WO2022210640A1 - Composition for forming release layer, and release layer - Google Patents

Composition for forming release layer, and release layer Download PDF

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Publication number
WO2022210640A1
WO2022210640A1 PCT/JP2022/015279 JP2022015279W WO2022210640A1 WO 2022210640 A1 WO2022210640 A1 WO 2022210640A1 JP 2022015279 W JP2022015279 W JP 2022015279W WO 2022210640 A1 WO2022210640 A1 WO 2022210640A1
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WO
WIPO (PCT)
Prior art keywords
group
release layer
resin
substrate
forming
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Application number
PCT/JP2022/015279
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French (fr)
Japanese (ja)
Inventor
優樹 古川
潤 伊藤
元信 松山
Original Assignee
日産化学株式会社
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Application filed by 日産化学株式会社 filed Critical 日産化学株式会社
Priority to JP2023511329A priority Critical patent/JPWO2022210640A1/ja
Priority to CN202280022122.3A priority patent/CN117015582A/en
Priority to KR1020237036908A priority patent/KR20230164113A/en
Publication of WO2022210640A1 publication Critical patent/WO2022210640A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor

Definitions

  • the present invention relates to a release layer-forming composition and a release layer.
  • the base material of the touch panel film has also changed from glass to a sheet made of plastic such as polyethylene terephthalate (PET), polyimide, cycloolefin, acrylic, etc., and a transparent flexible touch screen panel with flexibility has been developed.
  • PET polyethylene terephthalate
  • Patent Documents 5 to 7 a sheet made of plastic such as polyethylene terephthalate (PET), polyimide, cycloolefin, acrylic, etc.
  • a release (adhesive) layer is prepared on a support substrate such as a glass substrate.
  • a support substrate such as a glass substrate.
  • Patent Document 8 While the flexible touch panel screen should not be peeled off from the support substrate during the process, a low peel force is required when peeling. In particular, if the flexible touch screen panel is peeled off from the supporting substrate during the manufacturing process, the production line may be contaminated, resulting in a significant drop in yield. In addition, in order to improve productivity, it is necessary to store the formed release layer for a long period of time after forming the release layer. Therefore, the release layer is required to have stability after film formation.
  • the present invention has been made in view of the above circumstances, and provides a release layer that has high heat resistance and moderate release properties, can suppress unnecessary separation during the process, and has excellent stability after film formation.
  • An object of the present invention is to provide a composition for forming a release layer that provides
  • the present inventors have made intensive studies to achieve the above objects, and found that (A) a resin having a hydroxy group or a carboxy group, (B) a photoacid generator, and (C) a hydroxyalkyl group and/or an alkoxy group.
  • a resin composition containing a cross-linking agent selected from compounds having a nitrogen atom substituted with a methyl group, (D) a polymer additive containing a predetermined repeating unit, and (E) a solvent exposure and development steps A release layer can be formed in a predetermined region by can be given with good reproducibility, and completed the present invention.
  • the present invention provides the following release layer-forming composition and release layer.
  • A a resin having a hydroxy group or a carboxy group
  • B a photoacid generator
  • C a cross-linking agent selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and/or an alkoxymethyl group
  • D a polymer additive containing a repeating unit represented by the following formula (a), a repeating unit represented by the following formula (b) and a repeating unit represented by the following formula (c)
  • E a solvent wherein the (D) polymer additive is contained in an amount of 5 to 100 parts by mass based on 100 parts by mass of the resin (A) having a hydroxy group or a carboxyl group.
  • R A is each independently a hydrogen atom or a methyl group
  • RB 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, but the carbon atom to which the hydroxy group is attached is a secondary or tertiary carbon atom
  • R D is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.
  • the resin having a hydroxy group or a carboxy group is 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 or a derivative thereof having a hydroxyalkyl group.
  • a laminate in which a resin layer having a transmittance of 80% or more for light with a wavelength of 400 nm is laminated on the release layer of 4. 6.
  • a method for producing a release layer comprising: exposing a predetermined region of the resin film to radiation; and developing the exposed resin film to remove an unexposed portion. 7.
  • the composition for forming a release layer of the present invention By using the composition for forming a release layer of the present invention, a release layer that has excellent adhesion to a substrate and appropriate release properties from a resin substrate and can be formed in a predetermined area through exposure and development steps can be reproduced. You can get it sexually.
  • the composition for forming a release layer of the present invention can contribute to speeding up the manufacturing process of flexible electronic devices having a resin substrate, improving the yield thereof, and the like.
  • the release layer-forming composition of the present invention contains (A) a resin having a hydroxy group or a carboxy group, (B) a photoacid generator, and (C) a nitrogen atom substituted with a hydroxyalkyl group and/or an alkoxymethyl group. (D) a polymeric additive containing a predetermined repeating unit; and (E) a solvent.
  • the resin having a hydroxy group or a carboxy group of the component (A) is not particularly limited as long as it reacts with the acid generated from the component (B) and the cross-linking agent of the component (C) to be cured.
  • 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 or a derivative thereof having a hydroxyalkyl group.
  • polyurea having a hydroxy group one containing a repeating unit represented by the following formula (1) is preferable.
  • 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. All of A 1 to A 6 are preferably hydrogen atoms.
  • X 1 is a group represented by formula (X1), (X2), (X3) or (X4) below. (Wherein, * is a bond with a carbonyl group in the formula.** is a bond with a nitrogen atom in the formula.)
  • 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 is at least 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. It may be substituted with one group.
  • R 1 and R 2 may combine with each other to form a ring having 3 to 6 carbon atoms together with the carbon atoms to which they are combined.
  • 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 is at least 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. It may be substituted with one group.
  • Q 1 is a group represented by formula (Q1) or (Q2) below. (In the formula, * is a bond.)
  • X 2 is a group represented by formula (X1), formula (X2) or formula (X4).
  • formula (Q1) for example, when X 2 is a group represented by formula (X2), the structure is represented by formula (Q1-1) below. (Wherein, R 1 and R 2 are the same as above. * is a bond.)
  • 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 are alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxy groups, and alkylthio groups having 1 to 6 carbon atoms. may be substituted with at least one group selected from the group consisting of Moreover, when Q 2 is a phenylene group, a naphthylene group or an anthrylene group, the position of their bond is not particularly limited.
  • the naphthylene group is 1
  • the anthrylene group is It may be bonded at the 1st and 2nd positions, at the 1st and 4th positions, or at the 9th and 10th positions.
  • n 1 and n 2 are each independently 0 or 1;
  • the alkyl group having 1 to 6 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, isopropyl, n-butyl and cyclohexyl groups.
  • the alkenyl group having 3 to 6 carbon atoms may be linear, branched or cyclic, and examples thereof include 2-propenyl group and 3-butenyl group.
  • the alkoxy group having 1 to 6 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methoxy, ethoxy, isopropoxy, n-pentyloxy and cyclohexyloxy groups. is mentioned.
  • the alkylthio group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methylthio, ethylthio, isopropylthio, n-pentylthio, cyclohexylthio, and the like. mentioned.
  • Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the ring having 3 to 6 carbon atoms formed by combining R 1 and R 2 includes cyclobutane ring, cyclopentane ring, cyclohexane ring and the like.
  • the alkylene group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methylene, ethylene, propylene, pentamethylene, cyclohexylene, and 2-methyl A propylene group and the like can be mentioned.
  • X 1 when X 1 is a group represented by formula (X2), its structure is represented by the following formula (1A), and X 1 is a group represented by formula (X3). In the case of , the structure is represented by the following formula (1B). In formula (X3), R 3 is preferably a 2-propenyl group. (In the formula, A 1 to A 6 , R 1 to R 3 and Q 1 are the same as above.)
  • Q 1 preferably contains a cyclic structure from the viewpoint of the heat resistance of the polyurea component (A). That is, it is preferable that Q 1 is a group represented by formula (Q1) or a group represented by formula (Q2) and Q 2 is a cyclic alkylene group, a phenylene group, a naphthylene group or an anthrylene group, A group represented by formula (Q1) is more preferred.
  • the polyurea can be synthesized, for example, with reference to International Publication No. 2005/098542.
  • acrylic polymer having a hydroxy group or a carboxyl group examples include acrylic acid ester homopolymers, methacrylic acid ester homopolymers, copolymers thereof, and monomers having unsaturated double bonds such as styrene. Copolymers can be used.
  • a preferable 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 the main chain skeleton (other repeating units) and side chains constituting the acrylic polymer are not particularly limited.
  • 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).
  • R 11 is a hydrogen atom or a methyl group.
  • R 12 is a --(CH 2 CH 2 O) n --H group or a hydroxyalkyl group having 2 to 6 carbon atoms.
  • n is an integer of 2-30, preferably an integer of 2-10.
  • hydroxyalkyl group having 2 to 6 carbon atoms examples include 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group and 1-hydroxybutyl group. , 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, 2,3-dihydroxypropyl group and the like.
  • the acrylic polymer contains repeating units other than the repeating unit represented by formula (2), specifically, polyethylene glycol ester groups and hydroxyalkyl esters having 2 to 6 carbon atoms.
  • a repeating unit derived from a monomer having no group may be included.
  • the method for producing the acrylic polymer is not particularly limited. 6 and a monomer having no hydroxyalkyl ester group are polymerized in a solution of a polymerization initiator dissolved in a solvent at a temperature of 50 to 110°C.
  • the solvent to be used is not particularly limited as long as it dissolves the monomer, the polymerization initiator, and the like.
  • Examples of the monomer having a polyethylene glycol ester group include monoacrylates and monomethacrylates of H--(OCH 2 CH 2 ) n --OH (where n is the same as above).
  • 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, glycerin monomethacrylate and the like.
  • Examples of monomers that do 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, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, and butyl acrylate.
  • the acrylic polymer obtained by the above method is usually in the form of a solution dissolved in a solvent.
  • acrylic polymer examples include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, glycerin monoacrylate, glycerin.
  • acrylic polymers having hydroxyalkyl groups in side chains such as polymers obtained by copolymerizing one or more monomers selected from
  • the polyester having a hydroxy group is not particularly limited, but preferably has an aromatic group or an alicyclic group in its main chain.
  • a polyester obtained by reacting a compound having two or more epoxy moieties and a compound having two carboxyl groups is preferable.
  • 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, and tetrachlorobisphenol A diglycidyl.
  • Compounds having two carboxy groups include terephthalic acid, isophthalic acid, diphenic acid, 2-methylterephthalic acid, 2-hydroxyterephthalic acid, 2,5-dimethylterephthalic acid, 5-methylisophthalic acid, and 5-hydroxyisophthalic acid. , 2,6-naphthalenedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like. In addition, these compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the method for synthesizing the polyester is not particularly limited, but examples include a method of polymerizing at a temperature of 50 to 150°C in a solvent containing the ester compound, the carboxy group-containing compound, and the catalyst.
  • the solvent to be used is not particularly limited as long as it dissolves the above-mentioned compound, polymerization initiator, and the like.
  • the polyester obtained by the above method is usually in the form of a solution dissolved in a solvent.
  • the polyester preferably contains a repeating unit represented by the following formula (3).
  • Y 1 and Z 1 are each independently a divalent group having an aromatic ring or an alicyclic ring.
  • Y 1 is preferably a group represented by the following formula (Y1-1). (In the formula, * is a bond.)
  • each L 1 is independently an ether bond or an ester bond.
  • Each Y 2 is independently a C3-10 bivalent cyclic unsaturated hydrocarbon group or a C3-10 bivalent cyclic saturated hydrocarbon group.
  • R 21 is a single bond, an ether bond, a carbonyl group, a sulfonyl group, a C 1-30 divalent saturated hydrocarbon group, a C 2-30 divalent unsaturated hydrocarbon group, or substituted with a fluorine atom It is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.
  • p is 0, 1 or 2;
  • Y 2 is preferably a divalent cyclic unsaturated hydrocarbon group having 4 to 16 carbon atoms or a saturated cyclic divalent hydrocarbon group having 4 to 16 carbon atoms, and a divalent cyclic unsaturated hydrocarbon group having 4 to 8 carbon atoms. Or a C4-C8 bivalent cyclic saturated hydrocarbon group is more preferred.
  • some or all of the hydrogen atoms contained in Y 2 may be substituted with an aliphatic group, and a plurality of substituents among them may be bonded together to form a 4- to 6-membered ring. .
  • Y 2 include, but are not limited to, groups represented by the following formulas (Y2-1) to (Y2-12). (In the formula, * is a bond.)
  • Z 1 is preferably an arylene group having 6 to 20 carbon atoms or a saturated bivalent cyclic hydrocarbon group having 3 to 20 carbon atoms.
  • the arylene group or bivalent cyclic saturated hydrocarbon group may be substituted with a hydroxy group, a methyl group, or the like.
  • Z 1 examples include, but are not limited to, groups represented by the following formulas (Z1-1) to (Z1-4). (In the formula, * is a bond.)
  • polyester one having a repeating unit represented by the following formula (4) is also preferable.
  • 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).
  • Cy' is a trivalent cyclic saturated hydrocarbon group having 4 to 20 carbon atoms.
  • R 31 is a C 1-20 divalent saturated hydrocarbon group or a C 2-20 divalent unsaturated hydrocarbon group, which may contain an ester bond or the like.
  • *1 and *2 are bonds, and one of the two *1 and *2 each bonds to a hydroxy group.
  • the tetravalent cyclic saturated hydrocarbon group and trivalent cyclic saturated hydrocarbon group may be monocyclic or polycyclic, and in the case of polycyclic, condensed rings, bridged rings, spiro rings, and a plurality of these ring structures are included. can be either.
  • Cy groups represented by the following formulas (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 respectively bonds to a hydroxy group.)
  • Examples of the cellulose having a hydroxyalkyl group or derivatives thereof include hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose, hydroxyalkylalkylcelluloses such as hydroxyethylmethylcellulose, hydroxypropylmethylcellulose and hydroxyethylethylcellulose, and derivatives thereof. is mentioned. Among these, hydroxyalkyl celluloses and their derivatives are preferred, and hydroxyethyl cellulose, hydroxypropyl cellulose and their derivatives are more preferred.
  • the cellulose or derivative thereof having the hydroxyalkyl group may be used alone or in combination of two or more.
  • the weight average molecular weight (Mw) of component (A) 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. .
  • a weight average molecular weight is a polystyrene conversion measurement value by a gel permeation chromatography (GPC).
  • the release layer-forming composition of the present invention contains a photoacid generator as the component (B).
  • the photoacid generator of component (B) is not particularly limited as long as it is a compound that is photolyzed by irradiated radiation to generate an acid.
  • Examples of the acid generated when the photoacid generator is photolyzed include hydrochloric acid; methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p -toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4- Ethylbenzenesulfonic acid, 1H,1H,2H,2H-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic
  • photoacid generator examples include bis(tosyloxy)ethane, bis(tosyloxy)propane, bis(tosyloxy)butane, p-nitrobenzyltosylate, o-nitrobenzyltosylate, and 1,2,3-phenylenetris.
  • Photoacid generator Commercially available products can be used as the photoacid generator, and specific examples include Irgacure (registered trademark) PAG103, PAG121, PAG203 (manufactured by BASF Japan Co., Ltd.) Adeka Arcles (registered trademark) SP -056, SP-066, SP-140, SP-141, SP-082, SP-601, SP-606, SP-701, SP-150, SP-170, SP-171 (manufactured by ADEKA Co., Ltd.) ), CPI (registered trademark) -110P, -110B, -310B, -210S, -100P, -101A, -200K (manufactured by San-Apro Co., Ltd.), PAI-01, PAI-101, DPI-105, DPI -106, DPI-109, DPI-201, BI-105, MPI-105, MPI-106, MPI-109, BBI-102, BBI-103, BBI
  • the content of the photoacid generator as component (B) is preferably 0.01 to 15 parts by mass, preferably 0.1, per 100 parts by mass of the resin as component (A). ⁇ 10 parts by mass is more preferable.
  • the content of the photoacid generator is within the above range, it has high heat resistance and moderate peelability, can form a peeling layer on a predetermined region on the substrate, and has good stability after film formation. An excellent composition for forming a release layer is obtained.
  • the photoacid generator may be used singly or in combination of two or more.
  • the release layer-forming composition of the present invention contains a cross-linking agent as the component (C).
  • the cross-linking agent is selected from compounds having nitrogen atoms substituted with hydroxyalkyl groups and/or alkoxymethyl groups.
  • cross-linking agent a compound represented by any one of the following formulas (C-1) to (C-5) is preferable.
  • R 101 to R 116 are each independently an alkyl group having 1 to 6 carbon atoms.
  • RB is a hydrogen atom or a methyl group.
  • cross-linking agent examples include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril, and 1,3,4,6-tetrakis(butoxymethyl)glycoluril. , 1,3,4,6-tetrakis(hydroxymethyl)glycoluril and other nitrogen-containing compounds.
  • Methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, Cymel 301, Cymel 303, Cymel 350) and butoxymethyl type melamine compounds (trade names: Mycoat (registered trademark) 506, Mycoat 508) manufactured by Allnex Corporation , glycoluril compound (trade name Cymel 1170, POWDERLINK 1174), methylated urea resin (trade name UFR65), butylated urea resin (trade name UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC Corporation commercially available nitrogen-containing compounds such as urea/formaldehyde-based resins (trade names: Beckamin (registered trademark) J-300S, Beckamin P-955, Beckamin N).
  • a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, etc.
  • Polymers made using (meth)acrylamide compounds substituted with can be used.
  • polymers examples include poly(N-butoxymethyl(meth)acrylamide), copolymers of N-butoxymethyl(meth)acrylamide and styrene, N-hydroxymethyl(meth)acrylamide and methyl (meth) Copolymer with acrylate, copolymer of N-ethoxymethyl methacrylamide and benzyl methacrylate, copolymer of N-butoxymethyl (meth)acrylamide, benzyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate, etc. is mentioned.
  • Hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril (POWDERLINK 1174), 1,3,4,6-tetrakis(butoxymethyl) are more preferred as the cross-linking agent.
  • glycoluril and 1,3,4,6-tetrakis(hydroxymethyl)glycoluril are more preferred as the cross-linking agent.
  • cross-linking agents can cause a cross-linking reaction through self-condensation.
  • it can cause a cross-linking reaction with a hydroxyl group or a carboxy group in the resin of component (A).
  • the formed peeling layer is strengthened and becomes a peeling layer having low solubility in organic solvents.
  • the content of the cross-linking agent as component (C) is preferably 10 to 100 parts by mass, more preferably 20 to 50 parts by mass, with respect to 100 parts by mass of the resin as component (A). preferable. If the content of (C) the cross-linking agent is within the above range, it is possible to obtain a release layer resin composition that has high heat resistance and appropriate release properties and is excellent in stability after film formation.
  • a crosslinking agent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the (D) component is a repeating unit represented by the following formula (a), a repeating unit represented by the following formula (b), and a repeating unit represented by the following formula (c). Contains polymeric additives containing repeating units.
  • R A is each independently a hydrogen atom or a methyl group.
  • RB 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, and the carbon atom to which the hydroxy group is attached is a secondary or tertiary carbon atom.
  • R D is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.
