Composition for forming release layer, and release layer

Abstract

Provided is a composition for forming a release layer comprising a polymer including a repeating unit having a photosensitive group that undergoes photo-Fries rearrangement.

Description

Release layer-forming composition and release layer

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

[0002] In recent years, electronic devices have been required to be thin, lightweight, and flexible, which has led to the need to use lightweight, flexible plastic substrates instead of conventional heavy, fragile, and inflexible glass substrates.

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

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

[0005] Generally, flexible touch screen panels are produced in a stable manner by forming a release (adhesive) layer on a support substrate such as a glass substrate, fabricating a device made of a resin substrate on the release layer, and then peeling the device from the adhesive layer (Patent Document 8). The device made of a resin substrate fabricated on the release layer must not peel from the support substrate during the process, but requires a low peel force when peeling. Peeling from the support substrate during the fabrication process, in particular, can result in a significant decrease in yield.

[0006] International Publication No. 2012 / 147235 JP 2009-283410 A JP 2010-507199 A JP 2009-205924 A JP 2017 / 002664 JP 2016 / 160338 JP 2015-166145 A JP 2016-531358 A

[0007] The present invention has been made in consideration of the above circumstances, and aims to provide a composition for forming a release layer that has high heat resistance and good releasability and provides a release layer that can suppress unnecessary peeling during processing.

[0008] As a result of extensive research to achieve the above-mentioned object, the inventors have discovered that a release layer obtained from a release layer-forming composition containing a polymer containing a repeating unit having a photosensitive group that undergoes photo-fries rearrangement has good releasability for a resin substrate formed on the release layer, and that exposure to light can increase adhesion to the resin substrate only in specified areas, thereby completing the present invention.

[0009] That is, the present invention provides the following release layer-forming composition and release layer: 1. A release layer-forming composition comprising (A) a polymer including a repeating unit having a photosensitive group that undergoes photo-induced Fries rearrangement. 2. The release layer-forming composition of 1, wherein the repeating unit having a photosensitive group that undergoes photo-induced Fries rearrangement is derived from a monomer represented by the following formula (a1) or (a2): (In the formula, Ar 1 represents a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-biphenylyl group, a 3-biphenylyl group, or a 4-biphenylyl group, and some or all of the hydrogen atoms of these groups may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a chlorine atom, or a bromine atom, but at least one of the ortho- and para-positions of the oxygen atom in the formula is a hydrogen atom; Ar 2represents a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a 1,2-naphthylene group, a 1,3-naphthylene group, a 1,4-naphthylene group, a 1,5-naphthylene group, a 1,6-naphthylene group, a 1,7-naphthylene group, a 1,8-naphthylene group, a 2,3-naphthylene group, a 2,6-naphthylene group, a 2,2'-biphenylylene group, a 2,3'-biphenylylene group, a 2,4'-biphenylylene group, a 3,3'-biphenylylene group, a 3,4'-biphenylylene group, or a 4,4'-biphenylylene group, in which some or all of the hydrogen atoms in these groups may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a chlorine atom, or a bromine atom, but at least one of the ortho- and para-positions of the oxygen atom in the formula is a hydrogen atom; R 1 is an alkyl group having 1 to 6 carbon atoms or a phenyl group; X 1 and X 2 are each independently a single bond or an alkylene group having 1 to 20 carbon atoms, and one or more -CH2- groups in the alkylene group may be substituted with at least one group selected from -O-, -C(=O)-O-, and -O-C(=O)-; 1 and A 2 are each independently a radical polymerizable group containing a carbon-carbon double bond. 3. The resin composition for forming a release layer according to 2, wherein the radical polymerizable group is represented by any one of the following formulas (A-1) to (A-4): (R A are each independently a hydrogen atom or a methyl group.) 4. The resin composition for forming a release layer according to 1 or 2, wherein the polymer (A) is a polymer further containing a repeating unit derived from a monomer represented by the following formula (b) and a repeating unit derived from a monomer represented by the following formula (c): (In the formula, R A are each independently a hydrogen atom or a methyl group; R B 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 Cis a hydroxyalkyl group having 2 to 10 carbon atoms.) 5. A release layer-forming composition according to any one of 1 to 4, further comprising (B) a resin having a hydroxy group or a carboxyl group. 6. A release layer-forming composition according to any one of 1 to 5, wherein (B) the resin having a hydroxy group or a carboxyl group is polyurea having a hydroxy group, an acrylic polymer having a hydroxy group or a carboxyl group, polyester having a hydroxy group, or cellulose having a hydroxyalkyl group or a derivative thereof. 7. A release layer-forming composition according to any one of 1 to 6, further comprising (C) a crosslinking agent selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and / or an alkoxymethyl group. 8. A release layer-forming composition according to any one of 1 to 7, further comprising (D) a crosslinking catalyst. 9. A release layer obtained from a release layer-forming composition according to any one of 1 to 8. 10. A laminate comprising a resin layer having a light transmittance of 80% or more at a wavelength of 400 nm laminated on the release layer of 9. 11. A laminate according to 10, wherein the resin substrate is a thermosetting film containing an epoxy compound. 12. A method for forming a release layer, comprising the steps of forming a resin film on a substrate using the release layer-forming composition of any one of 1 to 8, and exposing a predetermined region of the resin film to ultraviolet light. 13. A method for manufacturing a resin substrate, comprising the steps of forming a resin film on a substrate using the release layer-forming composition of any one of 1 to 8, exposing a predetermined region of the resin film to ultraviolet light, 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 formed on the release layer with a peeling force of 1.0 N / 25 mm or less.

[0010] By using the release layer-forming composition of the present invention, it is possible to reproducibly obtain a release layer that has good release properties for the resin substrate formed on the release layer and can increase adhesion to the resin substrate only in a predetermined area by exposure. Furthermore, in the manufacturing process of a flexible electronic device, unnecessary peeling can be suppressed during manufacturing without damaging the resin substrate formed on the base or the circuits, etc. formed thereon, making it possible to separate the resin substrate together with the circuits, etc. from the base when necessary. Therefore, the release layer-forming composition of the present invention can contribute to speeding up the manufacturing process of flexible electronic devices equipped with resin substrates and improving their yield.

[0011] [Composition for forming a release layer] The composition for forming a release layer of the present invention contains (A) a polymer containing a repeating unit having a photosensitive group that undergoes photo-induced Fries rearrangement.

[0012] [(A) Polymer] The component (A) in the release layer-forming composition of the present invention is a polymer containing a repeating unit having a photosensitive group that undergoes photo-induced Fries rearrangement.

[0013] The photo-Fries rearrangement is a process in which phenyl esters are irradiated with light to produce acylphenols in which acyl groups are substituted at the ortho and para positions. Phenyl esters are a general term for esters formed between phenols and acids, including carboxylic acids. This rearrangement reaction is thought to proceed via a radical mechanism from an excited singlet state.

