WO2018159265A1 - Polymerizable composition and photosensitive composition for black column spacer - Google Patents

Polymerizable composition and photosensitive composition for black column spacer Download PDF

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Publication number
WO2018159265A1
WO2018159265A1 PCT/JP2018/004626 JP2018004626W WO2018159265A1 WO 2018159265 A1 WO2018159265 A1 WO 2018159265A1 JP 2018004626 W JP2018004626 W JP 2018004626W WO 2018159265 A1 WO2018159265 A1 WO 2018159265A1
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group
compound
carbon atoms
meth
represented
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PCT/JP2018/004626
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French (fr)
Japanese (ja)
Inventor
翔 六谷
祐也 中田
桂典 松平
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株式会社Adeka
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Priority to KR1020197019534A priority Critical patent/KR20190123259A/en
Priority to CN201880006925.3A priority patent/CN110177817A/en
Priority to JP2019502845A priority patent/JPWO2018159265A1/en
Publication of WO2018159265A1 publication Critical patent/WO2018159265A1/en

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    • 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
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
    • 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
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

Definitions

  • the present invention relates to a polymerizable composition containing a urethane (meth) acrylate compound, a colorant, an alkali developable compound, an ethylenically unsaturated compound and a polymerizable initiator, and a photosensitive composition for a black column spacer (hereinafter referred to as BCS). And a cured product obtained from the photosensitive composition.
  • a urethane (meth) acrylate compound a colorant, an alkali developable compound, an ethylenically unsaturated compound and a polymerizable initiator
  • BCS black column spacer
  • spacers are used to maintain the distance between the upper and lower substrates of the cell.
  • the spacer is formed by applying the polymerizable composition to the substrate, exposing through a predetermined mask, and developing.
  • BCS has been used in which column spacers and black matrix are integrated into one module to provide light shielding properties.
  • Patent Document 1 discloses a photosensitive resin composition for forming BCS, which contains carbon black subjected to a treatment for introducing an acidic group and can form a BCS having a low relative dielectric constant.
  • Patent Document 2 can form a BCS showing a good elastic recovery rate, containing a copolymer, an epoxy resin compound or a compound derived therefrom, and a colorant including a black colorant and a blue colorant.
  • a colored photosensitive resin composition is disclosed.
  • JP 2014-146029 A Japanese Patent Laying-Open No. 2015-093986
  • the problem to be solved by the present invention is that no BCS has excellent elastic recovery, low dielectric constant and good electrical characteristics.
  • an object of the present invention is to provide a polymerizable composition, a BCS photosensitive composition, and a BCS photosensitive composition that are excellent in elastic recovery, have a low dielectric constant, and have good electrical characteristics. It is providing the hardened
  • the present invention has achieved the above object by providing the following [1] to [9] after intensive studies.
  • M is a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, —O—, —S—, —SO 2 —, —SS—, —SO—, —CO—, —OCO— or Represents a substituent selected from the group represented by formula (a), (b), (c) or (d);
  • the hydrogen atom in the hydrocarbon group having 1 to 20 carbon atoms represented by M may be substituted with a halogen atom, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 (hereinafter also referred to as R 1 to R 8 ) are each independently a hydrogen atom or a carbon atom having 1 to 20 carbon atoms.
  • R 1 to R 8 Represents a hydrocarbon group or a halogen atom
  • the methylene group in the group represented by R 1 to R 8 may be substituted with an unsaturated bond, —O— or —S—, n is a number from 0 to 10, When n ⁇ 1, a plurality of R 1 to R 8 and M may be the same or different.
  • R 9 represents a hydrocarbon group having 1 to 20 carbon atoms
  • the methylene group in the group represented by R 10 to R 38 may be substituted with an unsaturated bond, —O— or —S—, R 10 and R 11 , R 11 and R 12
  • each of R 41 and R 42 independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring.
  • Represents Hydrogen atoms of the hydrocarbon group, or R 41 and having 2 to 20 carbon atoms containing heterocyclic ring represented by R 42 of R 41 and having 1 to 20 carbon atoms represented by R 42 is a halogen atom, a nitro Substituted with a group having 2 to 20 carbon atoms containing a group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group or heterocyclic ring
  • a photosensitive composition for a black column spacer comprising the polymerizable composition according to any one of [1] to [5].
  • [7] A method for producing a cured product using the polymerizable composition according to any one of [1] to [5] or the photosensitive composition for a black column spacer according to [6].
  • the polymerizable composition of the present invention comprises a urethane (meth) acrylate compound (A), a colorant (B), an alkali developable compound (C) [excluding the urethane (meth) acrylate compound (A)], ethylenic
  • An unsaturated compound (D) [however, excluding urethane (meth) acrylate compound (A) and alkali developable compound (C)] and a polymerization initiator (E) are contained.
  • each component will be described in order.
  • the urethane (meth) acrylate compound (A) is a compound having a urethane bond and a methacryl group or an acryl group in the same molecule.
  • the urethane (meth) acrylate compound (A) is not particularly limited as long as it is a compound having a urethane bond and a methacrylic group or an acrylic group in the same molecule, but reacts an alcohol containing a methacrylic group or an acrylic group with an isocyanate compound. Can be obtained.
  • Examples of the urethane (meth) acrylate compound (A) include phenyl glycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, and pentaerythritol triacrylate. Examples thereof include isophorone diisocyanate urethane prepolymer and dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer.
  • urethane (meth) acrylate compound (A) Commercially available products can also be used as the urethane (meth) acrylate compound (A).
  • the content of the urethane (meth) acrylate compound (A) is not particularly limited, but the urethane (meth) acrylate compound (A), the colorant (B), and alkali development. 1 to 20 parts by weight, more preferably 3 to 10 parts by weight, and still more preferably 100 parts by weight of the total amount of the organic compound (C), ethylenically unsaturated compound (D) and polymerization initiator (E). 3 to 8 parts by mass.
  • content of a polymeric compound (B) exists in said range, it is preferable from the elasticity recovery rate of the hardened
  • the content of the urethane (meth) acrylate compound (A) is not particularly limited, but the urethane (meth) acrylate compound (A), coloring
  • the elastic recovery rate of the cured product obtained is good with respect to 100 parts by mass in total of the agent (B), the alkali developable compound (C), the ethylenically unsaturated compound (D), and the polymerization initiator (E). Therefore, the amount is preferably 1 to 20 parts by mass, more preferably 3 to 10 parts by mass, and still more preferably 3 to 8 parts by mass.
  • pigments and dyes can be used as the colorant (B) used in the polymerizable composition of the present invention.
  • the pigment and the dye an inorganic color material or an organic color material can be used, respectively. These can be used alone or in admixture of two or more.
  • the pigment means a colorant that is insoluble in a solvent described later, and includes inorganic or organic colorants that are insoluble in a solvent, or those obtained by rake formation of an inorganic or organic dye.
  • the pigment examples include carbon black obtained by a furnace method, a channel method or a thermal method, or carbon black such as acetylene black, ketjen black or lamp black, a carbon black prepared or coated with an epoxy resin, and the carbon black
  • carbon black obtained by a furnace method, a channel method or a thermal method, or carbon black such as acetylene black, ketjen black or lamp black, a carbon black prepared or coated with an epoxy resin, and the carbon black
  • a resin is pre-dispersed in a resin and coated with 20 to 200 mg / g of resin, an acid or alkaline surface treatment of the above carbon black, an average particle size of 8 nm or more, and a DBP oil absorption of 90 ml / 100 g or less of carbon black, the total amount of oxygen calculated from CO and CO 2 in the volatile content at 950 ° C.
  • carbon black is surface area 100 m 2 per 9mg above, graphitized carbon black, graphite, activated carbon, carbon fibers, carbon nanotubes, Kabonma Black coil represented by crocoil, carbon nanohorn, carbon aerogel, fullerene, aniline black, pigment black 7, titanium black, lactam black and perylene black, chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese series, ferrocyan Fluoride, ultramarine blue, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red rose (red iron (III) oxide), cadmium red, synthetic iron black, amber, lake pigment And organic or inorganic pigments.
  • black pigments are preferably used because of their high light shielding properties, and organic black pigments such as lactam black and perylene black are more preferably used because of their low liquid crystal contamination.
  • a commercial item can also be used as said pigment, for example, pigment red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97. 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223 224, 226, 227, 254, 228, 240 and 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64 , 65 and 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 5, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147,
  • the dye examples include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, cyanine compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, anthanthrones.
  • the content of the colorant (B) is not particularly limited, but is preferably 3 to 30 masses with respect to 100 mass parts of the following alkali developable compound (C). Part, more preferably 5 to 20 parts by weight, still more preferably 150 to 300 parts by weight.
  • the content of the colorant (B) is within the above range, the polymerizable composition has excellent storage stability without aggregation of the colorant, and the light-shielding property of the cured product of the polymerizable composition is high. This is preferable.
  • the content of the colorant (B) is not particularly limited, but is preferably based on 100 parts by mass of the alkali-developable compound (C). Is 3 to 30 parts by mass, more preferably 5 to 20 parts by mass, and still more preferably 150 to 300 parts by mass.
  • the alkali developable compound (C) is not the urethane (meth) acrylate compound (A) but a compound having a hydrophilic group and exhibiting alkali developability.
  • conventionally used compounds can be used as the alkali-developable compound (C) as long as the above conditions are satisfied.
  • the hydrophilic group include a hydroxyl group, a thiol group, a carboxyl group, a sulfo group, an amino group, an amide group or a salt thereof, and the hydroxyl group and the carboxyl group have developability to an alkali of the alkali developable compound (C). It is preferable because it is high.
  • the functional group equivalent of the hydrophilic group in the alkali-developable compound (C) (the mass of the polymer compound containing 1 equivalent of the hydrophilic group) is from 50 to 10,000.
  • the preferred molecular weight of the alkali developable compound (C) is 1,000 to 500,000.
  • the acid value of the alkali-developable compound (C) is preferably 10 to 200 mg / KOH, more preferably 30 to 150 mg / KOH. If the acid value is less than 10 mg / KOH, sufficient alkali developability may not be obtained, and if it is greater than 200 mg / KOH, it may be difficult to produce the polymer compound.
  • the acid value is based on JIS K0050 and JIS K 0211.
  • alkali-developable compound (C) examples include acrylic acid ester copolymers; phenol and / or cresol novolac epoxy resins; polyphenylmethane type epoxy resins having polyfunctional epoxy groups; epoxy acrylate resins; An epoxy addition compound having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the general formula (I); an unsaturated monobasic acid is added to the epoxy compound represented by the general formula (I)
  • a resin (unsaturated compound) having a structure obtained by an esterification reaction between an epoxy addition compound having a different structure and a polybasic acid anhydride can be used.
  • an alkali-developable compound that is a reaction product obtained by an esterification reaction of an epoxy addition compound having a structure with a monobasic acid and a polybasic acid anhydride is used, the sensitivity of the polymerizable composition increases.
  • a cured product obtained from the polymerizable composition is preferable because of its excellent elastic recovery rate.
  • the alkali-developable compound preferably contains 0.2 to 1.0 equivalent of an unsaturated group.
  • the alkali developable compound (C) is an epoxy compound represented by the general formula (I); An epoxy compound having the following structure [(e)] obtained by adding an unsaturated monobasic acid to the epoxy compound represented by I); or by esterification reaction of such an unsaturated compound and a polybasic acid anhydride The obtained unsaturated compound having the following structure [(f)] is desirable.
  • Y 1 represents an unsaturated monobasic acid residue
  • Y 2 represents a polybasic acid anhydride residue
  • the hydrocarbon group having 1 to 20 carbon atoms represented by M in the general formula (I) is not particularly limited, but is preferably an alkylene group having 1 to 20 carbon atoms, 2 carbon atoms. Represents an alkenylene group having 20 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. Among these, since the sensitivity when used as the alkali-developable compound (C) is good, it is an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, or an alkyl group having 3 to 10 carbon atoms. A cycloalkylene group or an arylene group having 6 to 10 carbon atoms is more preferable.
  • Examples of the alkylene group having 1 to 20 carbon atoms represented by M in the general formula (I) include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, and dodecylene. , Tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, icosylene groups and the like.
  • Examples of the alkenylene group having 2 to 20 carbon atoms represented by M in the general formula (I) include 1,2-ethenediyl (also referred to as ethenylene or vinylene), 2-butene-1,4-diyl, Examples include 1,2-dimethyl-1,2-ethenediyl.
  • Examples of the cycloalkylene group having 3 to 20 carbon atoms represented by M in the general formula (I) include cyclopropylene, cyclopentylene, cyclohexylene, cycloheptylene, and cyclooctylene groups.
  • Examples of the arylene group having 6 to 20 carbon atoms represented by M in the general formula (I) include phenylene, tolylene, xylylene, naphthylene, biphenylene, fluorene, and indane.
  • halogen atom for substituting the hydrocarbon group having 1 to 20 carbon atoms represented by M in the above general formula (I), fluorine, chlorine, bromine and iodine can be mentioned.
  • the hydrocarbon group having 1 to 20 carbon atoms represented by R 1 to R 38 in the general formula (I) is not particularly limited, but is preferably an alkyl group having 1 to 20 carbon atoms, An alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a 7 to 20 carbon atom Represents an arylalkyl group or the like; Since the sensitivity when used as the alkali-developable compound (C) is good, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, A cycloalkylalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to
  • alkyl group having 1 to 20 carbon atoms examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl. 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl and the like.
  • alkyl group having 1 to 10 carbon atoms examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl. 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl and the like.
  • alkenyl group having 2 to 20 carbon atoms examples include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2 -Heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl-1-methyl, and 4 , 8,12-tetradecatrienylallyl and the like.
  • alkenyl group having 2 to 10 carbon atoms examples include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2 -Heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl and the like.
  • the above cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms.
  • Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, and bicyclo [1. 1.1] pentanyl and the like.
  • the cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which a hydrogen atom of the alkyl group is substituted with a cycloalkyl group.
  • Examples of the cycloalkylalkyl group having 4 to 10 carbon atoms include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, 2-cyclobutylethyl, 2 -Cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 4-cyclobutylbutyl, 4 -Cyclopentylbutyl, 4-cyclohexylbutyl and the like.
  • Examples of the aryl group having 6 to 20 carbon atoms include one or more of phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, the alkyl group, the alkenyl group, the carboxyl group, and the halogen atom.
  • Substituted phenyl, biphenylyl, naphthyl, anthryl and the like, for example, 4-chlorophenyl, 4-carboxylphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl and the like can be mentioned.
  • aryl group having 6 to 10 carbon atoms examples include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, etc., phenyl substituted with one or more of the above alkyl group, the above alkenyl group, carboxyl group, halogen atom, etc.
  • Biphenylyl, naphthyl, anthryl and the like for example, 4-chlorophenyl, 4-carboxylphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl and the like.
  • arylalkyl group having 7 to 20 carbon atoms means a group having 7 to 20 carbon atoms in which a hydrogen atom of the alkyl group is replaced with an aryl group.
  • examples include benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl and naphthylpropyl.
  • the arylalkyl group having 7 to 10 carbon atoms means a group having 7 to 10 carbon atoms in which the hydrogen atom of the alkyl group is replaced with an aryl group, and examples thereof include benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl and the like can be mentioned.
  • the group having 2 to 20 carbon atoms containing the heterocyclic ring represented by R 10 to R 38 in the general formula (I) is not particularly limited, and examples thereof include pyrrolyl, pyridyl, pyridylethyl, Pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyranylethyl, pyrazolyl, triazyl, triazylmethyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, Benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, morpholinyl, thi
  • each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • Z represents a direct bond or an alkylene group having 1 to 6 carbon atoms. Represents a bond in the * part of the group represented by these formulas.
  • Examples of the alkyl group having 1 to 6 carbon atoms represented by R in the above formula include those having 1 to 6 carbon atoms among those exemplified as the alkyl group having 1 to 20 carbon atoms described above. it can.
  • Examples of the 20 alkylene group having 1 to 6 carbon atoms represented by Z in the above formula include those having 1 to 6 carbon atoms among those exemplified above as the alkylene group having 1 to 20 carbon atoms. be able to.
  • Examples of the halogen atom represented by R 1 to R 8 and R 10 to R 38 include fluorine, chlorine, bromine and iodine.
  • Examples of the unsaturated bond that may substitute the methylene group in the groups represented by R 1 to R 8 and R 10 to R 38 include —C ⁇ C— and —C ⁇ C—.
  • the ring thus formed include cyclopentane, cyclohexane, cyclopentene, benzene, pyrrolidine, pyrrole, piperazine, morpholine, thiomorpholine, tetrahydropyridine, lactone ring and lactam ring, 5- to 7-membered rings, naphthalene and anthracene, etc. And the like.
  • the unsaturated monobasic acid is an acid having an unsaturated bond in the structure and having one hydrogen atom per molecule that can be ionized to form a hydrogen ion.
  • the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid and hydroxyethyl methacrylate / malate, hydroxypropyl methacrylate / malate, hydroxypropyl acrylate / malate, and dicyclopentadiene / malate. Is mentioned.
  • the polybasic acid anhydride that is acted after the unsaturated monobasic acid is allowed to act has an acid anhydride group formed by dehydration condensation of a carboxy group of a polybasic acid having a plurality of carboxy groups. Means a compound.
  • polybasic acid anhydride examples include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2 '-3,3'-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, nadic anhydride, methyl nadic acid Anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride Acid-
  • the reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows. That is, the epoxy addition compound is preferably added so that the carboxyl group of the unsaturated monobasic acid has a ratio of 0.1 to 1.0 with respect to one epoxy group of the epoxy compound.
  • the ethylenically unsaturated compound is preferably such that the acid anhydride structure of the polybasic acid anhydride is 0.1 to 1.0 with respect to one hydroxyl group of the epoxy adduct. .
  • the reaction of the epoxy compound represented by the general formula (I), the unsaturated monobasic acid and the polybasic acid anhydride can be performed according to a conventional method.
  • a monofunctional or polyfunctional epoxy compound may be further reacted with the alkali developable compound (C).
  • the alkali-developable compound (C) preferably has a solid content acid value in the range of 5 to 120 mgKOH / g, and the usage amount of the monofunctional or polyfunctional epoxy compound is selected so as to satisfy the acid value. Is preferred.
  • Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecy
  • the polyfunctional epoxy compound it is preferable to use one or more compounds selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers because a polymerizable composition with better characteristics can be obtained.
  • the bisphenol type epoxy compound an epoxy compound represented by the above general formula (I) can be used, and for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can also be used.
  • glycidyl ethers examples include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl Ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-to (Glycidyloxymethyl) ethane, 1,1,1-tri (glycidy
  • novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds; 3,4-epoxy-6-methyl Cycloaliphatic epoxy such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compound: Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, glycidyl dimer, tetraglycidyl diamino Glycidylamines such as phenylmethane, triglycidyl P-aminophenol and N, N-diglycidylaniline; heterocycl
  • a commercially available product can also be suitably used as the alkali developable compound (C).
  • Examples of the commercially available products include SPC1000, SPC-2000, SPC-3000, SPRR-1X, SPRR-2X, SPRR-3X, SPRR-5X, SPRR-6X, SPRR-7X, SPRR-8X, SPRR-9X, SPRR-10X, SPRR-11X, SPRR-12X, SPRR-13X, SPRR-14X, SPRR-15X, SPRR-16X, SPRR-17X, SPRR-18X, SPRR-19X, SPRR-20X, SPRR-21X (above, Showa Denko KK), JET2000, AGOR1060, AGOR3060, ORGA1060, ORGA2060 (above, manufactured by Osaka Organic Chemical Co., Ltd.), CCR-1171H (manufactured by Nippon Kayaku Co., Ltd.), and the like.
  • the content of the alkali developable compound (C) is not particularly limited, but the urethane (meth) acrylate compound (A), the colorant (B), and the alkali developable compound.
  • the total amount of (C), the ethylenically unsaturated compound (D) and the polymerization initiator (E) is preferably 100 to 80 parts by mass, more preferably 20 to 80 parts by mass, Preferably, it is 30 to 70 parts by mass.
  • content of an alkali developable compound (C) exists in said range, it is preferable from the alkali developability of polymeric composition being favorable.
  • the content of the alkali-developable compound (C) is not particularly limited, but the urethane (meth) acrylate compound (A), the colorant ( B), preferably 10 to 80 parts by mass, more preferably 20 to 100 parts by mass with respect to a total of 100 parts by mass of the alkali-developable compound (C), the ethylenically unsaturated compound (D) and the polymerization initiator (E). 80 parts by mass, more preferably 30 to 70 parts by mass.
  • the ethylenically unsaturated compound (D) used in the present invention is a compound having an ethylenically unsaturated bond and not the urethane (meth) acrylate compound (A) and the alkali developable compound (C). .
  • Examples of the ethylenically unsaturated compound (D) include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene; (meth) acrylic acid, ⁇ -Chloracrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, monosuccinic acid [2- (meth) Acryloyloxyethyl], mono [2- (meth) acryloyloxyethyl] phthalate, ⁇ -carboxypolycaprolactone mono (meth) acrylate, and other polymer mono (meth) acrylates having a carboxy group and a hydroxy
  • ethylenically unsaturated compound examples include Kayrad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30, R-684 (above, Nippon Kayaku); Aronix M-215, M-350 ( ND ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG and HD-N (above, Shin-Nakamura Chemical Co., Ltd.); SPC-1000, SPC-3000 (manufactured by Showa Denko KK);
  • the content of the ethylenically unsaturated compound (D) is not particularly limited, but the urethane (meth) acrylate compound (A), the colorant (B), and alkali developability.
  • the total amount of the compound (C), the ethylenically unsaturated compound (D) and the polymerization initiator (E) is preferably 100 to 50 parts by mass, more preferably 10 to 50 parts by mass, More preferably, it is 10 to 30 parts by mass.
  • the content of the ethylenically unsaturated compound (D) is not particularly limited, but the urethane (meth) acrylate compound (A), the colorant (B), the alkali-developable compound (C), the ethylenically unsaturated compound (D), and the polymerization initiator (E) in total 100 parts by mass, the ethylenically unsaturated compound (D) is preferably 10 to 70. It is 30 parts by mass, more preferably 30-60 parts by mass, and still more preferably 30-50 parts by mass.
  • ⁇ Polymerization initiator (E)> As the polymerization initiator (E) used in the polymerizable composition of the present invention, a conventionally known radical polymerization initiator can be used.
  • the radical polymerization initiator is a photo radical polymerization initiator and a thermal radical polymerization initiator.
  • a radical photopolymerization initiator is more preferred because of its high reactivity.
  • the radical photopolymerization initiator is not particularly limited as long as it generates radicals by light irradiation, and a conventionally known compound can be used.
  • a conventionally known compound can be used.
  • preferred compounds include oxime compounds and oxime ester compounds.
  • acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, and 2-hydroxymethyl-2.
  • benzyl compound examples include benzyl.
  • benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone and 4-benzoyl-4′-methyldiphenyl sulfide. .
  • thioxanthone compound examples include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.
  • the oxime ester-based compound means a compound having a group represented by the above general formula (II), and is preferable for the polymerizable composition of the present invention because of its good sensitivity among the above radical photopolymerization initiators. Can be used.
  • the hydrocarbon group having 1 to 20 carbon atoms represented by R 41 to R 43 in the general formula (II) is the same as the hydrocarbon group having 1 to 20 carbon atoms represented by R 1 to R 38 , respectively. It is.
  • the group having 2 to 20 carbon atoms containing a heterocyclic ring that may modify the group represented by R 41 and R 42 and R 41 or R 42 in the general formula (II) is R 10 to R 38.
  • the compound represented by the following general formula (III) is preferably used in the polymerizable composition of the present invention because of its particularly high sensitivity.
  • R 51 and R 52 each independently represent a direct bond, a hydrogen atom, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring
  • X 1 represents an oxygen atom, a sulfur atom, a selenium atom
  • CR 53 R 54 CO, NR 55 or PR 56
  • R 53 to R 56 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring, and represented by R 53 to R 56.
  • the hydrogen atom in the group may be substituted with a group having 2 to 20 carbon atoms containing a halogen atom, a nitro group, a cyan group, a hydroxyl group, a carboxyl group or a heterocyclic ring,
  • the methylene group in the group represented by R 51 to R 56 may be substituted with —O— under the condition that oxygen is not adjacent.
  • R 51 to R 56 may each independently form a ring together with one of the adjacent benzene rings, g represents a number from 0 to 5; h represents a number from 0 to 4. )
  • the hydrocarbon group having 1 to 20 carbon atoms represented by R 51 to R 56 in the general formula (III) is a hydrocarbon group having 1 to 20 carbon atoms represented by R 1 to R 38 , respectively. It is the same.