  • Examples of the branched alkyl group having 3 or 4 carbon atoms include isopropyl group, isobutyl group, sec-butyl group and tert-butyl group.
  • R B is preferably one in which at least one hydrogen atom of these branched alkyl groups is substituted with a fluorine atom, and specific examples thereof include 1,1,1-trifluoroisopropyl group, 1,1,1, 3,3,3-hexafluoroisopropyl group, nonafluoro-tert-butyl group and the like.
  • hydroxyalkyl group having 2 to 10 carbon atoms examples include 1-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 2-hydroxybutyl group, 2-hydroxyhexyl group, 2-hydroxyoctyl group, 2 -hydroxydecyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-2-methylpropyl group and the like.
  • Examples of the polycyclic alkyl group having 6 to 20 carbon atoms include 1-adamantyl group, 2-adamantyl group, isobornyl group and norbornyl group.
  • Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-biphenyl group and 2-biphenyl group.
  • repeating units represented by formula (a) include, but are not limited to, those represented by formulas (a-1) to (a-3) below.
  • RA is the same as described above.
  • repeating unit represented by formula (b) examples include, but are not limited to, those represented by formulas (b-1) to (b-4) below.
  • RA is the same as described above.
  • repeating unit represented by formula (c) examples include, but are not limited to, those represented by formulas (c-1) to (c-13) below.
  • RA is the same as described above.
  • the content of the repeating unit represented by formula (a) is preferably 30 to 60 mol%, more preferably 35 to 50 mol%, of all 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 all repeating units.
  • the content of the repeating unit represented by formula (c) is preferably 5 to 60 mol %, more preferably 20 to 50 mol %, of all repeating units.
  • the Mw of the polymer additive is preferably 2,000 to 10,000, more preferably 3,000 to 6,000. Also, the Mw/Mn is preferably 1.0 to 2.1, more preferably 1.0 to 1.9.
  • the content of the polymer additive as component (D) is 5 to 100 parts by mass, but 5 to 90 parts by mass with respect to 100 parts by mass of the resin as component (A). parts are preferred, and 5 to 80 parts by mass are more preferred. If the content of the polymer additive (D) is less than 5 parts by mass, the release force may increase, and if it exceeds 100 parts by mass, the film may be repelled during film formation.
  • Polymer additives may be used singly or in combination of two or more.
  • the release layer-forming composition of the present invention contains a solvent as component (E).
  • a solvent as component (E).
  • glycol ether-based solvent examples include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether, propylene glycol monopropyl ether, and the like.
  • ester solvent examples include ethyl lactate, ⁇ -butyrolactone, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate.
  • ketone solvent examples include methyl ethyl ketone, cyclohexanone, cyclopentanone, and benzophenone.
  • the cyclic compound solvent examples include N-methylpyrrolidone and ⁇ -butyrolactone.
  • the content of the component (E) solvent 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. , 0.5 to 20% by mass, and even more preferably 0.5 to 10% by mass.
  • the solid content is a general term for all components of the release layer-forming composition other than the solvent.
  • the solvent may be used singly or in combination of two or more.
  • the release layer-forming composition of the present invention may contain a surfactant, if necessary. Addition of a surfactant can improve the applicability of the release layer-forming composition to a substrate.
  • a surfactant known surfactants such as nonionic surfactants, fluorine-based surfactants, and silicone-based surfactants can be used.
  • nonionic surfactant examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl; polyoxyethylene alkylaryl ethers such as phenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene/polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, Sorbitan fatty acid esters such as sorbitan trioleate and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan Examples include polyoxyethylene sorbitan fatty acid esters such as tristearate.
  • fluorine-based surfactants examples include Ftop (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac (registered trademark) F171, F173, F554, F559, F563, R- 30, R-40, R-40-LM, DS-21 (manufactured by DIC Corporation), FLUORAD (registered trademark) FC430, FC431 (manufactured by 3M), Asahiguard (registered trademark) AG710, Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and the like.
  • Ftop registered trademark
  • EF303 EF352
  • Megafac registered trademark
  • F171, F173, F554, F559, F563, R- 30, R-40, R-40-LM examples of the fluorine-based surfactants
  • silicone-based surfactants examples include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the release layer-forming composition contains a surfactant
  • the content thereof is preferably 0.0001 to 1 part by mass, more preferably 0.001 to 0.5 part by mass, based on 100 parts by mass of the resin (A). more preferred.
  • the said surfactant may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the method for preparing the release layer-forming composition of the present invention is not particularly limited. Examples include a method in which the components are mixed in a predetermined ratio to form a uniform solution, and a method in which other additives are further added and mixed as necessary in an appropriate stage of the preparation method.
  • the polymer solution obtained by the polymerization reaction in the solvent can be used as it is.
  • component (B), component (C), component (D) and component (E) are added to the solution of component (A) in the same manner as described above to form a uniform solution.
  • a solvent may be additionally added for the purpose of adjusting the concentration.
  • the solvent used in the production process of the component (A) and the solvent used for adjusting the concentration of the release layer-forming composition may be the same or different.
  • the prepared solution of the composition for forming a release layer after filtering using a filter or the like having a pore size of about 0.2 to 1.0 ⁇ m.
  • the viscosity of the release layer-forming composition of the present invention is appropriately set in consideration of the coating method to be used, the thickness of the release layer to be produced, and the like. For the purpose of obtaining a high viscosity, it is usually about 1 to 5,000 mPa ⁇ s, preferably about 1 to 2,000 mPa ⁇ s at 25°C.
  • the viscosity can be measured using a commercially available viscometer for measuring the viscosity of a liquid, for example, with reference to the method described in JIS K7117-2, under the condition of a composition temperature of 25 ° C. .
  • a viscometer a cone-plate type (cone-plate type) rotational viscometer is used, preferably with a viscometer of the same type using a standard cone rotor of 1 ° 34' ⁇ R24, and the temperature of the composition is 25 It can be measured under the conditions of °C.
  • An example of such a rotational viscometer is TVE-25L manufactured by Toki Sangyo Co., Ltd.
  • the release layer of the present invention can be formed by a process of forming a resin film on a substrate using the release layer-forming composition (resin film forming process) and a process of exposing a predetermined region of the resin film to radiation (exposure process). , the resin film irradiated with radiation can be developed with a developing solution to remove the unexposed portion (developing step).
  • examples of the method of forming the resin film include a method of applying the composition for forming a release layer onto a substrate and then heating.
  • a step of volatilizing the solvent as preliminary drying may be included before heating.
  • substrate means a substrate on the surface of which the composition for forming a release layer of the present invention is applied and used for the production of flexible electronic devices and the like.
  • the substrate examples include glass, metal (silicon wafer, etc.), slate, and the like. Glass is preferred.
  • the substrate surface may be composed of a single material, or may be composed of two or more materials. Examples of embodiments in which the surface of the substrate is composed of two or more materials include an embodiment in which a certain area of the surface of the substrate is composed of a certain material and the rest of the surface is composed of another material; , a patterned material such as a line-and-space pattern exists in another material.
  • the coating method is not particularly limited, but for example, slit coating method, cast coating method, spin coating method, blade coating method, dip coating method, roll coating method, bar coating method, die coating method, inkjet method, printing method (letterpress , intaglio, lithography, screen printing, etc.).
  • a method of pre-drying for example, a method of enclosing the substrate coated with the release layer forming composition in a predetermined container and reducing the pressure to volatilize the solvent can be used.
  • the method of decompression is not particularly limited, but includes a method of decompressing the inside of the pressure vessel to a predetermined degree of decompression using a vacuum pump.
  • the degree of pressure reduction is usually 20-200 Pa, preferably 40-100 Pa.
  • the depressurization time varies depending on the performance of the vacuum pump and the size of the pressure vessel, and cannot be generally specified, but is usually 10 to 60 seconds, preferably 15 to 30 seconds.
  • Equipment used for heating includes, for example, hot plates and ovens.
  • the heating atmosphere may be under air or under an inert gas, and may be under normal pressure or under reduced pressure.
  • the heating temperature is usually 50-250°C, preferably 50-150°C.
  • the heating time varies depending on the heating temperature and cannot be generally specified, but is usually 1 minute to 5 hours, preferably 1 minute to 1 hour.
  • a method of irradiating a predetermined region with radiation is a method of irradiating through a mask having a predetermined pattern.
  • a release layer having a pattern such as a dot pattern or a line and space pattern is obtained.
  • the radiation is not particularly limited as long as it has a wavelength that can be absorbed by the photoacid generator, and examples thereof include ultraviolet light or visible light with a wavelength of 150 to 800 nm. Ultraviolet rays with a wavelength of 200 to 400 nm are preferred, and specific examples include i-line (365 nm). Moreover, the irradiation amount is sufficient so long as the exposed portion is completely cured, and is preferably 100 to 2,000 mJ/cm 2 , more preferably 300 to 1,000 mJ/cm 2 .
  • the irradiation direction of the radiation is not particularly limited, but it may be irradiated in a direction perpendicular to the substrate surface, or in an oblique direction, or in combination thereof. It is preferable to irradiate from an angle close to the direction perpendicular to the substrate surface.
  • the light source to be used is not particularly limited as long as it can irradiate light in the above wavelength band. mentioned. Radiation in the preferred wavelength range described above can be obtained by using the light source and a filter or the like in combination.
  • PEB heat treatment
  • the heating temperature for PEB is usually 50 to 250°C, preferably 80 to 200°C.
  • the heating time varies depending on the heating temperature and cannot be generally defined, but is usually 30 seconds to 30 minutes, preferably 1 to 20 minutes.
  • the developer used in the development step may be any one that can dissolve and remove the unexposed areas, and may be appropriately selected according to the resin of component (A).
  • the developer include glycol ether-based organic solvents such as propylene glycol monomethyl ether; aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide; tetramethylammonium hydroxide; Alkaline aqueous solutions such as aqueous solutions of quaternary ammonium hydroxide salts such as tetraethylammonium oxide and choline, and aqueous solutions of amines such as ethanolamine, propylamine and ethylenediamine can be used.
  • a surfactant or the like may be added to these developers.
  • any of a liquid heaping method, a dipping method, a rocking immersion method, and the like can be used as a developing method.
  • the development time at that time is usually 15 to 300 seconds.
  • the release layer was washed with running water for, for example, 20-120 seconds, followed by air drying with compressed air or compressed nitrogen, or by spinning to remove moisture on the substrate and patterned. A membrane is obtained.
  • Heat treatment may be performed after development.
  • the heating temperature is usually 50 to 300°C, preferably 80 to 250°C.
  • the heating time varies depending on the heating temperature and cannot be generally defined, but is usually 30 seconds to 30 minutes, preferably 1 to 20 minutes.
  • a predetermined effect can also be obtained by removing only the component (D) present on the release layer surface by development.
  • the thickness of the release layer is usually about 0.01 to 50 ⁇ m, but from the viewpoint of productivity, it is preferably about 0.01 to 20 ⁇ m, more preferably about 0.01 to 5 ⁇ m.
  • the thickness of the coating is adjusted to achieve the desired thickness.
  • the release layer of the present invention has excellent adhesion to substrates, particularly glass substrates, and moderate adhesion and moderate releasability to resin substrates. Therefore, the release layer of the present invention allows the resin substrate of the device to be peeled off from the substrate together with the circuit or the like formed on the resin substrate without damaging the resin substrate of the device in the manufacturing process of the flexible electronic device. It can be suitably used to allow
  • a release layer is formed on a predetermined region on a substrate by the method described above.
  • a resin substrate forming solution for forming a resin substrate is applied to the surface of the substrate on which the release layer is formed in a predetermined region so as to cover the entire release layer, and the obtained coating film is baked.
  • a resin substrate fixed to a substrate is formed through the release layer of the present invention.
  • the firing temperature of the coating film is appropriately set according to the type of resin, etc., but the maximum temperature during firing is preferably 200 to 250 ° C., more preferably 210 to 250 ° C., and 220 ° C. It is more preferable to set the temperature to 240°C.
  • the maximum temperature during baking in the production of the resin substrate within this range, the adhesiveness between the base release layer and the substrate, and the appropriate adhesion and releasability between the release layer and the resin substrate are further improved. be able to. Also in this case, as long as the maximum temperature falls within the above range, a step of firing at a temperature lower than that may be included.
  • the resin substrate is preferably formed with an area larger than that of the area where the release layer is formed.
  • the resin substrate include a resin substrate made of acrylic polymer and a resin substrate made of cycloolefin polymer.
  • a method for forming the resin substrate may follow a conventional method.
  • the resin substrate preferably has a transmittance of 80% or more for light with a wavelength of 400 nm.
  • the resin substrate fixed to the substrate via the release layer of the present invention a desired circuit is formed as necessary, and then, for example, the resin substrate is cut along the release layer to obtain the circuit. At the same time, the resin substrate is separated from the release layer to separate the resin substrate and the base. At this time, part of the substrate may be cut together with the release layer.
  • the release layer of the present invention the resin substrate can be separated from the release layer with a release force of 1.0 N/25 mm or less.
  • 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
  • PAG103 Irgacure PAG103 manufactured by BASF (compound represented by the above formula (PAG-4)
  • PAG121 Irgacure PAG121 manufactured by BASF (compound represented by the formula (PAG-2)
  • PAI101 PAI-101 manufactured by Midori Chemical Co., Ltd.
  • MAA methacrylate MMA: methyl methacrylate
  • HPMA 2-hydroxypropyl methacrylate
  • HEMA 2-hydroxyethyl methacrylate
  • ADMA 2-adamantyl methacrylate
  • CHMI N-cyclohexylmaleimide
  • PQMA 4-hydroxyphenyl methacrylate
  • HFiPMA methacrylic acid 1,1,1,3,3,3-hexafluoroisopropyl
  • AIBN azobisisobutyronitrile
  • EP bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: jER828)
  • IPhA isophthalic acid
  • BTEAC benzyltriethylammonium chloride
  • HPC hydroxypropyl cellulose
  • KOH potassium hydroxide
  • the weight average molecular weight (Mw) of the polymer was measured using a GPC apparatus manufactured by Shimadzu Corporation (column: Shodex (registered trademark) KF803L and KF804L (manufactured by Showa Denko Co., Ltd.); eluent: THF; flow rate: 1 0 mL/min; column temperature: 40° C.; Mw: standard polystyrene conversion value).
  • release layer-forming composition 100 parts by mass of polyurea (L1) obtained in Synthesis Example 1 as component (A), (B ) component 3 parts by mass of PAG121, 7.5 parts by mass of PL-LI as component (C), 7.5 parts by mass of acrylic polymer (S2) as component (D), and PGMEA are added, and the solid content concentration is The mixture was diluted with PGME so that the PGMEA concentration was 5% by mass and the PGMEA concentration was 30% by mass to prepare a release layer forming composition A-1.
  • Examples 1-2 to 1-6, Comparative Examples 1-1 and 1-2 Compositions A-2 to A-8 for forming a release layer 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 1.
  • release layer and resin substrate [Example 2-1] Using a spin coater (conditions: 800 rpm for about 30 seconds), the release layer forming composition A-1 was coated on a glass substrate (Corning Eagle XG, 100 mm ⁇ 100 mm ⁇ 0.5 mm, hereinafter the same) as a substrate. was applied on top of The obtained coating film was heated at 100° C. for 2 minutes using a hot plate. A part of this coating film is irradiated with 500 mJ/cm 2 of ultraviolet light having a wavelength of 365 nm and a light intensity of 3.5 mW/cm 2 using an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc., and then baked after exposure.
  • a spin coater condition: 800 rpm for about 30 seconds
  • the release layer forming composition A-1 was coated on a glass substrate (Corning Eagle XG, 100 mm ⁇ 100 mm ⁇ 0.5 mm, hereinafter the same) as a substrate. was applied on top
  • Example 2-2 to 2-6 Comparative Examples 2-1 and 2-2
  • a resin substrate and a glass substrate with a release layer were obtained in the same manner as in Example 2-1, except that the release layer-forming composition, PEB temperature, and developer were as shown in Table 2.

Abstract

The present invention provides a composition for forming a release layer, the composition containing: (A) a resin having a hydroxy group or a carboxy group; (B) a photoacid generator; (C) a crosslinking agent which is selected from among compounds having a nitrogen atom that is substituted by a hydroxyalkyl group and/or an alkoxymethyl group; (D) a polymer additive which comprises a repeating unit represented by formula (a), a repeating unit represented by formula (b), and a repeating unit represented by formula (c); and (E) a solvent. With respect to this composition for forming a release layer, the polymer additive (D) is contained in an amount of 5 parts by mass to 100 parts by mass with respect to 100 parts by mass of the resin (A) having a hydroxy group or a carboxy group.

Description

剥離層形成用組成物及び剥離層Release layer-forming composition and release layer
　本発明は、剥離層形成用組成物及び剥離層に関する。 The present invention relates to a release layer-forming composition and a release layer.
　近年、電子デバイスには、薄型化及び軽量化という特性に加え、曲げることができるという機能を付与することが求められている。このことから、従来の重く脆弱で曲げることができないガラス基板にかわって、軽量なフレキシブルプラスチック基板を用いることが求められる。 In recent years, in addition to the characteristics of thinness and weight reduction, electronic devices are required to be given the function of being able to bend. For this reason, it is required to use a lightweight flexible plastic substrate instead of the conventional heavy, fragile and unbendable glass substrate.
　特に、新世代ディスプレイとして、軽量なフレキシブルプラスチック基板（以下、樹脂基板ともいう。）を用いたアクティブマトリクス型フルカラーＴＦＴディスプレイパネルの開発が求められている。また、タッチパネル式ディスプレイは、ディスプレイパネルに組み合わせて使用されるタッチパネルの透明電極や樹脂基板等、フレキシブル化に対応する材料が開発されている。透明電極としては、従来使用されていたＩＴＯから、ＰＥＤＯＴ等曲げ加工が可能な透明導電性ポリマー、金属ナノワイヤ、及びその混合系等、別の透明電極材料が提案されている（特許文献１～４）。 In particular, as a new-generation display, there is a demand for the development of active matrix full-color TFT display panels that use lightweight flexible plastic substrates (hereinafter also referred to as resin substrates). In addition, for touch panel displays, flexible materials such as transparent electrodes and resin substrates of touch panels used in combination with display panels have been developed. As the transparent electrode, other transparent electrode materials have been proposed, such as transparent conductive polymers that can be bent such as PEDOT, metal nanowires, and mixtures thereof, in addition to conventionally used ITO (Patent Documents 1 to 4). ).
　一方、タッチパネルフィルムの基材も、ガラスからポリエチレンテレフタレート（ＰＥＴ）、ポリイミド、シクロオレフィン、アクリル等のプラスチックからなるシート等になり、フレキシブル性を持たせた透明フレキシブル性タッチスクリーンパネルが開発されている（特許文献５～７）。 On the other hand, the base material of the touch panel film has also changed from glass to a sheet made of plastic such as polyethylene terephthalate (PET), polyimide, cycloolefin, acrylic, etc., and a transparent flexible touch screen panel with flexibility has been developed. (Patent Documents 5 to 7).
