JP7831473B2 - Composition for forming a release layer and release layer - Google Patents

Description

This invention relates to a composition for forming a release layer and a release layer.

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.

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 support 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 bendable transparent conductive polymers like PEDOT, metal nanowires, and mixtures thereof, in addition to the conventionally used ITO (Patent Documents 1-4).

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).

Generally, flexible touchscreen panels are produced by creating a release (adhesive) layer on a support substrate such as a glass substrate, and then fabricating a 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 the support substrate during the process, but a low peeling force is required when peeling it off. Furthermore, to improve productivity, the release layer needs to be stored for a long period in film form after deposition. Therefore, the release layer needs to be stable after deposition.

International Publication No. 2012/147235 Japanese Patent Publication No. 2009-283410 Special Publication No. 2010-507199 Japanese Patent Publication No. 2009-205924 International Publication No. 2017/002664 International Publication No. 2016/160338 Japanese Patent Publication No. 2015-166145 Japanese Patent Publication No. 2016-531358

The present invention has been made in view of the above circumstances, and aims to provide a release layer forming composition that can provide a release layer having high heat resistance and appropriate release properties, and excellent stability after film formation.

The present inventors, after diligent research to achieve the above objective, 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 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.

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,
A composition for forming a release layer, comprising (D) a polymer additive containing repeating units represented by the following formula (a1), repeating units represented by the following formula (b), and repeating units represented by the following formula (c), and (E) a solvent, wherein the polymer additive (D) is present in an amount of 5 to 100 parts by mass per 100 parts by mass of component (A),
(In the formula, ^RA is independently a hydrogen atom or a methyl group, ^RB1 is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, ^RC is a hydroxyalkyl group having 1 to 10 carbon atoms, and ^RD is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.)
2. A release layer forming composition wherein, in the repeating unit represented by formula (b), R ^C is a hydroxyalkyl group having 2 to 10 carbon atoms, and the carbon atom to which the hydroxyl group is bonded is a secondary or tertiary carbon atom.
3. A release layer forming composition wherein, in the repeating unit represented by formula (b), R ^C is a hydroxyalkyl group having 1 to 10 carbon atoms, the carbon atom to which the hydroxyl group is bonded is a primary carbon atom, and the content of the repeating unit represented by formula (a1) is 25 mol% or more of the total repeating units of the polymer additive (D),
4. The (D) polymer additive comprises one release layer forming composition comprising 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).
(In the formula, R ^A , R ^C , and R ^D have the same meanings as described above; R ^B2 is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, but does not contain a 2-methyl-1,1,1,3,3,3-hexafluoroisopropyl group; R ^E is a single bond, a polycyclic alkylene group having 6 to 20 carbon atoms, or an arylene group having 6 to 12 carbon atoms; R ^F is a single bond or an alkylene group having 1 to 10 carbon atoms; and R ^G is a methyl group, an ethyl group, or a hydroxyl group.)
5. One of the 1 to 4 release layer forming compositions wherein the (A1) component is at least one selected from the group consisting of hydroxyethylcellulose, hydroxypropylcellulose, and derivatives thereof.
6. The release layer forming composition according to any one of claims 1 to 4, wherein the (A2) component is a polyester having an aromatic group or an alicyclic group in its main chain.
7. The release layer forming composition according to any one of 1 to 4 and 6, wherein the component (A2) is a polyester obtained by reacting a compound having two epoxy moieties with a compound having two carboxyl groups.
8. A release layer forming composition according to any one of 1 to 4, wherein the (A3) component is an acrylic polymer having a polyethylene glycol ester group or a primary or secondary hydroxyalkyl ester group having 2 to 6 carbon atoms.
9. A release layer forming composition of any one of 1 to 4 and 8, 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. A release layer forming composition according to any one of 1 to 9, wherein component (B) is a sulfonic acid compound or a salt thereof.
11. A release layer forming composition 1 to 10 in which the (C) crosslinking agent is a compound represented by any of the following formulas (C-1) to (C-5),
(In the formula, ^R11 to ^R26 are each independently alkyl groups having 1 to 6 carbon atoms, and ^R27 is a hydrogen atom or a methyl group.)
12. Any of the 1 to 11 release layer forming compositions, wherein the content of the crosslinking agent (C) is 10 to 100 parts by mass per 100 parts by mass of component (A),
13. A release layer obtained from any of the release layer forming compositions from 1 to 12,
14. A laminate in which a resin layer having a light transmittance of 80% or more at a wavelength of 400 nm is laminated on the release layer of 13.
15. A method for manufacturing a resin substrate is provided, comprising the steps of: applying one of the release layer forming compositions from 1 to 12 to a substrate to form a release layer; forming a resin substrate on the release layer having a light transmittance of 80% or more at a wavelength of 400 nm; and peeling off the resin substrate with a peeling force of 0.25 N/25 mm or less.