  • the group having 2 to 20 carbon atoms containing a heterocyclic ring represented by R 51 to R 56 in the general formula (III) is a carbon atom containing a heterocyclic ring represented by R 10 to R 38. This is the same as the group of formula 2-20.
  • the use of a compound represented by the following general formula (IV) as the polymerization initiator (E) is highly sensitive and has excellent adhesion to the substrate of the pattern after development. This is preferable because low liquid crystal contamination is improved.
  • R 51a and R 52a each independently represents a hydrogen atom, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring
  • R a represents CR a1 R a2 R a3
  • R a1 , R a2 and R a3 each independently represent a hydrogen atom, a hydroxyl group, an amino group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring
  • X 1a represents an oxygen atom, a sulfur atom, a selenium atom
  • CR 53a R 54a CO, NR 55a or PR 56a
  • R 53a to R 56a each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring
  • R 51a to R 56a may be substituted with —O— under the condition that oxygen is not adjacent to each other.
  • R 51a to R 56a may each independently form a ring together with one of the adjacent benzene rings, g1 represents a number from 0 to 5; h1 represents a number from 0 to 4. )
  • the hydrocarbon group having 1 to 20 carbon atoms represented by R a1 to R a3 and R 51 to R 56 is represented by 1 to C carbon atoms represented by R 1 to R 38 , respectively.
  • the group having 2 to 20 carbon atoms containing a heterocyclic ring represented by R a1 to R a3 and R 51 to R 56 in the general formula (IV) is a complex represented by R 10 to R 38. This is the same as the group having 2 to 20 carbon atoms containing a ring.
  • Preferred examples of the polymerization initiator (E) include compound Nos. Shown below. E1-No. E15 is exemplified, and examples of the compound represented by the general formula (III) include the compound No. 1 shown below. E1 and No. E3-No. E15 may be mentioned. Examples of the compound represented by the general formula (IV) include compound No. 1 shown below. E2.
  • the polymerization initiator (E) used in the present invention is not limited by the following compounds.
  • radical polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pill-1). -Yl)] titacene compounds such as titanium.
  • radical initiators include Adekaoptomer N-1414, N-1717, N-1919, Adeka Arcles NCI-831, NCI-930 (manufactured by ADEKA); IRGACURE 184, IRGACURE 369, IRGACURE 651, IRGACURE 907, IRGACURE OX 01, IRGACURE OXE02, IRGACURE784 (above, manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309, and TR-PBG-314 (above, manufactured by Troly);
  • the thermal radical polymerization initiator is not particularly limited as long as it generates radicals by heating, and conventionally known compounds can be used.
  • azo compounds, peroxides and persulfates are preferable. It can be illustrated as a thing.
  • azo compound examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'- And azobis (1-acetoxy-1-phenylethane).
  • peroxide examples include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butyl peroxypivalate, and di (4-t-butylcyclohexyl) peroxydicarbonate.
  • persulfates examples include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate.
  • a polymerization initiator having a hydroxyl group is particularly preferable because it can provide a display device having low liquid crystal contamination and excellent electrical characteristics.
  • R 41 in the general formula (II) is preferably an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 10 carbon atoms.
  • R 42 in the general formula (II) is preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • X 1 is preferably a sulfur atom.
  • g is preferably 1 and R 51 is preferably an alkyl group having 1 to 10 carbon atoms.
  • the terminal hydrogen atom of the alkyl group is preferably substituted with a hydroxyl group, and the methylene group in the alkyl group is preferably substituted with —O—.
  • X 1a is preferably a sulfur atom.
  • g1 is preferably 1, and R 51a is preferably an alkyl group having 1 to 10 carbon atoms.
  • the terminal hydrogen atom of the alkyl group is preferably substituted with a hydroxyl group, and the methylene group in the alkyl group is preferably substituted with —O—.
  • at least one of R a1 to R a3 is preferably a group having 2 to 20 carbon atoms containing a heterocyclic ring.
  • R a1 to R a3 are preferably an alkyl group having 1 to 10 carbon atoms.
  • R a1 is a group having 2 to 20 carbon atoms containing a heterocyclic ring
  • R a2 and R a3 are each independently An alkyl group having 1 to 10 carbon atoms is preferable.
  • the polymerization initiator (E) can be used alone or in combination of two or more kinds exemplified above.
  • the content of the polymerization initiator (E) is not particularly limited, but the urethane (meth) acrylate compound (A), the colorant (B), and the alkali developable compound.
  • the total curability of (C), ethylenically unsaturated compound (D) and polymerization initiator (E) is preferably from 0.3 to 20 parts by mass, more preferably from 0. 5 to 10 parts by mass, more preferably 3 to 8 parts by mass.
  • the content of the polymerizable compound (B) is in the above range, it is preferable because a polymerizable composition having good curability and excellent storage stability without precipitation of a polymerization initiator is obtained.
  • the content of the polymerization initiator (E) is not particularly limited, but the urethane (meth) acrylate compound (A), the colorant (B ), Alkali developable compound (C), ethylenically unsaturated compound (D), and polymerization initiator (E) in a total of 100 parts by mass, preferably 0.3 to 20 parts by mass, more preferably 0.5. -10 parts by mass, more preferably 3-8 parts by mass.
  • a solvent can be further added to the polymerizable composition of the present invention.
  • the solvent the above components (urethane (meth) acrylate compound (A), colorant (B), alkali-developable compound (C), ethylenically unsaturated compound (D) and polymerization are usually used as necessary.
  • a solvent capable of dissolving or dispersing the initiator (E) and the like can be used.
  • ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-di Ether solvents such as ethoxyethane and dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate and texanol; Cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol, ethanol, iso
  • solvents can be used as one or two or more mixed solvents.
  • ketones and ether ester solvents, etc., particularly PGMEA and cyclohexanone are preferable because the compatibility of the resist and the polymerization initiator is good in the polymerizable composition.
  • the content of the solvent is not particularly limited, but is preferably 30 to 95% by mass, more preferably 50% in 100% by mass of the total polymerizable composition. ⁇ 95% by mass.
  • the content of the solvent is in the above range, handling properties (viscosity and wettability of the polymerizable composition), reduction of unevenness during drying, and liquid stability (without precipitation or sedimentation of components contained in the composition) It is preferable because it becomes an excellent polymerizable composition, and the thickness of the cured product can be appropriately controlled when a cured product is obtained.
  • the polymerizable composition of the present invention may further contain an epoxy compound, an alkali developability imparting agent, a dispersant, a latent additive, an organic polymer, an inorganic compound, a coupling agent, a chain transfer agent, and a sensitization.
  • Examples of the epoxy compound include methyl glycidyl ether, 2-ethylhexyl glycidyl ether, butyl glycidyl ether, decyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, phenyl-2-methyl glycidyl ether, cetyl glycidyl ether, stearyl glycidyl ether, Glycidyl methacrylate, isopropyl glycidyl ether, allyl glycidyl ether, ethyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, 4-n-butylphenyl glycidyl ether, 4-phenylphenol glycidyl ether, cresyl glycidyl ether, dibromocresyl ether Glycid
  • Epoxidized polyolefin can also be used as the epoxy compound.
  • the epoxidized polyolefin is a polyolefin having an epoxy group introduced by modifying the polyolefin with an epoxy group-containing monomer. It can be produced by copolymerizing ethylene or an ⁇ -olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer, and, if necessary, another monomer by either a copolymerization method or a graft method. Ethylene or an ⁇ -olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer, and other monomers may be polymerized alone or in combination with other monomers.
  • the double bond of the nonconjugated polybutadiene which has a hydroxyl group at the terminal can be obtained by epoxidation by the peracetic acid method, and those having a hydroxyl group in the molecule may be used. It is also possible to urethanize a hydroxyl group with an isocyanate and introduce an epoxy group by reacting with a primary hydroxyl group-containing epoxy compound.
  • Examples of the ethylene or ⁇ -olefin having 3 to 20 carbon atoms include ethylene, propylene, butylene, isobutylene, 1,3-butadiene, 1,4-butadiene, 1,3-pentadiene, 2,3-dimethyl-1,3. -Butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and the like.
  • Examples of the epoxy group-containing monomer include glycidyl ester of ⁇ , ⁇ -unsaturated acid, vinyl benzyl glycidyl ether, and allyl glycidyl ether.
  • Specific examples of the glycidyl ester of ⁇ , ⁇ -unsaturated acid include glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylate, and glycidyl methacrylate is particularly preferable.
  • Suitable commercially available products can be used as the epoxy compound. Suitable commercially available products include, for example, Epolite 40E, 1500NP, 1600, 80MF, 4000 and 3002 (manufactured by Kyoeisha Chemical); Adekaglycilol ED-503, ED-503D, ED-503G, ED-523T, ED- 513, ED-501, ED-502, ED-509, ED-518, ED-529, Adeka Resin EP-4000, EP-4005, EP-4080 and EP-4085 (above, manufactured by ADEKA); Denacol EX-201, EX-203, EX-211, EX-212, EX-221, EX-251, EX-252, EX-711, EX-721, Denacol EX-111, EX-121, EX-141, EX-142, EX -145, EX-146, EX-147, EX-171, EX-192 and E -731 (above, manufactured by Nag
  • the alkali developability-imparting agent is a compound that does not have radical polymerizability and imparts alkali developability.
  • any compound that has an acid value and is soluble in an aqueous alkali solution can be used.
  • a typical example is an alkali-soluble novolak resin (hereinafter simply referred to as “novolak resin”).
  • the novolak resin is obtained by polycondensation of phenols and aldehydes in the presence of an acid catalyst.
  • phenols examples include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, p-phenylphenol, hydroquinone, catechol, resorcinol, 2- Methyl resorcinol, pyrogallol, ⁇ -naphthol, bisphenol A, dihydroxybenzoic acid ester, gallic acid ester and the like are used.
  • phenol, o-cresol, m-cresol, p-cresol, 2,5- Shirenoru, 3,5-xylenol, 2,3,5-trimethylphenol, resorcinol, 2-methyl resorcinol and bisphenol A are preferable. These phenols are used alone or in combination of two or more.
  • aldehydes examples include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, ⁇ -phenylpropylaldehyde, ⁇ -phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o -Chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde and p -N-butylbenzaldehy
  • the acid catalyst examples include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, or organic acids such as formic acid, oxalic acid, and acetic acid.
  • the amount of these acid catalysts used is preferably 1 ⁇ 10 ⁇ 4 to 5 ⁇ 10 ⁇ 1 mol per mol of phenol.
  • water is usually used as a reaction medium.
  • the reaction medium is hydrophilic.
  • a solvent can also be used.
  • hydrophilic solvents examples include alcohols such as methanol, ethanol, propanol and butanol, or cyclic ethers such as tetrahydrofuran and dioxane.
  • the amount of these reaction media used is usually 20 to 1000 parts by mass per 100 parts by mass of the reaction raw material.
  • the reaction temperature of the condensation reaction can be appropriately adjusted according to the reactivity of the reaction raw materials, but is usually 10 to 200 ° C., preferably 70 to 150 ° C. After completion of the condensation reaction, in order to remove unreacted raw materials, acid catalyst and reaction medium present in the system, the internal temperature is generally raised to 130 to 230 ° C., and the volatile component is distilled off under reduced pressure.
  • the melted novolac resin is collected on a steel belt or the like.
  • the reaction mixture is dissolved in the hydrophilic solvent and added to a precipitating agent such as water, n-hexane and n-heptane to precipitate a novolak resin, and the precipitate is separated and dried by heating. It can also be recovered by doing so.
  • Examples other than the novolak resin include polyhydroxystyrene or a derivative thereof, a styrene-maleic anhydride copolymer, and polyvinylhydroxybenzoate.
  • the dispersing agent may be anything as long as it can disperse and stabilize the colorant (B), and a commercially available dispersing agent, for example, BYK series, BYK series, etc. can be used, polyester having a basic functional group, Polymer dispersing agent made of polyether, polyurethane, nitrogen atom as basic functional group, functional group having nitrogen atom is amine and / or quaternary salt thereof, amine value is 1 to 100 mgKOH / g Those are preferably used.
  • the latent additive is inactive at room temperature, in the light exposure step and in the pre-bake step, and is protected at 100 to 250 ° C. or heated at 80 to 200 ° C. in the presence of an acid / base catalyst. Is activated by desorption. Examples of the effects obtained by activation include oxidation prevention, ultraviolet absorption, antifouling property, recoatability and adhesion.
  • the latent additive those described in the pamphlet of WO2014 / 021023 can be preferably used.
  • latent additive commercially available products can be used, and examples thereof include Adeka Arcles GPA-5001.
  • organic polymer examples include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate.
  • Copolymer ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated Polyester, phenolic resin, phenoxy resin, polyamideimide resin, polyamic acid resin, epoxy resin, and the like.
  • polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, and epoxy resin are included.
  • the organic polymer By using the organic polymer together with the alkali developable compound (C), the properties of the cured product can be improved.
  • the amount used is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the alkali-developable compound (C).
  • the above inorganic compound can be contained.
  • the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica and alumina; lamellar clay mineral, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver and copper Among these, titanium oxide, silica, layered clay mineral, silver and the like are preferable.
  • an inorganic compound in the polymerizable composition of the present invention By containing an inorganic compound in the polymerizable composition of the present invention, it can be used as a photosensitive paste composition.
  • the photosensitive paste composition is used to form a fired product pattern such as a partition pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel.
  • These inorganic compounds are also suitably used as, for example, fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, and ink repellent agents.
  • the content of the inorganic compound is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the alkali developable compound (C).
  • the amount is preferably 0.5 to 20 parts by mass, and one or more of these inorganic compounds can be used.
  • Examples of the coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane.
  • a sulfur atom-containing compound is generally used.
  • the surfactant examples include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides, amphoteric surfactants and silicone surfactants Surfactants such as agents can be used, and these may be used in combination.
  • fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates
  • anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates,
  • Examples of the melamine compound include all or part of active methylol groups (CH 2 OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. Mention may be made of compounds in which (at least two) are alkyl etherified.
  • examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same as or different from each other.
  • the methylol group which is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed.
  • an oligomer component may be formed.
  • hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril, and the like can be used.
  • alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.
  • urethane (meth) acrylate compound (A), colorant (B), alkali developable compound (C), ethylenically unsaturated compound (D), polymerization initiator (E), solvent The content of optional components other than inorganic compounds is appropriately selected according to the purpose of use, and is not particularly limited as long as the effects of the present invention are not impaired.
  • the urethane (meth) acrylate compound (A) is used. , 20 parts by mass or less in total with respect to 100 parts by mass in total of the colorant (B), the alkali-developable compound (C), the ethylenically unsaturated compound (D) and the polymerization initiator (E).
  • the photosensitive composition for BCS of the present invention includes, as essential components, a urethane (meth) acrylate compound (A), a colorant (B), an alkali developable compound (C), an ethylenically unsaturated compound (D), and polymerization initiation. It is a composition that contains an agent (E), has photosensitivity and alkali developability, and is particularly suitable for forming BCS.
  • the polymerizable composition or the photosensitive composition for BCS and the cured product of the present invention are curable paint, varnish, curable adhesive, printed circuit board, display display device (color TV, PC monitor, portable information terminal, digital camera, etc.
  • Color filters for liquid crystal display panels of color display color filters for various display applications, color filters for CCD image sensors, touch panels, electroluminescent display devices, plasma display panels, organic EL black barriers), powder coating, printing ink ,
  • the display device of the present invention has the same configuration as a conventionally known display device except that it includes the cured product (particularly BCS) of the present invention, but the BCS is preferably provided between cells.
  • an alkali-developable compound having a weight average molecular weight of 5000 or more is used because the pattern shape is vertical, development adhesion is improved, and heat resistance is improved. More preferably, an alkali developable compound having a weight average molecular weight of 7000 to 15000 is preferably used.
  • the alkali-developable compound is obtained by an esterification reaction between an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the general formula (I) and a polybasic acid anhydride. Particularly preferred is an unsaturated compound having the structure shown below.
  • the polymerizable composition of the present invention and the photosensitive composition for BCS are soda glass, quartz glass, and semiconductor by known means such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing and dipping.
  • the present invention can be applied on a support substrate such as a substrate, metal, paper, or plastic. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base
  • an ultrahigh pressure mercury lamp As a light source for energy rays used for curing the polymerizable composition of the present invention and the photosensitive composition for BCS, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, mercury vapor Electromagnetic wave energy or electron beam having a wavelength of 2000 angstrom to 7000 angstrom obtained from arc lamp, xenon arc lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, excimer lamp, germicidal lamp, light emitting diode, CRT light source, etc.
  • high energy rays such as X-rays and radiation
  • an ultra-high pressure mercury lamp that emits light having a wavelength of 300 to 450 nm
  • a mercury vapor arc lamp preferably, a carbon arc lamp, a xenon arc lamp, and the like.
  • the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy.
  • the laser light light having a wavelength of 340 to 430 nm is preferably used, but excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser.
  • lasers that emit light in the visible to infrared region such as various semiconductor lasers and YAG lasers, are also used. When these lasers are used, a sensitizing dye that absorbs the region from visible to infrared is added.
  • BCS is (1) a step of forming a coating film of the photosensitive composition for BCS of the present invention on a substrate, (2) a step of irradiating the coating film with radiation through a mask having a predetermined pattern shape, ( It is preferably formed by 3) a baking step after exposure, (4) a step of developing the coating after exposure, and (5) a step of heating the coating after development.
  • a multi-tone mask such as a halftone mask or a gray scale mask can be used.
  • the display device of the present invention has the same configuration as a conventionally known display device except that it includes the cured product (particularly BCS) of the present invention, but the BCS is preferably provided between cells.
  • zirconia beads having a diameter of 0.3 mm are added in the same weight as the dispersion (solvent: excluding PGMEA) and subjected to dispersion treatment with a paint shaker at a temperature of 25 to 60 ° C. for 6 hours. Thereafter, the zirconia beads were removed using a filter to obtain a dispersion.
  • PGMEA was added to the obtained dispersion to adjust the dispersion concentration to 20% by mass, and the mixture was made uniform with a stirrer to obtain lactam black dispersion B-1.
  • zirconia beads having a diameter of 0.3 mm are added in the same weight as the dispersion (solvent: excluding PGMEA) and subjected to dispersion treatment with a paint shaker at a temperature of 25 to 60 ° C. for 6 hours. Thereafter, the zirconia beads were removed using a filter to obtain a dispersion.
  • PGMEA was added to the obtained dispersion to adjust the dispersion concentration to 20% by mass, and the mixture was made uniform with a stirrer to obtain a perylene black dispersion B-2.
  • reaction solution was cooled to room temperature, 160 g of PGMEA, 59 g of biphthalic anhydride and 0.24 g of tetra-n-butylammonium bromide were added, and the mixture was stirred at 120 ° C. for 4 hours. Further, 20 g of tetrahydrophthalic anhydride was added, and after stirring at 120 ° C. for 4 hours, at 100 ° C. for 3 hours, at 80 ° C. for 4 hours, at 60 ° C. for 6 hours, and at 40 ° C.
  • the mixture was cooled to room temperature, 25.9 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride and 1.37 g of PGMEA were added, and the mixture was stirred at 100 ° C. for 5 hours. Further, 90.0 g of 9,9-bis (4-glycidyloxyphenyl) fluorene, 0.269 g of 2,6-di-t-butyl-p-cresol, and 1.50 g of PGMEA were added, and 90 minutes at 90 ° C. After stirring at 120 ° C.
  • Examples 1 to 24 and Comparative Examples 1 to 4 Preparation of Polymerizable Composition
  • Each component was mixed in accordance with the formulation of [Table 1] to [Table 4] to obtain a polymerizable composition (Examples 1 to 24 and Comparative Example). 1-4) were obtained.
  • surface represents a mass part.
  • surface represents the following component.
  • Elastic modulus recovery rate (%) was calculated by the following formula.
  • Elastic recovery rate (%) [(recovery distance / compression displacement) ⁇ 100]
  • a cured product having an elastic recovery rate (%) of 60% or more can be used as a BCS, and a cured product having an elastic recovery rate (%) of 70% or more can be preferably used as a BCS.
  • a cured product having (%) of 80% or more can be particularly preferably used as BCS.
  • the polymerizable compositions of Examples 1 to 24 and the comparative polymerizable compositions of Comparative Examples 1 to 4 were spin-coated (300 rpm, 7 seconds) and dried on a glass substrate, and then prebaked at 90 ° C. for 100 seconds. . After exposure using an ultrahigh pressure mercury lamp as a light source, the cured product was prepared by baking at 230 ° C. for 30 minutes. The OD value of the obtained film was measured using a Macbeth transmission densitometer, and the OD value per film thickness was calculated by dividing the OD value by the film thickness after post-baking.
  • a cured product having an OD value of 1.0 or more per film thickness can be used as BCS, and a cured product having an OD value of 1.5 or more per film thickness can be preferably used as BCS.
  • a cured product having an OD value of 2.0 or more can be particularly preferably used as BCS.
  • a cured product having an OD value per film thickness of less than 1.0 cannot be used as BCS.
  • a cured product having a relative dielectric constant of less than 5.0 can be used as a BCS, a cured product having a relative dielectric constant of 4.5 or less can be preferably used as a BCS, and a cured product having a relative dielectric constant of 4.0 or less. Can be particularly preferably used as BCS. A cured product having a relative dielectric constant of 5.0 or more cannot be used as BCS.
  • VHR The polymerizable composition obtained in Examples 1 to 24 and the comparative polymerizable composition obtained in Comparative Examples 1 to 4 were applied onto a glass substrate (100 mm ⁇ 100 mm) using a spin coater, and the coating composition was applied at 90 ° C. Pre-baking was performed for 100 seconds to form a coating film having a thickness of 3.0 ⁇ m. Next, using a mirror projection aligner (product name: TME-150 RTO, manufactured by Topcon Co., Ltd.), the coating film was irradiated with ultraviolet rays at a dose of 200 mJ / cm 2 without using a mask. Thereafter, post-baking was performed at 230 ° C. for 30 minutes.
  • a mirror projection aligner product name: TME-150 RTO, manufactured by Topcon Co., Ltd.
  • a cured product having a VHR of 90% or more can be used as a BCS, a cured product having a VHR of 95% or more can be preferably used as a BCS, and a cured product having a VHR of 98% or more is It can be particularly preferably used as a BCS.
  • a cured product having a VHR of less than 90% cannot be used as a BCS.
  • the cured product obtained from the polymerizable composition of the present invention and the photosensitive composition for BCS has a light shielding property (OD value), a dielectric constant, and low liquid crystal contamination. Since (VHR) is satisfied at a high level and the elastic modulus recovery rate is excellent, it is useful as a BCS.
  • the cured product obtained from the polymerizable composition of the present invention or the photosensitive composition for BCS is a cured product (particularly BCS) having excellent elastic recovery, low dielectric constant, and good electrical properties.
  • the cured product is particularly useful for a display device or the like.

Abstract

Disclosed is a polymerizable composition which comprises a urethane (meth)acrylate compound (A), a colorant (B), an alkali-developable compound (C) [that is not the urethane (meth)acrylate compound (A)], an ethylenically unsaturated compound (D) [that is neither the urethane (meth)acrylate compound (A) nor the alkali-developable compound (C)], and a polymerization initiator (E). The colorant (B) is preferably a black pigment. Also disclosed are a photosensitive composition for black column spacers which comprises the polymerizable composition, a cured object obtained from the photosensitive composition, and a display device including the cured object.

Description

重合性組成物及びブラックカラムスペーサー用感光性組成物Polymerizable composition and photosensitive composition for black column spacer
　本発明は、ウレタン（メタ）アクリレート化合物、着色剤、アルカリ現像性化合物、エチレン性不飽和化合物及び重合性開始剤を含有する重合性組成物及びブラックカラムスペーサー（以下、ＢＣＳという）用感光性組成物並びに該感光性組成物から得られる硬化物に関する。 The present invention relates to a polymerizable composition containing a urethane (meth) acrylate compound, a colorant, an alkali developable compound, an ethylenically unsaturated compound and a polymerizable initiator, and a photosensitive composition for a black column spacer (hereinafter referred to as BCS). And a cured product obtained from the photosensitive composition.
　液晶表示装置、有機ＥＬ表示装置等のディスプレイ表示装置において、セルの上部と下部の基板間の距離を保持するためにスペーサが用いられている。 In display display devices such as liquid crystal display devices and organic EL display devices, spacers are used to maintain the distance between the upper and lower substrates of the cell.
　スペーサは、重合性組成物を基板に塗布し、所定のマスクを介して露光した後現像することにより形成される。近年、カラムスペーサ及びブラックマトリクスを１つのモジュールに統合し、遮光性を持たせたＢＣＳが用いられている The spacer is formed by applying the polymerizable composition to the substrate, exposing through a predetermined mask, and developing. In recent years, BCS has been used in which column spacers and black matrix are integrated into one module to provide light shielding properties.