[0014] The release layer obtained from the polymer undergoes photo-induced Fries rearrangement upon irradiation with light to generate acylphenols, which are hydrophilic and capable of undergoing a crosslinking reaction with a resin substrate or the like on the release layer, making it possible to control the releasability of the resin substrate or the like on the release layer by irradiation with light.

[0015] The monomer is preferably one represented by the following formula (a1) or (a2).

[0016] In formulas (a1) and (a2), Ar 1 represents a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-biphenylyl group, a 3-biphenylyl group, or a 4-biphenylyl group, and some or all of the hydrogen atoms in these groups may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a chlorine atom, or a bromine atom, but at least one of the ortho- and para-positions of the oxygen atom in the formula is a hydrogen atom.

[0017] In formulas (a1) and (a2), Ar 2represents a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a 1,2-naphthylene group, a 1,3-naphthylene group, a 1,4-naphthylene group, a 1,5-naphthylene group, a 1,6-naphthylene group, a 1,7-naphthylene group, a 1,8-naphthylene group, a 2,3-naphthylene group, a 2,6-naphthylene group, a 2,2'-biphenylylene group, a 2,3'-biphenylylene group, It is a 2,4'-biphenylylene group, a 3,3'-biphenylylene group, a 3,4'-biphenylylene group, or a 4,4'-biphenylylene group, and some or all of the hydrogen atoms in these groups may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a chlorine atom, or a bromine atom, but at least one of the ortho- and para-positions of the oxygen atom in the formula is a hydrogen atom.

[0018] In formulas (a1) and (a2), R 1 is an alkyl group having 1 to 6 carbon atoms or a phenyl group.

[0019] In formulas (a1) and (a2), X 1 and X 2 are each independently a single bond or an alkylene group having 1 to 20 carbon atoms, and one or more -CH2- groups in the alkylene group may be substituted with at least one group selected from -O-, -C(=O)-O-, and -O-C(=O)-.

[0020] The alkyl group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, an n-pentyl group, a cyclopentyl group, an n-hexyl group, and a cyclohexyl group.

[0021] The alkoxy group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, a cyclopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, a cyclobutyloxy group, an n-pentyloxy group, a cyclopentyloxy group, an n-hexyloxy group, and a cyclohexyloxy group.

[0022] The alkylene group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.

[0023] Ar 1 As Ar, an unsubstituted phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 3-biphenylyl group, or a 4-biphenylyl group is preferred. 2 As X, an unsubstituted 1,4-phenylene group or a 4,4'-biphenylylene group is preferred. 1 and X 2 is preferably a single bond.

[0024] In formulas (a1) and (a2), A 1 and A 2 are each independently a radical polymerizable group containing a carbon-carbon double bond. The radical polymerizable group is preferably one represented by any one of the following formulas (A-1) to (A-4). (R A are each independently a hydrogen atom or a methyl group.

[0025] A 1 and A 2 As the alkyl group, those represented by formula (A-1) or (A-2) are preferred.

[0026] Specific examples of the monomer represented by formula (a1) include, but are not limited to, those represented by the following formulas (a1-1) to (a1-5). 1 and X 1 is the same as above.

[0027] Preferred specific examples of the monomer represented by formula (a1) include, but are not limited to, those represented by the following formulae (a1-1') to (a1-5').

[0028] Specific examples of the monomer represented by formula (a2) include, but are not limited to, those represented by the following formulas (a2-1) to (a2-4). 2 and X 2 is the same as above.

[0029] Preferred specific examples of the monomer represented by formula (a2) include, but are not limited to, those represented by the following formulas (a2-1′) to (a2-4′).

[0030] In the polymer of component (A), the content of repeating units derived from the monomers represented by formula (a1) and / or (a2) may be 100 mol % of all repeating units, but is preferably 10 to 60 mol %, and more preferably 15 to 50 mol %.

[0031] The polymer of component (A) preferably further contains a repeating unit derived from a monomer represented by the following formula (b) and a repeating unit derived from a monomer represented by the following formula (c).

[0032] In formulas (b) and (c), R A are each independently a hydrogen atom or a methyl group. B is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. C is a hydroxyalkyl group having 2 to 10 carbon atoms.

[0033] Examples of the branched alkyl group having 3 or 4 carbon atoms include an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. B As the branched alkyl group, those in which at least one hydrogen atom has been substituted with a fluorine atom are preferred, and specific examples include a 1,1,1-trifluoroisopropyl group, a 1,1,1,3,3,3-hexafluoroisopropyl group, and a nonafluoro-tert-butyl group.

[0034] Examples of the hydroxyalkyl group having 2 to 10 carbon atoms include a 1-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 2-hydroxybutyl group, a 2-hydroxyhexyl group, a 2-hydroxyoctyl group, a 2-hydroxydecyl group, a 1-hydroxy-1-methylethyl group, and a 2-hydroxy-2-methylpropyl group.

[0035] Examples of the monomer represented by formula (b) include, but are not limited to, those represented by the following formulas (b-1) to (b-3). A is the same as above.

[0036] Examples of the monomer represented by formula (c) include, but are not limited to, those represented by the following formulas (c-1) to (c-4). A is the same as above.

[0037] When the polymer of component (A) contains repeating units derived from a monomer represented by formula (b) and repeating units derived from a monomer represented by formula (c), the content of repeating units derived from the monomer represented by formula (b) is preferably 5 to 60 mol %, more preferably 10 to 50 mol %, of all repeating units. The content of repeating units derived from the monomer represented by formula (c) is preferably 5 to 60 mol %, more preferably 10 to 50 mol %, of all repeating units.

[0038] The polymer of component (A) may contain repeating units derived from monomers other than the above-mentioned monomers (hereinafter also referred to as "other monomers"), as long as the effects of the present invention are not impaired. Examples of other monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

[0039] Specific examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthrylmethyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclo[5.2.1.0(2,6)]decyl acrylate, and 8-ethyl-8-tricyclo[5.2.1.0(2,6)]decyl acrylate.

[0040] Specific examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclo[5.2.1.0(2,6)]decyl methacrylate, and 8-ethyl-8-tricyclo[5.2.1.0(2,6)]decyl methacrylate.

[0041] Specific examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

[0042] Specific examples of the styrene compound include styrene, 4-methylstyrene, 4-chlorostyrene, and 4-bromostyrene.

[0043] Specific examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0044] The weight average molecular weight (Mw) of the polymer of component (A) is preferably 1,000 to 20,000, and more preferably 2,000 to 10,000. The dispersity (Mw / Mn) is preferably 1.0 to 3.0, and more preferably 1.0 to 2.5. Mw is a value measured by gel permeation chromatography (GPC) relative to polystyrene standards.