　一般的に、フレキシブル性タッチスクリーンパネルは、安定的に生産するため、ガラス基板等の支持基板上に剥離（粘着）層を作製し、その上でデバイスを作製後剥離することで生産される（特許文献８）。このフレキシブル性タッチパネルスクリーンは、工程中には支持基板から剥離してはならない一方、剥離する際は低剥離力が必要とされる。特に、フレキシブル性タッチスクリーンパネルの作製工程中に支持基板から剥離してしまうと、製造ラインの汚染等歩留まりの大幅な低下を招くおそれがある。また、生産性を向上させるため、剥離層を製膜した後、製膜された状態で長期保管する必要がある。このため、剥離層には製膜後の安定性が必要とされる。 Generally, in order to stably produce flexible touch screen panels, a release (adhesive) layer is prepared on a support substrate such as a glass substrate. Patent Document 8). While the flexible touch panel screen should not be peeled off from the support substrate during the process, a low peel force is required when peeling. In particular, if the flexible touch screen panel is peeled off from the supporting substrate during the manufacturing process, the production line may be contaminated, resulting in a significant drop in yield. In addition, in order to improve productivity, it is necessary to store the formed release layer for a long period of time after forming the release layer. Therefore, the release layer is required to have stability after film formation.
国際公開第２０１２／１４７２３５号WO2012/147235 特開２００９－２８３４１０号公報JP 2009-283410 A 特表２０１０－５０７１９９号公報Japanese Patent Publication No. 2010-507199 特開２００９－２０５９２４号公報JP 2009-205924 A 国際公開第２０１７／００２６６４号WO2017/002664 国際公開第２０１６／１６０３３８号WO2016/160338 特開２０１５－１６６１４５号公報JP 2015-166145 A 特開２０１６－５３１３５８号公報JP 2016-531358 A
　本発明は、前記事情に鑑みてなされたものであり、高耐熱性と適度な剥離性とを有し、工程中の不必要な剥離を抑制でき、製膜後の安定性に優れる剥離層を与える剥離層形成用組成物を提供することを目的とする。 The present invention has been made in view of the above circumstances, and provides a release layer that has high heat resistance and moderate release properties, can suppress unnecessary separation during the process, and has excellent stability after film formation. An object of the present invention is to provide a composition for forming a release layer that provides
　本発明者らは、前記目的を達成するために鋭意検討を重ねた結果、（Ａ）ヒドロキシ基又はカルボキシ基を有する樹脂、（Ｂ）光酸発生剤、（Ｃ）ヒドロキシアルキル基及び／又はアルコキシメチル基で置換された窒素原子を有する化合物から選ばれる架橋剤、（Ｄ）所定の繰り返し単位を含む高分子添加剤、並びに（Ｅ）溶剤を含む樹脂組成物を用いることで、露光及び現像工程によって所定の領域に剥離層を形成でき、該剥離層が、基体との優れた密着性及び樹脂基板との適度な密着性と適度な剥離性とを有し、前記樹脂組成物が前記剥離層を再現性よく与え得ることを見出し、本発明を完成した。 The present inventors have made intensive studies to achieve the above objects, and found that (A) a resin having a hydroxy group or a carboxy group, (B) a photoacid generator, and (C) a hydroxyalkyl group and/or an alkoxy group. By using a resin composition containing a cross-linking agent selected from compounds having a nitrogen atom substituted with a methyl group, (D) a polymer additive containing a predetermined repeating unit, and (E) a solvent, exposure and development steps A release layer can be formed in a predetermined region by can be given with good reproducibility, and completed the present invention.
　すなわち、本発明は、下記剥離層形成用組成物及び剥離層を提供する。
１．（Ａ）ヒドロキシ基又はカルボキシ基を有する樹脂、
（Ｂ）光酸発生剤、
（Ｃ）ヒドロキシアルキル基及び／又はアルコキシメチル基で置換された窒素原子を有する化合物から選ばれる架橋剤、
（Ｄ）下記式（ａ）で表される繰り返し単位、下記式（ｂ）で表される繰り返し単位及び下記式（ｃ）で表される繰り返し単位を含む高分子添加剤、並びに
（Ｅ）溶剤
を含む剥離層形成用組成物であって、（Ｄ）高分子添加剤が、（Ａ）ヒドロキシ基又はカルボキシ基を有する樹脂１００質量部に対し、５～１００質量部含まれる剥離層形成用組成物。
Figure JPOXMLDOC01-appb-C000002
 （式中、ＲAは、それぞれ独立に、水素原子又はメチル基であり；
　ＲBは、少なくとも１つの水素原子がフッ素原子で置換された炭素数３又は４の分岐状のアルキル基であり；
　ＲCは、炭素数２～１０のヒドロキシアルキル基であるが、ヒドロキシ基が結合する炭素原子は第２級又は第３級炭素原子であり；
　ＲDは、炭素数の６～２０の多環式アルキル基又は炭素数６～１２のアリール基である。）
２．（Ａ）ヒドロキシ基又はカルボキシ基を有する樹脂が、ヒドロキシ基を有するポリウレア、ヒドロキシ基若しくはカルボキシ基を有するアクリルポリマー、ヒドロキシ基を有するポリエステル、又はヒドロキシアルキル基を有するセルロース若しくはその誘導体である１の剥離層形成用組成物。
３．（Ｂ）光酸発生剤が発生する酸が、塩酸又は有機スルホン酸である１又は２の剥離層形成用組成物。
４．１～３のいずれかの剥離層形成用組成物から得られる剥離層。
５．４の剥離層に、波長４００ｎｍの光の透過率が８０％以上である樹脂層が積層された積層体。
６．１～３のいずれかの剥離層形成用組成物を用いて基体上に樹脂膜を形成する工程、
　前記樹脂膜の所定の領域を放射線で露光する工程、及び
　前記露光した樹脂膜を現像し、未露光部を除去する工程
を含む剥離層の製造方法。
７．１～３のいずれかの剥離層形成用組成物を用いて基体上に樹脂膜を形成する工程、
　前記樹脂膜の所定の領域を放射線で露光する工程、
　前記放射線を照射した樹脂膜を現像液で現像し、未露光部を除去し、所定の領域に剥離層を形成する工程、
　前記剥離層が所定の領域に形成された基体の面に、前記剥離層を全て覆うように、波長４００ｎｍの光の透過率が８０％以上である樹脂基板を形成する工程、及び
　前記剥離層上に形成された樹脂基板を、１.０Ｎ／２５ｍｍ以下の剥離力で剥離する工程
を含む樹脂基板の製造方法。 That is, the present invention provides the following release layer-forming composition and release layer.
1. (A) a resin having a hydroxy group or a carboxy group;
(B) a photoacid generator,
(C) a cross-linking agent selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and/or an alkoxymethyl group;
(D) a polymer additive containing a repeating unit represented by the following formula (a), a repeating unit represented by the following formula (b) and a repeating unit represented by the following formula (c), and (E) a solvent wherein the (D) polymer additive is contained in an amount of 5 to 100 parts by mass based on 100 parts by mass of the resin (A) having a hydroxy group or a carboxyl group. thing.
Figure JPOXMLDOC01-appb-C000002
 (Wherein, R A is each independently a hydrogen atom or a methyl group;
RB 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, but the carbon atom to which the hydroxy group is attached is a secondary or tertiary carbon atom;
R D is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms. )
2. (A) The resin having a hydroxy group or a carboxy group is 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 or a derivative thereof having a hydroxyalkyl group. Layer-forming composition.
3. (B) The release layer-forming composition of 1 or 2, wherein the acid generated by the photoacid generator is hydrochloric acid or organic sulfonic acid.
4. A release layer obtained from the release layer-forming composition according to any one of 1 to 3.
5. A laminate in which a resin layer having a transmittance of 80% or more for light with a wavelength of 400 nm is laminated on the release layer of 4.
6. A step of forming a resin film on a substrate using the release layer forming composition according to any one of 1 to 3;
A method for producing a release layer, comprising: exposing a predetermined region of the resin film to radiation; and developing the exposed resin film to remove an unexposed portion.
7. A step of forming a resin film on a substrate using the release layer forming composition according to any one of 1 to 3;
exposing a predetermined region of the resin film to radiation;
a step of developing the resin film irradiated with radiation with a developer to remove unexposed portions and forming a release layer in a predetermined region;
a step of forming a resin substrate having a transmittance of 80% or more for light with a wavelength of 400 nm on the surface of the substrate on which the release layer is formed in a predetermined region so as to cover the entire release layer; A method of manufacturing a resin substrate, including a step of peeling off the resin substrate formed on the substrate with a peeling force of 1.0 N/25 mm or less.
　本発明の剥離層形成用組成物を用いることで、基体との優れた密着性及び樹脂基板との適度な剥離性とを有し、露光及び現像工程によって所定の領域に形成できる剥離層を再現性よく得ることできる。また、フレキシブル電子デバイスの製造プロセスにおいて、基体上に形成された樹脂基板や、更にその上に設けられる回路等に損傷を与えることなく、製造途中に不必要な剥離を抑制でき、必要な時に当該回路等とともに当該樹脂基板を当該基体から分離することが可能となる。したがって、本発明の剥離層形成用組成物は、樹脂基板を備えるフレキシブル電子デバイスの製造プロセスの高速化やその歩留り向上等に寄与し得る。 By using the composition for forming a release layer of the present invention, a release layer that has excellent adhesion to a substrate and appropriate release properties from a resin substrate and can be formed in a predetermined area through exposure and development steps can be reproduced. You can get it sexually. In addition, in the manufacturing process of flexible electronic devices, it is possible to suppress unnecessary peeling during manufacturing without damaging the resin substrate formed on the substrate and the circuit etc. provided thereon, and to prevent the peeling when necessary. It becomes possible to separate the resin substrate from the substrate together with the circuit or the like. Therefore, the composition for forming a release layer of the present invention can contribute to speeding up the manufacturing process of flexible electronic devices having a resin substrate, improving the yield thereof, and the like.
［剥離層形成用組成物］
　本発明の剥離層形成用組成物は、（Ａ）ヒドロキシ基又はカルボキシ基を有する樹脂、（Ｂ）光酸発生剤、（Ｃ）ヒドロキシアルキル基及び／又はアルコキシメチル基で置換された窒素原子を有する化合物から選ばれる架橋剤、（Ｄ）所定の繰り返し単位を含む高分子添加剤、及び（Ｅ）溶剤を含むものである。 [Composition for forming release layer]
The release layer-forming composition of the present invention contains (A) a resin having a hydroxy group or a carboxy group, (B) a photoacid generator, and (C) a nitrogen atom substituted with a hydroxyalkyl group and/or an alkoxymethyl group. (D) a polymeric additive containing a predetermined repeating unit; and (E) a solvent.
［（Ａ）ヒドロキシ基又はカルボキシ基を有する樹脂］
　（Ａ）成分のヒドロキシ基又はカルボキシ基を有する樹脂は、（Ｂ）成分から生じる酸及び（Ｃ）成分の架橋剤と反応し、硬化するものであれば特に限定されないが、ヒドロキシ基を有するポリウレア、ヒドロキシ基若しくはカルボキシ基を有するアクリルポリマー、ヒドロキシ基を有するポリエステル、又はヒドロキシアルキル基を有するセルロース若しくはその誘導体が好ましい。 [(A) Resin Having a Hydroxy Group or a Carboxy Group]
The resin having a hydroxy group or a carboxy group of the component (A) is not particularly limited as long as it reacts with the acid generated from the component (B) and the cross-linking agent of the component (C) to be cured. 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 or a derivative thereof having a hydroxyalkyl group.
　前記ヒドロキシ基を有するポリウレアとしては、下記式（１）で表される繰り返し単位を含むものが好ましい。
Figure JPOXMLDOC01-appb-C000003
 As the polyurea having a hydroxy group, one containing a repeating unit represented by the following formula (1) is preferable.
Figure JPOXMLDOC01-appb-C000003
　式（１）中、Ａ1、Ａ2、Ａ3、Ａ4、Ａ5及びＡ6は、それぞれ独立に、水素原子、メチル基又はエチル基であるが、剥離性と生産性の観点から、Ａ1～Ａ6が全て水素原子であることが好ましい。 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. All of A 1 to A 6 are preferably hydrogen atoms.
　式（１）中、Ｘ1は、下記式（Ｘ１）、（Ｘ２）、（Ｘ３）又は（Ｘ４）で表される基である。
Figure JPOXMLDOC01-appb-C000004
 （式中、*は、式中のカルボニル基との結合手である。**は、式中の窒素原子との結合手である。） In formula (1), X 1 is a group represented by formula (X1), (X2), (X3) or (X4) below.
Figure JPOXMLDOC01-appb-C000004
 (Wherein, * is a bond with a carbonyl group in the formula.** is a bond with a nitrogen atom in the formula.)
　式（Ｘ１）及び（Ｘ２）中、Ｒ1及びＲ2は、それぞれ独立に、水素原子、炭素数１～６のアルキル基、炭素数３～６のアルケニル基、ベンジル基又はフェニル基である。前記フェニル基は、炭素数１～６のアルキル基、ハロゲン原子、炭素数１～６のアルコキシ基、ニトロ基、シアノ基、ヒドロキシ基及び炭素数１～６のアルキルチオ基からなる群から選ばれる少なくとも１種の基で置換されていてもよい。また、Ｒ1及びＲ2は、互いに結合してこれらが結合する炭素原子と共に炭素数３～６の環を形成してもよい。 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 is at least 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. It may be substituted with one group. Also, R 1 and R 2 may combine with each other to form a ring having 3 to 6 carbon atoms together with the carbon atoms to which they are combined.
　式（Ｘ３）中、Ｒ3は、炭素数１～６のアルキル基、炭素数３～６のアルケニル基、ベンジル基又はフェニル基である。前記フェニル基は、炭素数１～６のアルキル基、ハロゲン原子、炭素数１～６のアルコキシ基、ニトロ基、シアノ基、ヒドロキシ基及び炭素数１～６のアルキルチオ基からなる群から選ばれる少なくとも１種の基で置換されていてもよい。 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 is at least 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. It may be substituted with one group.
　式（１）中、Ｑ1は、下記式（Ｑ１）又は（Ｑ２）で表される基である。
Figure JPOXMLDOC01-appb-C000005
 （式中、*は、結合手である。） In formula (1), Q 1 is a group represented by formula (Q1) or (Q2) below.
Figure JPOXMLDOC01-appb-C000005
 (In the formula, * is a bond.)
　式（Ｑ１）中、Ｘ2は、式（Ｘ１）、式（Ｘ２）又は式（Ｘ４）で表される基である。式（Ｑ１）において、例えば、Ｘ2が式（Ｘ２）で表される基の場合、その構造は下記式（Ｑ１－１）となる。
Figure JPOXMLDOC01-appb-C000006
 （式中、Ｒ1及びＲ2は、前記と同じ。*は、結合手である。） In formula (Q1), X 2 is a group represented by formula (X1), formula (X2) or formula (X4). In formula (Q1), for example, when X 2 is a group represented by formula (X2), the structure is represented by formula (Q1-1) below.
Figure JPOXMLDOC01-appb-C000006
 (Wherein, R 1 and R 2 are the same as above. * is a bond.)
　式（Ｑ２）中、Ｑ2は、炭素数１～１０のアルキレン基、フェニレン基、ナフチレン基又はアントリレン基である。前記フェニレン基、ナフチレン基及びアントリレン基は、炭素数１～６のアルキル基、ハロゲン原子、炭素数１～６のアルコキシ基、ニトロ基、シアノ基、ヒドロキシ基、及び炭素数１～６のアルキルチオ基からなる群から選ばれる少なくとも１種の基で置換されていてもよい。また、Ｑ2がフェニレン基、ナフチレン基又はアントリレン基である場合、それらの結合の位置は特に限定されない。すなわち、例えば、フェニレン基が１位と２位とで結合している場合、１位と３位とで結合している場合又は１位と４位とで結合している場合、ナフチレン基が１位と２位で結合している場合、１位と４位で結合している場合、１位と５位で結合している場合又は２位と３位で結合している場合、アントリレン基が１位と２位で結合している場合、１位と４位で結合している場合又は９位と１０位で結合している場合等がありえるが、いずれであってもよい。ｎ1及びｎ2は、それぞれ独立に、０又は１である。 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 are alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxy groups, and alkylthio groups having 1 to 6 carbon atoms. may be substituted with at least one group selected from the group consisting of Moreover, when Q 2 is a phenylene group, a naphthylene group or an anthrylene group, the position of their bond is not particularly limited. That is, for example, when the phenylene group is bonded at the 1-position and the 2-position, when it is bonded at the 1-position and the 3-position, or when it is bonded at the 1-position and the 4-position, the naphthylene group is 1 When bonded at the 1-position and the 2-position, when bonded at the 1-position and the 4-position, when bonded at the 1-position and the 5-position, or when bonded at the 2-position and the 3-position, the anthrylene group is It may be bonded at the 1st and 2nd positions, at the 1st and 4th positions, or at the 9th and 10th positions. n 1 and n 2 are each independently 0 or 1;
　前記炭素数１～６のアルキル基は、直鎖状、分岐状、環状のいずれでもよく、その具体例としては、メチル基、エチル基、イソプロピル基、ｎ－ブチル基、シクロヘキシル基等が挙げられる。前記炭素数３～６のアルケニル基としては、直鎖状、分岐状、環状のいずれでもよく、例えば、２－プロペニル基、３－ブテニル基等が挙げられる。 The alkyl group having 1 to 6 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, isopropyl, n-butyl and cyclohexyl groups. . The alkenyl group having 3 to 6 carbon atoms may be linear, branched or cyclic, and examples thereof include 2-propenyl group and 3-butenyl group.
　前記炭素数１～６のアルコキシ基は、直鎖状、分岐状、環状のいずれでもよく、その具体例としては、メトキシ基、エトキシ基、イソプロポキシ基、ｎ－ペンチルオキシ基及びシクロヘキシルオキシ基等が挙げられる。前記炭素数１～６のアルキルチオ基は、直鎖状、分岐状、環状のいずれでもよく、その具体例としては、メチルチオ基、エチルチオ基、イソプロピルチオ基、ｎ－ペンチルチオ基、シクロヘキシルチオ基等が挙げられる。前記ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。また、Ｒ1とＲ2が結合して形成される炭素数３～６の環としては、シクロブタン環、シクロペンタン環、シクロヘキサン環等が挙げられる。 The alkoxy group having 1 to 6 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methoxy, ethoxy, isopropoxy, n-pentyloxy and cyclohexyloxy groups. is mentioned. The alkylthio group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methylthio, ethylthio, isopropylthio, n-pentylthio, cyclohexylthio, and the like. mentioned. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The ring having 3 to 6 carbon atoms formed by combining R 1 and R 2 includes cyclobutane ring, cyclopentane ring, cyclohexane ring and the like.
　前記炭素数１～１０のアルキレン基は、直鎖状、分岐状、環状のいずれでもよく、その具体例としては、メチレン基、エチレン基、プロピレン基、ペンタメチレン基、シクロヘキシレン基、２－メチルプロピレン基等が挙げられる。 The alkylene group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methylene, ethylene, propylene, pentamethylene, cyclohexylene, and 2-methyl A propylene group and the like can be mentioned.