　特許文献１には、酸性基を導入する処理を施されたカーボンブラックを含有する、比誘電率の低いＢＣＳを形成することができるＢＣＳ形成用感光性樹脂組成物が開示されている。特許文献２には、共重合体、エポキシ樹脂化合物又はそれから誘導された化合物、並びに黒色着色剤及び青色着色剤を含む着色剤を含有する、良好な弾性回復率を示すＢＣＳを形成することができる着色感光性樹脂組成物が開示されている。 Patent Document 1 discloses a photosensitive resin composition for forming BCS, which contains carbon black subjected to a treatment for introducing an acidic group and can form a BCS having a low relative dielectric constant. Patent Document 2 can form a BCS showing a good elastic recovery rate, containing a copolymer, an epoxy resin compound or a compound derived therefrom, and a colorant including a black colorant and a blue colorant. A colored photosensitive resin composition is disclosed.
特開２０１４－１４６０２９号公報JP 2014-146029 A 特開２０１５－０９３９８６号公報Japanese Patent Laying-Open No. 2015-093986
　本発明が解決しようとする課題は、弾性回復に優れ、誘電率が低く、電気特性が良好なＢＣＳがこれまでなかったということである。 The problem to be solved by the present invention is that no BCS has excellent elastic recovery, low dielectric constant and good electrical characteristics.
　従って、本発明の目的は、弾性回復に優れ、誘電率が低く、電気特性が良好なＢＣＳが得られる重合性組成物及びＢＣＳ用感光性組成物、該重合性組成物及びＢＣＳ用感光性組成物より得られる硬化物、該硬化物を含有するディスプレイ表示装置、並びに該硬化物を製造する方法を提供することにある。 Accordingly, an object of the present invention is to provide a polymerizable composition, a BCS photosensitive composition, and a BCS photosensitive composition that are excellent in elastic recovery, have a low dielectric constant, and have good electrical characteristics. It is providing the hardened | cured material obtained from a product, the display apparatus containing this hardened | cured material, and the method of manufacturing this hardened | cured material.
　本発明は、鋭意検討の末、下記〔１〕～〔９〕を提供することにより、上記目的を達成したものである。 The present invention has achieved the above object by providing the following [1] to [9] after intensive studies.
　［１］ウレタン（メタ）アクリレート化合物（Ａ）、着色剤（Ｂ）、アルカリ現像性化合物（Ｃ）［但し、ウレタン（メタ）アクリレート化合物（Ａ）を除く］、エチレン性不飽和化合物（Ｄ）［但し、ウレタン（メタ）アクリレート化合物（Ａ）及びアルカリ現像性化合物（Ｃ）を除く］及び重合開始剤（Ｅ）を含有する重合性組成物。 [1] Urethane (meth) acrylate compound (A), colorant (B), alkali developable compound (C) [excluding urethane (meth) acrylate compound (A)], ethylenically unsaturated compound (D) [However, a polymerizable composition containing a urethane (meth) acrylate compound (A) and an alkali developable compound (C)] and a polymerization initiator (E).
　［２］着色剤（Ｂ）が黒色顔料である［１］に記載の重合性組成物。 [2] The polymerizable composition according to [1], wherein the colorant (B) is a black pigment.
　［３］アルカリ現像性化合物（Ｃ）が、下記一般式（Ｉ）で表されるエポキシ化合物に不飽和一塩基酸を付加させた構造を有するエポキシ付加化合物と、多塩基酸無水物とのエステル化反応により得られる構造を有する不飽和化合物である［１］又は［２］に記載の重合性組成物。 [3] An ester of an epoxy addition compound having a structure in which an alkali-developable compound (C) is obtained by adding an unsaturated monobasic acid to an epoxy compound represented by the following general formula (I), and a polybasic acid anhydride The polymerizable composition as described in [1] or [2], which is an unsaturated compound having a structure obtained by the oxidization reaction.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
（式中、Ｍは直接結合、炭素原子数１～２０の炭化水素基、－Ｏ－、－Ｓ－、－ＳＯ２－、－ＳＳ－、－ＳＯ－、－ＣＯ－、－ＯＣＯ－又は下記式（ａ）、（ｂ）、（ｃ）又は（ｄ）で表される群から選ばれる置換基を表し、
　Ｍで表される炭素原子数１～２０の炭化水素基中の水素原子はハロゲン原子で置換される場合があり、
　Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８（以下、Ｒ１～Ｒ８とも記載）は、それぞれ独立に、水素原子、炭素原子数１～２０の炭化水素基、又はハロゲン原子を表し、
　Ｒ１～Ｒ８で表される基中のメチレン基は、不飽和結合、－Ｏ－又は－Ｓ－で置換される場合があり、
　ｎは０～１０の数であり、
　ｎ≧１の場合、複数存在するＲ１～Ｒ８及びＭは、それぞれ、同一である場合もあり、異なる場合もある。） (In the formula, M is a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, —O—, —S—, —SO 2 —, —SS—, —SO—, —CO—, —OCO— or Represents a substituent selected from the group represented by formula (a), (b), (c) or (d);
The hydrogen atom in the hydrocarbon group having 1 to 20 carbon atoms represented by M may be substituted with a halogen atom,
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 (hereinafter also referred to as R 1 to R 8 ) are each independently a hydrogen atom or a carbon atom having 1 to 20 carbon atoms. Represents a hydrocarbon group or a halogen atom,
The methylene group in the group represented by R 1 to R 8 may be substituted with an unsaturated bond, —O— or —S—,
n is a number from 0 to 10,
When n ≧ 1, a plurality of R 1 to R 8 and M may be the same or different. )
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
（式中、Ｒ９は、炭素原子数１～２０の炭化水素基を表し、
　Ｒ１０、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９、Ｒ２０、Ｒ２１、Ｒ２２、Ｒ２３、Ｒ２４、Ｒ２５、Ｒ２６、Ｒ２７、Ｒ２８、Ｒ２９、Ｒ３０、Ｒ３１、Ｒ３２、Ｒ３３、Ｒ３４、Ｒ３５、Ｒ３６、Ｒ３７及びＲ３８（以下、Ｒ１０～Ｒ３８とも記載）は、それぞれ独立に、水素原子、炭素原子数１～２０の炭化水素基、複素環を含有する炭素原子数２～２０の基、又はハロゲン原子を表し、
　Ｒ１０～Ｒ３８で表される基中のメチレン基は、不飽和結合、－Ｏ－又は－Ｓ－で置換される場合があり、
　Ｒ１０とＲ１１、Ｒ１１とＲ１２、Ｒ１２とＲ１３、Ｒ１３とＲ１４、Ｒ２２とＲ１５、Ｒ１５とＲ１６、Ｒ３０とＲ２３、Ｒ２３とＲ２４、Ｒ２４とＲ２５、Ｒ３８とＲ３１、Ｒ３１とＲ３２、Ｒ３２とＲ３３、Ｒ３４とＲ３５、Ｒ３５とＲ３６及びＲ３６とＲ３７は結合して環を形成する場合があり、
　式（ａ）、（ｂ）、（ｃ）及び（ｄ）で表される基中の＊は、結合手を表す。） (Wherein R 9 represents a hydrocarbon group having 1 to 20 carbon atoms,
R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 and R 38 (hereinafter also referred to as R 10 to R 38 ) are respectively Independently, it represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 2 to 20 carbon atoms containing a heterocyclic ring, or a halogen atom,
The methylene group in the group represented by R 10 to R 38 may be substituted with an unsaturated bond, —O— or —S—,
R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 22 and R 15 , R 15 and R 16 , R 30 and R 23 , R 23 and R 24 , R 24 And R 25 , R 38 and R 31 , R 31 and R 32 , R 32 and R 33 , R 34 and R 35 , R 35 and R 36, and R 36 and R 37 may combine to form a ring. ,
* In the groups represented by the formulas (a), (b), (c) and (d) represents a bond. )
　［４］　重合開始剤（Ｅ）が、下記一般式（ＩＩ）で表される基を有する重合開始剤である［１］～［３］の何れか一項に記載の重合性組成物。 [4] The polymerizable composition according to any one of [1] to [3], wherein the polymerization initiator (E) is a polymerization initiator having a group represented by the following general formula (II).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
（式中、Ｒ４１及びＲ４２は、それぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素原子数１～２０の炭化水素基又は複素環を含有する炭素原子数２～２０の基を表し、
　Ｒ４１及びＲ４２で表される炭素原子数１～２０の炭化水素基又はＲ４１及びＲ４２で表される複素環を含有する炭素原子数２～２０の基の水素原子はハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、ビニルエーテル基、メルカプト基、イソシアネート基又は複素環を含有する炭素原子数２～２０の基で置換される場合があり、
　Ｒ４１及びＲ４２で表される炭素原子数１～２０の炭化水素基又はＲ４１及びＲ４２で表される複素環を含有する炭素原子数２～２０の基中のメチレン基は－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ４３－、－ＮＲ４３ＣＯ－、－Ｓ－、－ＣＳ－、－ＳＯ２－、－ＳＣＯ－、－ＣＯＳ－、－ＯＣＳ－又はＣＳＯ－で置換される場合もあり、
　Ｒ４３は、水素原子、炭素原子数１～２０の炭化水素基を表し、
　ｍは０又は１を表し、
　式中の＊は、結合手を表す。） (In the formula, each of R 41 and R 42 independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring. Represents
Hydrogen atoms of the hydrocarbon group, or R 41 and having 2 to 20 carbon atoms containing heterocyclic ring represented by R 42 of R 41 and having 1 to 20 carbon atoms represented by R 42 is a halogen atom, a nitro Substituted with a group having 2 to 20 carbon atoms containing a group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group or heterocyclic ring There is a case,
Methylene groups in the group having 2 to 20 carbon atoms having a hydrocarbon group or a heterocyclic ring represented by R 41 and R 42 having 1 to 20 carbon atoms represented by R 41 and R 42 -O- , —CO—, —COO—, —OCO—, —NR 43 —, —NR 43 CO—, —S—, —CS—, —SO 2 —, —SCO—, —COS—, —OCS— or CSO -May be replaced by-
R 43 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
m represents 0 or 1;
* In the formula represents a bond. )
　［５］重合開始剤（Ｅ）が、水酸基を有する重合開始剤である［１］～［４］の何れか一項に記載の重合性組成物。 [5] The polymerizable composition according to any one of [1] to [4], wherein the polymerization initiator (E) is a polymerization initiator having a hydroxyl group.
　［６］［１］～［５］の何れか一項に記載の重合性組成物からなるブラックカラムスペーサー用感光性組成物。 [6] A photosensitive composition for a black column spacer comprising the polymerizable composition according to any one of [1] to [5].
　［７］［１］～［５］の何れか一項に記載の重合性組成物又は［６］に記載のブラックカラムスペーサー用感光性組成物を用いて硬化物を製造する方法。 [7] A method for producing a cured product using the polymerizable composition according to any one of [1] to [5] or the photosensitive composition for a black column spacer according to [6].
　［８］［１］～［５］の何れか一項に記載の重合性組成物又は［６］に記載のブラックカラムスペーサー用感光性組成物の硬化物。 [8] A cured product of the polymerizable composition according to any one of [1] to [5] or the photosensitive composition for a black column spacer according to [6].
　［９］［８］に記載の硬化物を含有するディスプレイ表示装置。 [9] A display device containing the cured product according to [8].
　以下、本発明の重合性組成物について好ましい実施形態に基づき詳細に説明する。 Hereinafter, the polymerizable composition of the present invention will be described in detail based on preferred embodiments.
　本発明の重合性組成物は、ウレタン（メタ）アクリレート化合物（Ａ）、着色剤（Ｂ）、アルカリ現像性化合物（Ｃ）[但し、ウレタン（メタ）アクリレート化合物（Ａ）を除く]、エチレン性不飽和化合物（Ｄ）[但し、ウレタン（メタ）アクリレート化合物（Ａ）及びアルカリ現像性化合物（Ｃ）を除く]及び重合開始剤（Ｅ）を含有する。以下、各成分について順に説明する。 The polymerizable composition of the present invention comprises a urethane (meth) acrylate compound (A), a colorant (B), an alkali developable compound (C) [excluding the urethane (meth) acrylate compound (A)], ethylenic An unsaturated compound (D) [however, excluding urethane (meth) acrylate compound (A) and alkali developable compound (C)] and a polymerization initiator (E) are contained. Hereinafter, each component will be described in order.
＜ウレタン（メタ）アクリレート化合物（Ａ）＞
　上記ウレタン（メタ）アクリレート化合物（Ａ）は、ウレタン結合、及びメタクリル基又はアクリル基を同一分子内に有する化合物である。上記ウレタン（メタ）アクリレート化合物（Ａ）は、ウレタン結合、及びメタクリル基又はアクリル基を同一分子内に有する化合物であれば特に限定されないが、メタクリル基又はアクリル基を含有するアルコールとイソシアネート化合物を反応させることによって得ることができる。
　ウレタン（メタ）アクリレート化合物（Ａ）としては、例えば、フェニルグリシジルエーテルアクリレートヘキサメチレンジイソシアネートウレタンプレポリマー、ペンタエリスリトールトリアクリレートヘキサメチレンジイソシアネートウレタンプレポリマー、ペンタエリスリトールトリアクリレートトルエンジイソシアネートウレタンプレポリマー、ペンタエリスリトールトリアクリレートイソホロンジイソシアネートウレタンプレポリマー、ジペンタエリスリトールペンタアクリレートヘキサメチレンジイソシアネートウレタンプレポリマー等が挙げられる。 <Urethane (meth) acrylate compound (A)>
The urethane (meth) acrylate compound (A) is a compound having a urethane bond and a methacryl group or an acryl group in the same molecule. The urethane (meth) acrylate compound (A) is not particularly limited as long as it is a compound having a urethane bond and a methacrylic group or an acrylic group in the same molecule, but reacts an alcohol containing a methacrylic group or an acrylic group with an isocyanate compound. Can be obtained.
Examples of the urethane (meth) acrylate compound (A) include phenyl glycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, and pentaerythritol triacrylate. Examples thereof include isophorone diisocyanate urethane prepolymer and dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer.
　上記ウレタン（メタ）アクリレート化合物（Ａ）としては、市販品を用いることもできる。具体的には、ＮＫオリゴＵ－４ＨＡ、Ｕ－４Ｈ、Ｕ－６ＨＡ、Ｕ－１５ＨＡ、Ｕ－１０８Ａ、Ｕ－１０８４Ａ、Ｕ－２００ＡＸ、Ｕ－１２２Ａ、Ｕ－３４０Ａ、Ｕ－３２４Ａ、ＵＡ－５３Ｈ、ＵＡ－１００、ＡＨ－６００（以上、新中村化学工業（株）製）、ＵＡ－３０６Ｈ、ＡＩ－６００、ＵＡ－１０１Ｔ、ＵＡ－１０１Ｉ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ（以上、共栄社化学（株）製）、アートレジンＵＮ－９２００Ａ、ＵＮ－３３２０ＨＡ、ＵＮ－３３２０ＨＢ、ＵＮ－３３２０ＨＣ、ＵＮ－３３２０ＨＳ、ＳＨ－３８０Ｇ、ＳＨ－５００、ＳＨ－９８３２、ＵＮ－９０１Ｔ、ＵＮ－９０４、ＵＮ－９０５、ＵＮ－９０６、ＵＮ－９０６Ｓ、ＵＮ－９０７、ＵＮ－９５２、ＵＮ－９５３、ＵＮ－９５４、Ｈ－９１、Ｈ－１３５（以上、根上工業（株）製）、サートマーＣＮ９６８、ＣＮ９７５、ＣＮ９８９、ＣＮ９００１、ＣＮ９０１０、ＣＮ９０２５、ＣＮ９０２９、ＣＮ９１６５、ＣＮ２２６０（以上、サートマー社製）、ＥＢＥＣＲＹＬ８８１０（ダイセル社製）等を挙げることができる。 Commercially available products can also be used as the urethane (meth) acrylate compound (A). Specifically, NK oligo U-4HA, U-4H, U-6HA, U-15HA, U-108A, U-1084A, U-200AX, U-122A, U-340A, U-324A, UA-53H UA-100, AH-600 (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (above, Kyoeisha Chemical Co., Ltd.) Manufactured), Art Resin UN-9200A, UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, SH-380G, SH-500, SH-9832, UN-901T, UN-904, UN-905 , UN-906, UN-906S, UN-907, UN-952, UN-953, UN-954, H-91, H-135 (above Negami Chemical Industry Co., Ltd.), Sartomer CN968, CN975, CN989, CN9001, CN9010, CN9025, CN9029, CN9165, CN2260 (manufactured by Sartomer Company, Inc.), can be mentioned EBECRYL8810 (manufactured by Daicel Chemical Industries, Ltd.) and the like.
　本発明の重合性組成物において、ウレタン（メタ）アクリレート化合物（Ａ）の含有量は、特に限定されるものではないが、ウレタン（メタ）アクリレート化合物（Ａ）、着色剤（Ｂ）、アルカリ現像性化合物（Ｃ）、エチレン性不飽和化合物（Ｄ）及び重合開始剤（Ｅ）の合計１００質量部に対して、好ましくは１～２０質量部、より好ましくは３～１０質量部、更に好ましくは３～８質量部である。重合性化合物（Ｂ）の含有量が、上記の範囲内である場合、得られる硬化物の弾性回復率が優れることから好ましい。
　例えば厚さ２～５μｍの硬化膜を形成する場合には、ウレタン（メタ）アクリレート化合物（Ａ）の含有量は、特に限定されるものではないが、ウレタン（メタ）アクリレート化合物（Ａ）、着色剤（Ｂ）、アルカリ現像性化合物（Ｃ）、エチレン性不飽和化合物（Ｄ）及び重合開始剤（Ｅ）の合計１００質量部に対して、得られる硬化物の弾性回復率が良好となることから、好ましくは１～２０質量部、より好ましくは３～１０質量部、更に好ましくは３～８質量部である。 In the polymerizable composition of the present invention, the content of the urethane (meth) acrylate compound (A) is not particularly limited, but the urethane (meth) acrylate compound (A), the colorant (B), and alkali development. 1 to 20 parts by weight, more preferably 3 to 10 parts by weight, and still more preferably 100 parts by weight of the total amount of the organic compound (C), ethylenically unsaturated compound (D) and polymerization initiator (E). 3 to 8 parts by mass. When content of a polymeric compound (B) exists in said range, it is preferable from the elasticity recovery rate of the hardened | cured material obtained being excellent.
For example, when a cured film having a thickness of 2 to 5 μm is formed, the content of the urethane (meth) acrylate compound (A) is not particularly limited, but the urethane (meth) acrylate compound (A), coloring The elastic recovery rate of the cured product obtained is good with respect to 100 parts by mass in total of the agent (B), the alkali developable compound (C), the ethylenically unsaturated compound (D), and the polymerization initiator (E). Therefore, the amount is preferably 1 to 20 parts by mass, more preferably 3 to 10 parts by mass, and still more preferably 3 to 8 parts by mass.
＜着色剤（Ｂ）＞
　本発明の重合性組成物に用いられる着色剤（Ｂ）としては、顔料や染料を用いることができる。顔料及び染料としては、それぞれ、無機色材又は有機色材を用いることができる。これらを単独で又は２種以上を混合して用いることができる。ここで、顔料とは、後述する溶剤に不溶の着色剤を意味し、無機又は有機色材の中でも溶剤に不溶であるもの、或いは無機又は有機染料をレーキ化したものも含まれる。 <Colorant (B)>
As the colorant (B) used in the polymerizable composition of the present invention, pigments and dyes can be used. As the pigment and the dye, an inorganic color material or an organic color material can be used, respectively. These can be used alone or in admixture of two or more. Here, the pigment means a colorant that is insoluble in a solvent described later, and includes inorganic or organic colorants that are insoluble in a solvent, or those obtained by rake formation of an inorganic or organic dye.
　上記顔料としては、ファーネス法、チャンネル法又はサーマル法によって得られるカーボンブラック、或いはアセチレンブラック、ケッチェンブラック又はランプブラック等のカーボンブラック、上記カーボンブラックをエポキシ樹脂で調整又は被覆したもの、上記カーボンブラックを予め溶剤中で樹脂に分散処理し、２０～２００ｍｇ／ｇの樹脂で被覆したもの、上記カーボンブラックを酸性又はアルカリ性表面処理したもの、平均粒径が８ｎｍ以上でＤＢＰ吸油量が９０ｍｌ／１００ｇ以下のカーボンブラック、９５０℃における揮発分中のＣＯ及びＣＯ２から算出した全酸素量が、表面積１００ｍ２当たり９ｍｇ以上であるカーボンブラック、黒鉛化カーボンブラック、黒鉛、活性炭、炭素繊維、カーボンナノチューブ、カーボンマイクロコイル、カーボンナノホーン、カーボンエアロゲル、フラーレン、アニリンブラック、ピグメントブラック７、チタンブラック、ラクタムブラック及びペリレンブラック等に代表される黒色顔料、酸化クロム緑、ミロリブルー、コバルト緑、コバルト青、マンガン系、フェロシアン化物、リン酸塩群青、紺青、ウルトラマリン、セルリアンブルー、ピリジアン、エメラルドグリーン、硫酸鉛、黄色鉛、亜鉛黄、べんがら（赤色酸化鉄(III)）、カドミウム赤、合成鉄黒、アンバー、レーキ顔料等の有機又は無機顔料が挙げられる。 Examples of the pigment include carbon black obtained by a furnace method, a channel method or a thermal method, or carbon black such as acetylene black, ketjen black or lamp black, a carbon black prepared or coated with an epoxy resin, and the carbon black In which a resin is pre-dispersed in a resin and coated with 20 to 200 mg / g of resin, an acid or alkaline surface treatment of the above carbon black, an average particle size of 8 nm or more, and a DBP oil absorption of 90 ml / 100 g or less of carbon black, the total amount of oxygen calculated from CO and CO 2 in the volatile content at 950 ° C. is, carbon black is surface area 100 m 2 per 9mg above, graphitized carbon black, graphite, activated carbon, carbon fibers, carbon nanotubes, Kabonma Black coil represented by crocoil, carbon nanohorn, carbon aerogel, fullerene, aniline black, pigment black 7, titanium black, lactam black and perylene black, chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese series, ferrocyan Fluoride, ultramarine blue, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red rose (red iron (III) oxide), cadmium red, synthetic iron black, amber, lake pigment And organic or inorganic pigments.
　上記顔料の中でも、遮光性が高いことから黒色顔料を用いることが好ましく、液晶汚染性が低いことからラクタムブラック及びペリレンブラック等に代表される有機系の黒色顔料を用いることが更に好ましい。 Among the above pigments, black pigments are preferably used because of their high light shielding properties, and organic black pigments such as lactam black and perylene black are more preferably used because of their low liquid crystal contamination.
　上記顔料としては、市販品を用いることもでき、例えば、ピグメントレッド１、２、３、９、１０、１４、１７、２２、２３、３１、３８、４１、４８、４９、８８、９０、９７、１１２、１１９、１２２、１２３、１４４、１４９、１６６、１６８、１６９、１７０、１７１、１７７、１７９、１８０、１８４、１８５、１９２、２００、２０２、２０９、２１５、２１６、２１７、２２０、２２３、２２４、２２６、２２７、２５４、２２８、２４０及び２５４；ピグメントオレンジ１３、３１、３４、３６、３８、４３、４６、４８、４９、５１、５２、５５、５９、６０、６１、６２、６４、６５及び７１；ピグメントイエロー１、３、１２、１３、１４、１６、１７、２０、２４、５５、６０、７３、８１、８３、８６、９３、９５、９７、９８、１００、１０９、１１０、１１３、１１４、１１７、１２０、１２５、１２６、１２７、１２９、１３７、１３８、１３９、１４７、１４８、１５０、１５１、１５２、１５３、１５４、１６６、１６８、１７５、１８０及び１８５；ピグメントグリ－ン７、１０、３６及び５８；ピグメントブルー１５、１５：１、１５：２、１５：３、１５：４、１５：５、１５：６、２２、２４、５６、６０、６１、６２及び６４；ピグメントバイオレット１、１９、２３、２７、２９、３０、３２、３７、４０及び５０等が挙げられる。 A commercial item can also be used as said pigment, for example, pigment red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97. 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223 224, 226, 227, 254, 228, 240 and 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64 , 65 and 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 5, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180 and 185; Pigment Green 7, 10, 36 and 58; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, and 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, and 50.
