in the same manner as in Example 5-1, except that an acrylic polymer (A3-11) solution was used instead of an acrylic polymer (A3-1) solution.

[0214] [Comparative Example 3-3] Preparation of Composition 15 for Forming a Peeling Layer Composition 3-15 for forming a release layer was prepared in the same manner as in Example 5-1, except that an acrylic polymer (A3-12) solution was used instead of an acrylic polymer (A3-1) solution.

[0215] [4] Fabrication of the release layer and resin substrate [Example 6-1] Composition 3-1 for forming the release layer was applied to a glass substrate (100 mm × 100 mm, hereafter the same) using a spin coater (conditions: rotation speed 1,000 rpm for approximately 30 seconds). The resulting coating was heated on a hot plate at 100°C for 2 minutes, and then heated on a hot plate at 230°C for 10 minutes to form a release layer approximately 0.1 μm thick on the glass substrate, obtaining a glass substrate with a release layer. Subsequently, the resin substrate forming composition F1 was immediately applied to the release layer (resin thin film) on the formed glass substrate using a spin coater (conditions: rotation speed 200 rpm for approximately 15 seconds). The resulting coating was heated on a hot plate at 80°C for 2 minutes, and then heated on a hot plate at 230°C for 30 minutes to form a resin substrate with a thickness of approximately 3 μm on the release layer, obtaining a glass substrate with a resin substrate and release layer. After that, the light transmittance was measured using a UV-Vis spectrophotometer (Shimadzu Corporation UV-2600), and the resin substrate showed a transmittance of 90% or more at 400 nm.

[0216] [Example 6-2] Except for using release layer-forming composition 3-2 instead of release layer-forming composition 3-1, a release layer and a resin substrate were prepared in the same manner as in Example 6-1 to obtain a glass substrate with a release layer and a resin substrate / glass substrate with a release layer.

[0217] [Example 6-3] Except for using release layer-forming composition 3-3 instead of release layer-forming composition 3-1, a release layer and a resin substrate were prepared in the same manner as in Example 6-1, and a glass substrate with a release layer and a resin substrate / glass substrate with a release layer were obtained.

[0218] [Example 6-4] Except for using release layer formation composition 3-4 instead of release layer formation composition 3-1, a release layer and a resin substrate were prepared in the same manner as in Example 6-1, and a glass substrate with a release layer and a resin substrate / glass substrate with a release layer were obtained.

[0219] [Examples 6-5] Except for using release layer forming composition 3-5 instead of release layer forming composition 3-1, a release layer and a resin substrate were prepared in the same manner as in Example 6-1 to obtain a glass substrate with a release layer and a resin substrate / glass substrate with a release layer.

[0220] [Example 6-6] Except for using release layer-forming composition 3-6 instead of release layer-forming composition 3-1, a release layer and a resin substrate were prepared in the same manner as in Example 6-1 to obtain a glass substrate with a release layer and a resin substrate / glass substrate with a release layer.

[0221] [Examples 6-7] Except for using release layer formation composition 3-7 instead of release layer formation composition 3-1, a release layer and a resin substrate were prepared in the same manner as in Example 6-1 to obtain a glass substrate with a release layer and a resin substrate / glass substrate with a release layer.

[0222] [Examples 6-8] Except for using release layer formation composition 3-8 instead of release layer formation composition 3-1, a release layer and a resin substrate were prepared in the same manner as in Example 6-1 to obtain a glass substrate with a release layer and a resin substrate / glass substrate with a release layer.

[0223] [Examples 6-9] Except for using release layer-forming composition 3-9 instead of release layer-forming composition 3-1, a release layer and a resin substrate were prepared in the same manner as in Example 6-1 to obtain a glass substrate with a release layer and a resin substrate / glass substrate with a release layer.

[0224] [Examples 6-10] Except for using release layer-forming composition 3-10 instead of release layer-forming composition 3-1, a release layer and a resin substrate were prepared in the same manner as in Example 6-1 to obtain a glass substrate with a release layer and a resin substrate / glass substrate with a release layer.

[0225] [Examples 6-11] Except for using release layer-forming composition 3-11 instead of release layer-forming composition 3-1, a release layer and a resin substrate were prepared in the same manner as in Example 6-1 to obtain a glass substrate with a release layer and a resin substrate / glass substrate with a release layer.