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 the yield.

[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.

[(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.

(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.

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 hereinafter).

[(A2) Polyesters containing hydroxyl groups]
(A2) The polyester having a hydroxyl group is not particularly limited, but in the present invention, it is preferable that it has an aromatic group or an alicyclic group in its main chain.

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.

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.

<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 alicyclic dicarboxylic acid esters 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) pimelate, 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.

<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.

(A2) 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 above-mentioned ester compound, carboxyl group-containing compound, and catalyst. The solvent used in this case is not particularly limited as long as it dissolves each compound and polymerization initiator, etc.

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

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

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

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

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

The ^X1 is preferably a cyclic unsaturated hydrocarbon group having 4 to 16 carbon atoms or a cyclic saturated hydrocarbon group having 4 to 16 carbon atoms, and more preferably a cyclic unsaturated hydrocarbon group having 4 to 8 carbon atoms or a cyclic saturated hydrocarbon group having 4 to 8 carbon atoms. Furthermore, any hydrogen atom contained in ^X1 may be independently substituted with an aliphatic group, and multiple substituents among these aliphatic groups may bond to each other to form a 4 to 6 membered ring.

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

(In the formula, * represents a bond.)

Furthermore, as X, a structure derived from a resin having epoxy groups at both ends is also preferred.

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

(In the formula, * represents a bond.)

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

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].

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

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

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

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

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

(In the formula, * represents a bond.)

[(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.
(A3) 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 of the polymer constituting the acrylic polymer and the type of side chains.

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

In formula [A3-1], R ^A is independently a hydrogen atom or a _methyl group, and Y ¹ represents an H-( _OCH2CH2 ) _n- group (where n is an integer from 2 to 30, preferably an integer from 2 to 10), or a primary or secondary hydroxyalkyl group having 2 to 6 carbon atoms.

The weight-average molecular weight (Mw) of the acrylic polymer in 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.

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 polyethylene glycol ester groups include monoacrylates or monomethacrylates of H-( _OCH2CH2 ) _n - _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.

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.

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

(A3) Examples of preferred acrylic polymers for 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.

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

[(B) Acid compounds or salts thereof]
The release layer forming composition of the present invention comprises 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.

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.

[(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.
As the crosslinking agent, a compound represented by any of the following formulas (C-1) to (C-5) is preferred.

In each of the above formulas, ^R11 to ^R26 are independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, with alkyl groups having 1 to 6 carbon atoms being preferred. ^R27 is a hydrogen atom or a methyl group.

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.

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).

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.

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.

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 with reduced solubility in organic solvents.

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) the crosslinking agent may be used alone or in combination of two or more types.

[(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).

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

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

Specific examples of hydroxyalkyl groups with 1 to 10 carbon atoms in R ^C 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, and 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.

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

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).

(In the formula, ^RA , ^RC , and ^RD have the same meanings as described above.)

R ^B2 is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom (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.
^RE is a single bond, a polycyclic alkylene group having 6 to 20 carbon atoms, or an arylene group having 6 to 12 carbon atoms; ^RF is a single bond or an alkylene group having 1 to 10 carbon atoms; and ^RG is a methyl group, an ethyl group, or a hydroxyl group.

Examples of polycyclic alkylene groups with 6 to 20 carbon atoms in ^RE include groups obtained by removing one hydrogen atom from the aforementioned specific examples of polycyclic alkyl groups with 6 to 20 carbon atoms, such as adamantylene, isobornylene, norbornylene, etc.
Examples of aryl groups with 6 to 12 carbon atoms in ^RE include those obtained by removing one hydrogen atom from the aforementioned specific examples of aryl groups with 6 to 12 carbon atoms, such as phenylene, naphthylene, and biphenylene groups.

Specific examples of alkylene groups having 1 to 10 carbon atoms in R ^F 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.