　上記染料としては、例えば、ニトロソ化合物、ニトロ化合物、アゾ化合物、ジアゾ化合物、キサンテン化合物、キノリン化合物、アントラキノン化合物、クマリン化合物、シアニン化合物、フタロシアニン化合物、イソインドリノン化合物、イソインドリン化合物、キナクリドン化合物、アンタンスロン化合物、ペリノン化合物、ペリレン化合物、ジケトピロロピロール化合物、チオインジゴ化合物、ジオキサジン化合物、トリフェニルメタン化合物、キノフタロン化合物、ナフタレンテトラカルボン酸、アゾ染料、シアニン染料の金属錯体化合物等が挙げられる。 Examples of the dye include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, cyanine compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, anthanthrones. Compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acids, azo dyes, metal complex compounds of cyanine dyes, and the like.
　本発明の重合性組成物において、上記着色剤（Ｂ）の含有量は、特に限定されるものではないが、下記アルカリ現像性化合物（Ｃ）１００質量部に対して、好ましくは３～３０質量部、より好ましくは５～２０質量部、更に好ましくは１５０～３００質量部である。着色剤（Ｂ）の含有量が上記の範囲内である場合、重合性組成物が着色剤の凝集を伴わない保存安定性に優れたものとなり、重合性組成物の硬化物の遮光性が高くなることから好ましい。
　例えば厚さ１～３μｍの硬化物を形成する場合には、着色剤（Ｂ）の含有量は、特に限定されるものではないが、アルカリ現像性化合物（Ｃ）１００質量部に対して、好ましくは、３～３０質量部、より好ましくは、５～２０質量部であり、更に好ましくは、１５０～３００質量部である。 In the polymerizable composition of the present invention, the content of the colorant (B) is not particularly limited, but is preferably 3 to 30 masses with respect to 100 mass parts of the following alkali developable compound (C). Part, more preferably 5 to 20 parts by weight, still more preferably 150 to 300 parts by weight. When the content of the colorant (B) is within the above range, the polymerizable composition has excellent storage stability without aggregation of the colorant, and the light-shielding property of the cured product of the polymerizable composition is high. This is preferable.
For example, when forming a cured product having a thickness of 1 to 3 μm, the content of the colorant (B) is not particularly limited, but is preferably based on 100 parts by mass of the alkali-developable compound (C). Is 3 to 30 parts by mass, more preferably 5 to 20 parts by mass, and still more preferably 150 to 300 parts by mass.
＜アルカリ現像性化合物（Ｃ）＞
　本発明に係るアルカリ現像性化合物（Ｃ）は、上記ウレタン（メタ）アクリレート化合物（Ａ）ではなく、親水性基を有し、且つ、アルカリ現像性を示す化合物である。本発明においては、アルカリ現像性化合物（Ｃ）として、上記の条件を満たしている限り、従来用いられている化合物を用いることができる。
　上記親水性基としては、水酸基、チオール基、カルボキシル基、スルホ基、アミノ基、アミド基又はその塩等が挙げられ、水酸基及びカルボキシル基が、アルカリ現像性化合物（Ｃ）のアルカリへ現像性が高いため好ましい。
　アルカリ現像性化合物（Ｃ）における親水性基の好ましい官能基当量（親水性基１当量を含む高分子化合物の質量）は、５０～１００００である。
　アルカリ現像性化合物（Ｃ）の好ましい分子量は、１０００～５０００００である。 <Alkali developable compound (C)>
The alkali developable compound (C) according to the present invention is not the urethane (meth) acrylate compound (A) but a compound having a hydrophilic group and exhibiting alkali developability. In the present invention, conventionally used compounds can be used as the alkali-developable compound (C) as long as the above conditions are satisfied.
Examples of the hydrophilic group include a hydroxyl group, a thiol group, a carboxyl group, a sulfo group, an amino group, an amide group or a salt thereof, and the hydroxyl group and the carboxyl group have developability to an alkali of the alkali developable compound (C). It is preferable because it is high.
The functional group equivalent of the hydrophilic group in the alkali-developable compound (C) (the mass of the polymer compound containing 1 equivalent of the hydrophilic group) is from 50 to 10,000.
The preferred molecular weight of the alkali developable compound (C) is 1,000 to 500,000.
　上記アルカリ現像性化合物（Ｃ）は、酸価が、好ましくは１０～２００ｍｇ／ＫＯＨ、さらに好ましくは３０～１５０ｍｇ／ＫＯＨである。酸価が１０ｍｇ／ＫＯＨ未満であると、アルカリ現像性が十分に得られない場合があり、２００ｍｇ／ＫＯＨより大きいと、高分子化合物の製造が困難である恐れがある。ここで、酸価とは、ＪＩＳ　Ｋ００５０ 及び ＪＩＳ Ｋ　０２１１によるものである。 The acid value of the alkali-developable compound (C) is preferably 10 to 200 mg / KOH, more preferably 30 to 150 mg / KOH. If the acid value is less than 10 mg / KOH, sufficient alkali developability may not be obtained, and if it is greater than 200 mg / KOH, it may be difficult to produce the polymer compound. Here, the acid value is based on JIS K0050 and JIS K 0211.
　アルカリ現像性化合物（Ｃ）としては、具体的には、アクリル酸エステルの共重合体；フェノール及び／又はクレゾールノボラックエポキシ樹脂；多官能エポキシ基を有するポリフェニルメタン型エポキシ樹脂；エポキシアクリレート樹脂；上記一般式（Ｉ）で表されるエポキシ化合物等に不飽和一塩基酸を付加させた構造を有するエポキシ付加化合物；上記一般式（Ｉ）で表されるエポキシ化合物に不飽和一塩基酸を付加させた構造を有するエポキシ付加化合物と、多塩基酸無水物とのエステル化反応により得られる構造を有する樹脂（不飽和化合物）等を用いることができる。
　これらの中でも、上記一般式（Ｉ）で表されるエポキシ化合物に不飽和一塩基酸を付加させた構造を有するエポキシ付加化合物；又は、上記一般式（Ｉ）で表されるエポキシ化合物に不飽和一塩基酸を付加させた構造を有するエポキシ付加化合物と、多塩基酸無水物とのエステル化反応により得られる反応生成物であるアルカリ現像性化合物を用いると、重合性組成物の感度が高くなり、該重合性組成物から得られる硬化物が弾性回復率に優れることから好ましい。
　また、上記アルカリ現像性化合物は、不飽和基を０．２～１．０当量含有していることが好ましい。 Specific examples of the alkali-developable compound (C) include acrylic acid ester copolymers; phenol and / or cresol novolac epoxy resins; polyphenylmethane type epoxy resins having polyfunctional epoxy groups; epoxy acrylate resins; An epoxy addition compound having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the general formula (I); an unsaturated monobasic acid is added to the epoxy compound represented by the general formula (I) A resin (unsaturated compound) having a structure obtained by an esterification reaction between an epoxy addition compound having a different structure and a polybasic acid anhydride can be used.
Among these, an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the above general formula (I); or unsaturated to the epoxy compound represented by the above general formula (I) When an alkali-developable compound that is a reaction product obtained by an esterification reaction of an epoxy addition compound having a structure with a monobasic acid and a polybasic acid anhydride is used, the sensitivity of the polymerizable composition increases. A cured product obtained from the polymerizable composition is preferable because of its excellent elastic recovery rate.
The alkali-developable compound preferably contains 0.2 to 1.0 equivalent of an unsaturated group.
　着色剤（Ｂ）の分散性が良好になり、且つ、耐熱性が良好なことから、上記アルカリ現像性化合物（Ｃ）が、上記一般式（Ｉ）で表されるエポキシ化合物；上記一般式（Ｉ）で表されるエポキシ化合物に不飽和一塩基酸を付加させた、下記構造［（ｅ）］を有するエポキシ化合物；又は、斯かる不飽和化合物と多塩基酸無水物とのエステル化反応により得られる、下記構造［（ｆ）］を有する不飽和化合物であることが望ましい。 Since the dispersibility of the colorant (B) is good and the heat resistance is good, the alkali developable compound (C) is an epoxy compound represented by the general formula (I); An epoxy compound having the following structure [(e)] obtained by adding an unsaturated monobasic acid to the epoxy compound represented by I); or by esterification reaction of such an unsaturated compound and a polybasic acid anhydride The obtained unsaturated compound having the following structure [(f)] is desirable.
Figure JPOXMLDOC01-appb-C000007
 （式中、Ｙ１は不飽和一塩基酸の残基を表し、Ｙ２は多塩基酸無水物の残基を表し、
　＊は結合手を意味する。）
Figure JPOXMLDOC01-appb-C000007
 Wherein Y 1 represents an unsaturated monobasic acid residue, Y 2 represents a polybasic acid anhydride residue,
* Means a bond. )
　上記一般式（Ｉ）中のＭで表される炭素原子数１～２０の炭化水素基は、特に限定されるものではないが、好ましくは炭素原子数１～２０のアルキレン基、炭素原子数２～２０のアルケニレン基、炭素原子数３～２０のシクロアルキレン基、又は炭素原子数６～２０のアリーレン基を表す。これらの中でも、アルカリ現像性化合物（Ｃ）として用いた場合の感度が良好なことから、炭素原子数１～１０のアルキレン基、炭素原子数２～１０のアルケニレン基、炭素原子数３～１０のシクロアルキレン基、又は炭素原子数６～１０のアリーレン基がより好ましい。 The hydrocarbon group having 1 to 20 carbon atoms represented by M in the general formula (I) is not particularly limited, but is preferably an alkylene group having 1 to 20 carbon atoms, 2 carbon atoms. Represents an alkenylene group having 20 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. Among these, since the sensitivity when used as the alkali-developable compound (C) is good, it is an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, or an alkyl group having 3 to 10 carbon atoms. A cycloalkylene group or an arylene group having 6 to 10 carbon atoms is more preferable.
　上記一般式（Ｉ）中のＭで表される炭素原子数１～２０のアルキレン基としては、例えば、メチレン、エチレン、プロピレン、ブチレン、ペンチレン、ヘキシレン、ヘプチレン、オクチレン、ノニレン、デシレン、ウンデシレン、ドデシレン、トリデシレン、テトラデシレン、ペンタデシレン、ヘキサデシレン、ヘプタデシレン、オクタデシレン、ノナデシレン、イコシレン基等が挙げられる。 Examples of the alkylene group having 1 to 20 carbon atoms represented by M in the general formula (I) include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, and dodecylene. , Tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, icosylene groups and the like.
　上記一般式（Ｉ）中のＭで表される炭素原子数２～２０のアルケニレン基としては、例えば、１，２－エテンジイル（エテニレン又はビニレンともいう）、２－ブテン－１，４－ジイル、１，２－ジメチル－１，２－エテンジイル等が挙げられる。 Examples of the alkenylene group having 2 to 20 carbon atoms represented by M in the general formula (I) include 1,2-ethenediyl (also referred to as ethenylene or vinylene), 2-butene-1,4-diyl, Examples include 1,2-dimethyl-1,2-ethenediyl.
　上記一般式（Ｉ）中のＭで表される炭素原子数３～２０のシクロアルキレン基としては、シクロプロピレン、シクロペンチレン、シクロヘキシレン、シクロヘプチレン、シクロオクチレン基等が挙げられる。 Examples of the cycloalkylene group having 3 to 20 carbon atoms represented by M in the general formula (I) include cyclopropylene, cyclopentylene, cyclohexylene, cycloheptylene, and cyclooctylene groups.
　上記一般式（Ｉ）中のＭで表される炭素原子数６～２０のアリーレン基としては、例えばフェニレン、トリレン、キシリレン、ナフチレン、ビフェニレン、フルオレン、インダンが挙げられる。 Examples of the arylene group having 6 to 20 carbon atoms represented by M in the general formula (I) include phenylene, tolylene, xylylene, naphthylene, biphenylene, fluorene, and indane.
　上記一般式（Ｉ）中のＭで表される炭素原子数１～２０の炭化水素基を置換するハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられる。 As the halogen atom for substituting the hydrocarbon group having 1 to 20 carbon atoms represented by M in the above general formula (I), fluorine, chlorine, bromine and iodine can be mentioned.
　上記一般式（Ｉ）中のＲ１～Ｒ３８で表される炭素原子数１～２０の炭化水素基は、特に限定されるものではないが、好ましくは炭素原子数１～２０のアルキル基、炭素原子数２～２０のアルケニル基、炭素原子数３～２０のシクロアルキル基、炭素原子数４～２０のシクロアルキルアルキル基、炭素原子数６～２０のアリール基及び炭素原子数７～２０のアリールアルキル基等を表す。アルカリ現像性化合物（Ｃ）として用いた場合の感度が良好なことから、炭素原子数１～１０のアルキル基、炭素原子数２～１０のアルケニル基、炭素原子数３～１０のシクロアルキル基、炭素原子数４～１０のシクロアルキルアルキル基、炭素原子数６～１０のアリール基及び炭素原子数７～１０のアリールアルキル基等がより好ましい。 The hydrocarbon group having 1 to 20 carbon atoms represented by R 1 to R 38 in the general formula (I) is not particularly limited, but is preferably an alkyl group having 1 to 20 carbon atoms, An alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a 7 to 20 carbon atom Represents an arylalkyl group or the like; Since the sensitivity when used as the alkali-developable compound (C) is good, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, A cycloalkylalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, and the like are more preferable.
　上記炭素原子数１～２０のアルキル基としては、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓ－ブチル、ｔ－ブチル、アミル、イソアミル、ｔ－アミル、ヘキシル、ヘプチル、オクチル、イソオクチル、２－エチルヘキシル、ｔ－オクチル、ノニル、イソノニル、デシル、イソデシル、ウンデシル、ドデシル、テトラデシル、ヘキサデシル、オクタデシル及びイコシル等が挙げられる。上記炭素原子数１～１０のアルキル基としては、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓ－ブチル、ｔ－ブチル、アミル、イソアミル、ｔ－アミル、ヘキシル、ヘプチル、オクチル、イソオクチル、２－エチルヘキシル、ｔ－オクチル、ノニル、イソノニル、デシル及びイソデシル等が挙げられる。 Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl. 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl and the like. Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl. 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl and the like.
　上記炭素原子数２～２０のアルケニル基としては、例えば、ビニル、２－プロペニル、３－ブテニル、２－ブテニル、４－ペンテニル、３－ペンテニル、２－ヘキセニル、３－ヘキセニル、５－ヘキセニル、２－ヘプテニル、３－ヘプテニル、４－ヘプテニル、３－オクテニル、３－ノネニル、４－デセニル、３－ウンデセニル、４－ドデセニル、３－シクロヘキセニル、２，５－シクロヘキサジエニル－１－メチル、及び４，８，１２－テトラデカトリエニルアリル等が挙げられる。上記炭素原子数２～１０のアルケニル基としては、例えば、ビニル、２－プロペニル、３－ブテニル、２－ブテニル、４－ペンテニル、３－ペンテニル、２－ヘキセニル、３－ヘキセニル、５－ヘキセニル、２－ヘプテニル、３－ヘプテニル、４－ヘプテニル、３－オクテニル、３－ノネニル及び４－デセニル等が挙げられる。 Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2 -Heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl-1-methyl, and 4 , 8,12-tetradecatrienylallyl and the like. Examples of the alkenyl group having 2 to 10 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2 -Heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl and the like.
　上記炭素原子数３～２０のシクロアルキル基とは、３～２０の炭素原子を有する、飽和単環式又は飽和多環式アルキル基を意味する。例えば、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチル、シクロノニル、シクロデシル、アダマンチル、デカハイドロナフチル、オクタヒドロペンタレン、ビシクロ［１．１．１］ペンタニル及びテトラデカヒドロアントラセニル等が挙げられる。上記炭素原子数３～１０のシクロアルキル基としては、例えば、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチル、シクロノニル、シクロデシル、アダマンチル、デカハイドロナフチル、オクタヒドロペンタレン及びビシクロ［１．１．１］ペンタニル等が挙げられる。 The above cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, bicyclo [1.1.1] pentanyl and tetradecahydroanthracenyl Can be mentioned. Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, and bicyclo [1. 1.1] pentanyl and the like.
　上記炭素原子数４～２０のシクロアルキルアルキル基とは、アルキル基の水素原子が、シクロアルキル基で置換された４～２０の炭素原子を有する基を意味する。例えば、シクロプロピルメチル、シクロブチルメチル、シクロペンチルメチル、シクロヘキシルメチル、シクロヘプチルメチル、シクロオクチルメチル、シクロノニルメチル、シクロデシルメチル、２－シクロブチルエチル、２－シクロペンチルエチル、２－シクロヘキシルエチル、２－シクロヘプチルエチル、２－シクロオクチルエチル、２－シクロノニルエチル、２－シクロデシルエチル、３－シクロブチルプロピル、３－シクロペンチルプロピル、３－シクロヘキシルプロピル、３－シクロヘプチルプロピル、３－シクロオクチルプロピル、３－シクロノニルプロピル、３－シクロデシルプロピル、４－シクロブチルブチル、４－シクロペンチルブチル、４－シクロヘキシルブチル、４－シクロヘプチルブチル、４－シクロオクチルブチル、４－シクロノニルブチル、４－シクロデシルブチル、３－３－アダマンチルプロピル及びデカハイドロナフチルプロピル等が挙げられる。上記炭素原子数４～１０のシクロアルキルアルキル基としては、例えば、シクロプロピルメチル、シクロブチルメチル、シクロペンチルメチル、シクロヘキシルメチル、シクロヘプチルメチル、シクロオクチルメチル、シクロノニルメチル、２－シクロブチルエチル、２－シクロペンチルエチル、２－シクロヘキシルエチル、２－シクロヘプチルエチル、２－シクロオクチルエチル、３－シクロブチルプロピル、３－シクロペンチルプロピル、３－シクロヘキシルプロピル、３－シクロヘプチルプロピル、４－シクロブチルブチル、４－シクロペンチルブチル及び４－シクロヘキシルブチル等が挙げられる。 The cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which a hydrogen atom of the alkyl group is substituted with a cycloalkyl group. For example, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclodecylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2- Cycloheptylethyl, 2-cyclooctylethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 3-cyclooctylpropyl, 3-cyclononylpropyl, 3-cyclodecylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl, 4-cycloheptylbutyl, 4-cyclooctylbutyl Le, 4-cyclopropyl-nonyl-butyl, 4-cyclopropyl-decyl-butyl, 3-3-adamantyl propyl and deca hydro-naphthylpropyl and the like. Examples of the cycloalkylalkyl group having 4 to 10 carbon atoms include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, 2-cyclobutylethyl, 2 -Cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 4-cyclobutylbutyl, 4 -Cyclopentylbutyl, 4-cyclohexylbutyl and the like.
　上記炭素原子数６～２０のアリール基としては、例えば、フェニル、トリル、キシリル、エチルフェニル、ナフチル、アンスリル、フェナントレニル等や、上記アルキル基、上記アルケニル基やカルボキシル基、ハロゲン原子等で１つ以上置換されたフェニル、ビフェニリル、ナフチル、アンスリル等、例えば、４－クロロフェニル、４－カルボキシルフェニル、４－ビニルフェニル、４－メチルフェニル、２，４，６－トリメチルフェニル等が挙げられる。上記炭素原子数６～１０のアリール基としては、例えば、フェニル、トリル、キシリル、エチルフェニル及びナフチル等や、上記アルキル基、上記アルケニル基やカルボキシル基、ハロゲン原子等で１つ以上置換されたフェニル、ビフェニリル、ナフチル、アンスリル等、例えば、４－クロロフェニル、４－カルボキシルフェニル、４－ビニルフェニル、４－メチルフェニル、２，４，６－トリメチルフェニル等が挙げられる。 Examples of the aryl group having 6 to 20 carbon atoms include one or more of phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, the alkyl group, the alkenyl group, the carboxyl group, and the halogen atom. Substituted phenyl, biphenylyl, naphthyl, anthryl and the like, for example, 4-chlorophenyl, 4-carboxylphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl and the like can be mentioned. Examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, etc., phenyl substituted with one or more of the above alkyl group, the above alkenyl group, carboxyl group, halogen atom, etc. Biphenylyl, naphthyl, anthryl and the like, for example, 4-chlorophenyl, 4-carboxylphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl and the like.
　上記炭素原子数７～２０のアリールアルキル基とは、アルキル基の水素原子がアリール基で置き換えられた、７～２０個の炭素原子を有する基を意味する。例えば、ベンジル、α－メチルベンジル、α、α－ジメチルベンジル、フェニルエチル及びナフチルプロピル等が挙げられる。上記炭素原子数７～１０のアリールアルキル基としては、アルキル基の水素原子がアリール基で置き換えられれた、７～１０個の炭素原子を有する基を意味し、例えば、ベンジル、α－メチルベンジル、α、α－ジメチルベンジル及びフェニルエチル等が挙げられる。 The above-mentioned arylalkyl group having 7 to 20 carbon atoms means a group having 7 to 20 carbon atoms in which a hydrogen atom of the alkyl group is replaced with an aryl group. Examples include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and naphthylpropyl. The arylalkyl group having 7 to 10 carbon atoms means a group having 7 to 10 carbon atoms in which the hydrogen atom of the alkyl group is replaced with an aryl group, and examples thereof include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and the like can be mentioned.
　上記一般式（Ｉ）中のＲ１０～Ｒ３８で表される複素環を含有する炭素原子数２～２０の基は、特に限定されるものではないが、例えば、ピロリル、ピリジル、ピリジルエチル、ピリミジル、ピリダジル、ピペラジル、ピペリジル、ピラニル、ピラニルエチル、ピラゾリル、トリアジル、トリアジルメチル、ピロリジル、キノリル、イソキノリル、イミダゾリル、ベンゾイミダゾリル、トリアゾリル、フリル、フラニル、ベンゾフラニル、チエニル、チオフェニル、ベンゾチオフェニル、チアジアゾリル、チアゾリル、ベンゾチアゾリル、オキサゾリル、ベンゾオキサゾリル、イソチアゾリル、イソオキサゾリル、インドリル、モルフォリニル、チオモルフォリニル、モルホリニル、２－ピロリジノン－１－イル、２－ピペリドン－１－イル、２，４－ジオキシイミダゾリジン－３－イル及び２，４－ジオキシオキサゾリジン－３－イル等が挙げられ、置換基等を含めて具体的に記載すると下記の構造を有する基等が挙げられる。 The group having 2 to 20 carbon atoms containing the heterocyclic ring represented by R 10 to R 38 in the general formula (I) is not particularly limited, and examples thereof include pyrrolyl, pyridyl, pyridylethyl, Pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyranylethyl, pyrazolyl, triazyl, triazylmethyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, Benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, morpholinyl, thiomorpholinyl, morpholinyl, 2-pyrrolidinon-1-yl, 2-piperidone-1-y 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidine-3-yl, and the like, and specific examples including substituents include groups having the following structures: It is done.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
（上記式中、Ｒはそれぞれ独立して、水素原子又は炭素原子数１～６のアルキル基を表し、Ｚは直接結合又は炭素原子数１～６のアルキレン基を表す。尚、式中の＊は、これらの式で表される基が、＊部分で、結合手を意味する。） (In the above formula, each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z represents a direct bond or an alkylene group having 1 to 6 carbon atoms. Represents a bond in the * part of the group represented by these formulas.)
　上記式中のＲで表される炭素原子数１～６のアルキル基としては、上述した炭素原子数１～２０のアルキル基として例示したものの中の炭素原子数１～６のものを挙げることができる。
　上記式中のＺで表される炭素原子数１～６の２０のアルキレン基としては、上述した炭素原子数１～２０のアルキレン基として例示したものの中の炭素原子数１～６のものを挙げることができる。 Examples of the alkyl group having 1 to 6 carbon atoms represented by R in the above formula include those having 1 to 6 carbon atoms among those exemplified as the alkyl group having 1 to 20 carbon atoms described above. it can.
Examples of the 20 alkylene group having 1 to 6 carbon atoms represented by Z in the above formula include those having 1 to 6 carbon atoms among those exemplified above as the alkylene group having 1 to 20 carbon atoms. be able to.
　Ｒ１～Ｒ８及びＲ１０～Ｒ３８で表されるハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられる。 Examples of the halogen atom represented by R 1 to R 8 and R 10 to R 38 include fluorine, chlorine, bromine and iodine.
　Ｒ１～Ｒ８及びＲ１０～Ｒ３８で表される基中のメチレン基を置換する場合のある不飽和結合としては、－Ｃ＝Ｃ－、－Ｃ≡Ｃ－等が挙げられる。 Examples of the unsaturated bond that may substitute the methylene group in the groups represented by R 1 to R 8 and R 10 to R 38 include —C═C— and —C≡C—.