[0045] The method for synthesizing the polymer is not particularly limited, but examples include a method of carrying out a polymerization reaction in a solvent containing the above-mentioned monomers, polymerization initiator, etc. at a temperature of 50 to 110° C. The solvent used in this case is not particularly limited as long as it dissolves the monomers, polymerization initiator, etc. Specific examples include the solvents exemplified below as the solvent for component (E).

[0046] The polymer thus obtained is usually in the form of a solution dissolved in a solvent, and can be used as is as a solution of component (A) in the present invention.

[0047] Alternatively, the polymer solution may be reprecipitated by adding it to hexane, methanol, water, or the like under stirring, and the resulting precipitate may be filtered, washed, and then dried at room temperature or by heating under atmospheric or reduced pressure to recover a polymer powder. This procedure removes the polymerization initiator and unreacted monomers coexisting with the polymer, resulting in a purified polymer powder. If the polymer cannot be sufficiently purified in a single procedure, the resulting powder may be redissolved in a solvent and the procedure repeated. The polymer powder may be used as component (A) as is, or may be redissolved in a solvent, for example, as described below, and used in the form of a solution.

[0048] In the composition for forming a release layer of the present invention, the polymer of component (A) may be used alone or in combination of two or more.

[0049] [(B) Resin Having a Hydroxy Group or a Carboxy Group] The release layer-forming composition of the present invention may contain, as necessary, a resin having a hydroxy group or a carboxy group as component (B). Such a resin is not particularly limited, but is preferably a polyurea having a hydroxy group, an acrylic polymer having a hydroxy group or a carboxy group, a polyester having a hydroxy group, or a cellulose having a hydroxyalkyl group or a derivative thereof.

[0050] The polyurea having a hydroxy group preferably contains a repeating unit represented by the following formula (1):

[0051] In formula (1), A 1 , A 2 , A 3 , A 4 , A 5 and A 6 are each independently a hydrogen atom, a methyl group, or an ethyl group. From the viewpoint of releasability and productivity, A 1 ~A 6 are preferably all hydrogen atoms.

[0052] In formula (1), X 1 is a group represented by the following formula (X1), (X2), (X3) or (X4). (In the formula, * represents a bond to the carbonyl group in the formula, and ** represents a bond to the nitrogen atom in the formula.)

[0053] In formulas (X1) and (X2), R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group. The phenyl group may be substituted with at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 6 carbon atoms. 1 and R2 may be bonded to each other to form a ring having 3 to 6 carbon atoms together with the carbon atoms to which they are attached.

[0054] In formula (X3), R 3 is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group. The phenyl group may be substituted with at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 6 carbon atoms.

[0055] In formula (1), Q 1 is a group represented by the following formula (Q1) or (Q2): (In the formula, * represents a bond.)

[0056] In formula (Q1), X 2 is a group represented by formula (X1), formula (X2) or formula (X4). 2 is a group represented by formula (X2), its structure is represented by formula (Q1-1) below. (In the formula, R 1 and R 2 is the same as above. * is a bond.)

[0057] In formula (Q2), Q 2 is an alkylene group having 1 to 10 carbon atoms, a phenylene group, a naphthylene group, or an anthrylene group. The phenylene group, naphthylene group, and anthrylene group may be substituted with at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 6 carbon atoms. 2When n is a phenylene group, naphthylene group, or anthrylene group, the bonding positions thereof are not particularly limited. That is, for example, the phenylene group may be bonded at the 1st and 2nd positions, the 1st and 3rd positions, or the 1st and 4th positions, the naphthylene group may be bonded at the 1st and 2nd positions, the 1st and 4th positions, the 1st and 5th positions, or the 2nd and 3rd positions, and the anthrylene group may be bonded at the 1st and 2nd positions, the 1st and 4th positions, or the 9th and 10th positions, and any of these may be acceptable. 1 and n 2 are each independently 0 or 1.

[0058] The alkyl group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a cyclohexyl group, etc. The alkenyl group having 3 to 6 carbon atoms may be linear, branched, or cyclic, and examples thereof include a 2-propenyl group, a 3-butenyl group, etc.

[0059] The alkoxy group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include a methoxy group, an ethoxy group, an isopropoxy group, an n-pentyloxy group, and a cyclohexyloxy group. The alkylthio group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include a methylthio group, an ethylthio group, an isopropylthio group, an n-pentylthio group, and a cyclohexylthio group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In addition, R 1 and R 2 Examples of the ring having 3 to 6 carbon atoms formed by bonding include a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring.

[0060] The alkylene group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include a methylene group, an ethylene group, a propylene group, a pentamethylene group, a cyclohexylene group, and a 2-methylpropylene group.

[0061] In addition, in formula (1), X 1 When X is a group represented by formula (X2), the structure is represented by formula (1A) below. 1 is a group represented by formula (X3), its structure is represented by formula (1B) below. 3 However, it is preferably a 2-propenyl group. (In the formula, A 1 ~A 6 , R 1 ~R 3 and Q 1 is the same as above.)

[0062] In formula (1), Q 1 Preferably, Q contains a cyclic structure from the viewpoint of the heat resistance of the polyurea. 1 is a group represented by formula (Q1) or a group represented by formula (Q2), 2 is preferably a cyclic alkylene group, a phenylene group, a naphthylene group or an anthrylene group, and more preferably a group represented by formula (Q1).

[0063] The repeating unit represented by formula (1) is preferably one represented by the following formulas (1-1) to (1-19): In the following formulas, Me is a methyl group, and Et is an ethyl group.

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070] The polyurea can be synthesized, for example, by referring to International Publication No. 2005 / 098542.

[0071] Examples of the acrylic polymer having a hydroxy group or a carboxy group include a homopolymer of an acrylic acid ester, a homopolymer of a methacrylic acid ester, a copolymer thereof, and a copolymer of these with a monomer having an unsaturated double bond such as styrene.

[0072] A preferred example of the acrylic polymer is an acrylic polymer having a polyethylene glycol ester group or a hydroxyalkyl ester group having 2 to 6 carbon atoms. Such an acrylic polymer may be an acrylic polymer having any of these groups, and there are no particular limitations on the main chain skeleton (other repeating units) and the type of side chain that constitutes the acrylic polymer.

[0073] The acrylic polymer having a polyethylene glycol ester group or a hydroxyalkyl ester group having 2 to 6 carbon atoms preferably contains a repeating unit represented by the following formula (2):

[0074]

[0075] In formula (2), R 11 is a hydrogen atom or a methyl group. 12 is -(CH2CH2O) n It is a —H group or a hydroxyalkyl group having 2 to 6 carbon atoms, and n is an integer of 2 to 30, preferably an integer of 2 to 10.