Examples of 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). In the following formulas, ^RA has the same meaning as described above (the same applies hereinafter).

Examples of repeating units represented by formula (b) include, but are not limited to, those represented by formulas (b-1) to (b-16) below.

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

Examples of repeating units represented by formula (d) include, but are not limited to, those represented by formulas (d-1) to (d-8) below.

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.

On the other hand, if 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 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%.

(D) When the polymer additive contains repeating units represented by formula (a2), formula (b), formula (c), and formula (d) (hereinafter, such a polymer additive will be 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.

(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, its 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).

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.

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.

[(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.

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.

(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.

[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.

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.

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.).

If the peeling 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.

[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.

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 further for the purpose of adjusting the concentration, and this solvent may be the same as the solvent used to produce component (A) or a different solvent.

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.

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 objective 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 the viscosity 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.

[Exfoliation layer]
A release layer having excellent adhesion to the substrate and moderate adhesion and release properties to a resin substrate can be obtained by a firing method that includes the step of applying the release layer-forming composition of the present invention onto a substrate and then firing it at 180 to 250°C.
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.

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

Furthermore, 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.

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 material with a pattern such as a dot pattern or a line and space pattern is present in the other materials across the entire substrate surface.

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.).

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

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

The release layer of the present invention has excellent adhesion to a substrate, particularly a glass substrate, and moderate adhesion and release properties to a resin substrate. Therefore, 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.

[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.

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.

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 resin substrates made of acrylic polymer and resin substrates made of cycloolefin polymer, and those with a light transmittance of 80% or more at a wavelength of 400 nm are preferred.
The method for forming the resin substrate can be the standard method.

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.

The present invention will be described in more detail below with reference to synthesis examples, preparation examples, examples, and comparative examples, but the present invention is not limited to the following examples.

(I) (A1) Composition for forming a release layer containing cellulose 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: Hydroxypropyl cellulose, 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: p-Pyridinium Toluene Sulfonate HPMA: 2-Hydroxypropyl Methacrylate ADMA: 2-Adamantyl Methacrylate HFiPMA: 1,1,1,3,3,3-Hexafluoroisopropyl Methacrylate AIBN: Azobisisobutyronitrile DDT: Dodecanethiol

Furthermore, the weight-average molecular weight (Mw) of the polymer was measured using a GPC apparatus 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).

[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 80.1 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 a Mw/Mn of 1.8.

[Synthesis Example 1-2] Synthesis of Acrylic Polymer (S2) 8.57 g of HFiPMA, 2.62 g of HPMA, 8.00 g of ADMA, 0.74 g of AIBN, and 0.92 g of DDT were dissolved in 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 a Mw/Mn ratio of 1.8.

[2] Preparation of compositions for forming resin substrates [Preparation Example 1] Preparation of composition F1 for forming resin substrates 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 composition F1 for forming resin substrates.

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

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

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

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

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

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

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

[Example 1-8] Preparation of release layer forming composition 8 Release layer forming composition 1-8 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.

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

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

[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 x 100 mm, the same applies hereafter) 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 with a thickness of approximately 0.1 μm on the glass substrate, thereby 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.

[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 to obtain a glass substrate with a release layer and a resin substrate/glass substrate with a release layer.

[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 to obtain a glass substrate with a release layer and a resin substrate/glass substrate with a release layer.

[Example 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 to obtain a glass substrate with a release layer and a resin substrate/glass substrate with a release layer.

[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 to obtain a glass substrate with a release layer and a resin substrate/glass substrate with a release layer.

[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 to obtain a glass substrate with a release layer and a resin substrate/glass substrate with a release layer.

[Example 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.

[Example 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.

[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.

[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 to obtain a glass substrate with a release layer and a resin substrate/glass substrate with a release layer.

[5] Evaluation of Peelability The peelability of the glass substrates with release layers and 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.

(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 (2 mm intervals vertically and horizontally, the same applies hereinafter) and 25 grids were made. That is, 25 grids of 2 mm square were formed by this cross-cut.
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: 5% to less than 15% peeling 2B: 15% to less than 35% peeling 1B: 35% to less than 65% peeling 0B: 65% to less than 80% peeling B: 80% to less than 95% peeling A: 95% to less than 100% peeling AA: 100% peeling (complete peeling)

(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. 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.

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.