　なお、式（１）において、Ｘ1が式（Ｘ２）で表される基の場合、その構造は下記式（１Ａ）で表されるものとなり、Ｘ1が式（Ｘ３）で表される基の場合、その構造は下記式（１Ｂ）で表されるものとなる。また、式（Ｘ３）において、Ｒ3が、２－プロペニル基であるものが好ましい。
Figure JPOXMLDOC01-appb-C000007
 （式中、Ａ1～Ａ6、Ｒ1～Ｒ3及びＱ1は、前記と同じ。） In formula (1), when X 1 is a group represented by formula (X2), its structure is represented by the following formula (1A), and X 1 is a group represented by formula (X3). In the case of , the structure is represented by the following formula (1B). In formula (X3), R 3 is preferably a 2-propenyl group.
Figure JPOXMLDOC01-appb-C000007
 (In the formula, A 1 to A 6 , R 1 to R 3 and Q 1 are the same as above.)
　式（１）中、Ｑ1は、（Ａ）成分のポリウレアの耐熱性の観点から、環状構造を含んでいることが好ましい。すなわち、Ｑ1が、式（Ｑ１）で表される基、又は式（Ｑ２）で表される基であってＱ2が環状アルキレン基、フェニレン基、ナフチレン基若しくはアントリレン基であることが好ましく、式（Ｑ１）で表される基であることがより好ましい。 In formula (1), Q 1 preferably contains a cyclic structure from the viewpoint of the heat resistance of the polyurea component (A). That is, it is preferable that Q 1 is a group represented by formula (Q1) or a group represented by formula (Q2) and Q 2 is a cyclic alkylene group, a phenylene group, a naphthylene group or an anthrylene group, A group represented by formula (Q1) is more preferred.
　式（１）で表される繰り返し単位としては、下記式（１－１）～（１－１９）で表されるものが好ましい。なお、下記式中、Ｍｅはメチル基であり、Ｅｔはエチル基である。
Figure JPOXMLDOC01-appb-C000008
 As the repeating unit represented by formula (1), those represented by the following formulas (1-1) to (1-19) are preferable. In the formula below, Me is a methyl group and Et is an ethyl group.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　前記ポリウレアは、例えば、国際公開第２００５／０９８５４２号を参考にして合成することができる。 The polyurea can be synthesized, for example, with reference to International Publication No. 2005/098542.
　前記ヒドロキシ基又はカルボキシ基を有するアクリルポリマーとしては、アクリル酸エステルの単独重合体、メタクリル酸エステルの単独重合体、これらの共重合体、及びこれらとスチレン等の不飽和二重結合を有するモノマーの共重合体を用いることができる。 Examples of the acrylic polymer having a hydroxy group or a carboxyl group include acrylic acid ester homopolymers, methacrylic acid ester homopolymers, copolymers thereof, and monomers having unsaturated double bonds such as styrene. Copolymers can be used.
　前記アクリルポリマーの好ましい一例としては、ポリエチレングリコールエステル基又は炭素数２～６のヒドロキシアルキルエステル基を有するアクリルポリマーが挙げられる。このようなアクリルポリマーとしては、これらいずれかの基を有するアクリルポリマーであればよく、アクリルポリマーを構成する主鎖の骨格（その他の繰り返し単位）や側鎖の種類等については、特に限定されない。 A preferable 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 the main chain skeleton (other repeating units) and side chains constituting the acrylic polymer are not particularly limited.
　前記ポリエチレングリコールエステル基又は炭素数２～６のヒドロキシアルキルエステル基を有するアクリルポリマーとしては、下記式（２）で表される繰り返し単位を含むものが好ましい。
Figure JPOXMLDOC01-appb-C000015
 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).
Figure JPOXMLDOC01-appb-C000015
　式（２）中、Ｒ11は、水素原子又はメチル基である。Ｒ12は、－(ＣＨ2ＣＨ2Ｏ)n－Ｈ基又は炭素数２～６のヒドロキシアルキル基である。ｎは、２～３０の整数であり、好ましくは２～１０の整数である。 In formula (2), R 11 is a hydrogen atom or a methyl group. R 12 is a --(CH 2 CH 2 O) n --H group or a hydroxyalkyl group having 2 to 6 carbon atoms. n is an integer of 2-30, preferably an integer of 2-10.
　前記炭素数２～６のヒドロキシアルキル基としては、例えば、１－ヒドロキシエチル基、２－ヒドロキシエチル基、１－ヒドロキシプロピル基、２－ヒドロキシプロピル基、３－ヒドロキシプロピル基、１－ヒドロキシブチル基、２－ヒドロキシブチル基、３－ヒドロキシブチル基、４－ヒドロキシブチル基、２,３－ジヒドロキシプロピル基等が挙げられる。 Examples of the hydroxyalkyl group having 2 to 6 carbon atoms include 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group and 1-hydroxybutyl group. , 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, 2,3-dihydroxypropyl group and the like.
　また、前記アクリルポリマーは、本発明の効果を損なわない限り、式（２）で表される繰り返し単位以外の繰り返し単位、具体的には、ポリエチレングリコールエステル基及び炭素数２～６のヒドロキシアルキルエステル基を有しないモノマーに由来する繰り返し単位を含んでもよい。 In addition, unless the effects of the present invention are impaired, the acrylic polymer contains repeating units other than the repeating unit represented by formula (2), specifically, polyethylene glycol ester groups and hydroxyalkyl esters having 2 to 6 carbon atoms. A repeating unit derived from a monomer having no group may be included.
　前記アクリルポリマーの製造方法は、特に限定されないが、例えば、ポリエチレングリコール基及び炭素数２～６のヒドロキシアルキル基のうち少なくとも一方を有するモノマーと、必要に応じてポリエチレングリコールエステル基及び炭素数２～６のヒドロキシアルキルエステル基を有しないモノマーとを重合開始剤を溶剤に溶かした溶液中で、５０～１１０℃の温度下で重合反応させる方法が挙げられる。用いられる溶剤としては、モノマー、重合開始剤等を溶解するものであれば、特に限定されない。 The method for producing the acrylic polymer is not particularly limited. 6 and a monomer having no hydroxyalkyl ester group are polymerized in a solution of a polymerization initiator dissolved in a solvent at a temperature of 50 to 110°C. The solvent to be used is not particularly limited as long as it dissolves the monomer, the polymerization initiator, and the like.
　前記ポリエチレングリコールエステル基を有するモノマーとしては、Ｈ－(ＯＣＨ2ＣＨ2)n－ＯＨ（ｎは、前記と同じ。）のモノアクリレート又はモノメタクリレートが挙げられる。前記炭素数２～６のヒドロキシアルキル基を有するモノマーとしては、例えば、２－ヒドロキシエチルメタクリレート、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルメタクリレート、２－ヒドロキシプロピルアクリレート、４－ヒドロキシブチルアクリレート、４－ヒドロキシブチルメタクリレート、グリセリンモノアクリレート、グリセリンモノメタクリレート等が挙げられる。 Examples of the monomer having a polyethylene glycol ester group include monoacrylates and monomethacrylates of H--(OCH 2 CH 2 ) n --OH (where n is the same as above). 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, glycerin monomethacrylate and the like.
　前記ポリエチレングリコールエステル基及び炭素数２～６のヒドロキシアルキルエステル基を有しないモノマーとしては、例えば、アクリル酸、メタクリル酸等のカルボン酸化合物、メチルアクリレート、エチルアクリレート、プロピルアクリレート、イソプロピルアクリレート、ブチルアクリレート、イソブチルアクリレート、ｔ－ブチルアクリレート、フェニルアクリレート、４－ヒドロキシフェニルアクリレート等のアクリル酸エステル化合物、メチルメタクリレート、エチルメタクリレート、プロピルメタクリレート、イソプロピルメタクリレート、ブチルメタクリレート、イソブチルメタクリレート、ｔ－ブチルメタクリレート、フェニルメタクリレート、４－ヒドロキシフェニルメタクリレート等のメタクリル酸エステル化合物、マレイミド、Ｎ－メチルマレイミド、Ｎ－フェニルマレイミド、Ｎ－(４－ヒドロキシフェニル)マレイミド、Ｎ－シクロヘキシルマレイミド等のマレイミド化合物、アクリルアミド化合物、メタクリルアミド化合物、アクリロニトリル、マレイン酸無水物、スチレン化合物、ビニル化合物等が挙げられる。 Examples of monomers that do 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, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, and butyl acrylate. , isobutyl acrylate, t-butyl acrylate, phenyl acrylate, acrylic acid ester compounds such as 4-hydroxyphenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, phenyl methacrylate, methacrylic acid ester compounds such as 4-hydroxyphenyl methacrylate; maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide, N-(4-hydroxyphenyl)maleimide, and N-cyclohexylmaleimide; acrylamide compounds; methacrylamide compounds; Examples include acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.
　なお、前記方法で得られる前記アクリルポリマーは、通常、溶剤に溶解した溶液の状態である。 The acrylic polymer obtained by the above method is usually in the form of a solution dissolved in a solvent.
　前記アクリルポリマーの好適例としては、２－ヒドロキシエチルアクリレート、２－ヒドロキシエチルメタクリレート、２－ヒドロキシプロピルアクリレート、２－ヒドロキシプロピルメタクリレート、４－ヒドロキシブチルアクリレート、４－ヒドロキシブチルメタクリレート、グリセリンモノアクリレート、グリセリンモノメタクリレート等のヒドロキシアルキルエステルモノマーを重合したポリマー；前記ヒドロキシアルキルエステルモノマーと、これらのモノマー以外のモノマー、例えばポリエチレングリコールエステル基及び炭素数２～６のヒドロキシアルキルエステル基を有しないモノマーからなる群から選ばれる１種又は２種以上のモノマーとを共重合して得られるポリマー等のヒドロキシアルキル基を側鎖に有するアクリルポリマーが挙げられる。 Preferred examples of the acrylic polymer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, glycerin monoacrylate, glycerin. Polymers obtained by polymerizing hydroxyalkyl ester monomers such as monomethacrylate; a group consisting of the above hydroxyalkyl ester monomers and monomers other than these monomers, such as monomers that do not have a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 6 carbon atoms. acrylic polymers having hydroxyalkyl groups in side chains, such as polymers obtained by copolymerizing one or more monomers selected from
　前記ヒドロキシ基を有するポリエステルは、特に限定されないが、芳香族基又は脂環族基を主鎖に有するものが好ましい。このようなポリエステルとしては、エポキシ部位を２個以上有する化合物とカルボキシ基を２個有する化合物とを反応させて得られるポリエステルが好ましい。 The polyester having a hydroxy group is not particularly limited, but preferably has an aromatic group or an alicyclic group in its main chain. As such a polyester, a polyester obtained by reacting a compound having two or more epoxy moieties and a compound having two carboxyl groups is preferable.
　前記エポキシ部位を２個以上有する化合物としては、例えば、ビスフェノールＦジグリシジルエーテル、ビスフェノールＡジグリシジルエーテル、ビスフェノールＢジグリシジルエーテル、ビスフェノールＡＤジグリシジルエーテル、ビスフェノールＳジグリシジルエーテル、テトラクロロビスフェノールＡジグリシジルエーテル、カテキンジグリシジルエーテル、レゾルシノールジグリシジルエーテル、ハイドロキノンジグリシジルエーテル、１,５－ジヒドロキシナフタレンジグリシジルエーテル、ジヒドロキシビフェニルジグリシジルエーテル、オクタクロロ－４,４'－ジヒドロキシビフェニルジグリシジルエーテル、テトラメチルビフェニルジグリシジルエーテル、９,９'－ビス(４－ヒドロキシフェニル)フロオレンジグリシジルエーテル、９,９'－ビス(４－ヒドロキシフェニル)フロオレンジグリシジルエーテル、９,９'－ビス(６－ヒドロキシ－２－ナフチル)フロオレンジグリシジルエーテル等のビスフェノールジグリシジルエーテル；エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、テトラメチレングリコールジグリシジルエーテル、１,４－ブタンジオールジグリシジルエーテル、１,６－ヘキサンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル等の脂肪族ジオールジグリシジルエーテル；シクロヘキサンジオールジグリシジルエーテル、シクロヘキサンジメタノールジグリシジルエーテル、ジシクロペンタジエンジオールジグリシジルエーテル、水添ビスフェノールＦジグリシジルエーテル、水添ビスフェノールＡジグリシジルエーテル、水添ビスフェノールＢジグリシジルエーテル、水添ビスフェノールＳジグリシジルエーテル等の脂環式ジオールジグリシジルエーテル；フタル酸ジグリシジルエステル、イソフタル酸ジグリシジルエステル、テレフタル酸ジグリシジルエステル等の芳香族ジカルボン酸ジグリシジルエステル；シュウ酸ビスグリシジル、アジピン酸ビスグリシジル、ピメリン酸ビスグリシジル、２－エチル－３－プロピル－１,５－ペンタン二酸ビスグリシジル等の脂環式ジカルボン酸ジグリシジルエステル；シュウ酸ビス(３,４－エポキシシクロヘキシルメチル)、アジピン酸ビス(３,４－エポキシシクロヘキシルメチル)、アジピン酸ビス(３,４－エポキシ－６－メチルシクロヘキシルメチル)、ピメリン酸ビス(３,４－エポキシシクロヘキシルメチル)、２－エチル－３－プロピル－１,５－ペンタン二酸ビス(３,４－エポキシシクロヘキシルメチル)等の脂環式ジカルボン酸ジエステルジエポキシド；ビニルシクロヘキセンジオキサイド、リモネンジオキサイド、ジシクロペンタジエンジオキサイド、エポカリック（登録商標）ＴＨＩ－ＤＥ、ＤＥ－１０２、ＤＥ－１０３（ＥＮＥＯＳ(株)製）、３,４－エポキシシクロヘキシルメチル－３,４－エポキシシクロヘキサンカルボキシレート、２,２－ビス(３,４－エポキシシクロヘキシル)プロパン等の脂環式ジオキサイド等が挙げられる。なお、これらの化合物は、１種単独で使用してもよく、２種以上を組み合わせて使用してもよい。 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, and tetrachlorobisphenol A diglycidyl. ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, 1,5-dihydroxynaphthalenediglycidyl ether, dihydroxybiphenyldiglycidyl ether, octachloro-4,4'-dihydroxybiphenyldiglycidyl ether, tetramethylbiphenyl di glycidyl ether, 9,9'-bis(4-hydroxyphenyl) fluorenediglycidyl ether, 9,9'-bis(4-hydroxyphenyl)fluorenediglycidyl ether, 9,9'-bis(6-hydroxy-2- bisphenol diglycidyl ethers such as naphthyl)fluorodioxyl glycidyl ether; Aliphatic diol diglycidyl ether such as ether, neopentyl glycol diglycidyl ether; Alicyclic diol diglycidyl ether such as diglycidyl ether, hydrogenated bisphenol B diglycidyl ether, hydrogenated bisphenol S diglycidyl ether; Dicarboxylic acid diglycidyl esters; alicyclic dicarboxylic acid diglycidyl esters such as bisglycidyl oxalate, bisglycidyl adipate, bisglycidyl pimelate, and bisglycidyl 2-ethyl-3-propyl-1,5-pentanedioate; bis(3,4-epoxycyclohexylmethyl) acid, bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxy-6-methylcyclohexyl) adipate xylmethyl), bis(3,4-epoxycyclohexylmethyl) pimelate, bis(3,4-epoxycyclohexylmethyl) 2-ethyl-3-propyl-1,5-pentanedioate, and other alicyclic dicarboxylic acid diester diesters Epoxide; 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, 2,2-bis(3,4-epoxycyclohexyl)propane and other alicyclic dioxides. In addition, these compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
　カルボキシ基を２個有する化合物としては、テレフタル酸、イソフタル酸、ジフェン酸、２－メチルテレフタル酸、２－ヒドロキシテレフタル酸、２,５－ジメチルテレフタル酸、５－メチルイソフタル酸、５－ヒドロキシイソフタル酸、２,６－ナフタレンジカルボン酸、１,２－シクロヘキサンジカルボン酸、１,３－シクロヘキサンジカルボン酸、１,４－シクロヘキサンジカルボン酸等が挙げられる。なお、これらの化合物は、１種単独で使用してもよく、２種以上を組み合わせて使用してもよい。 Compounds having two carboxy groups include terephthalic acid, isophthalic acid, diphenic acid, 2-methylterephthalic acid, 2-hydroxyterephthalic acid, 2,5-dimethylterephthalic acid, 5-methylisophthalic acid, and 5-hydroxyisophthalic acid. , 2,6-naphthalenedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like. In addition, these compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
　前記ポリエステルを合成する方法は、特に限定されないが、例えば、前記エステル化合物とカルボキシ基含有化合物と触媒とを共存させた溶剤中において、５０～１５０℃の温度下で重合反応させる方法が挙げられる。その際、用いられる溶剤は、前記化合物、重合開始剤等を溶解するものであれば特に限定されない。前記方法により得られる前記ポリエステルは、通常、溶剤に溶解した溶液の状態である。 The method for synthesizing the polyester is not particularly limited, but examples include a method of polymerizing at a temperature of 50 to 150°C in a solvent containing the ester compound, the carboxy group-containing compound, and the catalyst. At that time, the solvent to be used is not particularly limited as long as it dissolves the above-mentioned compound, polymerization initiator, and the like. The polyester obtained by the above method is usually in the form of a solution dissolved in a solvent.
　前記ポリエステルとしては、下記式（３）で表される繰り返し単位を含むものが好ましい。
Figure JPOXMLDOC01-appb-C000016
 The polyester preferably contains a repeating unit represented by the following formula (3).
Figure JPOXMLDOC01-appb-C000016
　式（３）中、Ｙ1及びＺ1は、それぞれ独立に、芳香環又は脂環を有する２価の基である。 In formula (3), Y 1 and Z 1 are each independently a divalent group having an aromatic ring or an alicyclic ring.
　Ｙ1としては、下記式（Ｙ１－１）で表される基が好ましい。
Figure JPOXMLDOC01-appb-C000017
 （式中、*は、結合手である。） Y 1 is preferably a group represented by the following formula (Y1-1).
Figure JPOXMLDOC01-appb-C000017
 (In the formula, * is a bond.)