[0226] [Examples 6-12] Except for using release layer-forming composition 3-12 instead of release layer-forming composition 3-1, a release layer and a resin substrate were prepared in the same manner as in Example 6-1 to obtain a glass substrate with a release layer and a resin substrate / glass substrate with a release layer.

[0227] [Comparative Example 4-1] Except for using release layer-forming composition 3-13 instead of release layer-forming composition 3-1, a release layer and a resin substrate were prepared in the same manner as in Example 6-1 to obtain a glass substrate with a release layer and a resin substrate / glass substrate with a release layer.

[0228] [Comparative Example 4-2] Except for using release layer-forming composition 3-14 instead of release layer-forming composition 3-1, a release layer and a resin substrate were prepared in the same manner as in Example 6-1 to obtain a glass substrate with a release layer and a resin substrate / glass substrate with a release layer.

[0229] [Comparative Example 4-3] Except for using release layer forming composition 3-15 instead of release layer forming composition 3-1, a release layer and a resin substrate were prepared in the same manner as in Example 6-1 to obtain a glass substrate with a release layer and a resin substrate / glass substrate with a release layer.

[0230] [5] Evaluation of peelability The peelability of the glass substrates with release layers and the resin substrates with release layers obtained in Examples 6-1 to 6-12 and Comparative Examples 4-1 to 4-3 was confirmed using the same method as described in [4] of (I) above. The results are shown in Table 3.

[0231] [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. Then, they were heated on a hot plate at 100°C for 2 minutes and dried. The film thickness before and after PGME immersion was measured, and the residual film percentage was calculated using the following formula. The degree of curing was evaluated based on the following criteria. The results are shown in Table 3. <Remaining film rate calculation formula> {(Film thickness after immersion) / (Film thickness before immersion)} × 100 <Judgment criteria> ◎: Residual film percentage ≥ 95% ○: Residual film rate 70-94% △: Residual film rate 50-69% ×: Residual film percentage < 50%

[0232] [Table 3]

[0233] As shown in Table 3, the release layer of the example demonstrated excellent adhesion to the glass substrate and was easily peeled away from the resin film. On the other hand, the release layers of Comparative Examples 4-1 to 4-3 demonstrated excellent adhesion to the glass substrate, but were difficult to peel away from the resin substrate.

Claims

1. (A) (A1) Cellulose or derivative thereof having a hydroxyalkyl group, or (A3) Acrylic polymer having a primary or secondary hydroxyl group and not having a fluorine atom, (B) Acid compounds or salts thereof (C) A crosslinking agent selected from compounds having nitrogen atoms substituted with hydroxyalkyl groups and / or alkoxymethyl groups, (D) Polymer additives comprising a repeating unit represented by the following formula (a1), a repeating unit represented by the following formula (b), and a repeating unit represented by the following formula (c), and (E) Solvent Includes, The aforementioned component (B) is a sulfonic acid compound or a salt thereof, and is present in an amount of 0.01 to 15 parts by mass per 100 parts by mass of component (A). The aforementioned component (C) is present in an amount of 10 to 100 parts by mass per 100 parts by mass of component (A), A composition for forming a release layer, wherein the polymer additive (D) is contained in an amount of 5 to 100 parts by mass per 100 parts by mass of component (A). 【Chemistry 1】 (In the formula, R A Each is independently either a hydrogen atom or a methyl group, and 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, and R C R is a hydroxyalkyl group having 1 to 10 carbon atoms. D (This refers to a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.)