[0076] Examples of the hydroxyalkyl group having 2 to 6 carbon atoms include a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, a 4-hydroxybutyl group, and a 2,3-dihydroxypropyl group.

[0077] Furthermore, the acrylic polymer may contain a repeating unit other than the repeating unit represented by formula (2), specifically, a repeating unit derived from a monomer that does not have a polyethylene glycol ester group or a hydroxyalkyl ester group having 2 to 6 carbon atoms, as long as the effects of the present invention are not impaired.

[0078] The method for producing the acrylic polymer is not particularly limited, and examples thereof include a method in which a monomer having at least one of a polyethylene glycol group and a hydroxyalkyl group having 2 to 6 carbon atoms, and, if necessary, a monomer not having a polyethylene glycol ester group or a hydroxyalkyl ester group having 2 to 6 carbon atoms, are polymerized in a solution obtained by dissolving a polymerization initiator in a solvent at a temperature of 50 to 110° C. The solvent used is not particularly limited as long as it dissolves the monomer, polymerization initiator, etc.

[0079] The monomer having a polyethylene glycol ester group is H—(OCH2CH2) n Examples of the monomer having a hydroxyalkyl group having 2 to 6 carbon atoms include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, glycerin monoacrylate, and glycerin monomethacrylate.

[0080] Examples of the monomer that does not have a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 6 carbon atoms include carboxylic acid compounds such as acrylic acid and methacrylic acid; acrylic acid ester compounds such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate, phenyl acrylate, and 4-hydroxyphenyl acrylate; methacrylic acid ester compounds such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, phenyl methacrylate, and 4-hydroxyphenyl methacrylate; maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide, N-(4-hydroxyphenyl)maleimide, and N-cyclohexylmaleimide; acrylamide compounds; methacrylamide compounds; acrylonitrile, maleic anhydride, styrene compounds; and vinyl compounds.

[0081] The acrylic polymer obtained by the above method is usually in the form of a solution dissolved in a solvent.

[0082] Suitable examples of the acrylic polymer include polymers obtained by polymerizing 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; and acrylic polymers having a hydroxyalkyl group in the side chain, such as polymers obtained by copolymerizing the hydroxyalkyl ester monomers with monomers other than these monomers, for example, one or more monomers selected from the group consisting of monomers having no polyethylene glycol ester group and no hydroxyalkyl ester group having 2 to 6 carbon atoms.

[0083] The polyester having a hydroxy group is not particularly limited, but is preferably one having an aromatic group or an alicyclic group in the main chain, and is preferably a polyester obtained by reacting a compound having two or more epoxy moieties with a compound having two carboxy groups.

[0084] Examples of the compound having two or more epoxy moieties include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD ​​diglycidyl ether, bisphenol S diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyl diglycidyl ether, tetramethylbiphenyl diglycidyl ether, 9,9'-bis(4-hydroxyphenyl)furodienyl glycidyl ether, 9,9'-bis(4-hydroxyphenyl)furodienyl glycidyl ether, and 9,9'-bis(6-hydroxy-2-naphthyl)furodienyl glycidyl ether; ethylene glycol diglycidyl ether, and propylene glycol diglycidyl ether. aliphatic diol diglycidyl ethers such as glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and neopentyl glycol diglycidyl ether; cyclohexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, dicyclopentadiene diol diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, and hydrogenated bisphenol A diglycidyl ether; alicyclic diol diglycidyl ethers such as bisphenol B diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, and the like; aromatic diglycidyl esters of dicarboxylic acids such as phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, and terephthalic acid diglycidyl ester; alicyclic diglycidyl esters of dicarboxylic acids such as bisglycidyl oxalate, bisglycidyl adipate, bisglycidyl pimelate, and bisglycidyl 2-ethyl-3-propyl-1,5-pentanedioate;Alicyclic dicarboxylic acid diester diepoxides such as bis(3,4-epoxycyclohexylmethyl) oxalate, bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis(3,4-epoxycyclohexylmethyl) pimelic acid, and bis(3,4-epoxycyclohexylmethyl) 2-ethyl-3-propyl-1,5-pentanedioate; and alicyclic dioxides such as vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, Epocalic (registered trademark) THI-DE, DE-102, DE-103 (manufactured by ENEOS Corporation), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2,2-bis(3,4-epoxycyclohexyl)propane. These compounds may be used alone or in combination of two or more.

[0085] Examples of compounds having two carboxy groups include terephthalic acid, isophthalic acid, diphenic acid, 2-methylterephthalic acid, 2-hydroxyterephthalic acid, 2,5-dimethylterephthalic acid, 5-methylisophthalic acid, 5-hydroxyisophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc. These compounds may be used alone or in combination of two or more.

[0086] The method for synthesizing the polyester is not particularly limited, but examples thereof include a method in which the ester compound, the carboxyl group-containing compound, and the catalyst are polymerized in a solvent at a temperature of 50 to 150°C. The solvent used in this case is not particularly limited as long as it dissolves the compounds, the polymerization initiator, etc. The polyester obtained by this method is usually in the form of a solution dissolved in the solvent.

[0087] The polyester preferably contains a repeating unit represented by the following formula (3):

[0088] In formula (3), Y1 and Z 1 are each independently a divalent group having an aromatic ring or an alicyclic ring.

[0089] Y 1 As the group, a group represented by the following formula (Y1-1) is preferred. (In the formula, * represents a bond.)

[0090] In formula (Y1-1), L 1 are each independently an ether bond or an ester bond. 2 are each independently a divalent cyclic unsaturated hydrocarbon group having 3 to 10 carbon atoms or a divalent cyclic saturated hydrocarbon group having 3 to 10 carbon atoms. 21 represents a single bond, an ether bond, a carbonyl group, a sulfonyl group, a divalent saturated hydrocarbon group having 1 to 30 carbon atoms, a divalent unsaturated hydrocarbon group having 2 to 30 carbon atoms, or a divalent saturated hydrocarbon group having 1 to 30 carbon atoms substituted with a fluorine atom. p is 0, 1, or 2.

[0091] Y 2 is preferably a divalent cyclic unsaturated hydrocarbon group having 4 to 16 carbon atoms or a divalent cyclic saturated hydrocarbon group having 4 to 16 carbon atoms, more preferably a divalent cyclic unsaturated hydrocarbon group having 4 to 8 carbon atoms or a divalent cyclic saturated hydrocarbon group having 4 to 8 carbon atoms. 2 Some or all of the hydrogen atoms contained in may be substituted with an aliphatic group, and a plurality of such substituents may be bonded to each other to form a 4- to 6-membered ring.