　式（Ｙ１－１）中、Ｌ1は、それぞれ独立に、エーテル結合又はエステル結合である。Ｙ2は、それぞれ独立に、炭素数３～１０の２価環状不飽和炭化水素基又は炭素数３～１０の２価環状飽和炭化水素基である。Ｒ21は、単結合、エーテル結合、カルボニル基、スルホニル基、炭素数１～３０の２価飽和炭化水素基、炭素数２～３０の２価不飽和炭化水素基、又はフッ素原子で置換された炭素数１～３０の２価飽和炭化水素基である。ｐは、０、１又は２である。 In formula (Y1-1), each L 1 is independently an ether bond or an ester bond. Each Y 2 is independently a C3-10 bivalent cyclic unsaturated hydrocarbon group or a C3-10 bivalent cyclic saturated hydrocarbon group. R 21 is a single bond, an ether bond, a carbonyl group, a sulfonyl group, a C 1-30 divalent saturated hydrocarbon group, a C 2-30 divalent unsaturated hydrocarbon group, or substituted with a fluorine atom It is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms. p is 0, 1 or 2;
　Ｙ2としては、炭素数４～１６の２価環状不飽和炭化水素基又は炭素数４～１６の２価環状飽和炭化水素基が好ましく、炭素数４～８の２価環状不飽和炭化水素基又は炭素数４～８の２価環状飽和炭化水素基がより好ましい。また、Ｙ2に含まれる水素原子の一部又は全部が脂肪族基で置換されていてもよく、またそれらのうち複数の置換基が互いに結合して４～６員環を形成してもよい。 Y 2 is preferably a divalent cyclic unsaturated hydrocarbon group having 4 to 16 carbon atoms or a saturated cyclic divalent hydrocarbon group having 4 to 16 carbon atoms, and a divalent cyclic unsaturated hydrocarbon group having 4 to 8 carbon atoms. Or a C4-C8 bivalent cyclic saturated hydrocarbon group is more preferred. In addition, some or all of the hydrogen atoms contained in Y 2 may be substituted with an aliphatic group, and a plurality of substituents among them may be bonded together to form a 4- to 6-membered ring. .
　Ｙ2の具体例としては、下記式（Ｙ２－１）～（Ｙ２－１２）で表される基が挙げられるが、これらに限定されない。
Figure JPOXMLDOC01-appb-C000018
 （式中、*は、結合手である。） Specific examples of Y 2 include, but are not limited to, groups represented by the following formulas (Y2-1) to (Y2-12).
Figure JPOXMLDOC01-appb-C000018
 (In the formula, * is a bond.)
　Ｚ1としては、炭素数６～２０のアリーレン基又は炭素数３～２０の２価環状飽和炭化水素基が好ましい。前記アリーレン基又は２価環状飽和炭化水素基は、ヒドロキシ基、メチル基等で置換されていてもよい。 Z 1 is preferably an arylene group having 6 to 20 carbon atoms or a saturated bivalent cyclic hydrocarbon group having 3 to 20 carbon atoms. The arylene group or bivalent cyclic saturated hydrocarbon group may be substituted with a hydroxy group, a methyl group, or the like.
　Ｚ1の具体例は、下記式（Ｚ１－１）～（Ｚ１－４）で表される基が挙げられるが、これらに限定されない。
Figure JPOXMLDOC01-appb-C000019
 （式中、*は、結合手である。） Specific examples of Z 1 include, but are not limited to, groups represented by the following formulas (Z1-1) to (Z1-4).
Figure JPOXMLDOC01-appb-C000019
 (In the formula, * is a bond.)
　前記ポリエステルとしては、下記式（４）で表される繰り返し単位を有するものも好ましい。
Figure JPOXMLDOC01-appb-C000020
 As the polyester, one having a repeating unit represented by the following formula (4) is also preferable.
Figure JPOXMLDOC01-appb-C000020
　式（４）中、Ｚ1は、前記と同じ。環Ｃｙは、炭素数４～２０の４価環状飽和炭化水素基又は下記式（Ｃｙ－１）で表される４価の基である。
Figure JPOXMLDOC01-appb-C000021
 In formula (4), Z 1 is the same as above. 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).
Figure JPOXMLDOC01-appb-C000021
　式（Ｃｙ－１）中、Ｃｙ'は、炭素数４～２０の３価環状飽和炭化水素基である。Ｒ31は、炭素数１～２０の２価飽和炭化水素基又は炭素数２～２０の２価不飽和炭化水素基であり、エステル結合等を含んでいてもよい。*１及び*２は結合手であり、２つある*１及び*２の一方がそれぞれヒドロキシ基と結合する。 In formula (Cy-1), Cy' is a trivalent cyclic saturated hydrocarbon group having 4 to 20 carbon atoms. R 31 is a C 1-20 divalent saturated hydrocarbon group or a C 2-20 divalent unsaturated hydrocarbon group, which may contain an ester bond or the like. *1 and *2 are bonds, and one of the two *1 and *2 each bonds to a hydroxy group.
　前記４価環状飽和炭化水素基及び３価環状飽和炭化水素基は、単環でも、多環でもよく、多環の場合は、縮合環、有橋環、スピロ環、これらの環構造を複数含むもののいずれでもよい。 The tetravalent cyclic saturated hydrocarbon group and trivalent cyclic saturated hydrocarbon group may be monocyclic or polycyclic, and in the case of polycyclic, condensed rings, bridged rings, spiro rings, and a plurality of these ring structures are included. can be either.
　Ｃｙで表される基の具体例としては、下記式（Ｃｙ－２）～（Ｃｙ－８）で表される基が挙げられる。
Figure JPOXMLDOC01-appb-C000022
 （式中、*１及び*２は、結合手であり、各構造式に２つある*１及び*２の一方がそれぞれヒドロキシ基と結合する。） Specific examples of the group represented by Cy include groups represented by the following formulas (Cy-2) to (Cy-8).
Figure JPOXMLDOC01-appb-C000022
 (In the formula, *1 and *2 are bonds, and one of the two *1 and *2 in each structural formula respectively bonds to a hydroxy group.)
　前記ヒドロキシアルキル基を有するセルロース又はその誘導体としては、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース等のヒドロキシアルキルセルロース類、ヒドロキシエチルメチルセルロース、ヒドロキシプロピルメチルセルロース、ヒドロキシエチルエチルセルロース等のヒドロキシアルキルアルキルセルロース類、及びこれらの誘導体等が挙げられる。これらのうち、ヒドロキシアルキルセルロース類及びこれらの誘導体が好ましく、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、及びこれらの誘導体がより好ましい。前記ヒドロキシアルキル基を有するセルロース又はその誘導体は、１種単独で使用してもよく、２種以上を組み合わせて使用してもよい。 Examples of the cellulose having a hydroxyalkyl group or derivatives thereof include hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose, hydroxyalkylalkylcelluloses such as hydroxyethylmethylcellulose, hydroxypropylmethylcellulose and hydroxyethylethylcellulose, and derivatives thereof. is mentioned. Among these, hydroxyalkyl celluloses and their derivatives are preferred, and hydroxyethyl cellulose, hydroxypropyl cellulose and their derivatives are more preferred. The cellulose or derivative thereof having the hydroxyalkyl group may be used alone or in combination of two or more.
　（Ａ）成分の重量平均分子量（Ｍｗ）は、特に限定されないが、１,０００～５００,０００が好ましく、３,０００～４００,０００がより好ましく、５,０００～３００,０００がより一層好ましい。なお、重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリスチレン換算測定値である。 The weight average molecular weight (Mw) of component (A) 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. . In addition, a weight average molecular weight is a polystyrene conversion measurement value by a gel permeation chromatography (GPC).
［（Ｂ）光酸発生剤］
　本発明の剥離層形成用組成物は、（Ｂ）成分として光酸発生剤を含む。（Ｂ）成分の光酸発生剤は、照射される放射線によって光分解して酸を発生する化合物であれば特に限定されない。 [(B) Photoacid generator]
The release layer-forming composition of the present invention contains a photoacid generator as the component (B). The photoacid generator of component (B) is not particularly limited as long as it is a compound that is photolyzed by irradiated radiation to generate an acid.
　前記光酸発生剤が光分解した際に発生する酸としては、例えば、塩酸；メタンスルホン酸、エタンスルホン酸、プロパンスルホン酸、ブタンスルホン酸、ペンタンスルホン酸、オクタンスルホン酸、ベンゼンスルホン酸、ｐ－トルエンスルホン酸、カンファスルホン酸、トリフルオロメタンスルホン酸、ｐ－フェノールスルホン酸、２－ナフタレンスルホン酸、メシチレンスルホン酸、ｐ－キシレン－２－スルホン酸、ｍ－キシレン－２－スルホン酸、４－エチルベンゼンスルホン酸、１Ｈ,１Ｈ,２Ｈ,２Ｈ－パーフルオロオクタンスルホン酸、パーフルオロ(２－エトキシエタン)スルホン酸、ペンタフルオロエタンスルホン酸、ノナフルオロブタン－１－スルホン酸、ドデシルベンゼンスルホン酸等の有機スルホン酸等が挙げられる。 Examples of the acid generated when the photoacid generator is photolyzed include hydrochloric acid; methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p -toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4- Ethylbenzenesulfonic acid, 1H,1H,2H,2H-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, etc. organic sulfonic acid and the like.
　前記光酸発生剤としては、例えば、ビス(トシルオキシ)エタン、ビス(トシルオキシ)プロパン、ビス(トシルオキシ)ブタン、ｐ－ニトロベンジルトシレート、ｏ－ニトロベンジルトシレート、１,２,３－フェニレントリス(メチルスルホネート)、ｐ－トルエンスルホン酸ピリジニウム塩、ｐ－トルエンスルホン酸モルフォニウム塩、ｐ－トルエンスルホン酸エチルエステル、ｐ－トルエンスルホン酸プロピルエステル、ｐ－トルエンスルホン酸ブチルエステル、ｐ－トルエンスルホン酸イソブチルエステル、ｐ－トルエンスルホン酸メチルエステル、ｐ－トルエンスルホン酸フェネチルエステル、シアノメチルｐ－トルエンスルホネート、２，２，２－トリフルオロエチルｐ－トルエンスルホネート、２－ヒドロキシブチルｐ－トルエンスルホネート、Ｎ－エチル－ｐ－トルエンスルホンアミド、下記式（ＰＡＧ－１）～（ＰＡＧ－４１）で表される化合物等が挙げられる。 Examples of the photoacid generator include bis(tosyloxy)ethane, bis(tosyloxy)propane, bis(tosyloxy)butane, p-nitrobenzyltosylate, o-nitrobenzyltosylate, and 1,2,3-phenylenetris. (methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p-toluenesulfone acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, N -ethyl-p-toluenesulfonamide, compounds represented by the following formulas (PAG-1) to (PAG-41), and the like.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
　前記光酸発生剤としては市販品を使用することができ、その具体例としては、Irgacure（登録商標） PAG103、PAG121、PAG203（以上、ＢＡＳＦジャパン(株)製）アデカアークルズ（登録商標）SP-056、SP-066、SP-140、SP-141、SP-082、SP-601、SP-606、SP-701、SP-150、SP-170、SP-171（以上、(株)ＡＤＥＫＡ製）、CPI（登録商標）-110P、-110B、-310B、-210S、-100P、-101A、-200K（以上、サンアプロ(株)製）、PAI-01、PAI-101、DPI-105、DPI-106、DPI-109、DPI-201、BI-105、MPI-105、MPI-106、MPI-109、BBI-102、BBI-103、BBI-105、BBI-106、BBI-109、BBI-110、BBI-200、BBI-201、BBI-300、BBI-301、TPS-102、TPS-103、TPS-105、TPS-106、TPS-109、TPS-200、TPS-300、TPS-1000、HDS-109、MDS-103、MDS-105、MDS-205、MDS-209、BDS-109、MNPS-109、DTS-102、DTS-103、DTS-105、DTS-200、NDS-103、NDS-105、NDS-155、NDS-165、SI-105、NDI-105、NDI-109、NAI-105、NAI-109（以上、みどり化学(株)製）が挙げられる。 Commercially available products can be used as the photoacid generator, and specific examples include Irgacure (registered trademark) PAG103, PAG121, PAG203 (manufactured by BASF Japan Co., Ltd.) Adeka Arcles (registered trademark) SP -056, SP-066, SP-140, SP-141, SP-082, SP-601, SP-606, SP-701, SP-150, SP-170, SP-171 (manufactured by ADEKA Co., Ltd.) ), CPI (registered trademark) -110P, -110B, -310B, -210S, -100P, -101A, -200K (manufactured by San-Apro Co., Ltd.), PAI-01, PAI-101, DPI-105, DPI -106, DPI-109, DPI-201, BI-105, MPI-105, MPI-106, MPI-109, BBI-102, BBI-103, BBI-105, BBI-106, BBI-109, BBI-110 , BBI-200, BBI-201, BBI-300, BBI-301, TPS-102, TPS-103, TPS-105, TPS-106, TPS-109, TPS-200, TPS-300, TPS-1000, HDS -109, MDS-103, MDS-105, MDS-205, MDS-209, BDS-109, MNPS-109, DTS-102, DTS-103, DTS-105, DTS-200, NDS-103, NDS-105 , NDS-155, NDS-165, SI-105, NDI-105, NDI-109, NAI-105 and NAI-109 (manufactured by Midori Chemical Co., Ltd.).
　本発明の剥離層形成用組成物中、（Ｂ）成分の光酸発生剤の含有量は、（Ａ）成分の樹脂１００質量部に対し、０.０１～１５質量部が好ましく、０.１～１０質量部がより好ましい。（Ｂ）光酸発生剤の含有量が前記範囲であれば、高耐熱性と適度な剥離性とを有し、基体上の所定の領域に剥離層を形成でき、製膜後の安定性に優れる剥離層形成用組成物となる。（Ｂ）光酸発生剤は、１種単独で使用してもよく、２種以上を組み合わせて使用してもよい。 In the release layer-forming composition of the present invention, the content of the photoacid generator as component (B) is preferably 0.01 to 15 parts by mass, preferably 0.1, per 100 parts by mass of the resin as component (A). ~10 parts by mass is more preferable. (B) If the content of the photoacid generator is within the above range, it has high heat resistance and moderate peelability, can form a peeling layer on a predetermined region on the substrate, and has good stability after film formation. An excellent composition for forming a release layer is obtained. (B) The photoacid generator may be used singly or in combination of two or more.
［（Ｃ）架橋剤］
　本発明の剥離層形成用組成物は、（Ｃ）成分として架橋剤を含む。前記架橋剤は、ヒドロキシアルキル基及び／又はアルコキシメチル基で置換された窒素原子を有する化合物から選択されるものである。 [(C) Crosslinking agent]
The release layer-forming composition of the present invention contains a cross-linking agent as the component (C). The cross-linking agent is selected from compounds having nitrogen atoms substituted with hydroxyalkyl groups and/or alkoxymethyl groups.
　前記架橋剤としては、下記式（Ｃ－１）～（Ｃ－５）のいずれかで表される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000030
 As the cross-linking agent, a compound represented by any one of the following formulas (C-1) to (C-5) is preferable.
Figure JPOXMLDOC01-appb-C000030
　式（Ｃ－１）～（Ｃ－５）中、Ｒ101～Ｒ116は、それぞれ独立に、炭素数１～６のアルキル基である。ＲBは、水素原子又はメチル基である。 In formulas (C-1) to (C-5), R 101 to R 116 are each independently an alkyl group having 1 to 6 carbon atoms. RB is a hydrogen atom or a methyl group.
　前記架橋剤として具体的には、ヘキサメトキシメチルメラミン、テトラメトキシメチルベンゾグアナミン、１,３,４,６－テトラキス(メトキシメチル)グリコールウリル、１,３,４,６－テトラキス(ブトキシメチル)グリコールウリル、１,３,４,６－テトラキス(ヒドロキシメチル)グリコールウリル等の含窒素化合物が挙げられる。 Specific examples of the cross-linking agent include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril, and 1,3,4,6-tetrakis(butoxymethyl)glycoluril. , 1,3,4,6-tetrakis(hydroxymethyl)glycoluril and other nitrogen-containing compounds.
　また、オルネクス社製メトキシメチルタイプメラミン化合物（商品名サイメル（登録商標）300、サイメル301、サイメル303、サイメル350）、ブトキシメチルタイプメラミン化合物（商品名マイコート（登録商標）506、マイコート508）、グリコールウリル化合物（商品名サイメル1170、POWDERLINK 1174）、メチル化尿素樹脂（商品名UFR65）、ブチル化尿素樹脂（商品名UFR300、U-VAN10S60、U-VAN10R、U-VAN11HV）、ＤＩＣ(株)製尿素／ホルムアルデヒド系樹脂（商品名ベッカミン（登録商標）J-300S、ベッカミンP-955、ベッカミンＮ）等の市販されている含窒素化合物を挙げることができる。 Methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, Cymel 301, Cymel 303, Cymel 350) and butoxymethyl type melamine compounds (trade names: Mycoat (registered trademark) 506, Mycoat 508) manufactured by Allnex Corporation , glycoluril compound (trade name Cymel 1170, POWDERLINK 1174), methylated urea resin (trade name UFR65), butylated urea resin (trade name UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC Corporation commercially available nitrogen-containing compounds such as urea/formaldehyde-based resins (trade names: Beckamin (registered trademark) J-300S, Beckamin P-955, Beckamin N).
　また、架橋剤として、Ｎ－ヒドロキシメチル(メタ)アクリルアミド、Ｎ－メトキシメチル(メタ)アクリルアミド、Ｎ－エトキシメチル(メタ)アクリルアミド、Ｎ－ブトキシメチル(メタ)アクリルアミド等のヒドロキシメチル基又はアルコキシメチル基で置換された(メタ)アクリルアミド化合物を使用して製造されるポリマーを用いることができる。そのようなポリマーとしては、例えば、ポリ(Ｎ－ブトキシメチル(メタ)アクリルアミド)、Ｎ－ブトキシメチル(メタ)アクリルアミドとスチレンとの共重合体、Ｎ－ヒドロキシメチル(メタ)アクリルアミドとメチル(メタ)アクリレートとの共重合体、Ｎ－エトキシメチルメタクリルアミドとベンジルメタクリレートの共重合体、Ｎ－ブトキシメチル(メタ)アクリルアミドとベンジル(メタ)アクリレートと２－ヒドロキシプロピル(メタ)アクリレートとの共重合体等が挙げられる。 Also, as a cross-linking agent, a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, etc. Polymers made using (meth)acrylamide compounds substituted with can be used. Examples of such polymers include poly(N-butoxymethyl(meth)acrylamide), copolymers of N-butoxymethyl(meth)acrylamide and styrene, N-hydroxymethyl(meth)acrylamide and methyl (meth) Copolymer with acrylate, copolymer of N-ethoxymethyl methacrylamide and benzyl methacrylate, copolymer of N-butoxymethyl (meth)acrylamide, benzyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate, etc. is mentioned.
　前記架橋剤としてより好ましくは、ヘキサメトキシメチルメラミン、テトラメトキシメチルベンゾグアナミン、１,３,４,６－テトラキス(メトキシメチル)グリコールウリル（POWDERLINK 1174）、１,３,４,６－テトラキス(ブトキシメチル)グリコールウリル、１,３,４,６－テトラキス(ヒドロキシメチル)グリコールウリルが挙げられる。 Hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril (POWDERLINK 1174), 1,3,4,6-tetrakis(butoxymethyl) are more preferred as the cross-linking agent. ) glycoluril and 1,3,4,6-tetrakis(hydroxymethyl)glycoluril.
　これら架橋剤は、自己縮合による架橋反応を起こすことができる。また、（Ａ）成分の樹脂中のヒドロキシ基又はカルボキシ基と架橋反応を起こすことができる。そして、このような架橋反応によって、形成される剥離層は強固になり、有機溶剤に対する溶解性が低い剥離層となる。 These cross-linking agents can cause a cross-linking reaction through self-condensation. In addition, it can cause a cross-linking reaction with a hydroxyl group or a carboxy group in the resin of component (A). By such a cross-linking reaction, the formed peeling layer is strengthened and becomes a peeling layer having low solubility in organic solvents.