2. (A2) Polyester having a structural unit represented by the following formula [A2-1], a structural unit represented by the following formula [A2-2], or a structural unit represented by the following formula [A2-3] (B) Acid compounds or salts thereof (C) A crosslinking agent selected from compounds having nitrogen atoms substituted with hydroxyalkyl groups and / or alkoxymethyl groups, (D) Polymer additives comprising a repeating unit represented by the following formula (a1), a repeating unit represented by the following formula (b), and a repeating unit represented by the following formula (c), and (E) Solvent Includes, The aforementioned component (B) is a sulfonic acid compound or a salt thereof, and is present in an amount of 0.01 to 15 parts by mass per 100 parts by mass of component (A). The aforementioned component (C) is present in an amount of 10 to 100 parts by mass per 100 parts by mass of component (A), A composition for forming a release layer, wherein the polymer additive (D) is contained in an amount of 5 to 100 parts by mass per 100 parts by mass of component (A). 【Chemistry 2】 (In the formula, X represents the group X represented by the following formula (X-1), and Y represents a structure having an aromatic group or an alicyclic group.) 【Transformation 3】 (In the formula, L 1 X represents an ether bond or an ester bond. 1 R represents an alkylene group, a cyclic unsaturated hydrocarbon group, or a cyclic saturated hydrocarbon group having 1 to 10 carbon atoms. 1 (where p represents a single bond, ether bond, carbonyl, sulfonyl, saturated hydrocarbon group with 1 to 30 carbon atoms, unsaturated hydrocarbon group with 2 to 30 carbon atoms, or saturated hydrocarbon group with 1 to 30 carbon atoms substituted with a fluorine atom, and p represents 0, 1, or 2.) 【Chemistry 4】 (In the formula, Cy is a tetravalent organic group containing an aliphatic ring, in which two OH groups and two O atoms are bonded to the aliphatic ring, and Y has the same definition as Y in formula [A2-1].) 【Transformation 5】 (In the formula, X and Y have the same definitions as X and Y in formula [A2-1].) 【Transformation 6】 (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, R D is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.)

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

4. In the repeating unit represented by formula (b) above, R C The release layer forming composition according to claim 1 or 2, wherein the hydroxyalkyl group has 1 to 10 carbon atoms, the carbon atom to which the hydroxyl group is bonded is a primary carbon atom, and the content of the repeating unit represented by formula (a1) is 25 mol% or more of the total repeating units of the polymer additive (D).

5. The release layer forming composition according to claim 1 or 2, wherein 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). 【Transformation 7】 (In the formula, R A , R C and R D This has the same meaning as above, R B2 This is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom, but does not contain a 2-methyl-1,1,1,3,3,3-hexafluoroisopropyl group, R E R is a single bond, a polycyclic alkylene group having 6 to 20 carbon atoms, or an arylene group having 6 to 12 carbon atoms. F R is a single bond or an alkylene group having 1 to 10 carbon atoms. G (These are methyl, ethyl, or hydroxyl groups.)

6. The release layer forming composition according to claim 1, wherein the (A1) component is at least one selected from the group consisting of hydroxyethylcellulose, hydroxypropylcellulose, and derivatives thereof.

7. The release layer forming composition according to claim 2, wherein the (A2) component is a polyester obtained by reacting a compound having two epoxy moieties with a compound having two carboxyl groups.

8. The release layer forming composition according to claim 1, wherein the (A3) component is a polyethylene glycol ester group or an acrylic polymer having a primary or secondary hydroxyalkyl ester group having 2 to 6 carbon atoms.

9. The release layer forming composition according to claim 1, wherein the (A3) component is an acrylic polymer having a primary or secondary hydroxyalkyl group having 2 to 6 carbon atoms in its side chain.

10. The release layer forming composition according to any one of claims 1 to 9, wherein the (C) crosslinking agent is a compound represented by any one of the following formulas (C-1) to (C-5). 【Transformation 8】 (In the formula, R 11 ~R 26 Each of these is an alkyl group having 1 to 6 carbon atoms, and R 27 (This is either a hydrogen atom or a methyl group.)

11. The composition for forming a peeling layer according to any one of claims 1 to 10, wherein the content of the crosslinking agent (C) is 10 to 100 parts by mass per 100 parts by mass of component (A).

12. A release layer obtained from the release layer forming composition according to any one of claims 1 to 11.

13. A laminate comprising a release layer according to claim 12, wherein a resin layer having a light transmittance of 80% or more at a wavelength of 400 nm is laminated on the release layer.

14. A step of applying the release layer forming composition according to any one of claims 1 to 11 to a substrate to form a release layer, A step of forming a resin substrate on the peel layer having a light transmittance of 80% or more at a wavelength of 400 nm, and The process of peeling the resin substrate with a peeling force of 0.25 N / 25 mm or less. A method for manufacturing a resin substrate containing [the specified material].

Images