　上記一般式（Ｉ）中のＲ１０とＲ１１、Ｒ１１とＲ１２、Ｒ１２とＲ１３、Ｒ１３とＲ１４、Ｒ２２とＲ１５、Ｒ１５とＲ１６、Ｒ３０とＲ２３、Ｒ２３とＲ２４、Ｒ２４とＲ２５、Ｒ３８とＲ３１、Ｒ３１とＲ３２、Ｒ３２とＲ３３、Ｒ３４とＲ３５、Ｒ３５とＲ３６及びＲ３６とＲ３７が、結合して形成する環としては、例えば、シクロペンタン、シクロヘキサン、シクロペンテン、ベンゼン、ピロリジン、ピロール、ピペラジン、モルホリン、チオモルホリン、テトラヒドロピリジン、ラクトン環及びラクタム環等の５～７員環並びにナフタレン及びアントラセン等の縮合環等が挙げられる。 R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 22 and R 15 , R 15 and R 16 , R 30 and R 23 in the general formula (I), R 23 and R 24 , R 24 and R 25 , R 38 and R 31 , R 31 and R 32 , R 32 and R 33 , R 34 and R 35 , R 35 and R 36, and R 36 and R 37 are combined Examples of the ring thus formed include cyclopentane, cyclohexane, cyclopentene, benzene, pyrrolidine, pyrrole, piperazine, morpholine, thiomorpholine, tetrahydropyridine, lactone ring and lactam ring, 5- to 7-membered rings, naphthalene and anthracene, etc. And the like.
　上記不飽和一塩基酸とは、構造中に不飽和結合を有し、電離して水素イオンになることのできる水素原子を１分子あたり１個もつ酸を表す。
　上記不飽和一塩基酸としては、例えば、アクリル酸、メタクリル酸、クロトン酸、桂皮酸、ソルビン酸及びヒドロキシエチルメタクリレート・マレート、ヒドロキシプロピルメタクリレート・マレート、ヒドロキシプロピルアクリレート・マレート及びジシクロペンタジエン・マレート等が挙げられる。 The unsaturated monobasic acid is an acid having an unsaturated bond in the structure and having one hydrogen atom per molecule that can be ionized to form a hydrogen ion.
Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid and hydroxyethyl methacrylate / malate, hydroxypropyl methacrylate / malate, hydroxypropyl acrylate / malate, and dicyclopentadiene / malate. Is mentioned.
　また、上記不飽和一塩基酸を作用させた後に作用させる上記多塩基酸無水物とは、複数のカルボキシ基を有する多塩基酸のカルボキシ基が脱水縮合して形成された酸無水物基を有する化合物を意味する。
　上記多塩基酸無水物としては、ビフェニルテトラカルボン酸二無水物、テトラヒドロ無水フタル酸、無水コハク酸、ビフタル酸無水物、無水マレイン酸、トリメリット酸無水物、ピロメリット酸無水物、２，２’－３，３’－ベンゾフェノンテトラカルボン酸無水物、エチレングリコールビスアンヒドロトリメリテート、グリセロールトリスアンヒドロトリメリテート、ヘキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、ナジック酸無水物、メチルナジック酸無水物、トリアルキルテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、５－（２，５－ジオキソテトラヒドロフリル）－３－メチル－３－シクロヘキセン－１，２－ジカルボン酸無水物、トリアルキルテトラヒドロ無水フタル酸－無水マレイン酸付加物、ドデセニル無水コハク酸、無水メチルハイミック酸等が挙げられる。 In addition, the polybasic acid anhydride that is acted after the unsaturated monobasic acid is allowed to act has an acid anhydride group formed by dehydration condensation of a carboxy group of a polybasic acid having a plurality of carboxy groups. Means a compound.
Examples of the polybasic acid anhydride include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2 '-3,3'-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, nadic anhydride, methyl nadic acid Anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride Acid-maleic anhydride adduct, dodeceni Succinic anhydride include anhydride methylhymic Mick acid.
　上記エポキシ化合物、上記不飽和一塩基酸及び上記多塩基酸無水物の反応モル比は、以下の通りとすることが好ましい。
　即ち、上記エポキシ付加化合物は、上記エポキシ化合物のエポキシ基１個に対し、上記不飽和一塩基酸のカルボキシル基が０．１～１．０個の比率となるように付加させるのが好ましく、また上記エチレン性不飽和化合物は、上記エポキシ付加物の水酸基１個に対し、上記多塩基酸無水物の酸無水物構造が０．１～１．０個となる比率となるようにするのが好ましい。
　上記一般式（Ｉ）で表されるエポキシ化合物、上記不飽和一塩基酸及び上記多塩基酸無水物の反応は、常法に従って行なうことができる。 The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows.
That is, the epoxy addition compound is preferably added so that the carboxyl group of the unsaturated monobasic acid has a ratio of 0.1 to 1.0 with respect to one epoxy group of the epoxy compound. The ethylenically unsaturated compound is preferably such that the acid anhydride structure of the polybasic acid anhydride is 0.1 to 1.0 with respect to one hydroxyl group of the epoxy adduct. .
The reaction of the epoxy compound represented by the general formula (I), the unsaturated monobasic acid and the polybasic acid anhydride can be performed according to a conventional method.
　酸価調整して本発明の重合性組成物及びＢＣＳ用感光性組成物の現像性を改良するため、上記アルカリ現像性化合物（Ｃ）と共に、更に単官能又は多官能エポキシ化合物を反応させることができる。上記アルカリ現像性化合物（Ｃ）は、固形分の酸価が５～１２０ｍｇＫＯＨ／ｇの範囲であることが好ましく、単官能又は多官能エポキシ化合物の使用量は、上記酸価を満たすように選択するのが好ましい。 In order to improve the developability of the polymerizable composition of the present invention and the photosensitive composition for BCS by adjusting the acid value, a monofunctional or polyfunctional epoxy compound may be further reacted with the alkali developable compound (C). it can. The alkali-developable compound (C) preferably has a solid content acid value in the range of 5 to 120 mgKOH / g, and the usage amount of the monofunctional or polyfunctional epoxy compound is selected so as to satisfy the acid value. Is preferred.
　上記単官能エポキシ化合物としては、グリシジルメタクリレート、メチルグリシジルエーテル、エチルグリシジルエーテル、プロピルグリシジルエーテル、イソプロピルグリシジルエーテル、ブチルグリシジルエーテル、イソブチルグリシジルエーテル、ｔ－ブチルグリシジルエーテル、ペンチルグリシジルエーテル、ヘキシルグリシジルエーテル、ヘプチルグリシジルエーテル、オクチルグリシジルエーテル、ノニルグリシジルエーテル、デシルグリシジルエーテル、ウンデシルグリシジルエーテル、ドデシルグリシジルエーテル、トリデシルグリシジルエーテル、テトラデシルグリシジルエーテル、ペンタデシルグリシジルエーテル、ヘキサデシルグリシジルエーテル、２－エチルヘキシルグリシジルエーテル、アリルグリシジルエーテル、プロパルギルグリシジルエーテル、ｐ－メトキシエチルグリシジルエーテル、フェニルグリシジルエーテル、ｐ－メトキシグリシジルエーテル、ｐ－ブチルフェノールグリシジルエーテル、クレジルグリシジルエーテル、２－メチルクレジルグリシジルエーテル、４－ノニルフェニルグリシジルエーテル、ベンジルグリシジルエーテル、ｐ－クミルフェニルグリシジルエーテル、トリチルグリシジルエーテル、２，３－エポキシプロピルメタクリレート、エポキシ化大豆油、エポキシ化アマニ油、グリシジルブチレート、ビニルシクロヘキサンモノオキシド、１，２－エポキシ－４－ビニルシクロヘキサン、スチレンオキシド、ピネンオキシド、メチルスチレンオキシド、シクロヘキセンオキシド、プロピレンオキシド、下記エポキシ化合物Ｎｏ．１、Ｎｏ．２等が挙げられる。 Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidyl A , Propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl Glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4- Vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide, the following epoxy Compound No. 1, no. 2 etc. are mentioned.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　上記多官能エポキシ化合物としては、ビスフェノール型エポキシ化合物及びグリシジルエーテル類からなる群から選択される一種以上の化合物を用いると、特性の一層良好な重合性組成物を得ることができるので好ましい。
　上記ビスフェノール型エポキシ化合物としては、上記一般式（Ｉ）で表されるエポキシ化合物を用いることができる他、例えば、水添ビスフェノール型エポキシ化合物等のビスフェノール型エポキシ化合物も用いることができる。
　また上記グリシジルエーテル類としては、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、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、１，８－オクタンジオールジグリシジルエーテル、１，１０－デカンジオールジグリシジルエーテル、２，２－ジメチル－１，３－プロパンジオールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、トリエチレングリコールジグリシジルエーテル、テトラエチレングリコールジグリシジルエーテル、ヘキサエチレングリコールジグリシジルエーテル、１，４－シクロヘキサンジメタノールジグリシジルエーテル、１，１，１－トリ（グリシジルオキシメチル）プロパン、１，１，１－トリ（グリシジルオキシメチル）エタン、１，１，１－トリ（グリシジルオキシメチル）メタン、１，１，１，１－テトラ（グリシジルオキシメチル）メタン等を用いることができる。
　その他、フェノールノボラック型エポキシ化合物、ビフェニルノボラック型エポキシ化合物、クレゾールノボラック型エポキシ化合物、ビスフェノールＡノボラック型エポキシ化合物、ジシクロペンタジエンノボラック型エポキシ化合物等のノボラック型エポキシ化合物；３，４－エポキシ－６－メチルシクロヘキシルメチル－３，４－エポキシ－６－メチルシクロヘキサンカルボキシレート、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、１－エポキシエチル－３，４－エポキシシクロヘキサン等の脂環式エポキシ化合物；フタル酸ジグリシジルエステル、テトラヒドロフタル酸ジグリシジルエステル、ダイマー酸グリシジルエステル等のグリシジルエステル類；テトラグリシジルジアミノジフェニルメタン、トリグリシジルＰ－アミノフェノール、Ｎ，Ｎ－ジグリシジルアニリン等のグリシジルアミン類；１，３－ジグリシジル－５，５－ジメチルヒダントイン、トリグリシジルイソシアヌレート等の複素環式エポキシ化合物；ジシクロペンタジエンジオキシド等のジオキシド化合物；ナフタレン型エポキシ化合物；トリフェニルメタン型エポキシ化合物；ジシクロペンタジエン型エポキシ化合物等を用いることもできる。 As the polyfunctional epoxy compound, it is preferable to use one or more compounds selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers because a polymerizable composition with better characteristics can be obtained.
As the bisphenol type epoxy compound, an epoxy compound represented by the above general formula (I) can be used, and for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can also be used.
Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl Ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-to (Glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1- tetra (glycidyloxymethyl) can be used such as methane.
Other novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds; 3,4-epoxy-6-methyl Cycloaliphatic epoxy such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compound: Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, glycidyl dimer, tetraglycidyl diamino Glycidylamines such as phenylmethane, triglycidyl P-aminophenol and N, N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds such as pentadiene dioxide; naphthalene type epoxy compounds; triphenylmethane type epoxy compounds; dicyclopentadiene type epoxy compounds can also be used.
　アルカリ現像性化合物（Ｃ）としては、市販品も好適に用いることができる。
　該市販品としては、例えば、ＳＰＣ１０００、ＳＰＣ－２０００、ＳＰＣ－３０００、ＳＰＲＲ－１Ｘ、ＳＰＲＲ－２Ｘ、ＳＰＲＲ－３Ｘ、ＳＰＲＲ－５Ｘ、ＳＰＲＲ－６Ｘ、ＳＰＲＲ－７Ｘ、ＳＰＲＲ－８Ｘ、ＳＰＲＲ－９Ｘ、ＳＰＲＲ－１０Ｘ、ＳＰＲＲ－１１Ｘ、ＳＰＲＲ－１２Ｘ、ＳＰＲＲ－１３Ｘ、ＳＰＲＲ－１４Ｘ、ＳＰＲＲ－１５Ｘ、ＳＰＲＲ－１６Ｘ、ＳＰＲＲ－１７Ｘ、ＳＰＲＲ－１８Ｘ、ＳＰＲＲ－１９Ｘ、ＳＰＲＲ－２０Ｘ、ＳＰＲＲ－２１Ｘ（以上、昭和電工社製）、ＪＥＴ２０００、ＡＧＯＲ１０６０、ＡＧＯＲ３０６０、ＯＲＧＡ１０６０、ＯＲＧＡ２０６０（以上、大阪有機化学社製）、ＣＣＲ－１１７１Ｈ（日本化薬社製）等が挙げられる。 A commercially available product can also be suitably used as the alkali developable compound (C).
Examples of the commercially available products include SPC1000, SPC-2000, SPC-3000, SPRR-1X, SPRR-2X, SPRR-3X, SPRR-5X, SPRR-6X, SPRR-7X, SPRR-8X, SPRR-9X, SPRR-10X, SPRR-11X, SPRR-12X, SPRR-13X, SPRR-14X, SPRR-15X, SPRR-16X, SPRR-17X, SPRR-18X, SPRR-19X, SPRR-20X, SPRR-21X (above, Showa Denko KK), JET2000, AGOR1060, AGOR3060, ORGA1060, ORGA2060 (above, manufactured by Osaka Organic Chemical Co., Ltd.), CCR-1171H (manufactured by Nippon Kayaku Co., Ltd.), and the like.
　本発明の重合性組成物において、アルカリ現像性化合物（Ｃ）の含有量は、特に限定されるものではないが、ウレタン（メタ）アクリレート化合物（Ａ）、着色剤（Ｂ）、アルカリ現像性化合物（Ｃ）、エチレン性不飽和化合物（Ｄ）及び重合開始剤（Ｅ）の合計１００質量部に対して、好ましくは、１０～８０質量部、より好ましくは、２０～８０質量部であり、更に好ましくは、３０～７０質量部である。アルカリ現像性化合物（Ｃ）の含有量が、上記の範囲内である場合、重合性組成物のアルカリ現像性が良好なことから好ましい。
　例えば厚さ２～５μｍの硬化膜を形成する場合には、アルカリ現像性化合物（Ｃ）の含有量は、特に限定されるものではないが、ウレタン（メタ）アクリレート化合物（Ａ）、着色剤（Ｂ）、アルカリ現像性化合物（Ｃ）、エチレン性不飽和化合物（Ｄ）及び重合開始剤（Ｅ）の合計１００質量部に対して、好ましくは、１０～８０質量部、より好ましくは、２０～８０質量部であり、更に好ましくは、３０～７０質量部である。 In the polymerizable composition of the present invention, the content of the alkali developable compound (C) is not particularly limited, but the urethane (meth) acrylate compound (A), the colorant (B), and the alkali developable compound. The total amount of (C), the ethylenically unsaturated compound (D) and the polymerization initiator (E) is preferably 100 to 80 parts by mass, more preferably 20 to 80 parts by mass, Preferably, it is 30 to 70 parts by mass. When content of an alkali developable compound (C) exists in said range, it is preferable from the alkali developability of polymeric composition being favorable.
For example, when a cured film having a thickness of 2 to 5 μm is formed, the content of the alkali-developable compound (C) is not particularly limited, but the urethane (meth) acrylate compound (A), the colorant ( B), preferably 10 to 80 parts by mass, more preferably 20 to 100 parts by mass with respect to a total of 100 parts by mass of the alkali-developable compound (C), the ethylenically unsaturated compound (D) and the polymerization initiator (E). 80 parts by mass, more preferably 30 to 70 parts by mass.
＜エチレン性不飽和化合物（Ｄ）＞
　本発明で用いられるエチレン性不飽和化合物（Ｄ）は、エチレン性不飽和結合を有し、且つ、上記ウレタン（メタ）アクリレート化合物（Ａ）及び上記アルカリ現像性化合物（Ｃ）ではない化合物である。エチレン性不飽和化合物（Ｄ）としては、例えば、エチレン、プロピレン、ブチレン、イソブチレン、塩化ビニル、塩化ビニリデン、フッ化ビニリデン、テトラフルオロエチレン等の不飽和脂肪族炭化水素；(メタ)アクリル酸、α―クロルアクリル酸、イタコン酸、マレイン酸、シトラコン酸、フマル酸、ハイミック酸、クロトン酸、イソクロトン酸、ビニル酢酸、アリル酢酸、桂皮酸、ソルビン酸、メサコン酸、コハク酸モノ［２－（メタ）アクリロイロキシエチル］、フタル酸モノ［２－（メタ）アクリロイロキシエチル］、ω－カルボキシポリカプロラクトンモノ（メタ）アクリレート等の両末端にカルボキシ基と水酸基とを有するポリマーのモノ（メタ）アクリレート；ヒドロキシエチル（メタ）アクリレート・マレート、ヒドロキシプロピル（メタ）アクリレート・マレート、ジシクロペンタジエン・マレート或いは１個のカルボキシル基と２個以上の(メタ)アクリロイル基とを有する多官能（メタ）アクリレート等の不飽和多塩基酸；(メタ)アクリル酸－２－ヒドロキシエチル、（メタ）アクリル酸－２－ヒドロキシプロピル、（メタ）アクリル酸グリシジル、下記アクリル化合物Ｎｏ．１～Ｎｏ．４、（メタ）アクリル酸メチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸－ｔ－ブチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸ジメチルアミノメチル、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸アミノプロピル、（メタ）アクリル酸ジメチルアミノプロピル、（メタ）アクリル酸エトキシエチル、（メタ）アクリル酸ポリ（エトキシ）エチル、（メタ）アクリル酸ブトキシエトキシエチル、（メタ）アクリル酸エチルヘキシル、（メタ）アクリル酸フェノキシエチル、（メタ）アクリル酸テトラヒドロフリル、（メタ）アクリル酸ビニル、（メタ）アクリル酸アリル、（メタ）アクリル酸ベンジル、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリシクロデカンジメチロールジ（メタ）アクリレート、トリ［（メタ）アクリロイルエチル］イソシアヌレート、ポリエステル（メタ）アクリレートオリゴマー等の不飽和一塩基酸及び多価アルコール又は多価フェノールのエステル；（メタ）アクリル酸亜鉛、（メタ）アクリル酸マグネシウム等の不飽和多塩基酸の金属塩；マレイン酸無水物、イタコン酸無水物、シトラコン酸無水物、メチルテトラヒドロ無水フタル酸、テトラヒドロ無水フタル酸、トリアルキルテトラヒドロ無水フタル酸、５－（２，５－ジオキソテトラヒドロフリル）－３－メチル－３－シクロヘキセン－１，２－ジカルボン酸無水物、トリアルキルテトラヒドロ無水フタル酸－無水マレイン酸付加物、ドデセニル無水コハク酸、無水メチルハイミック酸等の不飽和多塩基酸の酸無水物；（メタ）アクリルアミド、メチレンビス－（メタ）アクリルアミド、ジエチレントリアミントリス（メタ）アクリルアミド、キシリレンビス（メタ）アクリルアミド、α－クロロアクリルアミド、Ｎ－２－ヒドロキシエチル（メタ）アクリルアミド等の不飽和一塩基酸及び多価アミンのアミド；アクロレイン等の不飽和アルデヒド；（メタ）アクリロニトリル、α－クロロアクリロニトリル、シアン化ビニリデン、シアン化アリル等の不飽和ニトリル；スチレン、４－メチルスチレン、４－エチルスチレン、４－メトキシスチレン、４－ヒドロキシスチレン、４－クロロスチレン、ジビニルベンゼン、ビニルトルエン、ビニル安息香酸、ビニルフェノール、ビニルスルホン酸、４－ビニルベンゼンスルホン酸、ビニルベンジルメチルエーテル、ビニルベンジルグリシジルエーテル等の不飽和芳香族化合物；メチルビニルケトン等の不飽和ケトン；ビニルアミン、アリルアミン、Ｎ－ビニルピロリドン、ビニルピペリジン等の不飽和アミン化合物；アリルアルコール、クロチルアルコール等のビニルアルコール；ビニルメチルエーテル、ビニルエチルエーテル、ｎ－ブチルビニルエーテル、イソブチルビニルエーテル、アリルグリシジルエーテル等のビニルエーテル；マレイミド、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド等の不飽和イミド類；インデン、１－メチルインデン等のインデン類；１，３－ブタジエン、イソプレン、クロロプレン等の脂肪族共役ジエン類；ポリスチレン、ポリメチル（メタ）アクリレート、ポリ－ｎ－ブチル（メタ）アクリレート、ポリシロキサン等の重合体分子鎖の末端にモノ（メタ）アクリロイル基を有するマクロモノマー類；ビニルクロリド、ビニリデンクロリド、ジビニルスクシナート、ジアリルフタラート、トリアリルホスファート、トリアリルイソシアヌラート、ビニルチオエーテル、ビニルイミダゾール、ビニルオキサゾリン、ビニルカルバゾール、ビニルピロリドン、ビニルピリジン、水酸基含有ビニルモノマー及びポリイソシアネート化合物のビニルウレタン化合物、水酸基含有ビニルモノマー及びポリエポキシ化合物のビニルエポキシ化合物が挙げられる。
　上記エチレン性不飽和化合物（Ｄ）は、単独で又は２種以上を混合して使用することができる。 <Ethylenically unsaturated compound (D)>
The ethylenically unsaturated compound (D) used in the present invention is a compound having an ethylenically unsaturated bond and not the urethane (meth) acrylate compound (A) and the alkali developable compound (C). . Examples of the ethylenically unsaturated compound (D) include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene; (meth) acrylic acid, α -Chloracrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, monosuccinic acid [2- (meth) Acryloyloxyethyl], mono [2- (meth) acryloyloxyethyl] phthalate, ω-carboxypolycaprolactone mono (meth) acrylate, and other polymer mono (meth) acrylates having a carboxy group and a hydroxyl group at both ends Hydroxyethyl (meth) acrylate malate, hydroxy Unsaturated polybasic acids such as propyl (meth) acrylate malate, dicyclopentadiene malate or polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups; (meth) acrylic 2-hydroxyethyl acid, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, acrylic compound No. 1-No. 4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meta ) Ethylhexyl acrylate, (meth) acrylic acid Noxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol te Unsaturated monobasic acids such as la (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate, polyester (meth) acrylate oligomers and the like Esters of polyhydric alcohols or polyphenols; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydro Phthalic anhydride-maleic anhydride Acid anhydrides of unsaturated polybasic acids such as in-acid adducts, dodecenyl succinic anhydride, methyl hymic anhydride; (meth) acrylamide, methylene bis- (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyvalent amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanide Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinyl Unsaturated aromatic compounds such as phenol, vinyl sulfonic acid, 4-vinyl benzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allylamine, N-vinyl pyrrolidone, vinyl piperidine Unsaturated vinyl compounds such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; maleimide, N-phenylmaleimide, N- Unsaturated imides such as cyclohexylmaleimide; indenes such as indene and 1-methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Macromonomers having a mono (meth) acryloyl group at the end of a polymer molecular chain such as styrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane, etc .; vinyl chloride, vinylidene chloride, divinyl succi Narate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomer and polyisocyanate compound vinyl urethane compound, hydroxyl group content The vinyl epoxy compound of a vinyl monomer and a polyepoxy compound is mentioned.
The said ethylenically unsaturated compound (D) can be used individually or in mixture of 2 or more types.
　上記エチレン性不飽和化合物としては、市販品を用いることもできる。該市販品としては、例えば、カヤラッドＤＰＨＡ、ＤＰＥＡ－１２、ＰＥＧ４００ＤＡ、ＴＨＥ－３３０、ＲＰ－１０４０、ＮＰＧＤＡ、ＰＥＴ３０、Ｒ－６８４（以上、日本化薬製）；アロニックスＭ－２１５、Ｍ－３５０（以上、東亞合成製）；ＮＫエステルＡ－ＤＰＨ、Ａ－ＴＭＰＴ、Ａ－ＤＣＰ、Ａ－ＨＤ－Ｎ、ＴＭＰＴ、ＤＣＰ、ＮＰＧ及びＨＤ－Ｎ（以上、新中村化学工業製）；ＳＰＣ－１０００、ＳＰＣ－３０００（以上、昭和電工社製）；等が挙げられる。 Commercially available products can be used as the ethylenically unsaturated compound. Examples of the commercially available products include Kayrad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30, R-684 (above, Nippon Kayaku); Aronix M-215, M-350 ( ND ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG and HD-N (above, Shin-Nakamura Chemical Co., Ltd.); SPC-1000, SPC-3000 (manufactured by Showa Denko KK);
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
　本発明の重合性組成物において、エチレン性不飽和化合物（Ｄ）の含有量は、特に限定されるものではないが、ウレタン（メタ）アクリレート化合物（Ａ）、着色剤（Ｂ）、アルカリ現像性化合物（Ｃ）、エチレン性不飽和化合物（Ｄ）及び重合開始剤（Ｅ）の合計１００質量部に対して、好ましくは、５～７０質量部、より好ましくは、１０～５０質量部であり、更に好ましくは、１０～３０質量部である。エチレン性不飽和化合物（Ｄ）の含有量が、上記の範囲内である場合、得られる硬化物が硬化性及び遮光性に優れることから好ましい。
　例えば厚さ１～３μｍの硬化膜を形成する場合には、エチレン性不飽和化合物（Ｄ）の含有量は、特に限定されるものではないが、ウレタン（メタ）アクリレート化合物（Ａ）、着色剤（Ｂ）、アルカリ現像性化合物（Ｃ）、エチレン性不飽和化合物（Ｄ）及び重合開始剤（Ｅ）の合計１００質量部に対して、エチレン性不飽和化合物（Ｄ）好ましくは、１０～７０質量部、より好ましくは、３０～６０質量部であり、更に好ましくは、３０～５０質量部である。 In the polymerizable composition of the present invention, the content of the ethylenically unsaturated compound (D) is not particularly limited, but the urethane (meth) acrylate compound (A), the colorant (B), and alkali developability. The total amount of the compound (C), the ethylenically unsaturated compound (D) and the polymerization initiator (E) is preferably 100 to 50 parts by mass, more preferably 10 to 50 parts by mass, More preferably, it is 10 to 30 parts by mass. When content of an ethylenically unsaturated compound (D) exists in said range, since the hardened | cured material obtained is excellent in sclerosis | hardenability and light-shielding property, it is preferable.