(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: p-Pyridinium Toluene Sulfonate 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 Corporation, 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 5H IPhA: 5-Hydroxyisophthalic acid 14CHA: 1,4-Cyclohexyl dicarboxylic acid BTEAC: Benzyltriethylammonium chloride ETPPB: Ethyltriphenylphosphonium bromide

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

[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 a Mw/Mn of 3.9.

[Synthesis Example 2-2] Synthesis of Polyester (A2-2) 10.0 g of EP3, 5.2 g of TPhA, and 0.24 g of BTEAC were dissolved in 36.0 g of PGME and reacted at 120°C for 20 hours to 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.

[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.

[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.

[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.

[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 a Mw/Mn ratio of 3.3.

[Synthesis Example 2-7] Synthesis of Polyester (A2-7) 10.0 g of EP5, 3.4 g of IPhA, and 0.15 g of BTEAC were dissolved in 4.2 g of PGME 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.

[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 a Mw/Mn of 2.4.

[Synthesis Example 2-9] Synthesis of Polyester (A2-9) 10.0 g of EP5, 3.7 g of 5HIPhA, and 0.15 g of BTEAC were dissolved in 55.5 g of PGME 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.

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

[Synthesis Example 2-11] Synthesis of Polyester (A2-11) 10.0 g of EP6, 6.8 g of 14CHA, and 0.59 g of ETPPB were dissolved in 40.7 g of PGME and reacted at 120°C for 20 hours to 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 a Mw/Mn ratio of 1.7.

[Synthesis Example 2-12] Synthesis of Acrylic Polymer (S1) 6.43 g of HFiPMA, 3.93 g of HPMA, 8.00 g of ADMA, 0.74 g of AIBN, and 0.92 g of DDT were dissolved in 80.1 g of PGME and reacted at 70°C for 20 hours 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 a Mw/Mn ratio of 1.8.

[2] Preparation of compositions for forming resin substrates [Preparation Example 1] Preparation of composition F1 for forming resin substrates 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 composition F1 for forming resin substrates.

[3] Preparation of the release layer forming composition [Example 3-1] Preparation of release layer forming composition 1 To 1 g of the polyester (A2-1) solution obtained in Synthesis Example 1, 0.06 g of PL-LI, 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 release layer forming composition 2-1.

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

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

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

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

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

[Example 3-7] Preparation of release layer forming composition 7 Release layer forming composition 2-7 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.

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

[Example 3-9] Preparation of release layer forming composition 9 Release layer forming composition 2-9 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.

[Example 3-10] Preparation of release layer forming composition 10 Release layer forming composition 2-10 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.

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

[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 x 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.

[Example 4-2]
Except for using release layer-forming composition 2-2 instead of release layer-forming 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.

[Example 4-3]
Except for using release layer-forming composition 2-3 instead of release layer-forming 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.

[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.

[Examples 4-5]
Except for using release layer forming composition 2-5 instead of release layer forming 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.

[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 to obtain a glass substrate with a release layer and a resin substrate/glass substrate with a release layer.

[Example 4-7]
Except for using release layer-forming composition 2-7 instead of release layer-forming 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.

[Examples 4-8]
Except for using release layer-forming composition 2-8 instead of release layer-forming 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.

[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 to obtain a glass substrate with a release layer and a resin substrate/glass substrate with a release layer.

[Example 4-10]
Except for using release layer forming composition 2-10 instead of release layer forming 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.

[Example 4-11]
Except for using release layer-forming composition 2-11 instead of release layer-forming 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.

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

As shown in Table 2, the release layer in the example exhibited excellent adhesion to the glass substrate and was easily detached from the resin film.

(III) (A3) A composition for forming a release layer containing an acrylic polymer having a primary or secondary hydroxyl group and no fluorine atom. The compounds used in the following example are as follows:
PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate CHN: Cyclohexanone PL-LI: 1,3,4,6-Tetrakis(methoxyethyl) glycoluryl (manufactured by Ornex, trade name: POWDERLINK 1174)
PPTS: p-toluenesulfonate pyridinium 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

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

[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 a Mw/Mn of 1.7.

[Synthesis Example 3-2] Synthesis of Acrylic Polymer (A3-2) 20.0 g of HEMA and 1.26 g of AIBN were dissolved in 85 g of PGME 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 a Mw/Mn ratio of 2.5.