[0092] Y 2 Specific examples of the group include, but are not limited to, groups represented by the following formulae (Y2-1) to (Y2-12). (In the formula, * represents a bond.)

[0093] Z 1 is preferably an arylene group having 6 to 20 carbon atoms or a divalent cyclic saturated hydrocarbon group having 3 to 20 carbon atoms. The arylene group or the divalent cyclic saturated hydrocarbon group may be substituted with a hydroxy group, a methyl group, or the like.

[0094] Z 1 Specific examples of the group include, but are not limited to, groups represented by the following formulae (Z1-1) to (Z1-4). (In the formula, * represents a bond.)

[0095] The polyester preferably has a repeating unit represented by the following formula (4):

[0096] In formula (4), Z 1 The ring Cy is a tetravalent cyclic saturated hydrocarbon group having 4 to 20 carbon atoms or a tetravalent group represented by the following formula (Cy-1):

[0097] In formula (Cy-1), Cy′ is a trivalent cyclic saturated hydrocarbon group having 4 to 20 carbon atoms. 31 is a divalent saturated hydrocarbon group having 1 to 20 carbon atoms or a divalent unsaturated hydrocarbon group having 2 to 20 carbon atoms, which may contain an ester bond, etc. *1 and *2 are bonds, and one of the two *1 and *2 is bonded to a hydroxy group.

[0098] The tetravalent cyclic saturated hydrocarbon group and the trivalent cyclic saturated hydrocarbon group may be monocyclic or polycyclic, and in the case of a polycyclic ring, it may be any of a fused ring, a bridged ring, a spiro ring, or a ring containing a plurality of these ring structures.

[0099] Specific examples of the group represented by Cy include groups represented by the following formulae (Cy-2) to (Cy-8). (In the formula, *1 and *2 are bonds, and one of the two *1 and *2 in each structural formula is bonded to a hydroxy group.)

[0100] Examples of the cellulose or derivatives thereof having a hydroxyalkyl group include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkyl alkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl ethyl cellulose, and derivatives thereof. Among these, hydroxyalkyl celluloses and derivatives thereof are preferred, and hydroxyethyl cellulose, hydroxypropyl cellulose, and derivatives thereof are more preferred. The cellulose or derivatives thereof having a hydroxyalkyl group may be used alone or in combination of two or more.

[0101] There are no particular limitations on the weight average molecular weight (Mw) of component (B), but it is preferably 1,000 to 500,000, more preferably 3,000 to 400,000, and even more preferably 5,000 to 300,000.

[0102] When the release layer-forming composition of the present invention contains component (B), the content thereof is preferably 0.1 to 100 parts by mass, more preferably 0.5 to 50 parts by mass, per part by mass of component (A). When the content of component (B) is within the above range, a release layer resin composition can be obtained that has high heat resistance, appropriate release properties, and excellent stability after film formation. The component (B) may be used alone or in combination of two or more types.

[0103] [Crosslinking Agent (C)] The release layer-forming composition of the present invention may optionally contain a crosslinking agent as component (C). The crosslinking agent is selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and / or an alkoxymethyl group.

[0104] The crosslinking agent is preferably a compound represented by any one of the following formulas (C-1) to (C-5).

[0105] In formulas (C-1) to (C-5), R 101 ~R 116 are each independently an alkyl group having 1 to 6 carbon atoms. B is a hydrogen atom or a methyl group.

[0106] Specific examples of the crosslinking agent include nitrogen-containing compounds such as hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, and 1,3,4,6-tetrakis(hydroxymethyl)glycoluril.

[0107] Other examples of commercially available nitrogen-containing compounds include methoxymethyl-type melamine compounds (trade names: Cymel (registered trademark) 300, Cymel 301, Cymel 303, Cymel 350), butoxymethyl-type melamine compounds (trade names: Mycoat (registered trademark) 506, Mycoat 508), glycoluril compounds (trade names: Cymel 1170, POWDERLINK 1174), methylated urea resins (trade names: UFR65), butylated urea resins (trade names: UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea / formaldehyde resins (trade names: Beckamine (registered trademark) J-300S, Beckamine P-955, Beckamine N), all manufactured by Allnex Corporation.

[0108] Also usable as a crosslinking agent are 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. 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.

[0109] More preferred examples of the crosslinking agent include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril (POWDERLINK 1174), 1,3,4,6-tetrakis(butoxymethyl)glycoluril, and 1,3,4,6-tetrakis(hydroxymethyl)glycoluril.

[0110] These crosslinking agents can undergo a crosslinking reaction by self-condensation. They can also undergo a crosslinking reaction with the hydroxyl or carboxyl groups in the resin of component (A) or (B). This crosslinking reaction strengthens the resulting release layer, resulting in a release layer with low solubility in organic solvents.

[0111] When the release layer-forming composition of the present invention contains component (C), its content is preferably 1 to 1,000 parts by weight, more preferably 2 to 800 parts by weight, per 100 parts by weight of component (A) if component (B) is not contained. When component (B) is contained, its content is preferably 5 to 200 parts by weight, more preferably 10 to 100 parts by weight, per 100 parts by weight of components (A) and (B) combined. When the content of component (C) is within the above range, a release layer resin composition can be obtained that has high heat resistance, appropriate release properties, and excellent stability after film formation. The (C) crosslinking agent may be used alone or in combination of two or more types.

[0112] [(D) Crosslinking Catalyst] The release layer-forming composition of the present invention may contain a crosslinking catalyst as component (D). Examples of the crosslinking catalyst include sulfonic acid compounds, carboxylic acid compounds, and salts thereof.

[0113] Specific examples of the sulfonic acid compound include 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. Specific examples of the carboxylic acid compound include salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, and hydroxybenzoic acid.

[0114] Examples of the salts of the acid compounds include pyridinium salts, isopropanolamine salts, and N-methylmorpholine salts of the acids. Specific examples of the salts of the sulfonic acid compounds include pyridinium p-toluenesulfonate, pyridinium 1-naphthalenesulfonate, isopropanolamine p-toluenesulfonate, and N-methylmorpholine p-toluenesulfonate. Specific examples of the salts of the carboxylic acid compounds include isopropanolamine salicylate and isopropanolamine sulfosalicylic acid.

[0115] When the release layer-forming composition of the present invention contains component (D), its content is preferably 0.01 to 100 parts by mass, more preferably 0.1 to 80 parts by mass, per 100 parts by mass of component (A) if component (B) is not contained. When component (B) is contained, its content is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of components (A) and (B) combined. When the content of component (D) is within the above range, a release layer resin composition can be obtained that provides a release layer having high heat resistance and appropriate release properties. The (D) crosslinking catalyst may be used alone or in combination of two or more types.