For example, when a cured film having a thickness of 1 to 3 μm is formed, the content of the ethylenically unsaturated compound (D) is not particularly limited, but the urethane (meth) acrylate compound (A), the colorant (B), the alkali-developable compound (C), the ethylenically unsaturated compound (D), and the polymerization initiator (E) in total 100 parts by mass, the ethylenically unsaturated compound (D) is preferably 10 to 70. It is 30 parts by mass, more preferably 30-60 parts by mass, and still more preferably 30-50 parts by mass.
　＜重合開始剤（Ｅ）＞
　本発明の重合性組成物に用いられる重合開始剤（Ｅ）としては、従来既知のラジカル重合開始剤を用いることが可能である。 <Polymerization initiator (E)>
As the polymerization initiator (E) used in the polymerizable composition of the present invention, a conventionally known radical polymerization initiator can be used.
　上記ラジカル重合開始剤とは、光ラジカル重合開始剤と熱ラジカル重合開始剤である。反応性が高いことから光ラジカル重合開始剤がより好ましい。 The radical polymerization initiator is a photo radical polymerization initiator and a thermal radical polymerization initiator. A radical photopolymerization initiator is more preferred because of its high reactivity.
　光ラジカル重合開始剤としては、光照射によりラジカルを発生するものであれば特に制限されず従来既知の化合物を用いることが可能であり、例えば、アセトフェノン系化合物、ベンジル系化合物、ベンゾフェノン系化合物、チオキサントン系化合物及びオキシムエステル系化合物等を好ましいものとして例示することができる。 The radical photopolymerization initiator is not particularly limited as long as it generates radicals by light irradiation, and a conventionally known compound can be used. For example, acetophenone compounds, benzyl compounds, benzophenone compounds, thioxanthone Examples of preferred compounds include oxime compounds and oxime ester compounds.
　アセトフェノン系化合物としては例えば、ジエトキシアセトフェノン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、４’－イソプロピル－２－ヒドロキシ－２－メチルプロピオフェノン、２－ヒドロキシメチル－２－メチルプロピオフェノン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、ｐ－ジメチルアミノアセトフェノン、ｐ－ターシャリブチルジクロロアセトフェノン、ｐ－ターシャリブチルトリクロロアセトフェノン、ｐ－アジドベンザルアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパノン－１、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾイン－ｎ－ブチルエーテル、ベンゾインイソブチルエーテル及び１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン等が挙げられる。 Examples of acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, and 2-hydroxymethyl-2. -Methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tertiarybutyldichloroacetophenone, p-tertiarybutyltrichloroacetophenone, p-azidobenzal Acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1, benzo , Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane -1-one and the like.
　ベンジル系化合物としては、ベンジル等が挙げられる。 Examples of the benzyl compound include benzyl.
　ベンゾフェノン系化合物としては、例えば、ベンゾフェノン、ｏ－ベンゾイル安息香酸メチル、ミヒラーケトン、４，４’－ビスジエチルアミノベンゾフェノン、４，４’－ジクロロベンゾフェノン及び４－ベンゾイル－４’－メチルジフェニルスルフィド等が挙げられる。 Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone and 4-benzoyl-4′-methyldiphenyl sulfide. .
　チオキサントン系化合物としては、チオキサントン、２－メチルチオキサントン、２－エチルチオキサントン、２－クロロチオキサントン、２－イソプロピルチオキサントン、２，４－ジエチルチオキサントン等が挙げられる。 Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.
　オキシムエステル系化合物とは、上記一般式（ＩＩ）で表される基を有する化合物を意味し、上記光ラジカル重合開始剤の中でも感度が良好であることから、本発明の重合性組成物に好ましく使用することができる。 The oxime ester-based compound means a compound having a group represented by the above general formula (II), and is preferable for the polymerizable composition of the present invention because of its good sensitivity among the above radical photopolymerization initiators. Can be used.
　上記一般式（ＩＩ）中のＲ４１～Ｒ４３で表される炭素原子数１～２０の炭化水素基は、それぞれＲ１～Ｒ３８表される炭素原子数１～２０の炭化水素基と同様である。 The hydrocarbon group having 1 to 20 carbon atoms represented by R 41 to R 43 in the general formula (II) is the same as the hydrocarbon group having 1 to 20 carbon atoms represented by R 1 to R 38 , respectively. It is.
　上記一般式（ＩＩ）中のＲ４１及びＲ４２並びにＲ４１又はＲ４２で表される基を修飾する場合がある複素環を含有する炭素原子数２～２０の基は、Ｒ１０～Ｒ３８で表される複素環を含有する炭素原子数２～２０の基と同様である。 The group having 2 to 20 carbon atoms containing a heterocyclic ring that may modify the group represented by R 41 and R 42 and R 41 or R 42 in the general formula (II) is R 10 to R 38. And a group having 2 to 20 carbon atoms containing a heterocyclic ring represented by
　上記一般式（ＩＩ）で表される基を有する化合物の中でも下記一般式（ＩＩＩ）で表される化合物は、特に感度が高いことから、本発明の重合性組成物に用いることが好ましい。 Among the compounds having the group represented by the above general formula (II), the compound represented by the following general formula (III) is preferably used in the polymerizable composition of the present invention because of its particularly high sensitivity.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
（式中、Ｒ４１、Ｒ４２及びｍは、それぞれ一般式（ＩＩ）におけるＲ４１、Ｒ４２及びｍと同一であり、
　Ｒ５１及びＲ５２は、それぞれ独立に、直接結合、水素原子、シアノ基、炭素原子数１～２０の炭化水素基又は複素環を含有する炭素原子数２～２０の基を表し、
　Ｘ１は、酸素原子、硫黄原子、セレン原子、ＣＲ５３Ｒ５４、ＣＯ、ＮＲ５５又はＰＲ５６を表し、
　Ｒ５３～Ｒ５６は、それぞれ独立に、水素原子、炭素原子数１～２０の炭化水素基又は複素環を含有する炭素原子数２～２０の基を表し、Ｒ５３～Ｒ５６で表される基中の水素原子は、ハロゲン原子、ニトロ基、シアン基、水酸基、カルボキシル基又は複素環を含有する炭素原子数２～２０の基で置換される場合もあり、
　Ｒ５１～Ｒ５６で表される基中のメチレン基は、酸素が隣り合わない条件で－Ｏ－に置換される場合もあり、
　Ｒ５１～Ｒ５６は、それぞれ独立に、隣接するどちらかのベンゼン環と一緒になって環を形成する場合もあり、
　ｇは、０～５の数を表し、
　ｈは、０～４の数を表す。） (Wherein, R 41, R 42 and m are the same as R 41, R 42 and m, respectively, in formula (II),
R 51 and R 52 each independently represent a direct bond, a hydrogen atom, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring,
X 1 represents an oxygen atom, a sulfur atom, a selenium atom, CR 53 R 54 , CO, NR 55 or PR 56 ,
R 53 to R 56 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring, and represented by R 53 to R 56. The hydrogen atom in the group may be substituted with a group having 2 to 20 carbon atoms containing a halogen atom, a nitro group, a cyan group, a hydroxyl group, a carboxyl group or a heterocyclic ring,
The methylene group in the group represented by R 51 to R 56 may be substituted with —O— under the condition that oxygen is not adjacent.
R 51 to R 56 may each independently form a ring together with one of the adjacent benzene rings,
g represents a number from 0 to 5;
h represents a number from 0 to 4. )
　上記一般式（ＩＩＩ）中のＲ５１～Ｒ５６で表される炭素原子数１～２０の炭化水素基は、それぞれＲ１～Ｒ３８で表される炭素原子数１～２０の炭化水素基と同様である。 The hydrocarbon group having 1 to 20 carbon atoms represented by R 51 to R 56 in the general formula (III) is a hydrocarbon group having 1 to 20 carbon atoms represented by R 1 to R 38 , respectively. It is the same.
　上記一般式（ＩＩＩ）中のＲ５１～Ｒ５６で表される、複素環を含有する炭素原子数２～２０の基は、Ｒ１０～Ｒ３８で表される、複素環を含有する炭素原子数２～２０の基と同様である。 The group having 2 to 20 carbon atoms containing a heterocyclic ring represented by R 51 to R 56 in the general formula (III) is a carbon atom containing a heterocyclic ring represented by R 10 to R 38. This is the same as the group of formula 2-20.
　また、本発明においては、重合開始剤（Ｅ）として下記の一般式（ＩＶ）で表される化合物を用いることが、感度が良く、現像後のパターンの基材への密着性に優れ、更に低液晶汚染性が向上することから好ましい。 In the present invention, the use of a compound represented by the following general formula (IV) as the polymerization initiator (E) is highly sensitive and has excellent adhesion to the substrate of the pattern after development. This is preferable because low liquid crystal contamination is improved.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
（Ｒ５１ａ及びＲ５２ａは、それぞれ独立に、水素原子、シアノ基、炭素原子数１～２０の炭化水素基又は複素環を含有する炭素原子数２～２０の基を表し、
　Ｒａは、ＣＲａ１Ｒａ２Ｒａ３を表し、
　Ｒａ１、Ｒａ２及びＲａ３は、それぞれ独立に、水素原子、水酸基、アミノ基、炭素原子数１～２０の炭化水素基又は複素環を含有する炭素原子数２～２０の基、を表し、
　Ｘ１ａは、酸素原子、硫黄原子、セレン原子、ＣＲ５３ａＲ５４ａ、ＣＯ、ＮＲ５５ａ又はＰＲ５６ａを表し、
　Ｒ５３ａ～Ｒ５６ａは、それぞれ独立に、水素原子、炭素原子数１～２０の炭化水素基又は複素環を含有する炭素原子数２～２０の基を表し、
　Ｒａ１～Ｒａ３及びＲ５３ａ～Ｒ５６ａで表される基中の水素原子は、ハロゲン原子、ニトロ基、シアン基、水酸基、カルボキシル基又は複素環を含有する炭素原子数２～２０の基で置換される場合もあり、
　Ｒａ１～Ｒａ３及びＲ５１ａ～Ｒ５６ａで表される基中のメチレン基は、酸素が隣り合わない条件で－Ｏ－に置換される場合もあり、
　Ｒ５１ａ～Ｒ５６ａは、それぞれ独立に、隣接するどちらかのベンゼン環と一緒になって環を形成する場合もあり、
　ｇ１は、０～５の数を表し、
　ｈ１は、０～４の数を表す。） (R 51a and R 52a each independently represents a hydrogen atom, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring,
R a represents CR a1 R a2 R a3 ,
R a1 , R a2 and R a3 each independently represent a hydrogen atom, a hydroxyl group, an amino group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring,
X 1a represents an oxygen atom, a sulfur atom, a selenium atom, CR 53a R 54a , CO, NR 55a or PR 56a ,
R 53a to R 56a each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring,
The hydrogen atom in the group represented by R a1 to R a3 and R 53a to R 56a is a group having 2 to 20 carbon atoms containing a halogen atom, nitro group, cyan group, hydroxyl group, carboxyl group or heterocyclic ring. May be replaced,
The methylene group in the groups represented by R a1 to R a3 and R 51a to R 56a may be substituted with —O— under the condition that oxygen is not adjacent to each other.
R 51a to R 56a may each independently form a ring together with one of the adjacent benzene rings,
g1 represents a number from 0 to 5;
h1 represents a number from 0 to 4. )
　上記一般式（ＩＶ）中のＲａ１～Ｒａ３及びＲ５１～Ｒ５６で表される炭素原子数１～２０の炭化水素基は、それぞれＲ１～Ｒ３８で表される炭素原子数１～２０の炭化水素基と同様である。 In the general formula (IV), the hydrocarbon group having 1 to 20 carbon atoms represented by R a1 to R a3 and R 51 to R 56 is represented by 1 to C carbon atoms represented by R 1 to R 38 , respectively. The same as 20 hydrocarbon groups.
　上記一般式（ＩＶ）中のＲａ１～Ｒａ３及びＲ５１～Ｒ５６で表される、複素環を含有する炭素原子数２～２０の基は、Ｒ１０～Ｒ３８で表される、複素環を含有する炭素原子数２～２０の基と同様である。 The group having 2 to 20 carbon atoms containing a heterocyclic ring represented by R a1 to R a3 and R 51 to R 56 in the general formula (IV) is a complex represented by R 10 to R 38. This is the same as the group having 2 to 20 carbon atoms containing a ring.
　好ましい重合開始剤（Ｅ）としては、例えば下記に示す化合物Ｎｏ．Ｅ１～Ｎｏ．Ｅ１５が挙げられ、上記一般式（ＩＩＩ）で表される化合物としては、例えば下記に示す化合物Ｎｏ．Ｅ１及びＮｏ．Ｅ３～Ｎｏ．Ｅ１５が挙げられる。上記一般式（ＩＶ）で表される化合物としては、例えば下記に示す化合物Ｎｏ．Ｅ２が挙げられる。但し、本発明で用いられる重合開始剤（Ｅ）は以下の化合物により何ら制限を受けるものではない。 Preferred examples of the polymerization initiator (E) include compound Nos. Shown below. E1-No. E15 is exemplified, and examples of the compound represented by the general formula (III) include the compound No. 1 shown below. E1 and No. E3-No. E15 may be mentioned. Examples of the compound represented by the general formula (IV) include compound No. 1 shown below. E2. However, the polymerization initiator (E) used in the present invention is not limited by the following compounds.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　その他のラジカル重合開始剤としては、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド等のホスフィンオキサイド系化合物及びビス（シクロペンタジエニル）－ビス［２，６－ジフルオロ－３－（ピル－１－イル）］チタニウム等のチタノセン系化合物等が挙げられる。 Other radical polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pill-1). -Yl)] titacene compounds such as titanium.
　市販のラジカル開始剤としては、アデカオプトマーＮ－１４１４、Ｎ－１７１７、Ｎ－１９１９、アデカアークルズＮＣＩ－８３１、ＮＣＩ－９３０（以上、ＡＤＥＫＡ製）；ＩＲＧＡＣＵＲＥ１８４、ＩＲＧＡＣＵＲＥ３６９、ＩＲＧＡＣＵＲＥ６５１、ＩＲＧＡＣＵＲＥ９０７、ＩＲＧＡＣＵＲＥ　ＯＸＥ　０１、ＩＲＧＡＣＵＲＥ　ＯＸＥ　０２、ＩＲＧＡＣＵＲＥ７８４（以上、ＢＡＳＦ製）；ＴＲ－ＰＢＧ－３０４、ＴＲ－ＰＢＧ－３０５、ＴＲ－ＰＢＧ－３０９及びＴＲ－ＰＢＧ－３１４（以上、Ｔｒｏｎｌｙ製）；等が挙げられる。 Commercially available radical initiators include Adekaoptomer N-1414, N-1717, N-1919, Adeka Arcles NCI-831, NCI-930 (manufactured by ADEKA); IRGACURE 184, IRGACURE 369, IRGACURE 651, IRGACURE 907, IRGACURE OX 01, IRGACURE OXE02, IRGACURE784 (above, manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309, and TR-PBG-314 (above, manufactured by Troly);
　熱ラジカル重合開始剤としては、加熱によりラジカルを発生するものであれば特に制限されず従来既知の化合物を用いることが可能であり、例えば、アゾ系化合物、過酸化物及び過硫酸塩等を好ましいものとして例示することができる。 The thermal radical polymerization initiator is not particularly limited as long as it generates radicals by heating, and conventionally known compounds can be used. For example, azo compounds, peroxides and persulfates are preferable. It can be illustrated as a thing.
　アゾ系化合物としては、２，２′－アゾビスイソブチロニトリル、２，２′－アゾビス（メチルイソブチレ－ト）、２，２’－アゾビス－２，４－ジメチルバレロニトリル、１，１’－アゾビス（１－アセトキシ－１－フェニルエタン）等が挙げられる。 Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'- And azobis (1-acetoxy-1-phenylethane).
　過酸化物としては、ベンゾイルパーオキサイド、ジ－ｔ－ブチルベンゾイルパーオキサイド、ｔ－ブチルパーオキシピバレート及びジ（４－ｔ－ブチルシクロヘキシル）パーオキシジカーボネート等が挙げられる。 Examples of the peroxide include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butyl peroxypivalate, and di (4-t-butylcyclohexyl) peroxydicarbonate.
　過硫酸塩としては、過硫酸アンモニウム、過硫酸ナトリウム及び過硫酸カリウム等の過硫酸塩等が挙げられる。 Examples of persulfates include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate.
　上記重合開始剤（Ｅ）の中でも水酸基を有する重合開始剤は、液晶汚染性が低く、電気特性の優れるディスプレイ表示装置を提供できることから特に好ましい。 Among the polymerization initiators (E), a polymerization initiator having a hydroxyl group is particularly preferable because it can provide a display device having low liquid crystal contamination and excellent electrical characteristics.
　上記重合開始剤（Ｅ）の中でも、一般式（ＩＩ）においてＲ４１が炭素原子数１～１０のアルキル基又は炭素原子数４～１０のシクロアルキル基であることが好ましい。
　また、上記重合開始剤（Ｅ）の中でも、一般式（ＩＩ）においてＲ４２が炭素原子数１～１０のアルキル基又は炭素原子数６～１０のアリール基であることが好ましい。 Among the polymerization initiators (E), R 41 in the general formula (II) is preferably an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 10 carbon atoms.
Among the polymerization initiators (E), R 42 in the general formula (II) is preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.
　上記重合開始剤（Ｅ）の中でも、上記一般式（ＩＩＩ）において、Ｘ１が硫黄原子であることが好ましい。
　また、上記重合開始剤（Ｅ）の中でも、上記一般式（ＩＩＩ）において、ｇが１であり、且つＲ５１が炭素数１～１０のアルキル基であることが好ましい。該アルキル基の末端水素原子が水酸基で置換されていることが好ましく、該アルキル基中のメチレン基が－Ｏ－に置換されていることも好ましい。 Among the polymerization initiators (E), in the general formula (III), X 1 is preferably a sulfur atom.
Among the polymerization initiators (E), in the general formula (III), g is preferably 1 and R 51 is preferably an alkyl group having 1 to 10 carbon atoms. The terminal hydrogen atom of the alkyl group is preferably substituted with a hydroxyl group, and the methylene group in the alkyl group is preferably substituted with —O—.
　上記重合開始剤（Ｅ）の中でも、上記一般式（ＩＶ）において、Ｘ１ａが硫黄原子であることが好ましい。
　また、上記重合開始剤（Ｅ）の中でも、上記一般式（ＩＶ）において、ｇ１が１であり、且つＲ５１ａが炭素数１～１０のアルキル基であることが好ましい。該アルキル基の末端水素原子が水酸基で置換されていることが好ましく、該アルキル基中のメチレン基が－Ｏ－に置換されていることも好ましい。
　また、上記重合開始剤（Ｅ）の中でも、上記一般式（ＩＶ）において、Ｒａ１～Ｒａ３の少なくとも一つが、複素環を含有する炭素原子数２～２０の基であることが好ましい。
　また、上記重合開始剤（Ｅ）の中でも、上記一般式（ＩＶ）において、Ｒａ１～Ｒａ３の少なくとも一つが、炭素数１～１０のアルキル基であることが好ましい。
　更に、上記重合開始剤（Ｅ）の中でも、上記一般式（ＩＶ）において、Ｒａ１が、複素環を含有する炭素原子数２～２０の基であり、Ｒａ２及びＲａ３が、それぞれ独立に、炭素数１～１０のアルキル基であることが好ましい。 Among the polymerization initiators (E), in the general formula (IV), X 1a is preferably a sulfur atom.
Among the polymerization initiators (E), in the general formula (IV), g1 is preferably 1, and R 51a is preferably an alkyl group having 1 to 10 carbon atoms. The terminal hydrogen atom of the alkyl group is preferably substituted with a hydroxyl group, and the methylene group in the alkyl group is preferably substituted with —O—.
Among the polymerization initiators (E), in the general formula (IV), at least one of R a1 to R a3 is preferably a group having 2 to 20 carbon atoms containing a heterocyclic ring.
Among the polymerization initiators (E), in the general formula (IV), at least one of R a1 to R a3 is preferably an alkyl group having 1 to 10 carbon atoms.
Further, among the polymerization initiators (E), in the general formula (IV), R a1 is a group having 2 to 20 carbon atoms containing a heterocyclic ring, and R a2 and R a3 are each independently An alkyl group having 1 to 10 carbon atoms is preferable.
　上記重合開始剤（Ｅ）は、これまでに例示した一種又は２種以上を混合して用いることができる。 The polymerization initiator (E) can be used alone or in combination of two or more kinds exemplified above.
　本発明の重合性組成物において、上記重合開始剤（Ｅ）の含有量は、特に限定されるものではないが、ウレタン（メタ）アクリレート化合物（Ａ）、着色剤（Ｂ）、アルカリ現像性化合物（Ｃ）、エチレン性不飽和化合物（Ｄ）及び重合開始剤（Ｅ）の合計１００質量部に対して、硬化性が良好なことから好ましくは０．３～２０質量部、より好ましくは０．５～１０質量部、より好ましくは３～８質量部である。重合性化合物（Ｂ）の含有量が、上記の範囲内の場合、硬化性が良好で重合開始剤の析出を伴わない保存安定性に優れる重合性組成物が得られるので好ましい。
　例えば厚さ２～５μｍの硬化膜を形成する場合には、重合開始剤（Ｅ）の含有量は、特に限定されるものではないが、ウレタン（メタ）アクリレート化合物（Ａ）、着色剤（Ｂ）、アルカリ現像性化合物（Ｃ）、エチレン性不飽和化合物（Ｄ）及び重合開始剤（Ｅ）の合計１００質量部に対して、好ましくは０．３～２０質量部、より好ましくは０．５～１０質量部、より好ましくは３～８質量部である。 In the polymerizable composition of the present invention, the content of the polymerization initiator (E) is not particularly limited, but the urethane (meth) acrylate compound (A), the colorant (B), and the alkali developable compound. The total curability of (C), ethylenically unsaturated compound (D) and polymerization initiator (E) is preferably from 0.3 to 20 parts by mass, more preferably from 0. 5 to 10 parts by mass, more preferably 3 to 8 parts by mass. When the content of the polymerizable compound (B) is in the above range, it is preferable because a polymerizable composition having good curability and excellent storage stability without precipitation of a polymerization initiator is obtained.
For example, when a cured film having a thickness of 2 to 5 μm is formed, the content of the polymerization initiator (E) is not particularly limited, but the urethane (meth) acrylate compound (A), the colorant (B ), Alkali developable compound (C), ethylenically unsaturated compound (D), and polymerization initiator (E) in a total of 100 parts by mass, preferably 0.3 to 20 parts by mass, more preferably 0.5. -10 parts by mass, more preferably 3-8 parts by mass.