[Synthesis Example 3-3] Synthesis of Acrylic Polymer (A3-3) 20.0 g of HPMA, 1.14 g of AIBN, and 1.40 g of DDT were dissolved in 90.2 g of PGME and reacted at 70°C for 20 hours to obtain 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.

[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.

[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 a Mw/Mn ratio of 1.3.

[Synthesis Example 3-6] Synthesis of Acrylic Polymer (A3-6) 10.0 g of MMA, 13.0 g of HEMA, 1.64 g of AIBN, and 1.21 g of DDT were dissolved in 3.4 g of PGME 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 a Mw/Mn ratio of 1.9.

[Synthesis Example 3-7] Synthesis of Acrylic Polymer (A3-7) 10.0 g of MMA, 14.3 g of HPMA, 1.64 g of AIBN, and 1.21 g of DDT were dissolved in 109.0 g of PGME and reacted at 70°C for 20 hours to obtain an acrylic polymer (A3-7) solution (solid 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 a Mw/Mn ratio of 2.3.

[Synthesis Example 3-8] Synthesis of Acrylic Polymer (A3-8) 15.0 g of MMA, 8.36 g of HEMA, 1.74 g of AIBN, and 1.30 g of DDT were dissolved in 105.7 g of PGME 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. GPC analysis revealed that the obtained acrylic polymer (A3-8) had a Mw of 5,500 and a Mw/Mn ratio of 2.0.

[Synthesis Example 3-9] Synthesis of Acrylic Polymer (A3-9) 15.0 g of MMA, 9.26 g of HPMA, 1.74 g of AIBN, and 1.30 g of DDT 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. GPC analysis revealed that the obtained acrylic polymer (A3-9) had a Mw of 6,000 and a Mw/Mn ratio of 2.0.

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

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

[Synthesis Example 3-12] Synthesis of Acrylic Polymer (A3-12) 10.0 g of MMA, 0.82 g of AIBN, and 0.61 g of DDT were dissolved in 45.7 g of PGME 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.

[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 a Mw/Mn ratio of 1.8.

[Synthesis Example 3-14] Synthesis of Acrylic Polymer (S2) 8.57 g of HFiPMA, 2.62 g of HPMA, 8.00 g of ADMA, 0.74 g of AIBN, and 0.92 g of DDT were dissolved in 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 a Mw/Mn ratio of 1.8.

[2] Preparation of compositions for forming resin substrates [Preparation Example 1] Preparation of composition F1 for forming resin substrates 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 composition F1 for forming resin substrates.

[3] Preparation of the release layer forming composition [Example 5-1] Preparation of release layer forming composition 1 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 release layer forming composition 3-1.

[Example 5-2] Preparation of release layer forming composition 2 Release layer forming composition 3-2 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.

[Example 5-3] Preparation of release layer forming composition 3 Release layer forming composition 3-3 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.

[Example 5-4] Preparation of release layer forming composition 4 Release layer forming composition 3-4 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.

[Example 5-5] Preparation of release layer forming composition 5 Release layer forming composition 3-5 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.

[Example 5-6] Preparation of release layer forming composition 6 Release layer forming composition 3-6 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.

[Example 5-7] Preparation of release layer forming composition 7 Release layer forming composition 3-7 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 and the amount of acrylic polymer (S1) was changed to 0.17 g.

[Example 5-8] Preparation of release layer forming composition 8 Release layer forming composition 3-8 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.

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

[Example 5-10] Preparation of release layer forming composition 10 Release layer forming composition 3-10 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.

[Example 5-11] Preparation of release layer forming composition 11 Release layer forming composition 3-11 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.

[Example 5-12] Preparation of release layer forming composition 12 Release layer forming composition 3-12 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.

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

[Comparative Example 3-2] Preparation of release layer forming composition 14 Release layer forming composition 3-14 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.

[Comparative Example 3-3] Preparation of release layer forming composition 15 Release layer forming composition 3-15 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.

[4] Fabrication of the release layer and resin substrate [Example 6-1]
Composition 3-1 for forming a release layer was applied to a glass substrate (100 mm x 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.

[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.

[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 to obtain a glass substrate with a release layer and a resin substrate/glass substrate with a release layer.

[Example 6-4]
Except for using release layer-forming composition 3-4 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.

[Example 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.

[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.

[Examples 6-7]
Except for using release layer-forming composition 3-7 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.

[Examples 6-8]
Except for using release layer-forming composition 3-8 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.