　本発明の剥離層形成用組成物中、（Ｃ）成分の架橋剤の含有量は、（Ａ）成分の樹脂１００質量部に対し、１０～１００質量部が好ましく、２０～５０質量部がより好ましい。（Ｃ）架橋剤の含有量が前記範囲であれば、高耐熱性と適度な剥離性とを有し、製膜後の安定性に優れる剥離層樹脂組成物を得ることができる。（Ｃ）架橋剤は、１種単独で使用してもよく、２種以上を組み合わせて使用してもよい。 In the release layer-forming composition of the present invention, the content of the cross-linking agent as component (C) is preferably 10 to 100 parts by mass, more preferably 20 to 50 parts by mass, with respect to 100 parts by mass of the resin as component (A). preferable. If the content of (C) the cross-linking agent is within the above range, it is possible to obtain a release layer resin composition that has high heat resistance and appropriate release properties and is excellent in stability after film formation. (C) A crosslinking agent may be used individually by 1 type, and may be used in combination of 2 or more type.
［（Ｄ）高分子添加剤］
　本発明の剥離層形成用組成物は、（Ｄ）成分として、下記式（ａ）で表される繰り返し単位、下記式（ｂ）で表される繰り返し単位及び下記式（ｃ）で表される繰り返し単位を含む高分子添加剤を含む。
Figure JPOXMLDOC01-appb-C000031
 [(D) polymer additive]
In the release layer-forming composition of the present invention, the (D) component is a repeating unit represented by the following formula (a), a repeating unit represented by the following formula (b), and a repeating unit represented by the following formula (c). Contains polymeric additives containing repeating units.
Figure JPOXMLDOC01-appb-C000031
　式（ａ）～（ｃ）中、ＲAは、それぞれ独立に、水素原子又はメチル基である。ＲBは、少なくとも１つの水素原子がフッ素原子で置換された炭素数３又は４の分岐状アルキル基である。ＲCは、炭素数２～１０のヒドロキシアルキル基であるが、ヒドロキシ基が結合する炭素原子は第２級又は第３級炭素原子である。ＲDは、炭素数６～２０の多環式アルキル基又は炭素数６～１２のアリール基である。 In formulas (a) to (c), R A is each independently a hydrogen atom or a methyl group. RB 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, and the carbon atom to which the hydroxy group is attached is a secondary or tertiary carbon atom. R D is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.
　前記炭素数３又は４の分岐状アルキル基としては、イソプロピル基、イソブチル基、ｓｅｃ－ブチル基及びｔｅｒｔ－ブチル基が挙げられる。ＲBとしては、これらの分岐状アルキル基の少なくとも１つの水素原子がフッ素原子で置換されたものが好ましく、具体例としては、１,１,１－トリフルオロイソプロピル基、１,１,１,３,３,３－ヘキサフルオロイソプロピル基、ノナフルオロ－ｔｅｒｔ－ブチル基等が挙げられる。 Examples of the branched alkyl group having 3 or 4 carbon atoms include isopropyl group, isobutyl group, sec-butyl group and tert-butyl group. R B is preferably one in which at least one hydrogen atom of these branched alkyl groups is substituted with a fluorine atom, and specific examples thereof include 1,1,1-trifluoroisopropyl group, 1,1,1, 3,3,3-hexafluoroisopropyl group, nonafluoro-tert-butyl group and the like.
　前記炭素数２～１０のヒドロキシアルキル基としては、１－ヒドロキシエチル基、１－ヒドロキシプロピル基、２－ヒドロキシプロピル基、２－ヒドロキシブチル基、２－ヒドロキシヘキシル基、２－ヒドロキシオクチル基、２－ヒドロキシデシル基、１－ヒドロキシ－１－メチルエチル基、２－ヒドロキシ－２－メチルプロピル基等が挙げられる。 Examples of the hydroxyalkyl group having 2 to 10 carbon atoms include 1-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 2-hydroxybutyl group, 2-hydroxyhexyl group, 2-hydroxyoctyl group, 2 -hydroxydecyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-2-methylpropyl group and the like.
　前記炭素数６～２０の多環式アルキル基としては、１－アダマンチル基、２－アダマンチル基、イソボルニル基、ノルボルニル基等が挙げられる。前記炭素数６～１２のアリール基としては、フェニル基、１－ナフチル基、２－ナフチル基、１－ビフェニル基、２－ビフェニル基等が挙げられる。 Examples of the polycyclic alkyl group having 6 to 20 carbon atoms include 1-adamantyl group, 2-adamantyl group, isobornyl group and norbornyl group. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-biphenyl group and 2-biphenyl group.
　式（ａ）で表される繰り返し単位としては、下記式（ａ－１）～（ａ－３）で表されるものが挙げられるが、これらに限定されない。なお、下記式中、ＲAは、前記と同じである。
Figure JPOXMLDOC01-appb-C000032
 Examples of repeating units represented by formula (a) include, but are not limited to, those represented by formulas (a-1) to (a-3) below. In addition, in the following formula, RA is the same as described above.
Figure JPOXMLDOC01-appb-C000032
　式（ｂ）で表される繰り返し単位としては、下記式（ｂ－１）～（ｂ－４）で表されるものが挙げられるが、これらに限定されない。なお、下記式中、ＲAは、前記と同じである。
Figure JPOXMLDOC01-appb-C000033
 Examples of the repeating unit represented by formula (b) include, but are not limited to, those represented by formulas (b-1) to (b-4) below. In addition, in the following formula, RA is the same as described above.
Figure JPOXMLDOC01-appb-C000033
　式（ｃ）で表される繰り返し単位としては、下記式（ｃ－１）～（ｃ－１３）で表されるものが挙げられるが、これらに限定されない。なお、下記式中、ＲAは、前記と同じである。
Figure JPOXMLDOC01-appb-C000034
 Examples of the repeating unit represented by formula (c) include, but are not limited to, those represented by formulas (c-1) to (c-13) below. In addition, in the following formula, RA is the same as described above.
Figure JPOXMLDOC01-appb-C000034
　（Ｄ）高分子添加剤において、式（ａ）で表される繰り返し単位の含有率は、全繰り返し単位中、３０～６０モル％が好ましく、３５～５０モル％がより好ましい。式（ｂ）で表される繰り返し単位の含有率は、全繰り返し単位中、１０～３５モル％が好ましく、１５～３０モル％がより好ましい。式（ｃ）で表される繰り返し単位の含有率は、全繰り返し単位中、５～６０モル％が好ましく、２０～５０モル％がより好ましい。 In the polymer additive (D), the content of the repeating unit represented by formula (a) is preferably 30 to 60 mol%, more preferably 35 to 50 mol%, of all 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 all repeating units. The content of the repeating unit represented by formula (c) is preferably 5 to 60 mol %, more preferably 20 to 50 mol %, of all repeating units.
　（Ｄ）高分子添加剤のＭｗは、２,０００～１０,０００が好ましく、３,０００～６,０００がより好ましい。また、そのＭｗ／Ｍｎは、１.０～２.１が好ましく、１.０～１.９がより好ましい。 (D) The Mw of the polymer additive is preferably 2,000 to 10,000, more preferably 3,000 to 6,000. Also, the Mw/Mn is preferably 1.0 to 2.1, more preferably 1.0 to 1.9.
　本発明の剥離層形成用組成物中、（Ｄ）成分の高分子添加剤の含有量は、（Ａ）成分の樹脂１００質量部に対し、５～１００質量部であるが、５～９０質量部が好ましく、５～８０質量部がより好ましい。（Ｄ）高分子添加剤の含有量が５質量部未満であると、剥離力が大きくなることがあり、１００質量部を超えると、製膜時にはじくことがある。（Ｄ）高分子添加剤は、１種単独で使用してもよく、２種以上を組み合わせて使用してもよい。 In the composition for forming a release layer of the present invention, the content of the polymer additive as component (D) is 5 to 100 parts by mass, but 5 to 90 parts by mass with respect to 100 parts by mass of the resin as component (A). parts are preferred, and 5 to 80 parts by mass are more preferred. If the content of the polymer additive (D) is less than 5 parts by mass, the release force may increase, and if it exceeds 100 parts by mass, the film may be repelled during film formation. (D) Polymer additives may be used singly or in combination of two or more.
［（Ｅ）溶剤］
　本発明の剥離層形成用組成物は、（Ｅ）成分として溶剤を含む。前記溶剤としては、炭素数３～２０のグリコールエーテル系溶剤、炭素数３～２０のエステル系溶剤、炭素数３～２０のケトン系溶剤又は炭素数３～２０の環状化合物系溶剤が好ましい。 [(E) solvent]
The release layer-forming composition of the present invention contains a solvent as component (E). As the solvent, a glycol ether solvent having 3 to 20 carbon atoms, an ester solvent having 3 to 20 carbon atoms, a ketone solvent having 3 to 20 carbon atoms, or a cyclic compound solvent having 3 to 20 carbon atoms is preferable.
　前記グリコールエーテル系溶剤としては、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル等が挙げられる。前記エステル系溶剤としては、乳酸エチル、γ－ブチロラクトン、２－ヒドロシキイソ酪酸メチル、２－ヒドロシキイソ酪酸エチル等が挙げられる。前記ケトン系溶剤としては、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、ベンゾフェノン等が挙げられる。前記環状化合物系溶剤としては、Ｎ－メチルピロリドン、γ－ブチロラクトン等が挙げられる。 Examples of the glycol ether-based solvent include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether, propylene glycol monopropyl ether, and the like. Examples of the ester solvent include ethyl lactate, γ-butyrolactone, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate. Examples of the ketone solvent include methyl ethyl ketone, cyclohexanone, cyclopentanone, and benzophenone. Examples of the cyclic compound solvent include N-methylpyrrolidone and γ-butyrolactone.
　本発明の剥離層形成用組成物中、（Ｅ）成分の溶剤の含有量は、本発明の剥離層形成用組成物中の固形分濃度が、０.１～４０質量％となる量が好ましく、０.５～２０質量％となる量がより好ましく、０.５～１０質量％となる量がより一層好ましい。なお、固形分とは、剥離層形成用組成物の全成分のうち、溶剤以外のものの総称である。（Ｅ）溶剤は、１種単独で使用してもよく、２種以上を混合して使用してもよい。 In the release layer-forming composition of the present invention, the content of the component (E) solvent 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. , 0.5 to 20% by mass, and even more preferably 0.5 to 10% by mass. The solid content is a general term for all components of the release layer-forming composition other than the solvent. (E) The solvent may be used singly or in combination of two or more.
［その他の添加物］
　本発明の剥離層形成用組成物は、必要に応じて界面活性剤を含んでもよい。界面活性剤を添加することで、前記剥離層形成用組成物の基板に対する塗布性を向上させることができる。前記界面活性剤としては、ノニオン系界面活性剤、フッ素系界面活性剤、シリコーン系界面活性剤等の公知の界面活性剤を用いることができる。 [Other additives]
The release layer-forming composition of the present invention may contain a surfactant, if necessary. Addition of a surfactant can improve the applicability 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.
　前記ノニオン系界面活性剤の具体例としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンオレイルエーテル等のポリオキシエチレンアルキルエーテル類；ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル等のポリオキシエチレンアルキルアリールエーテル類；ポリオキシエチレン・ポリオキシプロピレンブロックコポリマー類；ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタントリオレエート、ソルビタントリステアレート等のソルビタン脂肪酸エステル類；ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタントリオレエート、ポリオキシエチレンソルビタントリステアレート等のポリオキシエチレンソルビタン脂肪酸エステル類等が挙げられる。 Specific examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl; polyoxyethylene alkylaryl ethers such as phenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene/polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, Sorbitan fatty acid esters such as sorbitan trioleate and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan Examples include polyoxyethylene sorbitan fatty acid esters such as tristearate.
　前記フッ素系界面活性剤等としては、エフトップ（登録商標）EF301、EF303、EF352（三菱マテリアル電子化成(株)製）、メガファック（登録商標）F171、F173、F554、F559、F563、R-30、R-40、R-40-LM、DS-21（ＤＩＣ(株)製）、FLUORAD（登録商標）FC430、FC431（スリーエム社製）、アサヒガード（登録商標）AG710、サーフロン（登録商標）S-382、SC101、SC102、SC103、SC104、SC105、SC106（旭硝子(株)製）等が挙げられる。 Examples of the fluorine-based surfactants include Ftop (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac (registered trademark) F171, F173, F554, F559, F563, R- 30, R-40, R-40-LM, DS-21 (manufactured by DIC Corporation), FLUORAD (registered trademark) FC430, FC431 (manufactured by 3M), Asahiguard (registered trademark) AG710, Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and the like.
　また、シリコーン系界面活性剤としては、オルガノシロキサンポリマーKP341（信越化学工業(株)製）等が挙げられる。 In addition, examples of silicone-based surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).
　前記剥離層形成用組成物が界面活性剤を含む場合、その含有量は、（Ａ）樹脂１００質量部に対し、０.０００１～１質量部が好ましく、０.００１～０.５質量部がより好ましい。前記界面活性剤は、１種単独で使用してもよく、２種以上を組み合わせて使用してもよい。 When the release layer-forming composition contains a surfactant, the content thereof is preferably 0.0001 to 1 part by mass, more preferably 0.001 to 0.5 part by mass, based on 100 parts by mass of the resin (A). more preferred. The said surfactant may be used individually by 1 type, and may be used in combination of 2 or more type.
［剥離層形成用組成物の調製方法］
　本発明の剥離層形成用組成物の調製方法は、特に限定されないが、例えば、溶剤に溶解した（Ａ）成分の溶液に（Ｂ）成分、（Ｃ）成分、（Ｄ）成分及び（Ｅ）成分等を所定の割合で混合し、均一な溶液とする方法や、前記調製方法の適当な段階において、必要に応じてその他添加剤を更に添加して混合する方法が挙げられる。 [Method for preparing release layer-forming composition]
The method for preparing the release layer-forming composition of the present invention is not particularly limited. Examples include a method in which the components are mixed in a predetermined ratio to form a uniform solution, and a method in which other additives are further added and mixed as necessary in an appropriate stage of the preparation method.
　本発明の剥離層形成用組成物の調製においては、溶剤中の重合反応によって得られたポリマー溶液をそのまま使用することができる。この場合、例えば、（Ａ）成分の溶液に、前記と同様に（Ｂ）成分、更には（Ｃ）成分、（Ｄ）成分、（Ｅ）成分等を入れて均一な溶液とする。この際に、濃度調整を目的として更に溶剤を追加投入してもよい。このとき、（Ａ）成分の生成過程で用いられる溶剤と、剥離層形成用組成物の濃度調整に用いられる溶剤とは同一であってもよく、また異なってもよい。 In preparing the release layer-forming composition of the present invention, the polymer solution obtained by the polymerization reaction in the solvent can be used as it is. In this case, for example, component (B), component (C), component (D) and component (E) are added to the solution of component (A) in the same manner as described above to form a uniform solution. At this time, a solvent may be additionally added for the purpose of adjusting the concentration. At this time, the solvent used in the production process of the component (A) and the solvent used for adjusting the concentration of the release layer-forming composition may be the same or different.
　また、調製された剥離層形成用組成物の溶液は、孔径が０.２～１.０μｍ程度のフィルター等を用いて濾過した後、使用することが好ましい。 In addition, it is preferable to use the prepared solution of the composition for forming a release layer after filtering using a filter or the like having a pore size of about 0.2 to 1.0 μm.
　本発明の剥離層形成用組成物の粘度は、使用する塗布方法や作製する剥離層の厚み等を勘案して適宜設定されるが、特に０.０１～５μｍ程度の厚さの膜を再現性よく得ることを目的とする場合、通常、２５℃で１～５,０００ｍＰａ・ｓ程度、好ましくは１～２,０００ｍＰａ・ｓ程度である。 The viscosity of the release layer-forming composition of the present invention is appropriately set in consideration of the coating method to be used, the thickness of the release layer to be produced, and the like. For the purpose of obtaining a high viscosity, it is usually about 1 to 5,000 mPa·s, preferably about 1 to 2,000 mPa·s at 25°C.
　ここで、粘度は、市販の液体の粘度測定用粘度計を使用して、例えば、JIS K7117-2に記載の方法を参照して、組成物の温度２５℃の条件にて測定することができる。好ましくは、粘度計としては、円錐平板型（コーンプレート型）回転粘度計を使用し、好ましくは同型の粘度計で標準コーンロータとして１°３４'×Ｒ２４を使用して、組成物の温度２５℃の条件にて測定することができる。このような回転粘度計としては、例えば、東機産業(株)製TVE-25Lが挙げられる。 Here, the viscosity can be measured using a commercially available viscometer for measuring the viscosity of a liquid, for example, with reference to the method described in JIS K7117-2, under the condition of a composition temperature of 25 ° C. . Preferably, as a viscometer, a cone-plate type (cone-plate type) rotational viscometer is used, preferably with a viscometer of the same type using a standard cone rotor of 1 ° 34' × R24, and the temperature of the composition is 25 It can be measured under the conditions of °C. An example of such a rotational viscometer is TVE-25L manufactured by Toki Sangyo Co., Ltd.
［剥離層］
　本発明の剥離層は、前記剥離層形成用組成物を用いて基体上に樹脂膜を形成する工程（樹脂膜形成工程）、前記樹脂膜の所定の領域を放射線で露光する工程（露光工程）、放射線を照射した樹脂膜を現像液で現像し、未露光部を除去する工程（現像工程）を含む方法によって製造することができる。 [Release layer]
The release layer of the present invention can be formed by a process of forming a resin film on a substrate using the release layer-forming composition (resin film forming process) and a process of exposing a predetermined region of the resin film to radiation (exposure process). , the resin film irradiated with radiation can be developed with a developing solution to remove the unexposed portion (developing step).
　樹脂膜形成工程において、前記樹脂膜を形成する方法としては、前記剥離層形成用組成物を基体上に塗布した後、加熱する方法が挙げられる。また、加熱する前に、予備乾燥として溶媒を揮発させる工程を含んでもよい。なお、本発明において、基体とは、その表面に本発明の剥離層形成用組成物が塗布されるものであって、フレキシブル電子デバイス等の製造に用いられるものを意味する。 In the resin film forming step, examples of the method of forming the resin film include a method of applying the composition for forming a release layer onto a substrate and then heating. In addition, a step of volatilizing the solvent as preliminary drying may be included before heating. In the present invention, the term "substrate" means a substrate on the surface of which the composition for forming a release layer of the present invention is applied and used for the production of flexible electronic devices and the like.
　基体としては、例えば、ガラス、金属（シリコンウエハ等）、スレート等が挙げられるが、特に、本発明の剥離層形成用組成物から得られる剥離層がそれに対する十分な密着性を有することから、ガラスが好ましい。なお、基体表面は、単一の材料で構成されていてもよく、２以上の材料で構成されていてもよい。２以上の材料で基体表面が構成される態様としては、基体表面のうち、ある範囲はある材料で構成され、その余の表面はその他の材料で構成されている態様、基体表面全体にドットパターン、ラインアンドスペースパターン等のパターン状にある材料がその他の材料中に存在する態様等がある。 Examples of the substrate include glass, metal (silicon wafer, etc.), slate, and the like. Glass is preferred. The substrate surface may be composed of a single material, or may be composed of two or more materials. Examples of embodiments in which the surface of the substrate is composed of two or more materials include an embodiment in which a certain area of the surface of the substrate is composed of a certain material and the rest of the surface is composed of another material; , a patterned material such as a line-and-space pattern exists in another material.