　本発明の重合性組成物には、更に溶剤を加えることができる。該溶剤としては、通常、必要に応じて上記の各成分（ウレタン（メタ）アクリレート化合物（Ａ）、着色剤（Ｂ）、アルカリ現像性化合物（Ｃ）、エチレン性不飽和化合物（Ｄ）及び重合開始剤（Ｅ）等）を溶解又は分散しえる溶剤を用いることができる。例えば、メチルエチルケトン、メチルアミルケトン、ジエチルケトン、アセトン、メチルイソプロピルケトン、メチルイソブチルケトン、シクロヘキサノン及び２－ヘプタノン等のケトン類；エチルエーテル、ジオキサン、テトラヒドロフラン、１，２－ジメトキシエタン、１，２－ジエトキシエタン及びジプロピレングリコールジメチルエーテル等のエーテル系溶剤；酢酸メチル、酢酸エチル、酢酸－ｎ－プロピル、酢酸イソプロピル、酢酸ｎ－ブチル、酢酸シクロヘキシル、乳酸エチル、コハク酸ジメチル及びテキサノール等のエステル系溶剤；エチレングリコールモノメチルエーテル及びエチレングリコールモノエチルエーテル等のセロソルブ系溶剤；メタノール、エタノール、イソ－又はｎ－プロパノール、イソ－又はｎ－ブタノール及びアミルアルコール等のアルコール系溶剤；エチレングリコールモノメチルアセテート、エチレングリコールモノエチルアセテート、プロピレングリコール－１－モノメチルエーテル（ＰＧＭ）、プロピレングリコール－１－モノメチルエーテル－２－アセテート（ＰＧＭＥＡ）、ジプロピレングリコールモノメチルエーテルアセテート、３－メトキシブチルアセテート及びエトキシエチルプロピオネート等のエーテルエステル系溶剤；ベンゼン、トルエン及びキシレン等のＢＴＸ系溶剤；ヘキサン、ヘプタン、オクタン及びシクロヘキサン等の脂肪族炭化水素系溶剤；テレピン油、Ｄ－リモネン及びピネン等のテルペン系炭化水素油；ミネラルスピリット、スワゾール＃３１０（以上、コスモ松山石油製）；及びソルベッソ＃１００（以上、エクソン化学製）；等のパラフィン系溶剤；四塩化炭素、クロロホルム、トリクロロエチレン、塩化メチレン及び１，２－ジクロロエタン等のハロゲン化脂肪族炭化水素系溶剤；クロロベンゼン等のハロゲン化芳香族炭化水素系溶剤；カルビトール系溶剤、アニリン、トリエチルアミン、ピリジン、酢酸、アセトニトリル、二硫化炭素、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドン、ジメチルスルホキシド及び水等が挙げられ、これらの溶剤は１種又は２種以上の混合溶剤として使用することができる。これらの中でもケトン類及びエーテルエステル系溶剤等、特にＰＧＭＥＡ及びシクロヘキサノン等が、重合性組成物においてレジストと重合開始剤の相溶性がよいので好ましい。 A solvent can be further added to the polymerizable composition of the present invention. As the solvent, the above components (urethane (meth) acrylate compound (A), colorant (B), alkali-developable compound (C), ethylenically unsaturated compound (D) and polymerization are usually used as necessary. A solvent capable of dissolving or dispersing the initiator (E) and the like can be used. For example, ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-di Ether solvents such as ethoxyethane and dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate and texanol; Cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol, ethanol, iso- or n-propanol, iso- or n-butanol And alcohol solvents such as amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether (PGM), propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl Ether ester solvents such as ether acetate, 3-methoxybutyl acetate and ethoxyethyl propionate; BTX solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpene hydrocarbon oils such as D-limonene and pinene; mineral spirit, Swazol # 310 (above, manufactured by Cosmo Matsuyama Oil); and Solvesso # 100 ( Paraffinic solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1,2-dichloroethane; halogenated aromatic hydrocarbons such as chlorobenzene Solvents: carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water, etc. These solvents can be used as one or two or more mixed solvents. Among these, ketones and ether ester solvents, etc., particularly PGMEA and cyclohexanone are preferable because the compatibility of the resist and the polymerization initiator is good in the polymerizable composition.
　本発明の重合性組成物において、上記溶剤の含有量は、特に限定されるものではないが、重合性組成物全量１００質量％中３０～９５質量％になることが好ましく、より好ましくは、５０～９５質量％である。
　溶剤の含有量が上記範囲の場合、ハンドリング性（重合性組成物の粘度や濡れ性）、乾燥時のムラの低減及び液安定性（組成物に含まれる成分の析出や沈降を伴わない）に優れる重合性組成物となり、硬化物を得る際に硬化物の厚さを適切にコントロールできることから好ましい。 In the polymerizable composition of the present invention, the content of the solvent is not particularly limited, but is preferably 30 to 95% by mass, more preferably 50% in 100% by mass of the total polymerizable composition. ~ 95% by mass.
When the content of the solvent is in the above range, handling properties (viscosity and wettability of the polymerizable composition), reduction of unevenness during drying, and liquid stability (without precipitation or sedimentation of components contained in the composition) It is preferable because it becomes an excellent polymerizable composition, and the thickness of the cured product can be appropriately controlled when a cured product is obtained.
　本発明の重合性組成物には、必要に応じて、更にエポキシ化合物、アルカリ現像性付与剤、分散剤、潜在性添加剤、有機重合体、無機化合物、カップリング剤、連鎖移動剤、増感剤、界面活性剤及びメラミン化合物、ｐ－アニソール、ハイドロキノン、ピロカテコール、ｔ－ブチルカテコール及びフェノチアジン等の熱重合抑制剤；可塑剤；接着促進剤；充填剤；消泡剤；レベリング剤；表面調整剤；酸化防止剤；紫外線吸収剤；分散助剤；凝集防止剤；触媒；効果促進剤；架橋剤；増粘剤等の慣用の添加物を加えることができる。 If necessary, the polymerizable composition of the present invention may further contain an epoxy compound, an alkali developability imparting agent, a dispersant, a latent additive, an organic polymer, an inorganic compound, a coupling agent, a chain transfer agent, and a sensitization. Agents, surfactants and melamine compounds, p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine and other thermal polymerization inhibitors; plasticizers; adhesion promoters; fillers; antifoaming agents; leveling agents; Conventional additives such as an agent, an antioxidant, an ultraviolet absorber, a dispersion aid, an aggregation inhibitor, a catalyst, an effect accelerator, a cross-linking agent, and a thickener can be added.
　上記エポキシ化合物としては、例えば、メチルグリシジルエーテル、２－エチルヘキシルグリシジルエーテル、ブチルグリシジルエーテル、デシルグリシジルエーテル、Ｃ１２～１３混合アルキルグリシジルエーテル、フェニル－２－メチルグリシジルエーテル、セチルグリシジルエーテル、ステアリルグリシジルエーテル、グリシジルメタクリレート、イソプロピルグリシジルエーテル、アリルグリシジルエーテル、エチルグリシジルエーテル、２－メチルオクチルグリシジルエーテル、フェニルグリシジルエーテル、４－ｎ－ブチルフェニルグリシジルエーテル、４－フェニルフェノールグリシジルエーテル、クレジルグリシジルエーテル、ジブロモクレジルグリシジルエーテル、デシルグリシジルエーテル、メトキシポリエチレングリコールモノグリシジルエーテル、エトキシポリエチレングリコールモノグリシジルエーテル、ブトキシポリエチレングリコールモノグリシジルエーテル、フェノキシポリエチレングリコールモノグリシジルエーテル、ジブロモフェニル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、１，５－ペン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、１，１，２，２－テトラキス（グリシジルオキシフェニル）エタン及びペンタエリスリトールテトラグリシジルエーテル等のグリシジルエーテル化物；グリシジルアセテート、グリシジルステアレート等のグリシジルエステル類;２－（３，４－エポキシシクロヘキシル－５，５－スピロ－３，４－エポキシ）シクロヘキサン－メタジオキサン、メチレンビス（３，４－エポキシシクロヘキサン）、プロパン－２，２－ジイル－ビス（３，４－エポキシシクロヘキサン）、２，２－ビス（３，４－エポキシシクロヘキシル）プロパン、エチレンビス（３，４－エポキシシクロヘキサンカルボキシレート）、ビス（３，４－エポキシシクロヘキシルメチル）アジペート、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、３，４－エポキシ－１－メチルシクロヘキシル　３，４－エポキシ－１－メチルヘキサンカルボキシレート、６－メチル－３，４－エポキシシクロヘキシルメチル　６－メチル－３，４－エポキシシクロヘキサンカルボキシレート、３，４－エポキシ－３－メチルシクロヘキシルメチル　３，４－エポキシ－３－メチルシクロヘキサンカルボキシレート、３，４－エポキシ－５－メチルシクロヘキシルメチル　３，４－エポキシ－５－メチルシクロヘキサンカルボキシレート、１－エポキシエチル－３，４－エポキシシクロヘキサン、１，２－エポキシ－２－エポキシエチルシクロヘキサン、ジシクロペンタジエンジエポキサイド、３，４－エポキシ－６－メチルシクロヘキシルカルボキシレート、α－ピネンオキシド、スチレンオキシド、シクロヘキセンオキサイド及びシクロペンテンオキサイド等のエポキシシクロアルキル型化合物及びＮ－グリシジルフタルイミド等が挙げられる。 Examples of the epoxy compound include methyl glycidyl ether, 2-ethylhexyl glycidyl ether, butyl glycidyl ether, decyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, phenyl-2-methyl glycidyl ether, cetyl glycidyl ether, stearyl glycidyl ether, Glycidyl methacrylate, isopropyl glycidyl ether, allyl glycidyl ether, ethyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, 4-n-butylphenyl glycidyl ether, 4-phenylphenol glycidyl ether, cresyl glycidyl ether, dibromocresyl ether Glycidyl ether, decyl glycidyl ether, methoxypolyethylene group Cole monoglycidyl ether, ethoxy polyethylene glycol monoglycidyl ether, butoxy polyethylene glycol monoglycidyl ether, phenoxy polyethylene glycol monoglycidyl ether, dibromophenyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,1,2,2-tetrakis (glycidyloxyphenyl) ethane, and pentaerythritol tetraglycidyl ether; glycidyl acetate, glycidyl stearate Glycidyl esters such as citrate; 2- (3,4-epoxycyclohexyl-5,5-spi -3,4-epoxy) cyclohexane-metadioxane, methylenebis (3,4-epoxycyclohexane), propane-2,2-diyl-bis (3,4-epoxycyclohexane), 2,2-bis (3,4 Epoxycyclohexyl) propane, ethylenebis (3,4-epoxycyclohexanecarboxylate), bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4- Epoxy-1-methylcyclohexyl, 3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl, 6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3 -Methyl Chlohexylmethyl 3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl 3,4-epoxy-5-methylcyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxy Epoxycyclohexane such as cyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, dicyclopentadiene diepoxide, 3,4-epoxy-6-methylcyclohexylcarboxylate, α-pinene oxide, styrene oxide, cyclohexene oxide and cyclopentene oxide Examples thereof include alkyl type compounds and N-glycidyl phthalimide.
　上記エポキシ化合物としては、エポキシ化ポリオレフィンを用いることもできる。エポキシ化ポリオレフィンとは、ポリオレフィンをエポキシ基含有単量体で変性して、エポキシ基を導入したポリオレフィンである。エチレン又は炭素数３～２０のα－オレフィン、エポキシ基含有単量体、及び必要に応じて他のモノマーを、共重合法及びグラフト法の何れかにより共重合させることによって製造することができる。エチレン又は炭素数３～２０のα－オレフィン、エポキシ基含有単量体及び他のモノマーは、それぞれ単独で重合させてもよく、他の単量体と複数で重合させてもよい。また、末端に水酸基を有する非共役のポリブタジエンの二重結合を、過酢酸法によりエポキシ化して得ることもでき、分子内に水酸基を持つものを使用してもよい。また、水酸基をイソシアネートでウレタン化し、ここに１級水酸基含有エポキシ化合物を反応させてエポキシ基を導入することもできる。 Epoxidized polyolefin can also be used as the epoxy compound. The epoxidized polyolefin is a polyolefin having an epoxy group introduced by modifying the polyolefin with an epoxy group-containing monomer. It can be produced by copolymerizing ethylene or an α-olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer, and, if necessary, another monomer by either a copolymerization method or a graft method. Ethylene or an α-olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer, and other monomers may be polymerized alone or in combination with other monomers. Moreover, the double bond of the nonconjugated polybutadiene which has a hydroxyl group at the terminal can be obtained by epoxidation by the peracetic acid method, and those having a hydroxyl group in the molecule may be used. It is also possible to urethanize a hydroxyl group with an isocyanate and introduce an epoxy group by reacting with a primary hydroxyl group-containing epoxy compound.
　上記エチレン又は炭素数３～２０のα－オレフィンとしては、エチレン、プロピレン、ブチレン、イソブチレン、１，３－ブタジエン、１，４－ブタジエン、１，３－ペンタジエン、２，３－ジメチル－１，３－ブタジエン、ピペリレン、３－ブチル－１，３－オクタジエン及びイソプレン等が挙げられる。 Examples of the ethylene or α-olefin having 3 to 20 carbon atoms include ethylene, propylene, butylene, isobutylene, 1,3-butadiene, 1,4-butadiene, 1,3-pentadiene, 2,3-dimethyl-1,3. -Butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and the like.
　上記エポキシ基含有単量体としては、例えばα，β－不飽和酸のグリシジルエステル、ビニルベンジルグリシジルエーテル及びアリルグリシジルエーテル等が挙げられる。α，β－不飽和酸のグリシジルエステルとしては、具体的にはアクリル酸グリシジル、メタクリル酸グリシジル及びエタクリル酸グリシジル等が挙げられ、特にメタクリル酸グリシジルが好ましい。 Examples of the epoxy group-containing monomer include glycidyl ester of α, β-unsaturated acid, vinyl benzyl glycidyl ether, and allyl glycidyl ether. Specific examples of the glycidyl ester of α, β-unsaturated acid include glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylate, and glycidyl methacrylate is particularly preferable.
　上記エポキシ化合物としては、市販品も公的に使用することができる。好適な市販品としては、例えば、エポライト４０Ｅ、１５００ＮＰ、１６００、８０ＭＦ、４０００及び３００２（以上、共栄社化学製）；アデカグリシロールＥＤ－５０３、ＥＤ－５０３Ｄ、ＥＤ－５０３Ｇ、ＥＤ－５２３Ｔ、ＥＤ－５１３、ＥＤ－５０１、ＥＤ－５０２、ＥＤ－５０９、ＥＤ－５１８、ＥＤ－５２９、アデカレジンＥＰ－４０００、ＥＰ－４００５、ＥＰ－４０８０及びＥＰ－４０８５（以上、ＡＤＥＫＡ製）；デナコールＥＸ－２０１、ＥＸ－２０３、ＥＸ－２１１、ＥＸ－２１２、ＥＸ－２２１、ＥＸ－２５１、ＥＸ－２５２、ＥＸ－７１１、ＥＸ－７２１、デナコールＥＸ－１１１、ＥＸ－１２１、ＥＸ－１４１、ＥＸ－１４２、ＥＸ－１４５、ＥＸ－１４６、ＥＸ－１４７、ＥＸ－１７１、ＥＸ－１９２及びＥＸ－７３１（以上、ナガセケムテックス製）；ＥＨＰＥ－３１５０、セロキサイド２０２１Ｐ、２０８１、２０００及び３０００（以上、ダイセル社製）；エピオールＭ、ＥＨ、Ｌ－４１、ＳＫ、ＳＢ、ＴＢ及びＯＨ（以上、日油製）；エポライトＭ－１２３０及び１００ＭＦ（以上、共栄社化学製）；アロンオキセタンＯＸＴ－１２１、ＯＸＴ－２２１、ＥＸＯＨ、ＰＯＸ、ＯＸＡ、ＯＸＴ－１０１、ＯＸＴ－２１１及びＯＸＴ－２１２（以上、東亞合成製）；エタナコールＯＸＢＰ及びＯＸＴＰ（以上、宇部興産製）；２－ヒドロキシエチルビニルエーテル、ジエチレングリコールモノビニルエーテル及び4－ヒドロキシブチルビニルエーテル（以上、丸善石油化学製）；デナコールＥＸ－１２１、ＥＸ－１４１、ＥＸ－１４２、ＥＸ－１４５、ＥＸ－１４６、ＥＸ－１４７、ＥＸ－２０１、ＥＸ－２０３、ＥＸ－７１１、ＥＸ－７２１、オンコートＥＸ－１０２０、ＥＸ－１０３０、ＥＸ－１０４０、ＥＸ－１０５０、ＥＸ－１０５１、ＥＸ－１０１０、ＥＸ－１０１１及び１０１２（以上、ナガセケムテックス製）；オグソールＰＧ－１００、ＥＧ－２００、ＥＧ－２１０及びＥＧ－２５０（以上、大阪ガスケミカル製）；ＨＰ４０３２、ＨＰ４０３２Ｄ及びＨＰ４７００（以上、ＤＩＣ製）；ＥＳＮ－４７５Ｖ（東都化成製）；マープルーフＧ－０１０５ＳＡ及びＧ－０１３０ＳＰ（以上、日油製）；エピクロンＮ－６６５及びＨＰ－７２００（以上、ＤＩＣ製）；ＥＯＣＮ－１０２０、ＥＯＣＮ－１０２Ｓ、ＥＯＣＮ－１０３Ｓ、ＥＯＣＮ－１０４Ｓ、ＸＤ－１０００、ＮＣ－３０００、ＥＰＰＮ－５０１Ｈ、ＥＰＰＮ－５０１ＨＹ、ＥＰＰＮ－５０２Ｈ及びＮＣ－７０００Ｌ（以上、日本化薬製）等が挙げられる。 Commercially available products can be used as the epoxy compound. Suitable commercially available products include, for example, Epolite 40E, 1500NP, 1600, 80MF, 4000 and 3002 (manufactured by Kyoeisha Chemical); Adekaglycilol ED-503, ED-503D, ED-503G, ED-523T, ED- 513, ED-501, ED-502, ED-509, ED-518, ED-529, Adeka Resin EP-4000, EP-4005, EP-4080 and EP-4085 (above, manufactured by ADEKA); Denacol EX-201, EX-203, EX-211, EX-212, EX-221, EX-251, EX-252, EX-711, EX-721, Denacol EX-111, EX-121, EX-141, EX-142, EX -145, EX-146, EX-147, EX-171, EX-192 and E -731 (above, manufactured by Nagase ChemteX); EHPE-3150, Celoxide 2021P, 2081, 2000, and 3000 (above, manufactured by Daicel); Epiol M, EH, L-41, SK, SB, TB, and OH (above, EPOLIGHT M-1230 and 100MF (above, manufactured by Kyoeisha Chemical Co., Ltd.); Aron Oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211 and OXT-212 (above, Tojo) Synthetic); Etanacol OXBP and OXTP (above, Ube Industries); 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether and 4-hydroxybutyl vinyl ether (above, Maruzen Petrochemical); Denacol EX-121, EX-141, EX -142, EX-1 5, EX-146, EX-147, EX-201, EX-203, EX-711, EX-721, on-coat EX-1020, EX-1030, EX-1040, EX-1050, EX-1051, EX- 1010, EX-1011 and 1012 (above, manufactured by Nagase ChemteX); Ogsol PG-100, EG-200, EG-210, and EG-250 (above, manufactured by Osaka Gas Chemical); HP4032, HP4032D, and HP4700 (above, DIC) ESN-475V (manufactured by Toto Kasei); Marproof G-0105SA and G-0130SP (manufactured by NOF); Epicron N-665 and HP-7200 (manufactured by DIC); EOCN-1020, EOCN- 102S, EOCN-103S, EOCN-104S, XD-1000, C-3000, EPPN-501H, EPPN-501HY, EPPN-502H and NC-7000L (manufactured by Nippon Kayaku Co., Ltd.) and the like.
　上記アルカリ現像性付与剤とは、ラジカル重合性を有さず、アルカリ現像性を付与する化合物であり、そのような化合物としては、酸価を有することでアルカリ水溶液に可溶な化合物であれば特に限定されないが、代表的なものとしてアルカリ可溶性ノボラック樹脂（以下、単に「ノボラック樹脂」という）が挙げられる。ノボラック樹脂は、フェノール類とアルデヒド類とを酸触媒の存在下に重縮合して得られる。 The alkali developability-imparting agent is a compound that does not have radical polymerizability and imparts alkali developability. As such a compound, any compound that has an acid value and is soluble in an aqueous alkali solution can be used. Although not particularly limited, a typical example is an alkali-soluble novolak resin (hereinafter simply referred to as “novolak resin”). The novolak resin is obtained by polycondensation of phenols and aldehydes in the presence of an acid catalyst.
　上記フェノール類としては、例えばフェノール、ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾール、ｏ－エチルフェノール、ｍ－エチルフェノール、ｐ－エチルフェノール、ｏ－ブチルフェノール、ｍ－ブチルフェノール、ｐ－ブチルフェノール、２，３－キシレノール、２，４－キシレノール、２，５－キシレノール、３，４－キシレノール、３，５－キシレノール、２，３，５－トリメチルフェノール、ｐ－フェニルフェノール、ヒドロキノン、カテコール、レゾルシノール、２－メチルレゾルシノール、ピロガロール、α－ナフトール、ビスフェノールＡ、ジヒドロキシ安息香酸エステル及び没食子酸エステル等が用いられ、これらのフェノール類のうちフェノール、ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾール、２，５－キシレノール、３，５－キシレノール、２，３，５－トリメチルフェノール、レゾルシノール、２－メチルレゾルシノール及びビスフェノールＡ等が好ましい。これらのフェノール類は、単独で又は２種以上混合して用いられる。 Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, p-phenylphenol, hydroquinone, catechol, resorcinol, 2- Methyl resorcinol, pyrogallol, α-naphthol, bisphenol A, dihydroxybenzoic acid ester, gallic acid ester and the like are used. Among these phenols, phenol, o-cresol, m-cresol, p-cresol, 2,5- Shirenoru, 3,5-xylenol, 2,3,5-trimethylphenol, resorcinol, 2-methyl resorcinol and bisphenol A are preferable. These phenols are used alone or in combination of two or more.
　上記アルデヒド類としては、例えばホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、プロピルアルデヒド、ベンズアルデヒド、フェニルアセトアルデヒド、α－フェニルプロピルアルデヒド、β－フェニルプロピルアルデヒド、ｏ－ヒドロキシベンズアルデヒド、ｍ－ヒドロキシベンズアルデヒド、ｐ－ヒドロキシベンズアルデヒド、ｏ－クロロベンズアルデヒド、ｍ－クロロベンズアルデヒド、ｐ－クロロベンズアルデヒド、ｏ－ニトロベンズアルデヒド、ｍ－ニトロベンズアルデヒド、ｐ－ニトロベンズアルデヒド、ｏ－メチルベンズアルデヒド、ｍ－メチルベンズアルデヒド、ｐ－メチルベンズアルデヒド、ｐ－エチルベンズアルデヒド及びｐ－ｎ－ブチルベンズアルデヒド等が用いられ、これらの化合物のうちホルムアルデヒド、アセトアルデヒド及びベンズアルデヒド等が好ましい。これらのアルデヒド類は、単独で又は２種以上混合して用いられる。アルデヒド類はフェノール類１モル当たり、好ましくは０．７～３モル、特に好ましくは０．７～２モルの割合で使用される。 Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o -Chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde and p -N-butylbenzaldehyde is used, and among these compounds, form Aldehyde, acetaldehyde, benzaldehyde and the like are preferable. These aldehydes may be used alone or in combination of two or more. Aldehydes are preferably used in a proportion of 0.7 to 3 mol, particularly preferably 0.7 to 2 mol, per mol of phenol.
　上記酸触媒としては、例えば塩酸、硝酸、硫酸等の無機酸、又は蟻酸、蓚酸、酢酸等の有機酸が用いられる。これらの酸触媒の使用量は、フェノール類１モル当たり、１×１０－４～５×１０－１モルが好ましい。縮合反応においては、通常、反応媒質として水が用いられるが、縮合反応に用いられるフェノール類がアルデヒド類の水溶液に溶解せず、反応初期から不均一系になる場合には、反応媒質として親水性溶媒を使用することもできる。これらの親水性溶媒としては、例えばメタノール、エタノール、プロパノール及びブタノール等のアルコール類、またはテトラヒドロフラン及びジオキサン等の環状エーテル類が挙げられる。これらの反応媒質の使用量は、通常、反応原料１００質量部当たり、２０～１０００質量部である。縮合反応の反応温度は、反応原料の反応性に応じて適宜調整することができるが、通常、１０～２００℃、好ましくは７０～１５０℃である。縮合反応終了後、系内に存在する未反応原料、酸触媒及び反応媒質を除去するため、一般的には内温を１３０～２３０℃に上昇させ、減圧下に揮撥分を留去し、次いで熔融したノボラック樹脂をスチール製ベルト等の上に流涎して回収する。
　また縮合反応終了後に、前記親水性溶媒に反応混合物を溶解し、水、ｎ－ヘキサン及びｎ－ヘプタン等の沈殿剤に添加することにより、ノボラック樹脂を析出させ、析出物を分離し、加熱乾燥することにより回収することもできる。 Examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, or organic acids such as formic acid, oxalic acid, and acetic acid. The amount of these acid catalysts used is preferably 1 × 10 −4 to 5 × 10 −1 mol per mol of phenol. In the condensation reaction, water is usually used as a reaction medium. However, if the phenols used in the condensation reaction do not dissolve in an aqueous solution of aldehydes and become heterogeneous from the beginning of the reaction, the reaction medium is hydrophilic. A solvent can also be used. Examples of these hydrophilic solvents include alcohols such as methanol, ethanol, propanol and butanol, or cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media used is usually 20 to 1000 parts by mass per 100 parts by mass of the reaction raw material. The reaction temperature of the condensation reaction can be appropriately adjusted according to the reactivity of the reaction raw materials, but is usually 10 to 200 ° C., preferably 70 to 150 ° C. After completion of the condensation reaction, in order to remove unreacted raw materials, acid catalyst and reaction medium present in the system, the internal temperature is generally raised to 130 to 230 ° C., and the volatile component is distilled off under reduced pressure. Next, the melted novolac resin is collected on a steel belt or the like.