[0116] [Solvent (E)] The release layer-forming composition of the present invention may contain a solvent as component (E). The solvent is not particularly limited as long as it can dissolve component (A), as well as components (B), (C), and (D) used as needed, and / or other additives described below. In the present invention, glycol ether-based solvents having 3 to 20 carbon atoms, ester-based solvents having 3 to 20 carbon atoms, ketone-based solvents having 3 to 20 carbon atoms, and amide-based solvents are preferred.

[0117] Specific examples of the 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 the ester solvents include ethyl lactate, γ-butyrolactone, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate. Specific examples of the ketone solvents include methyl ethyl ketone, cyclohexanone, cyclopentanone, and benzophenone. Specific examples of the amide solvents include N-methylpyrrolidone, N,N-dimethylacetamide, and 3-methoxy-N,N-dimethylpropanamide.

[0118] The content of component (E) is preferably an amount such that the solids 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 solids are a collective term for all components of the release layer-forming composition other than the solvent. The solvent (E) may be used alone or in combination of two or more.

[0119] [Other Components] The release layer-forming composition of the present invention may contain a surfactant as needed. Addition of a surfactant can improve the coatability of the release layer-forming composition to a substrate. As the surfactant, known surfactants such as nonionic surfactants, fluorine-based surfactants, and silicone-based surfactants can be used.

[0120] 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.

[0121] Specific examples of the fluorine-based surfactant include FTOP (registered trademark) EF301, EF303, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), MEGAFAC (registered trademark) F171, F173, F554, F559, F563, R-30, R-40, R-40-LM, and DS-21 (manufactured by DIC Corporation), FLUORAD (registered trademark) FC430 and FC431 (manufactured by 3M), Asahiguard (registered trademark) AG710, and Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by AGC Inc.).

[0122] Specific examples of silicone surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0123] When the release layer-forming composition of the present invention contains a surfactant, the content thereof is preferably 0.0001 to 1 part by mass, and more preferably 0.001 to 0.5 parts by mass, per 100 parts by mass of component (A). The surfactant may be used alone or in combination of two or more types.

[0124] In addition, the release layer forming composition of an embodiment of the present invention may contain other additives such as silane coupling agents, rheology adjusters, pigments, dyes, storage stabilizers, antifoaming agents, antioxidants, etc., as long as the effects of the present invention are not impaired.

[0125] [Method for preparing the composition for forming a release layer] The method for preparing the composition for forming a release layer of the present invention is not particularly limited, and for example, a method can be mentioned in which a solution of the component (A) dissolved in a solvent is mixed with the component (B), the component (C) and / or other components, etc., at a predetermined ratio, simultaneously or in any order, as necessary, to prepare a homogeneous solution. Note that the solution of the composition for forming a release layer prepared is preferably used after filtering using a filter having a pore size of about 0.2 μm.

[0126] The viscosity of the release layer-forming composition of the present invention is appropriately set taking into consideration the thickness of the release layer to be produced, etc., but when the aim is to reproducibly obtain a film having a thickness of about 0.01 to 50 μm, the viscosity is usually preferably about 1 to 5,000 mPa·s at 25°C, and more preferably about 1 to 2,000 mPa·s.

[0127] The viscosity can be measured using a commercially available viscometer for measuring the viscosity of liquids, for example, by referring to the method described in JIS K 7117-2, at a composition temperature of 25°C. Preferably, a cone-plate type rotational viscometer is used as the viscometer, and preferably the same type of viscometer is used with a standard cone rotor of 1°34' x R24, and the viscosity can be measured at a composition temperature of 25°C. An example of such a rotational viscometer is the TVE-25L manufactured by Toki Sangyo Co., Ltd.

[0128] [Release layer] The release layer of the present invention can be produced by a method including a step of forming a resin film on a substrate using the release layer-forming composition (resin film formation step), and a step of exposing a predetermined area of ​​the resin film to ultraviolet light (exposure step).

[0129] In the resin film forming step, the resin film can be formed by applying the release layer-forming composition to a substrate and baking it. In the present invention, the substrate means a substrate on whose surface the release layer-forming composition of the present invention is applied, and which is used in the manufacture of flexible electronic devices, etc.

[0130] Examples of the substrate include glass, metal (such as silicon wafer), slate, etc., but glass is particularly preferred because the release layer obtained from the release layer-forming composition of the present invention has sufficient adhesion thereto.The substrate surface may be composed of a single material, or may be composed of two or more materials.The substrate surface may be composed of two or more materials in the form of a substrate surface in which a certain area of ​​the substrate surface is composed of one material, and the remaining surface is composed of other materials, or in which a material in a pattern such as a dot pattern or a line and space pattern is present in the other material on the entire substrate surface.

[0131] The coating method is not particularly limited, and examples thereof include slit coating, cast coating, spin coating, blade coating, dip coating, roll coating, bar coating, die coating, inkjet printing, and printing methods (relief printing, intaglio printing, planographic printing, screen printing, etc.).

[0132] Examples of the apparatus used for firing include a hot plate, an oven, etc. The heating atmosphere may be in air or in an inert gas, and may be under normal pressure or reduced pressure.

[0133] The firing temperature is usually 50 to 250°C. The firing time cannot be generally specified because it varies depending on the temperature, but is usually 1 minute to 5 hours. Furthermore, the firing step may include a step of firing at a temperature lower than the maximum temperature, as long as the maximum temperature is within the above range.

[0134] A preferred example of the heating mode in the present invention is to heat at 50 to 150°C for 1 minute to 1 hour, and then increase the heating temperature to 100 to 250°C for 5 minutes to 4 hours. A particularly preferred example of the heating mode is to heat at 50 to 150°C for 1 minute to 1 hour, and then heat at 150 to 250°C for 5 minutes to 2 hours. Another more preferred example of the heating mode is to heat at 50 to 150°C for 1 minute to 30 minutes, and then heat at 200 to 250°C for 5 minutes to 1 hour.

[0135] In the exposure step, ultraviolet light may be irradiated onto the entire surface of the resin film, or may be irradiated through a mask having a predetermined pattern. When irradiated through a mask, a release layer having a pattern such as a dot pattern or a line and space pattern formed thereon can be obtained.

[0136] The ultraviolet light is not particularly limited as long as it has a wavelength that can cause the photo-fries rearrangement, but preferably has a wavelength of 200 to 400 nm, specifically 254 nm, etc. The irradiation dose is 10 to 2,000 mJ / cm. 2 is preferred, and 50 to 1,000 mJ / cm 2 is more preferred.

[0137] When the release layer of the present invention is formed on a substrate, the release layer may be formed on a part of the surface of the substrate or on the entire surface. Forms of forming the release layer on a part of the surface of the substrate include a form in which the release layer is formed only on a predetermined area of ​​the substrate surface, and a form in which the release layer is formed in a pattern such as a dot pattern or a line and space pattern on the entire surface or a predetermined area of ​​the substrate surface.