[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.

[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.

[Example 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.

[Example 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.

[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.

[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.

[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.

[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.

[6] Curing 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%

As shown in Table 3, the release layer of the example was found to have excellent adhesion to the glass substrate and to peel off easily from the resin film. On the other hand, the release layers of Comparative Examples 4-1 to 4-3 were found to have excellent adhesion to the glass substrate but to be difficult to peel off from the resin substrate.

Claims (14)

(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) A polymer additive comprising a repeating unit represented by the following formula (a1), a repeating unit represented by the following formula (b), and a repeating unit represented by the following formula (c), and (E) a solvent,
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).
(In the formula, ^RA is independently a hydrogen atom or a methyl group, ^RB1 is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, ^RC is a hydroxyalkyl group having 1 to 10 carbon atoms, and ^RD is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.) (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) A polymer additive comprising a repeating unit represented by the following formula (a1), a repeating unit represented by the following formula (b), and a repeating unit represented by the following formula (c), and (E) a solvent,
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).
(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.)
(In the formula, L ¹ represents an ether bond or an ester bond, X ¹ represents an alkylene group having 1 to 10 carbon atoms, a cyclic unsaturated hydrocarbon group, or a cyclic saturated hydrocarbon group, R ¹ represents a single bond, an ether bond, a carbonyl bond, a sulfonyl bond, a saturated hydrocarbon group having 1 to 30 carbon atoms, an unsaturated hydrocarbon group having 2 to 30 carbon atoms, or a saturated hydrocarbon group having 1 to 30 carbon atoms substituted with a fluorine atom, and p represents 0, 1, or 2.)
(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].)
(In the formula, X and Y have the same definitions as X and Y in formula [A2-1].)
(In the formula, ^RA is independently a hydrogen atom or a methyl group, ^RB1 is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, ^RC is a hydroxyalkyl group having 1 to 10 carbon atoms, and ^RD is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.) The release layer forming composition according to claim 1 or 2, wherein in the repeating unit represented by formula (b), R ^C is a hydroxyalkyl group having 2 to 10 carbon atoms, and the carbon atom to which the hydroxyl group is bonded is a secondary or tertiary carbon atom. The release layer forming composition according to claim 1 or 2, wherein in the repeating unit represented by formula (b), R ^C is a hydroxyalkyl group having 1 to 10 carbon atoms, the carbon atom to which the hydroxyl group is bonded is a primary carbon atom, and the content of the repeating unit represented by formula (a1) is 25 mol% or more of the total repeating units of the polymer additive (D). 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).
(In the formula, R ^A , R ^C , and R ^D have the same meanings as described above; R ^B2 is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, but does not contain a 2-methyl-1,1,1,3,3,3-hexafluoroisopropyl group; R ^E is a single bond, a polycyclic alkylene group having 6 to 20 carbon atoms, or an arylene group having 6 to 12 carbon atoms; R ^F is a single bond or an alkylene group having 1 to 10 carbon atoms; and R ^G is a methyl group, an ethyl group, or a hydroxyl group.) The release layer forming composition according to claim 1, wherein component (A1) is at least one selected from the group consisting of hydroxyethylcellulose, hydroxypropylcellulose, and derivatives thereof. The release layer forming composition according to claim 2, wherein component (A2) is a polyester obtained by reacting a compound having two epoxy moieties with a compound having two carboxyl groups. The release layer forming composition according to claim 1, wherein the (A3) component is an acrylic polymer having a polyethylene glycol ester group or a primary or secondary hydroxyalkyl ester group having 2 to 6 carbon atoms. 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. 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).
(In the formula, ^R11 to ^R26 are each independently alkyl groups having 1 to 6 carbon atoms, and ^R27 is a hydrogen atom or a methyl group.) The composition for forming a peeling layer according to any one of claims 1 to 10 , wherein the amount of the crosslinking agent (C) is 10 to 100 parts by mass per 100 parts by mass of component (A). A release layer obtained from the release layer forming composition according to any one of claims 1 to 11 . 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. A step of applying a release layer-forming composition according to any one of claims 1 to 11 to a substrate to form a release layer,
A method for manufacturing a resin substrate, comprising the steps of forming a resin substrate on the release layer having a light transmittance of 80% or more at a wavelength of 400 nm, and peeling the resin substrate with a peeling force of 0.25 N/25 mm or less.