　塗布する方法は、特に限定されないが、例えば、スリットコート法、キャストコート法、スピンコート法、ブレードコート法、ディップコート法、ロールコート法、バーコート法、ダイコート法、インクジェット法、印刷法（凸版、凹版、平版、スクリーン印刷等）等が挙げられる。 The coating method is not particularly limited, but for example, slit coating method, cast coating method, spin coating method, blade coating method, dip coating method, roll coating method, bar coating method, die coating method, inkjet method, printing method (letterpress , intaglio, lithography, screen printing, etc.).
　予備乾燥の方法としては、例えば、剥離層形成用組成物を塗布した基体を所定の容器内に封入し、減圧することで溶媒を揮発させる方法等が挙げられる。減圧の方法は、特に限定されないが、真空ポンプを用いて耐圧容器内を所定の減圧度まで減圧する方法等が挙げられる。減圧度は、通常２０～２００Ｐａであるが、４０～１００Ｐａが好ましい。減圧時間は、真空ポンプの性能や耐圧容器の大きさによって異なるため一概に規定できないが、通常１０～６０秒間であり、１５～３０秒間が好ましい。 As a method of pre-drying, for example, a method of enclosing the substrate coated with the release layer forming composition in a predetermined container and reducing the pressure to volatilize the solvent can be used. The method of decompression is not particularly limited, but includes a method of decompressing the inside of the pressure vessel to a predetermined degree of decompression using a vacuum pump. The degree of pressure reduction is usually 20-200 Pa, preferably 40-100 Pa. The depressurization time varies depending on the performance of the vacuum pump and the size of the pressure vessel, and cannot be generally specified, but is usually 10 to 60 seconds, preferably 15 to 30 seconds.
　加熱に用いる器具としては、例えば、ホットプレート、オーブン等が挙げられる。加熱雰囲気は、空気下であっても不活性ガス下であってもよく、また、常圧下であっても減圧下であってもよい。 Equipment used for heating includes, for example, hot plates and ovens. The heating atmosphere may be under air or under an inert gas, and may be under normal pressure or under reduced pressure.
　加熱温度は、通常５０～２５０℃であるが、５０～１５０℃が好ましい。加熱時間は、加熱温度によって異なるため一概に規定できないが、通常１分間～５時間であり、１分間～１時間が好ましい。 The heating temperature is usually 50-250°C, preferably 50-150°C. The heating time varies depending on the heating temperature and cannot be generally specified, but is usually 1 minute to 5 hours, preferably 1 minute to 1 hour.
　前記露光工程においては、樹脂膜の所定の領域に放射線をし、露光部を硬化させる。所定の領域に放射線を照射する方法の一例としては、所定のパターンを有するマスクを介して照射する方法が挙げられる。マスクを介して照射した場合、例えば、ドットパターン、ラインアンドスペースパターン等のパターンが形成された剥離層が得られる。 In the exposure step, radiation is applied to a predetermined region of the resin film to cure the exposed portion. One example of a method of irradiating a predetermined region with radiation is a method of irradiating 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 is obtained.
　前記放射線としては、光酸発生剤に吸収される波長であれば特に限定されないが、波長１５０～８００ｎｍの紫外線又は可視光線等が挙げられる。好ましくは、波長が２００～４００ｎｍの紫外線であり、具体的には、ｉ線（３６５ｎｍ）等が挙げられる。また、その照射量は、露光部が完全に硬化すればよく、１００～２,０００ｍＪ／ｃｍ2が好ましく、３００～１,０００ｍJ／ｃｍ2がより好ましい。 The radiation is not particularly limited as long as it has a wavelength that can be absorbed by the photoacid generator, and examples thereof include ultraviolet light or visible light with a wavelength of 150 to 800 nm. Ultraviolet rays with a wavelength of 200 to 400 nm are preferred, and specific examples include i-line (365 nm). Moreover, the irradiation amount is sufficient so long as the exposed portion is completely cured, and is preferably 100 to 2,000 mJ/cm 2 , more preferably 300 to 1,000 mJ/cm 2 .
　放射線の照射方向は、特に限定されないが、基体面に対して垂直方向から照射しても、斜め方向から照射してもよく、またこれらを組み合わせて照射してもよい。好ましくは、基体面に対して垂直方向に近い角度から照射することが好ましい。 The irradiation direction of the radiation is not particularly limited, but it may be irradiated in a direction perpendicular to the substrate surface, or in an oblique direction, or in combination thereof. It is preferable to irradiate from an angle close to the direction perpendicular to the substrate surface.
　使用する光源は、特に限定されないが、前記波長帯の光を照射することのできるものであればよく、例えば低圧水銀ランプ、高圧水銀ランプ、メタルハライドランプ、キセノンランプ、エキシマランプ、無電極ランプ等が挙げられる。前述した好ましい波長領域の放射線は、前記光源とフィルター等とを併用することによって得られる。 The light source to be used is not particularly limited as long as it can irradiate light in the above wavelength band. mentioned. Radiation in the preferred wavelength range described above can be obtained by using the light source and a filter or the like in combination.
　露光後、加熱処理（ＰＥＢ）を行ってもよい。ＰＥＢの加熱温度は、通常５０～２５０℃であるが、８０～２００℃が好ましい。加熱時間は、加熱温度によって異なるため一概に規定できないが、通常３０秒間～３０分間であり、１～２０分間が好ましい。 After exposure, heat treatment (PEB) may be performed. The heating temperature for PEB is usually 50 to 250°C, preferably 80 to 200°C. The heating time varies depending on the heating temperature and cannot be generally defined, but is usually 30 seconds to 30 minutes, preferably 1 to 20 minutes.
　前記現像工程で使用される現像液は、未露光部を溶解して除去できるものであればよく、（Ａ）成分の樹脂に応じて適宜選択すればよい。前記現像液としては、例えば、プロピレングリコールモノメチルエーテル等のグリコールエーテル系有機溶剤、炭酸カリウム、炭酸ナトリウム、水酸化カリウム、水酸化ナトリウム等のアルカリ金属水酸化物の水溶液、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、コリン等の水酸化第四級アンモニウム塩の水溶液、エタノールアミン、プロピルアミン、エチレンジアミン等のアミン水溶液等のアルカリ性水溶液が挙げられる。これらの現像液には、界面活性剤等を加えてもよい。 The developer used in the development step may be any one that can dissolve and remove the unexposed areas, and may be appropriately selected according to the resin of component (A). Examples of the developer include glycol ether-based organic solvents such as propylene glycol monomethyl ether; aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide; tetramethylammonium hydroxide; Alkaline aqueous solutions such as aqueous solutions of quaternary ammonium hydroxide salts such as tetraethylammonium oxide and choline, and aqueous solutions of amines such as ethanolamine, propylamine and ethylenediamine can be used. A surfactant or the like may be added to these developers.
　また、現像方法としては、液盛り法、ディッピング法、揺動浸漬法等、いずれも用いることができる。その際の現像時間は、通常、１５～３００秒間である。 In addition, as a developing method, any of a liquid heaping method, a dipping method, a rocking immersion method, and the like can be used. The development time at that time is usually 15 to 300 seconds.
　現像後、剥離層に対して流水による洗浄を例えば２０～１２０秒間行い、続いて圧縮空気又は圧縮窒素を用いて、又はスピニングにより風乾することにより、基板上の水分が除去され、パターン形成された膜が得られる。 After development, the release layer was washed with running water for, for example, 20-120 seconds, followed by air drying with compressed air or compressed nitrogen, or by spinning to remove moisture on the substrate and patterned. A membrane is obtained.
　現像後、加熱処理を行ってもよい。加熱温度は、通常５０～３００℃であるが、８０～２５０℃が好ましい。加熱時間は、加熱温度によって異なるため一概に規定できないが、通常３０秒間～３０分間であり、１～２０分間が好ましい。 Heat treatment may be performed after development. The heating temperature is usually 50 to 300°C, preferably 80 to 250°C. The heating time varies depending on the heating temperature and cannot be generally defined, but is usually 30 seconds to 30 minutes, preferably 1 to 20 minutes.
　また、現像により、剥離層表面に存在する（Ｄ）成分のみが除かれることでも所定の効果を得ることができる。 A predetermined effect can also be obtained by removing only the component (D) present on the release layer surface by development.
　前記剥離層の厚さは、通常０.０１～５０μｍ程度であるが、生産性の観点から、好ましくは０.０１～２０μｍ程度であり、より好ましくは０.０１～５μｍ程度であり、加熱前の塗膜の厚さを調整して所望の厚さを実現する。 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. The thickness of the coating is adjusted to achieve the desired thickness.
　本発明の剥離層は、基体、特にガラスの基体との優れた密着性、並びに樹脂基板との適度な密着性及び適度な剥離性を有する。それ故、本発明の剥離層は、フレキシブル電子デバイスの製造プロセスにおいて、当該デバイスの樹脂基板に損傷を与えることなく、当該樹脂基板を、その樹脂基板上に形成された回路等とともに、基体から剥離させるために好適に用いることができる。 The release layer of the present invention has excellent adhesion to substrates, particularly glass substrates, and moderate adhesion and moderate releasability to resin substrates. Therefore, the release layer of the present invention allows the resin substrate of the device to be peeled off from the substrate together with the circuit or the like formed on the resin substrate without damaging the resin substrate of the device in the manufacturing process of the flexible electronic device. It can be suitably used to allow
［樹脂基板の製造方法］
　本発明の剥離層を用いたフレキシブル電子デバイスの製造方法の一例について説明する。まず、本発明の剥離層形成用組成物を用いて、前述の方法によって、基体上の所定の領域に剥離層を形成する。この剥離層が所定の領域に形成された基体の面に、剥離層を全て覆うようにして、樹脂基板を形成するための樹脂基板形成用溶液を塗布し、得られた塗膜を焼成することで、本発明の剥離層を介して、基体に固定された樹脂基板を形成する。 [Method for manufacturing resin substrate]
An example of a method for manufacturing a flexible electronic device using the release layer of the present invention will be described. First, using the composition for forming a release layer of the present invention, a release layer is formed on a predetermined region on a substrate by the method described above. A resin substrate forming solution for forming a resin substrate is applied to the surface of the substrate on which the release layer is formed in a predetermined region so as to cover the entire release layer, and the obtained coating film is baked. Then, a resin substrate fixed to a substrate is formed through the release layer of the present invention.
　前記塗膜の焼成温度は、樹脂の種類等に応じて適宜設定されるが、この焼成時の最高温度を２００～２５０℃とすることが好ましく、２１０～２５０℃とすることがより好ましく、２２０～２４０℃とすることが更に好ましい。樹脂基板作製の際の焼成時の最高温度をこの範囲とすることで、下地である剥離層と基体との密着性や、剥離層と樹脂基板との適度な密着性及び剥離性をより向上させることができる。この場合も、最高温度が前記範囲となる限り、それ以下の温度で焼成する工程を含んでもよい。 The firing temperature of the coating film is appropriately set according to the type of resin, etc., but the maximum temperature during firing is preferably 200 to 250 ° C., more preferably 210 to 250 ° C., and 220 ° C. It is more preferable to set the temperature to 240°C. By setting the maximum temperature during baking in the production of the resin substrate within this range, the adhesiveness between the base release layer and the substrate, and the appropriate adhesion and releasability between the release layer and the resin substrate are further improved. be able to. Also in this case, as long as the maximum temperature falls within the above range, a step of firing at a temperature lower than that may be included.
　樹脂基板は、剥離層が形成された領域の面積と比較して大きい面積で形成されることが好ましい。樹脂基板としては、アクリルポリマーからなる樹脂基板やシクロオレフィンポリマーからなる樹脂基板が挙げられる。当該樹脂基板の形成方法は、常法に従えばよい。また、前記樹脂基板としては、波長４００ｎｍの光の透過率が８０％以上であるものが好ましい。 The resin substrate is preferably formed with an area larger than that of the area where the release layer is formed. Examples of the resin substrate include a resin substrate made of acrylic polymer and a resin substrate made of cycloolefin polymer. A method for forming the resin substrate may follow a conventional method. The resin substrate preferably has a transmittance of 80% or more for light with a wavelength of 400 nm.
　次に、本発明の剥離層を介して基体に固定された前記樹脂基板の上に、必要に応じて所望の回路を形成し、その後、例えば剥離層に沿って樹脂基板をカットし、この回路とともに樹脂基板を剥離層から剥離して、樹脂基板と基体とを分離する。この際、基体の一部を剥離層とともにカットしてもよい。本発明の剥離層を用いれば、樹脂基板を剥離層から１.０Ｎ／２５ｍｍ以下の剥離力で剥離することができる。 Next, on the resin substrate fixed to the substrate via the release layer of the present invention, a desired circuit is formed as necessary, and then, for example, the resin substrate is cut along the release layer to obtain the circuit. At the same time, the resin substrate is separated from the release layer to separate the resin substrate and the base. At this time, part of the substrate may be cut together with the release layer. By using the release layer of the present invention, the resin substrate can be separated from the release layer with a release force of 1.0 N/25 mm or less.
　以下、合成例、調製例、実施例及び比較例を挙げて本発明を更に詳しく説明するが、本発明は、下記実施例に限定されない。 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.
　下記例で使用した化合物は、以下のとおりである。
ＰＧＭＥ：プロピレングリコールモノメチルエーテル
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
ＰＬ－ＬＩ：１,３,４,６－テトラキス(メトキシエチル)グリコールウリル（オルネクス社製、商品名：POWDERLINK 1174）
ＰＰＴＳ：ｐ－トルエンスルホン酸ピリジニウム
ＰＡＧ１０３：ＢＡＳＦ社製Irgacure PAG103（前記式（ＰＡＧ－４）で表される化合物）
ＰＡＧ１２１：ＢＡＳＦ社製Irgacure PAG121（前記式（ＰＡＧ－２）で表される化合物）
ＰＡＩ１０１：みどり化学社製PAI-101（前記式（ＰＡＧ－２６）で表される化合物）
ＭＡＡ：メタクリル酸
ＭＭＡ：メタクリル酸メチル
ＨＰＭＡ：メタクリル酸２－ヒドロキシプロピル
ＨＥＭＡ：メタクリル酸２－ヒドロキシエチル
ＡＤＭＡ：メタクリル酸２－アダマンチル
ＣＨＭＩ：Ｎ－シクロヘキシルマレイミド
ＰＱＭＡ：メタクリル酸４－ヒドロキシフェニル
ＨＦｉＰＭＡ：メタクリル酸１,１,１,３,３,３－ヘキサフルオロイソプロピル
ＡＩＢＮ：アゾビスイソブチロニトリル
ＥＰ：ビスフェノールＡ型エポキシ樹脂（三菱ケミカル(株)製、商品名：jER828）
ＩＰｈＡ：イソフタル酸
ＢＴＥＡＣ：ベンジルトリエチルアンモニウムクロリド
ＨＰＣ：ヒドロキシプロピルセルロース
ＫＯＨ：水酸化カリウム The compounds used in the examples below 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 PAG103: Irgacure PAG103 manufactured by BASF (compound represented by the above formula (PAG-4))
PAG121: Irgacure PAG121 manufactured by BASF (compound represented by the formula (PAG-2))
PAI101: PAI-101 manufactured by Midori Chemical Co., Ltd. (compound represented by the above formula (PAG-26))
MAA: methacrylate MMA: methyl methacrylate HPMA: 2-hydroxypropyl methacrylate HEMA: 2-hydroxyethyl methacrylate ADMA: 2-adamantyl methacrylate CHMI: N-cyclohexylmaleimide PQMA: 4-hydroxyphenyl methacrylate HFiPMA: methacrylic acid 1,1,1,3,3,3-hexafluoroisopropyl AIBN: azobisisobutyronitrile EP: bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: jER828)
IPhA: isophthalic acid BTEAC: benzyltriethylammonium chloride HPC: hydroxypropyl cellulose KOH: potassium hydroxide
　また、ポリマーの重量平均分子量（Ｍｗ）の測定は、(株)島津製作所製ＧＰＣ装置（カラム：Ｓｈｏｄｅｘ（登録商標）ＫＦ８０３Ｌ及びＫＦ８０４Ｌ（昭和電工(株)製）；溶離液：ＴＨＦ；流量：１.０ｍＬ／分；カラム温度：４０℃；Ｍｗ：標準ポリスチレン換算値）を用いて行った。 In addition, the weight average molecular weight (Mw) of the polymer was measured using a GPC apparatus manufactured by Shimadzu Corporation (column: Shodex (registered trademark) KF803L and KF804L (manufactured by Showa Denko Co., Ltd.); eluent: THF; flow rate: 1 0 mL/min; column temperature: 40° C.; Mw: standard polystyrene conversion value).
［１］ポリマーの合成
［合成例１］ポリウレア（Ｌ１）の合成
　モノアリルジグリシジルイソシアヌル酸（四国化成工業(株)製）１００ｇ、５,５－ジエチルバルビツール酸６６.４ｇ及びベンジルトリエチルアンモニウムクロリド４.１ｇをＰＧＭＥ６８２ｇに溶解させた後、１３０℃で２４時間反応させ、ポリウレア（Ｌ１）を含む溶液を得た。ＧＰＣ分析の結果、得られたポリウレア（Ｌ１）のＭｗは８,０００、Ｍｗ／Ｍｎは１.５であった。 [1] Synthesis of Polymer [Synthesis Example 1] Synthesis of polyurea (L1) 100 g of monoallyldiglycidyl isocyanurate (manufactured by Shikoku Kasei Kogyo Co., Ltd.), 66.4 g of 5,5-diethylbarbituric acid and benzyltriethylammonium chloride After dissolving 4.1 g of PGME in 682 g, the solution was reacted at 130° C. for 24 hours to obtain a solution containing polyurea (L1). As a result of GPC analysis, the resulting polyurea (L1) had an Mw of 8,000 and an Mw/Mn of 1.5.
［合成例２］アクリルポリマー（Ｌ２）の合成
　ＭＡＡ１.００ｇ、ＨＥＭＡ３.１３ｇ、ＭＭＡ２.７５ｇ、ＰＱＭＡ０.６３ｇ、ＣＨＭＩ５.００ｇ及びＡＩＢＮ０.７８ｇをＰＧＭＥ２９.８ｇに溶解し、７０℃にて２０時間反応させ、アクリルポリマー（Ｌ２）溶液（固形分濃度３１質量％）を得た。ＧＰＣ分析の結果、得られたアクリルポリマー（Ｌ２）のＭｗは７,０００、Ｍｗ／Ｍｎは１.６であった。 [Synthesis Example 2] Synthesis of acrylic polymer (L2) 1.00 g of MAA, 3.13 g of HEMA, 2.75 g of MMA, 0.63 g of PQMA, 5.00 g of CHMI and 0.78 g of AIBN were dissolved in 29.8 g of PGME and reacted at 70°C for 20 hours. to obtain an acrylic polymer (L2) solution (solid concentration: 31% by mass). As a result of GPC analysis, the obtained acrylic polymer (L2) had an Mw of 7,000 and an Mw/Mn of 1.6.