[0138] The thickness of the release layer is usually about 0.01 to 50 μm, preferably about 0.01 to 20 μm, more preferably about 0.01 to 5 μm, from the viewpoint of productivity, and the desired thickness is achieved by adjusting the thickness of the coating film before heating.

[0139] The release layer of the present invention has excellent adhesion to a substrate, particularly a glass substrate, and also has adequate adhesion to and adequate release properties with a resin substrate. Therefore, the release layer of the present invention can be suitably used in the manufacturing process of a flexible electronic device to release a resin substrate of the device together with circuits and the like formed on the resin substrate from the substrate without damaging the resin substrate.

[0140] [Manufacturing Method of Resin Substrate] An example of a manufacturing method of a flexible electronic device using the release layer of the present invention will be described. First, a release layer is formed in a predetermined region on a substrate by the method described above using the release layer-forming composition of the present invention. A resin substrate-forming solution for forming a resin substrate is applied to the entire surface of the substrate on which the release layer has been formed in the predetermined region, and the resulting coating is baked to form a resin substrate fixed to the substrate via the release layer of the present invention.

[0141] The baking temperature of the coating film is set appropriately depending on the type of resin, etc., but the maximum temperature during baking is preferably 200 to 250°C, more preferably 210 to 250°C, and even more preferably 220 to 240°C. By setting the maximum temperature during baking in this range when producing a resin substrate, it is possible to further improve the adhesion between the underlying release layer and the base, as well as the appropriate adhesion and releasability between the release layer and the resin substrate. In this case, too, as long as the maximum temperature is within the above range, a step of baking at a temperature lower than that may be included.

[0142] Examples of the resin substrate include a resin substrate made of a thermosetting film containing an epoxy compound, a resin substrate made of an acrylic polymer, and a resin substrate made of a cycloolefin polymer. The resin substrate may be formed by a conventional method. Furthermore, the resin substrate preferably has a light transmittance of 80% or more at a wavelength of 400 nm.

[0143] Next, a desired circuit is formed as needed on the resin substrate fixed to the base via the release layer of the present invention, and then the resin substrate is cut, for example, along the release layer, and the resin substrate together with the circuit is peeled off from the release layer to separate the resin substrate from the base. At this time, a portion of the base may be cut together with the release layer. By using the release layer of the present invention, the resin substrate can be peeled off from the release layer with a peel force of 1.0 N / 25 mm or less.

[0144] The present invention will be explained in more detail below by way of synthesis examples, preparation examples, working examples and comparative examples, but the present invention is not limited to the following examples.

[0145] The compounds used in the following examples are as follows: PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate PL-LI: 1,3,4,6-tetrakis(methoxyethyl)glycoluril (manufactured by Allnex, trade name: POWDERLINK 1174) PPTS: Pyridinium p-toluenesulfonate MMA: Methyl methacrylate HPMA: 2-hydroxypropyl methacrylate HEMA: 2-hydroxyethyl methacrylate ADMA: 2-adamantyl methacrylate DCPMA: Dicyclopentanyl methacrylate PhMA: Phenyl methacrylate PhA: Phenyl acrylate AcSt: 4-acetoxystyrene NMA: 2-naphthyl methacrylate HFiPMA: 1,1,1,3,3,3-hexafluoroisopropyl methacrylate AIBN: Azobisisobutyronitrile DT: Dodecanethiol

[0146] The weight average molecular weight (Mw) of the polymer was measured using a GPC apparatus manufactured by Shimadzu Corporation (column: Shodex (registered trademark) KF803L and KF804L (manufactured by Showa Denko K.K.) ; eluent: THF; flow rate: 1.0 mL / min; column temperature: 40°C; Mw: value converted into standard polystyrene).

[0147] [1] Synthesis of Component (A) [Synthesis Example 1] 5.00 g (21.18 mmol) of HFiPMA, 1.53 g (10.59 mmol) of HPMA, 3.43 g (21.18 mmol) of PhMA, 0.54 g (2.65 mmol) of AIBN as a polymerization catalyst, and 0.43 g (2.65 mmol) of DT as a chain transfer agent were dissolved in 50.0 g of PGME and reacted under reflux for 20 hours to obtain a polymer solution. The obtained polymer solution was gradually added dropwise to a mixed solvent of 200 g of water and 200 g of methanol to precipitate a solid. The precipitated solid was filtered and dried under reduced pressure to obtain polymer (PA-1). The Mw of the acrylic copolymer (PA-1) was 6,400.

[0148] Polymers (PA-2) to (PA-7) were obtained in the same manner as in Synthesis Example 1, except that the types and amounts of raw material compounds were as shown in Table 1. The Mw of the obtained polymers is shown in Table 1.

[0149]

[0150] [2] Synthesis of Component (B) [Synthesis Example 8] 50 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemicals Corporation), 33.2 g of 5,5-diethylbarbituric acid, and 2.0 g of benzyltriethylammonium chloride were dissolved in 341 g of PGME, and the mixture was allowed to react at 130°C for 24 hours to obtain a solution containing polyurea. The obtained solution containing polyurea was slowly added dropwise to 2,000 g of hexane to precipitate a solid. The precipitated solid was filtered and dried under reduced pressure to obtain polyurea (L1). GPC analysis showed that the Mw of polyurea (L1) was 8,000.

[0151] Synthesis Example 9 100.0 g of MMA, 11.1 g of HEMA, and 5.6 g of AIBN as a polymerization catalyst were dissolved in 450.0 g of PGME and reacted at 80° C. for 20 hours to obtain an acrylic copolymer solution. The obtained acrylic copolymer solution was slowly added dropwise to 5,000 g of hexane to precipitate a solid. The precipitated solid was filtered and dried under reduced pressure to obtain acrylic polymer (L2). GPC analysis revealed that the Mw of the acrylic polymer (L2) was 7,600.

[0152] [3] Preparation of Resin Substrate Forming Composition [Preparation Example 1] Preparation of Resin Substrate Forming Composition F1 To a recovery flask containing 100 g of carbon tetrachloride, 10 g of Zeonor (registered trademark) 1020R (a cycloolefin polymer manufactured by Zeon Corporation) and 3 g of Epolead (registered trademark) GT401 (manufactured by Daicel Corporation) were added. The solution was stirred under a nitrogen atmosphere for 24 hours to dissolve the mixture, thereby preparing Resin Substrate Forming Composition F1.

[0153] [4] Preparation of release layer-forming composition [Example 1-1] 7.5 parts by mass of polymer (PA-1) as component (A), 100 parts by mass of polyurea (L1) as component (B), 25 parts by mass of PL-LI as component (C), and 3 parts by mass of PPTS as component (D) were mixed, and PGME and PGMEA were added as solvents in a mass ratio of PGME:PGMEA = 70:30 to prepare a release layer-forming composition (A-1) with a solids concentration of 5.0 mass%.

[0154] [Examples 1-2 to 1-7, Comparative Examples 1-1 and 1-2] Release layer-forming compositions A-2 to A-9 were prepared in the same manner as in Example 1-1, except that the types and amounts of each component were as shown in Table 2.

[0155]

[0156] [5] Preparation of Release Layer and Evaluation Thereof [Example 2-1] Using a spin coater (conditions: rotation speed 800 rpm for approximately 30 seconds), the release layer-forming composition (A-1) was applied onto a glass substrate (Corning Eagle XG, 100 mm x 100 mm x 0.5 mm, the same applies below) as a base. The resulting coating was heated at 100°C for 2 minutes using a hot plate, and then heated at 230°C for 10 minutes using a hot plate to form a release layer with a thickness of approximately 0.1 μm on the glass substrate. A high-pressure mercury lamp was used to irradiate a part of this release layer with ultraviolet light containing a 254 nm emission line at 100 mJ / cm. 2(254 nm equivalent) was irradiated. Then, using a spin coater (conditions: rotation speed 200 rpm, approximately 15 seconds), the resin substrate forming composition F1 was applied to the entire surface of the glass substrate on which the release layer was formed in a predetermined region. The resulting coating film was heated at 80 ° C. for 2 minutes using a hot plate, and then heated at 230 ° C. for 30 minutes using a hot plate to form a resin substrate with a thickness of approximately 3 μm on the release layer, thereby obtaining a resin substrate and a glass substrate with a release layer.

[0157] [Examples 2-2 to 2-7, Comparative Examples 2-1 and 2-2] Resin substrates and glass substrates with release layers of Examples 2-2 to 2-6 and Comparative Examples 2-1 and 2-2 were obtained in the same manner as in Example 2-1, except that the release layer-forming compositions (A-2) to (A-9) were used instead of the release layer-forming composition (A-1).

[0158] [Evaluation of Peel Force] The resin substrates and glass substrates with release layers obtained in Examples 2-1 to 2-7 and Comparative Examples 2-1 and 2-2 were cut into 25 mm x 50 mm strips using a cutter. Furthermore, Cellotape (registered trademark) (CT-24, manufactured by Nichiban Co., Ltd.) was applied, and then peeled using an Autograph AGS-X500N (manufactured by Shimadzu Corporation) at a peel angle of 90° and a peel rate of 300 mm / min, to measure the peel force. The evaluation results are shown as "peeling force" and are summarized in Table 3.

[0159]

[0160] From the results shown in Table 3, the release layer of the Example exhibited a low peel strength in the unexposed area, whereas the exposed area exhibited a higher peel strength than the unexposed area. On the other hand, the release layer of the Comparative Example exhibited a low peel strength regardless of whether it was exposed or not.

Claims

1. A release layer-forming composition comprising: (A) a polymer including a repeating unit having a photosensitive group that causes a photo-induced Fries rearrangement; and (B) a resin having a hydroxyl group or a carboxyl group, The repeating unit having a photosensitive group capable of causing a photo-induced Fries rearrangement is derived from a monomer represented by the following formula (a1) or (a2): (B) The resin having a hydroxy group or a carboxyl group is a polyurea having a hydroxy group, an acrylic polymer having a hydroxy group or a carboxyl group, a polyester having a hydroxy group, or a cellulose having a hydroxyalkyl group or a derivative thereof. A release layer forming composition. 【Chemistry 1】 (In the formula, Ar 1 is a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-biphenylyl group, a 3-biphenylyl group or a 4-biphenylyl group, and some or all of the hydrogen atoms of these groups may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a chlorine atom or a bromine atom, but at least one of the ortho-position and para-position of the oxygen atom in the formula is a hydrogen atom; Ar 2 is a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a 1,2-naphthylene group, a 1,3-naphthylene group, a 1,4-naphthylene group, a 1,5-naphthylene group, a 1,6-naphthylene group, a 1,7-naphthylene group, a 1,8-naphthylene group, a 2,3-naphthylene group, a 2,6-naphthylene group, a 2,2'-biphenylylene group, a 2,3'-biphenylylene group, a 2,4'-biphenylylene group, a 3,3'-biphenylylene group, a 3,4'-biphenylylene group or a 4,4'-biphenylylene group, in which some or all of the hydrogen atoms may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a chlorine atom or a bromine atom, but at least one of the ortho- and para-positions of the oxygen atom in the formula is a hydrogen atom; R 1 is an alkyl group having 1 to 6 carbon atoms or a phenyl group; X 1 and X 2 each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms, in which one or more -CH 2 - groups may be substituted with at least one group selected from -O-, -C(═O)-O-, and -O-C(═O)-; A 1 and A 2 each independently represent a radical polymerizable group containing a carbon-carbon double bond.

2. The resin composition for forming a release layer according to claim 1, wherein the radical polymerizable group is represented by any one of the following formulas (A-1) to (A-4): 【Chemistry 2】 (R A are each independently a hydrogen atom or a methyl group.

3. The resin composition for forming a release layer according to claim 1, wherein the polymer (A) further contains a repeating unit derived from a monomer represented by the following formula (b) and a repeating unit derived from a monomer represented by the following formula (c). 【Chemistry 3】 (In the formula, R A are each independently a hydrogen atom or a methyl group; R B 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 2 to 10 carbon atoms.

4. 2. The composition for forming a release layer according to claim 1, further comprising (C) a crosslinking agent selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and / or an alkoxymethyl group.

5. The composition for forming a release layer according to claim 1 , further comprising (D) a crosslinking catalyst.

6. A release layer obtained from the composition for forming a release layer according to any one of claims 1 to 5.

7. (A) A laminate in which a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm is laminated on a release layer obtained from a release layer-forming composition containing a polymer having a repeating unit having a photosensitive group that causes a photo-induced Fries rearrangement, The laminate, wherein the resin substrate is a thermosetting film containing an epoxy compound.

8. A method for forming a release layer, comprising the steps of forming a resin film on a substrate using the composition for forming a release layer according to any one of claims 1 to 5, and exposing a predetermined area of ​​the resin film to ultraviolet light.

9. A method for manufacturing a resin substrate, comprising the steps of: forming a resin film on a substrate using a release layer forming composition containing a polymer including a repeating unit having a photosensitive group that undergoes optical Friesian rearrangement; exposing a predetermined area of ​​the resin film to ultraviolet light; 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 formed on the release layer with a peeling force of 1.0 N / 25 mm or less.

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