［合成例３］ポリエステル（Ｌ３）の合成
　ＥＰ　１０.０ｇ、ＩＰｈＡ５.４ｇ及びＢＴＥＡＣ０.２５ｇをＰＧＭＥ３６.４ｇに溶解し、１２０℃にて２０時間反応させ、ポリエステル（Ｌ３）溶液（固形分濃度３０質量％）を得た。ＧＰＣ分析の結果、得られたポリエステル（Ｌ３）のＭｗは１３,２００、Ｍｗ／Ｍｎは３.９であった。 [Synthesis Example 3] Synthesis of polyester (L3) EP 10.0 g, IPhA 5.4 g and BTEAC 0.25 g were dissolved in PGME 36.4 g, reacted at 120 ° C. for 20 hours, and polyester (L3) solution (solid content concentration 30 mass %) was obtained. As a result of GPC analysis, the obtained polyester (L3) had an Mw of 13,200 and an Mw/Mn of 3.9.
［合成例４］アクリルポリマー（Ｓ１）の合成
　ＨＦｉＰＭＡ１.００ｇ、ＨＰＭＡ０.６１ｇ、ＡＤＭＡ１.２４ｇ及びＡＩＢＮ０.１２ｇをＰＧＭＥ１１.９ｇに溶解し、７０℃にて２０時間反応させ、アクリルポリマー（Ｓ１）溶液（固形分濃度２０質量％）を得た。ＧＰＣ分析の結果、得られたアクリルポリマー（Ｓ１）のＭｗは４,４７０、Ｍｗ／Ｍｎは１.８であった。 [Synthesis Example 4] Synthesis of Acrylic Polymer (S1) 1.00 g of HFiPMA, 0.61 g of HPMA, 1.24 g of ADMA and 0.12 g of AIBN were dissolved in 11.9 g of PGME and reacted at 70°C for 20 hours to give an acrylic polymer (S1) solution. (solid content concentration 20% by mass) was obtained. As a result of GPC analysis, the obtained acrylic polymer (S1) had an Mw of 4,470 and an Mw/Mn of 1.8.
［調製例］樹脂基板形成用組成物Ｆ１の調製
　四塩化炭素１００ｇを入れたナスフラスコに、ゼオノア（登録商標）１０２０Ｒ（日本ゼオン(株)製シクロオレフィンポリマー）１０ｇ及びエポリード（登録商標）ＧＴ４０１（(株)ダイセル製）３ｇを添加した。この溶液を、窒素雰囲気下、２４時間攪拌して溶解し、樹脂基板形成用組成物Ｆ１を調製した。 [Preparation Example] Preparation of Resin Substrate Forming Composition F1 In an eggplant flask containing 100 g of carbon tetrachloride, 10 g of Zeonor (registered trademark) 1020R (a cycloolefin polymer manufactured by Nippon Zeon Co., Ltd.) and Epolead (registered trademark) GT401 ( Daicel Co., Ltd.) 3 g was added. This solution was dissolved by stirring for 24 hours in a nitrogen atmosphere to prepare a resin substrate-forming composition F1.
［２］剥離層形成用組成物の調製
［実施例１－１］剥離層形成用組成物１の調製
　（Ａ）成分として合成例１で得られたポリウレア（Ｌ１）を１００質量部、（Ｂ）成分としてＰＡＧ１２１を３質量部、（Ｃ）成分としてＰＬ－ＬＩを７.５質量部、（Ｄ）成分としてアクリルポリマー（Ｓ２）を７.５質量部、及びＰＧＭＥＡを加え、固形分濃度が５質量％、ＰＧＭＥＡ濃度が３０質量％となるようにＰＧＭＥで希釈し、剥離層形成用組成物Ａ－１を調製した。 [2] Preparation of release layer-forming composition [Example 1-1] Preparation of release layer-forming composition 1 100 parts by mass of polyurea (L1) obtained in Synthesis Example 1 as component (A), (B ) component 3 parts by mass of PAG121, 7.5 parts by mass of PL-LI as component (C), 7.5 parts by mass of acrylic polymer (S2) as component (D), and PGMEA are added, and the solid content concentration is The mixture was diluted with PGME so that the PGMEA concentration was 5% by mass and the PGMEA concentration was 30% by mass to prepare a release layer forming composition A-1.
［実施例１－２～１－６、比較例１－１、１－２］
　各成分の種類と量を、それぞれ表１に記載のとおりとした以外は、実施例１－１と同様の方法で、剥離層形成用組成物Ａ－２～Ａ－８をそれぞれ調製した。 [Examples 1-2 to 1-6, Comparative Examples 1-1 and 1-2]
Compositions A-2 to A-8 for forming a release layer 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 1.
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000035
［３］剥離層及び樹脂基板の作製
［実施例２－１］
　スピンコータ（条件：回転数８００ｒｐｍで約３０秒）を用いて、剥離層形成用組成物Ａ－１を、基体としてのガラス基板（コーニング社製イーグルＸＧ、１００ｍｍ×１００ｍｍ×０.５ｍｍ、以下同様）の上に塗布した。得られた塗膜を、ホットプレートを用いて１００℃で２分間加熱した。この塗膜の一部に、キヤノン(株)製の紫外線照射装置PLA-600FAを用いて光強度が３.５ｍＷ／ｃｍ2の波長３６５ｎｍの紫外線を５００ｍＪ／ｃｍ2照射し、その後、露光後ベーク（ＰＥＢ）として１８０℃で１０分間加熱し、剥離層を硬化させ、ＰＧＭＥに５分間浸漬し現像を行った後、超純水で２０秒間流水洗浄を行い、さらに２３０℃で１０分間加熱することで、未露光部を除去し、ガラス基板上の所定の領域に厚さ約０.１μｍの剥離層を形成した。
　その後、スピンコータ（条件：回転数２００ｒｐｍで約１５秒）を用いて、剥離層が所定の領域に形成された前記ガラス基板の面の全面に樹脂基板形成用組成物Ｆ１を塗布した。得られた塗膜を、ホットプレートを用いて８０℃で２分間加熱し、その後、ホットプレートを用いて２３０℃で３０分間加熱し、剥離層上に厚さ約３μｍの樹脂基板を形成し、樹脂基板・剥離層付きガラス基板を得た。 [3] Preparation of release layer and resin substrate [Example 2-1]
Using a spin coater (conditions: 800 rpm for about 30 seconds), the release layer forming composition A-1 was coated on a glass substrate (Corning Eagle XG, 100 mm × 100 mm × 0.5 mm, hereinafter the same) as a substrate. was applied on top of The obtained coating film was heated at 100° C. for 2 minutes using a hot plate. A part of this coating film is irradiated with 500 mJ/cm 2 of ultraviolet light having a wavelength of 365 nm and a light intensity of 3.5 mW/cm 2 using an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc., and then baked after exposure. (PEB) is heated at 180° C. for 10 minutes to cure the release layer, immersed in PGME for 5 minutes for development, washed with running ultrapure water for 20 seconds, and further heated at 230° C. for 10 minutes. , the unexposed portion was removed, and a peeling layer having a thickness of about 0.1 μm was formed in a predetermined region on the glass substrate.
After that, using a spin coater (conditions: 200 rpm for about 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 the predetermined region. The resulting coating film is heated using a hot plate at 80° C. for 2 minutes, and then heated at 230° C. for 30 minutes using a hot plate to form a resin substrate having a thickness of about 3 μm on the release layer, A glass substrate with a resin substrate and a release layer was obtained.
［実施例２－２～２－６、比較例２－１、２－２］
　剥離層形成用組成物、ＰＥＢ温度及び現像液を、それぞれ表２に記載のとおりとした以外は、実施例２－１と同様の方法で、樹脂基板・剥離層付きガラス基板を得た。 [Examples 2-2 to 2-6, Comparative Examples 2-1 and 2-2]
A resin substrate and a glass substrate with a release layer were obtained in the same manner as in Example 2-1, except that the release layer-forming composition, PEB temperature, and developer were as shown in Table 2.
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000036
［４］剥離層の評価
［実施例３－１～３－６、比較例３－１、３－２］
［剥離力の評価］
　実施例２－１～２－６、比較例２－１、２－２で得られた樹脂基板・剥離層付きガラス基板の剥離層に、カッターを用いて２５ｍｍ×５０ｍｍの短冊状に切り込みを入れた。さらに、セロテープ（登録商標）（ニチバン(株)製CT-24）を貼った後、オートグラフAGS-X500N（(株)島津製作所製）を用いて、剥離角度９０°、剥離速度３００ｍｍ／ｍｉｎで剥離し、剥離力を測定した。なお、剥離できないものは、剥離不可とした。評価結果は「剥離力」とし、結果を表３にまとめて示す。 [4] Evaluation of release layer [Examples 3-1 to 3-6, Comparative Examples 3-1 and 3-2]
[Evaluation of peel strength]
The release layer of the resin substrate/glass substrate with release layer obtained in Examples 2-1 to 2-6 and Comparative Examples 2-1 and 2-2 was cut into strips of 25 mm × 50 mm using a cutter. rice field. Furthermore, after applying Cellotape (registered trademark) (CT-24 manufactured by Nichiban Co., Ltd.), Autograph AGS-X500N (manufactured by Shimadzu Corporation) was used at a peeling angle of 90 ° and a peeling speed of 300 mm / min. It was peeled off and the peel force was measured. In addition, what could not be peeled was made into non-peelable. The evaluation result is "peeling force", and the results are summarized in Table 3.
［剥離界面の評価］
　剥離力の評価後のガラス基板上に残存する剥離層を、触針式膜厚計で膜厚を測定した。剥離層形成時の膜厚と比較を行い、剥離界面を判別した。評価結果は「剥離界面」とし、残膜率（残膜率（％）＝剥離後の剥離層膜厚／剥離層形成時の剥離層膜厚×１００）が９０％以上の場合は剥離層/樹脂界面、１０％以上９０％未満の場合は剥離層の凝集破壊、１０％未満の場合はガラス基板／剥離層界面とした。評価結果を表３にまとめて示す。 [Evaluation of peeling interface]
The film thickness of the peeling layer remaining on the glass substrate after evaluation of the peeling force was measured with a stylus type film thickness meter. The film thickness at the time of forming the peeling layer was compared to determine the peeling interface. The evaluation result is the "peeling interface", and if the residual film rate (remaining film rate (%) = peeling layer thickness after peeling / peeling layer thickness at the time of peeling layer formation × 100) is 90% or more, the peeling layer / The resin interface, the cohesive failure of the peeling layer when it is 10% or more and less than 90%, and the glass substrate/peeling layer interface when it is less than 10%. Table 3 summarizes the evaluation results.
Figure JPOXMLDOC01-appb-T000037
Figure JPOXMLDOC01-appb-T000037
　表３に示した結果より、実施例の剥離層は、露光部のみ樹脂基板を剥離することが確認された。一方、比較例３－１は現像で未露光部を除去できず、露光の有無を問わず樹脂基板が剥離してしまい、比較例３－２は露光の有無を問わず樹脂基板が剥離しないことが確認された。 From the results shown in Table 3, it was confirmed that the release layers of Examples release the resin substrate only in the exposed areas. On the other hand, in Comparative Example 3-1, the unexposed area could not be removed by development, and the resin substrate was peeled off regardless of exposure. In Comparative Example 3-2, the resin substrate was not peeled off regardless of exposure. was confirmed.

Claims (7)

  1. 　（Ａ）ヒドロキシ基又はカルボキシ基を有する樹脂、
    （Ｂ）光酸発生剤、
    （Ｃ）ヒドロキシアルキル基及び／又はアルコキシメチル基で置換された窒素原子を有する化合物から選ばれる架橋剤、
    （Ｄ）下記式（ａ）で表される繰り返し単位、下記式（ｂ）で表される繰り返し単位及び下記式（ｃ）で表される繰り返し単位を含む高分子添加剤、並びに
    （Ｅ）溶剤
    を含む剥離層形成用組成物であって、（Ｄ）高分子添加剤が、（Ａ）ヒドロキシ基又はカルボキシ基を有する樹脂１００質量部に対し、５～１００質量部含まれる剥離層形成用組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式中、ＲAは、それぞれ独立に、水素原子又はメチル基であり；
    　ＲBは、少なくとも１つの水素原子がフッ素原子で置換された炭素数３又は４の分岐状のアルキル基であり；
    　ＲCは、炭素数２～１０のヒドロキシアルキル基であるが、ヒドロキシ基が結合する炭素原子は第２級又は第３級炭素原子であり；
    　ＲDは、炭素数の６～２０の多環式アルキル基又は炭素数６～１２のアリール基である。）     (A) a resin having a hydroxy group or a carboxy group;
    (B) a photoacid generator,
    (C) a cross-linking agent selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and/or an alkoxymethyl group;
    (D) a polymer additive containing a repeating unit represented by the following formula (a), a repeating unit represented by the following formula (b) and a repeating unit represented by the following formula (c), and (E) a solvent wherein the (D) polymer additive is contained in an amount of 5 to 100 parts by mass based on 100 parts by mass of the resin (A) having a hydroxy group or a carboxyl group. thing.
    Figure JPOXMLDOC01-appb-C000001
     (Wherein, R A is each independently a hydrogen atom or a methyl group;
    RB 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, but the carbon atom to which the hydroxy group is attached is a secondary or tertiary carbon atom;
    R D is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms. )
  2. 　（Ａ）ヒドロキシ基又はカルボキシ基を有する樹脂が、ヒドロキシ基を有するポリウレア、ヒドロキシ基若しくはカルボキシ基を有するアクリルポリマー、ヒドロキシ基を有するポリエステル、又はヒドロキシアルキル基を有するセルロース若しくはその誘導体である請求項１記載の剥離層形成用組成物。 (A) The resin having a hydroxy group or a carboxy group is 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. A composition for forming a release layer as described above.
  3. 　（Ｂ）光酸発生剤が発生する酸が、塩酸又は有機スルホン酸である請求項１又は２記載の剥離層形成用組成物。 (B) The composition for forming a release layer according to claim 1 or 2, wherein the acid generated by the photoacid generator is hydrochloric acid or organic sulfonic acid.
  4. 　請求項１～３のいずれか１項記載の剥離層形成用組成物から得られる剥離層。 A release layer obtained from the release layer-forming composition according to any one of claims 1 to 3.
  5. 　請求項４記載の剥離層に、波長４００ｎｍの光の透過率が８０％以上である樹脂層が積層された積層体。 A laminate in which a resin layer having a transmittance of 80% or more for light with a wavelength of 400 nm is laminated on the release layer according to claim 4.
  6. 　請求項１～３のいずれか１項記載の剥離層形成用組成物を用いて基体上に樹脂膜を形成する工程、
    　前記樹脂膜の所定の領域を放射線で露光する工程、及び
    　前記露光した樹脂膜を現像し、未露光部を除去する工程
    を含む剥離層の製造方法。     forming a resin film on a substrate using the release layer forming composition according to any one of claims 1 to 3;
    A method for producing a release layer, comprising: exposing a predetermined region of the resin film to radiation; and developing the exposed resin film to remove an unexposed portion.
  7. 　請求項１～３のいずれか１項記載の剥離層形成用組成物を用いて基体上に樹脂膜を形成する工程、
    　前記樹脂膜の所定の領域を放射線で露光する工程、
    　前記放射線を照射した樹脂膜を現像液で現像し、未露光部を除去し、所定の領域に剥離層を形成する工程、
    　前記剥離層が所定の領域に形成された基体の面に、前記剥離層を全て覆うように、波長４００ｎｍの光の透過率が８０％以上である樹脂基板を形成する工程、及び
    　前記剥離層上に形成された樹脂基板を、１.０Ｎ／２５ｍｍ以下の剥離力で剥離する工程
    を含む樹脂基板の製造方法。     forming a resin film on a substrate using the release layer forming composition according to any one of claims 1 to 3;
    exposing a predetermined region of the resin film to radiation;
    a step of developing the resin film irradiated with radiation with a developer to remove unexposed portions and forming a release layer in a predetermined region;
    a step of forming a resin substrate having a transmittance of 80% or more for light with a wavelength of 400 nm on the surface of the substrate on which the release layer is formed in a predetermined region so as to cover the entire release layer; A method of manufacturing a resin substrate, including a step of peeling off the resin substrate formed on the substrate with a peeling force of 1.0 N/25 mm or less.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016041790A (en) * 2014-08-19 2016-03-31 住友ベークライト株式会社 Production method of resin film
JP2017066173A (en) * 2015-09-28 2017-04-06 株式会社ネオス Fluorine-based surface treatment agent
WO2018034342A1 (en) * 2016-08-19 2018-02-22 大阪有機化学工業株式会社 Curable resin composition for forming easily-peelable film, and method for producing same
WO2018079337A1 (en) * 2016-10-27 2018-05-03 リンテック株式会社 Release sheet
WO2019022185A1 (en) * 2017-07-27 2019-01-31 日産化学株式会社 Composition for forming release layer, and release layer

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG10201502808UA (en) 2006-10-12 2015-05-28 Cambrios Technologies Corp Nanowire-Based Transparent Conductors And Applications Thereof
JP2009205924A (en) 2008-02-27 2009-09-10 Kuraray Co Ltd Transparent conductive film, transparent conductive member, and silver nano wire dispersion solution and manufacturing method of transparent conductive film
JP2009283410A (en) 2008-05-26 2009-12-03 Alps Electric Co Ltd Organic substrate with organic transparent conductive film and its manufacturing method
US9198298B2 (en) 2011-04-26 2015-11-24 Nippon Mektron, Ltd. Method for manufacturing transparent printed circuit and method for manufacturing transparent touch panel
KR102064277B1 (en) 2013-08-12 2020-01-13 동우 화인켐 주식회사 Preparing method for flexible touch screen panel
JP5661959B1 (en) 2014-03-03 2015-01-28 ユニチカ株式会社 Transparent sheet, and touch panel and electronic device including the same
US9649594B2 (en) 2015-03-27 2017-05-16 General Electric Technology Gmbh Dual injection grid arrangement
JP2017014377A (en) 2015-06-30 2017-01-19 Ｊｘエネルギー株式会社 Polyimide film, organic electroluminescent element, transparent conductive laminate, touch panel, solar cell and display device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016041790A (en) * 2014-08-19 2016-03-31 住友ベークライト株式会社 Production method of resin film
JP2017066173A (en) * 2015-09-28 2017-04-06 株式会社ネオス Fluorine-based surface treatment agent
WO2018034342A1 (en) * 2016-08-19 2018-02-22 大阪有機化学工業株式会社 Curable resin composition for forming easily-peelable film, and method for producing same
WO2018079337A1 (en) * 2016-10-27 2018-05-03 リンテック株式会社 Release sheet
WO2019022185A1 (en) * 2017-07-27 2019-01-31 日産化学株式会社 Composition for forming release layer, and release layer

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