After completion of the condensation reaction, the reaction mixture is dissolved in the hydrophilic solvent and added to a precipitating agent such as water, n-hexane and n-heptane to precipitate a novolak resin, and the precipitate is separated and dried by heating. It can also be recovered by doing so.
　上記ノボラック樹脂以外の例としては、ポリヒドロキシスチレン又はその誘導体、スチレン－無水マレイン酸共重合体及びポリビニルヒドロキシベンゾエート等が挙げられる。 Examples other than the novolak resin include polyhydroxystyrene or a derivative thereof, a styrene-maleic anhydride copolymer, and polyvinylhydroxybenzoate.
　上記分散剤としては、着色剤（Ｂ）を分散、安定化できるものであれば何でも良く、市販の分散剤、例えばビックケミー製、ＢＹＫシリーズ等を用いることができ、塩基性官能基を有するポリエステル、ポリエーテル、ポリウレタンからなる高分子分散剤、塩基性官能基として窒素原子を有し、窒素原子を有する官能基がアミン、及び／又はその四級塩であり、アミン価が１～１００ｍｇＫＯＨ/ｇのものが好適に用いられる。 The dispersing agent may be anything as long as it can disperse and stabilize the colorant (B), and a commercially available dispersing agent, for example, BYK series, BYK series, etc. can be used, polyester having a basic functional group, Polymer dispersing agent made of polyether, polyurethane, nitrogen atom as basic functional group, functional group having nitrogen atom is amine and / or quaternary salt thereof, amine value is 1 to 100 mgKOH / g Those are preferably used.
　上記潜在性添加剤とは、常温、光露光工程及びプリベーク工程では不活性であり、１００～２５０℃で加熱するか、又は酸／塩基触媒存在下で８０～２００℃で加熱することにより保護基が脱離して活性化するものである。活性化したことにより得られる効果としては、酸化防止、紫外線吸収、防汚性、リコート性及び密着性等が挙げられる。
　上記潜在性添加剤としてはＷＯ２０１４／０２１０２３号パンフレットに記載されているものを好ましく使うことができる。 The latent additive is inactive at room temperature, in the light exposure step and in the pre-bake step, and is protected at 100 to 250 ° C. or heated at 80 to 200 ° C. in the presence of an acid / base catalyst. Is activated by desorption. Examples of the effects obtained by activation include oxidation prevention, ultraviolet absorption, antifouling property, recoatability and adhesion.
As the latent additive, those described in the pamphlet of WO2014 / 021023 can be preferably used.
　上記潜在性添加剤としては市販品を用いることができ、例えば、アデカアークルズＧＰＡ－５００１等が挙げられる。 As the latent additive, commercially available products can be used, and examples thereof include Adeka Arcles GPA-5001.
　上記有機重合体としては、例えば、ポリスチレン、ポリメチルメタクリレート、メチルメタクリレート－エチルアクリレート共重合体、ポリ（メタ）アクリル酸、スチレン－（メタ）アクリル酸共重合体、（メタ）アクリル酸－メチルメタクリレート共重合体、エチレン－塩化ビニル共重合体、エチレン－ビニル共重合体、ポリ塩化ビニル樹脂、ＡＢＳ樹脂、ナイロン６、ナイロン６６、ナイロン１２、ウレタン樹脂、ポリカーボネートポリビニルブチラール、セルロースエステル、ポリアクリルアミド、飽和ポリエステル、フェノール樹脂、フェノキシ樹脂、ポリアミドイミド樹脂、ポリアミック酸樹脂、エポキシ樹脂等が挙げられ、これらの中でも、ポリスチレン、（メタ）アクリル酸－メチルメタクリレート共重合体、エポキシ樹脂が好ましい。
　上記アルカリ現像性化合物（Ｃ）と共に、上記有機重合体を用いることによって、硬化物の特性を改善することもできる。
　有機重合体を使用する場合、その使用量は、上記アルカリ現像性化合物（Ｃ）１００質量部に対して、好ましくは１０～５００質量部である。 Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate. Copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated Polyester, phenolic resin, phenoxy resin, polyamideimide resin, polyamic acid resin, epoxy resin, and the like. Among these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, and epoxy resin are included. Masui.
By using the organic polymer together with the alkali developable compound (C), the properties of the cured product can be improved.
When the organic polymer is used, the amount used is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the alkali-developable compound (C).
　上記無機化合物を含有させることができる。該無機化合物としては、例えば、酸化ニッケル、酸化鉄、酸化イリジウム、酸化チタン、酸化亜鉛、酸化マグネシウム、酸化カルシウム、酸化カリウム、シリカ及びアルミナ等の金属酸化物；層状粘土鉱物、ミロリブルー、炭酸カルシウム、炭酸マグネシウム、コバルト系、マンガン系、ガラス粉末、マイカ、タルク、カオリン、フェロシアン化物、各種金属硫酸塩、硫化物、セレン化物、アルミニウムシリケート、カルシウムシリケート、水酸化アルミニウム、白金、金、銀及び銅等が挙げられ、これらの中でも、酸化チタン、シリカ、層状粘土鉱物、及び銀等が好ましい。 The above inorganic compound can be contained. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica and alumina; lamellar clay mineral, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver and copper Among these, titanium oxide, silica, layered clay mineral, silver and the like are preferable.
　本発明の重合性組成物に無機化合物を含有させることで、感光性ペースト組成物として用いることができる。該感光性ペースト組成物は、プラズマディスプレイパネルの隔壁パターン、誘電体パターン、電極パターン及びブラックマトリクスパターンなどの焼成物パターンを形成するために用いられる。
　また、これら無機化合物は、例えば、充填剤、反射防止剤、導電剤、安定剤、難燃剤、機械的強度向上剤、特殊波長吸収剤及び撥インク剤等としても好適に用いられる。 By containing an inorganic compound in the polymerizable composition of the present invention, it can be used as a photosensitive paste composition. The photosensitive paste composition is used to form a fired product pattern such as a partition pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel.
These inorganic compounds are also suitably used as, for example, fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, and ink repellent agents.
　本発明の重合性組成物において、無機化合物が添加される場合、無機化合物の含有量は、上記アルカリ現像性化合物（Ｃ）１００質量部に対して、好ましくは０．１～５０質量部、より好ましくは０．５～２０質量部であり、これらの無機化合物は１種又は２種以上を使用することができる。 In the polymerizable composition of the present invention, when an inorganic compound is added, the content of the inorganic compound is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the alkali developable compound (C). The amount is preferably 0.5 to 20 parts by mass, and one or more of these inorganic compounds can be used.
　上記カップリング剤としては、例えば、ジメチルジメトキシシラン、ジメチルジエトキシシラン、メチルエチルジメトキシシラン、メチルエチルジエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリメトキシシラン等のアルキル官能性アルコキシシラン、ビニルトリクロロシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、アリルトリメトキシシラン等のアルケニル官能性アルコキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、２－メタクリロキシプロピルトリメトキシシラン等の（メタ）アクリル酸エステル官能性アルコキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルメチルジエトキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、γ－（３，４－エポキシシクロヘキシル）プロピルトリメトキシシラン等のエポキシ官能性アルコキシシラン、Ｎ－β（アミノエチル）－γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン等のアミノ官能性アルコキシシラン、γ－メルカプトプロピルトリメトキシシラン等のメルカプト官能性アルコキシシラン、３－イソシアネートプロピルトリエトキシシラン等のイソシアネート官能性アルコキシシラン、３－ウレイドプロピルトリアルコキシシラン等のウレイド官能性アルコキシシラン、トリス－（トリメトキシシリルプロピル）イソシアヌレート等のイソシアヌレート官能性アルコキシシラン、チタンテトライソプロポキシド、チタンテトラノルマルブトキシド等のチタンアルコキシド類、チタンジオクチロキシビス（オクチレングリコレート）、チタンジイソプロポキシビス（エチルアセトアセテート）等のチタンキレート類、ジルコニウムテトラアセチルアセトネート、ジルコニウムトリブトキシモノアセチルアセトネート等のジルコニウムキレート類、ジルコニウムトリブトキシモノステアレート等のジルコニウムアシレート類、メチルトリイソシアネートシラン等のイソシアネートシラン類等を用いることができる。
　カップリング剤を添加することにより、硬化物と基材間の密着性を向上するので好ましい。 Examples of the coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Alkyl-functional alkoxysilanes, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and other alkenyl-functional alkoxysilanes, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, Such as 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane ( T) Acrylic ester functional alkoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (3 , 4-epoxycyclohexyl) propyltrimethoxysilane and other epoxy functional alkoxysilanes, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyl Aminofunctional alkoxysilanes such as trimethoxysilane, mercaptofunctional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, isocyanate functional alkoxysilanes such as 3-isocyanatopropyltriethoxysilane, 3-ureidopropyl Ureido functional alkoxysilanes such as trialkoxysilanes, isocyanurate functional alkoxysilanes such as tris- (trimethoxysilylpropyl) isocyanurate, titanium alkoxides such as titanium tetraisopropoxide, titanium tetranormal butoxide, titanium dioctyloxy Titanium chelates such as bis (octylene glycolate) and titanium diisopropoxy bis (ethylacetoacetate), zirconium chelates such as zirconium tetraacetylacetonate and zirconium tributoxymonoacetylacetonate, zirconium tributoxymonostearate, etc. Zirconium acylates and isocyanate silanes such as methyl triisocyanate silane can be used.
It is preferable to add a coupling agent because the adhesion between the cured product and the substrate is improved.
　上記カップリング剤としては市販品を用いることができ、例えば、ＫＡ－１００３、ＫＢＭ－１００３、ＫＢＥ－１００３、ＫＢＭ－３０３、ＫＢＭ－４０３、ＫＢＥ－４０２、ＫＢＥ－４０３、ＫＢＭ－１４０３、ＫＢＭ－５０２、ＫＢＭ－５０３、ＫＢＥ－５０２、ＫＢＥ－５０３、ＫＢＭ－５１０３、ＫＢＭ－６０２、ＫＢＭ－６０３、ＫＢＥ－６０３，ＫＢＭ－９０３，ＫＢＥ－９０３，ＫＢＥ－９１０３，ＫＢＭ－５７３、ＫＢＭ－５７５、ＫＢＭ－６１２３、ＫＢＥ－５８５、ＫＢＭ－７０３、ＫＢＭ－８０２、ＫＢＭ－８０３、ＫＢＥ－８４６、ＫＢＥ－９００７、ＫＢＭ－０４、ＫＢＥ－０４、ＫＢＭ－１３、ＫＢＥ－１３、ＫＢＥ－２２、ＫＢＥ－１０３、ＨＭＤＳ－３、ＫＢＭ－３０６３、ＫＢＭ－３１０３Ｃ、ＫＰＮ－３５０４及びＫＦ－９９（以上、信越シリコーン製）等が挙げられる。 Commercially available products can be used as the coupling agent. For example, KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-1403, KBM- 502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007, KBM-04, KBE-04, KBM-13, KBE-13, KBE-22, KBE- 103, HMDS-3, KBM-3063, KBM-3103C, KP -3504 and KF-99 (manufactured by Shin-Etsu Silicone), and the like.
　上記連鎖移動剤及び増感剤としては、一般的に硫黄原子含有化合物が用いられる。例えばチオグリコール酸、チオリンゴ酸、チオサリチル酸、２－メルカプトプロピオン酸、３－メルカプトプロピオン酸、３－メルカプト酪酸、Ｎ－（２－メルカプトプロピオニル）グリシン、２－メルカプトニコチン酸、３－［Ｎ－（２－メルカプトエチル）カルバモイル］プロピオン酸、３－［Ｎ－（２－メルカプトエチル）アミノ］プロピオン酸、Ｎ－（３－メルカプトプロピオニル）アラニン、２－メルカプトエタンスルホン酸、３－メルカプトプロパンスルホン酸、４－メルカプトブタンスルホン酸、ドデシル（４－メチルチオ）フェニルエーテル、２－メルカプトエタノール、３－メルカプト－１，２－プロパンジオール、１－メルカプト－２－プロパノール、３－メルカプト－２－ブタノール、メルカプトフェノール、２－メルカプトエチルアミン、２－メルカプトイミダゾール、２－メルカプトベンゾイミダゾール、２－メルカプト－３－ピリジノール、２－メルカプトベンゾチアゾール、メルカプト酢酸、トリメチロールプロパントリス（３－メルカプトプロピオネート）及びペンタエリスリトールテトラキス（３－メルカプトプロピオネート）等のメルカプト化合物；該メルカプト化合物を酸化して得られるジスルフィド化合物、ヨード酢酸、ヨードプロピオン酸、２－ヨードエタノール、２－ヨードエタンスルホン酸及び３－ヨードプロパンスルホン酸等のヨード化アルキル化合物；トリメチロールプロパントリス（３－メルカプトイソブチレート）、ブタンジオールビス（３－メルカプトイソブチレート）、ヘキサンジチオール、デカンジチオール、１，４－ジメチルメルカプトベンゼン、ブタンジオールビスチオプロピオネート、ブタンジオールビスチオグリコレート、エチレングリコールビスチオグリコレート、トリメチロールプロパントリスチオグリコレート、ブタンジオールビスチオプロピオネート、トリメチロールプロパントリスチオプロピオネート、トリメチロールプロパントリスチオグリコレート、ペンタエリスリトールテトラキスチオプロピオネート、ペンタエリスリトールテトラキスチオグリコレート、トリスヒドロキシエチルトリスチオプロピオネート、下記化合物Ｎｏ．Ｃ１、昭和電工社製カレンズＰＥ１及びＮＲ１等が挙げられる。 As the chain transfer agent and sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- ( 2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate) and pentaerythritol tetrakis (3- Mercapto compounds such as mercaptopropionate); iodo such as disulfide compounds obtained by oxidizing the mercapto compound, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid and 3-iodopropanesulfonic acid Alkyl compound; trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1, -Dimethyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropioate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, the following compound No. C1, Karenz PE1 and NR1 manufactured by Showa Denko KK and the like.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　上記界面活性剤としては、パーフルオロアルキルリン酸エステル、パーフルオロアルキルカルボン酸塩等のフッ素界面活性剤、高級脂肪酸アルカリ塩、アルキルスルホン酸塩、アルキル硫酸塩等のアニオン系界面活性剤、高級アミンハロゲン酸塩、第四級アンモニウム塩等のカチオン系界面活性剤、ポリエチレングリコールアルキルエーテル、ポリエチレングリコール脂肪酸エステル、ソルビタン脂肪酸エステル、脂肪酸モノグリセリド等の非イオン界面活性剤、両性界面活性剤及びシリコーン系界面活性剤等の界面活性剤を用いることができ、これらは組み合わせて用いてもよい。 Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides, amphoteric surfactants and silicone surfactants Surfactants such as agents can be used, and these may be used in combination.
　上記メラミン化合物としては、（ポリ）メチロールメラミン、（ポリ）メチロールグリコールウリル、（ポリ）メチロールベンゾグアナミン及び（ポリ）メチロールウレア等の窒素化合物中の活性メチロール基（ＣＨ２ＯＨ基）の全部又は一部（少なくとも２つ）がアルキルエーテル化された化合物を挙げることができる。ここで、アルキルエーテルを構成するアルキル基としては、メチル基、エチル基及びブチル基が挙げられ、互いに同一であってもよいし、異なっていてもよい。また、アルキルエーテル化されていないメチロール基は、一分子内で自己縮合していてもよく、二分子間で縮合して、その結果オリゴマー成分が形成されていてもよい。具体的には、ヘキサメトキシメチルメラミン、ヘキサブトキシメチルメラミン、テトラメトキシメチルグリコールウリル及びテトラブトキシメチルグリコールウリル等を用いることができる。これらの中でも、ヘキサメトキシメチルメラミン及びヘキサブトキシメチルメラミン等のアルキルエーテル化されたメラミンが好ましい。 Examples of the melamine compound include all or part of active methylol groups (CH 2 OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. Mention may be made of compounds in which (at least two) are alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same as or different from each other. Moreover, the methylol group which is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril, and the like can be used. Among these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.
　本発明の重合性組成物において、ウレタン（メタ）アクリレート化合物（Ａ）、着色剤（Ｂ）、アルカリ現像性化合物（Ｃ）、エチレン性不飽和化合物（Ｄ）及び重合開始剤（Ｅ）、溶剤及び無機化合物以外の任意成分の含有量は、その使用目的に応じて適宜選択され、本発明の効果を損なわない限りにおいては、特に制限されないが、好ましくは、ウレタン（メタ）アクリレート化合物（Ａ）、着色剤（Ｂ）、アルカリ現像性化合物（Ｃ）、エチレン性不飽和化合物（Ｄ）及び重合開始剤（Ｅ）の合計１００質量部に対して、合計で２０質量部以下である。 In the polymerizable composition of the present invention, urethane (meth) acrylate compound (A), colorant (B), alkali developable compound (C), ethylenically unsaturated compound (D), polymerization initiator (E), solvent The content of optional components other than inorganic compounds is appropriately selected according to the purpose of use, and is not particularly limited as long as the effects of the present invention are not impaired. Preferably, the urethane (meth) acrylate compound (A) is used. , 20 parts by mass or less in total with respect to 100 parts by mass in total of the colorant (B), the alkali-developable compound (C), the ethylenically unsaturated compound (D) and the polymerization initiator (E).
　本発明のＢＣＳ用感光性組成物は、必須成分として、ウレタン（メタ）アクリレート化合物（Ａ）、着色剤（Ｂ）、アルカリ現像性化合物（Ｃ）、エチレン性不飽和化合物（Ｄ）及び重合開始剤（Ｅ）を含有し、感光性及びアルカリ現像性を有し、ＢＣＳを形成することに特に適した組成物である。 The photosensitive composition for BCS of the present invention includes, as essential components, a urethane (meth) acrylate compound (A), a colorant (B), an alkali developable compound (C), an ethylenically unsaturated compound (D), and polymerization initiation. It is a composition that contains an agent (E), has photosensitivity and alkali developability, and is particularly suitable for forming BCS.
　本発明の重合性組成物又はＢＣＳ用感光性組成物並びに硬化物は、硬化性塗料、ワニス、硬化性接着剤、プリント基板、ディスプレイ表示装置（カラーテレビ、ＰＣモニタ、携帯情報端末及びデジタルカメラ等のカラー表示の液晶表示パネルにおけるカラーフィルタ、種々の表示用途用のカラーフィルタ、ＣＣＤイメージセンサのカラーフィルタ、タッチパネル、電気発光表示装置、プラズマ表示パネル、有機ＥＬの黒色隔壁）、粉末コーティング、印刷インク、印刷版、接着剤、ゲルコート、電子工学用のフォトレジスト、電気メッキレジスト、エッチングレジスト、はんだレジスト、絶縁膜、ブラックマトリクス、及びＬＣＤの製造工程において構造を形成するためのレジスト、電気及び電子部品を封入するための組成物、ソルダーレジスト、磁気記録材料、微小機械部品、導波路、光スイッチ、めっき用マスク、エッチングマスク、カラー試験系、ガラス繊維ケーブルコーティング、スクリーン印刷用ステンシル、ステレオリトグラフィによって三次元物体を製造するための材料、ホログラフィ記録用材料、画像記録材料、微細電子回路、脱色材料、画像記録材料のための脱色材料、マイクロカプセルを使用する画像記録材料用の脱色材料、印刷配線板用フォトレジスト材料、ＵＶ及び可視レーザー直接画像系用のフォトレジスト材料、プリント回路基板の逐次積層における誘電体層形成に使用するフォトレジスト材料及び保護膜等の各種の用途に使用することができ、その用途に特に制限はないが、上記用途の中でもディスプレイ表示装置には、特に好適に用いることがでる。 The polymerizable composition or the photosensitive composition for BCS and the cured product of the present invention are curable paint, varnish, curable adhesive, printed circuit board, display display device (color TV, PC monitor, portable information terminal, digital camera, etc. Color filters for liquid crystal display panels of color display, color filters for various display applications, color filters for CCD image sensors, touch panels, electroluminescent display devices, plasma display panels, organic EL black barriers), powder coating, printing ink , Printing plates, adhesives, gel coats, photoresists for electronics, electroplating resists, etching resists, solder resists, insulating films, black matrices, and resists for forming structures in LCD manufacturing processes, electrical and electronic components Composition for encapsulating, solderale Materials for manufacturing 3D objects by strikes, magnetic recording materials, micromechanical components, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, screen printing stencils, stereolithography Holographic recording material, image recording material, fine electronic circuit, decoloring material, decoloring material for image recording material, decoloring material for image recording material using microcapsules, photoresist material for printed wiring board, UV and visible It can be used for various applications such as photoresist materials for laser direct image systems, photoresist materials used for dielectric layer formation in the sequential lamination of printed circuit boards, and protective films, but there are no particular restrictions on their applications Of these uses, it is particularly suitable for a display device. That.
　本発明のディスプレイ表示装置は、本発明の硬化物（特にＢＣＳ）を備える以外は従来公知の表示装置と同じ構成であるが、ＢＣＳは、セルとセルの間に設けるのがよい。 The display device of the present invention has the same configuration as a conventionally known display device except that it includes the cured product (particularly BCS) of the present invention, but the BCS is preferably provided between cells.
　有機ＥＬの黒色隔壁として本発明の重合性組成物を用いる場合、パターン形状の垂直化、現像密着性の向上、耐熱性が向上することから重量平均分子量５０００以上のアルカリ現像性化合物を用いることが好ましく、更に好ましくは重量平均分子量７０００～１５０００のアルカリ現像性化合物を用いることが好ましい。更に、アルカリ現像性化合物が、上記一般式（Ｉ）で表されるエポキシ化合物に不飽和一塩基酸を付加させた構造を有するエポキシ付加化合物と、多塩基酸無水物とのエステル化反応により得られる構造を有する不飽和化合物である場合が特に好ましい。 When the polymerizable composition of the present invention is used as a black partition wall of an organic EL, an alkali-developable compound having a weight average molecular weight of 5000 or more is used because the pattern shape is vertical, development adhesion is improved, and heat resistance is improved. More preferably, an alkali developable compound having a weight average molecular weight of 7000 to 15000 is preferably used. Further, the alkali-developable compound is obtained by an esterification reaction between an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the general formula (I) and a polybasic acid anhydride. Particularly preferred is an unsaturated compound having the structure shown below.
　本発明の重合性組成物及びＢＣＳ用感光性組成物を用いて硬化物を製造する方法について、以下に詳細に説明する。 A method for producing a cured product using the polymerizable composition of the present invention and the photosensitive composition for BCS will be described in detail below.
　本発明の重合性組成物及びＢＣＳ用感光性組成物は、スピンコーター、ロールコーター、バーコーター、ダイコーター、カーテンコーター、各種の印刷、浸漬等の公知の手段で、ソーダガラス、石英ガラス、半導体基板、金属、紙、プラスチック等の支持基体上に適用することができる。また、一旦フィルム等の支持基体上に施した後、他の支持基体上に転写することもでき、その適用方法に制限はない。 The polymerizable composition of the present invention and the photosensitive composition for BCS are soda glass, quartz glass, and semiconductor by known means such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing and dipping. The present invention can be applied on a support substrate such as a substrate, metal, paper, or plastic. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.
　また、本発明の重合性組成物及びＢＣＳ用感光性組成物を硬化させる際に用いられるエネルギー線の光源としては、超高圧水銀ランプ、高圧水銀ランプ、中圧水銀ランプ、低圧水銀ランプ、水銀蒸気アーク灯、キセノンアーク灯、カーボンアーク灯、メタルハライドランプ、蛍光灯、タングステンランプ、エキシマーランプ、殺菌灯、発光ダイオード、ＣＲＴ光源等から得られる２０００オングストロームから７０００オングストロームの波長を有する電磁波エネルギーや電子線、Ｘ線、放射線等の高エネルギー線を利用することができるが、好ましくは、波長３００～４５０ｎｍの光を発光する超高圧水銀ランプ、水銀蒸気アーク灯、カーボンアーク灯、キセノンアーク灯等が挙げられる。 Further, as a light source for energy rays used for curing the polymerizable composition of the present invention and the photosensitive composition for BCS, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, mercury vapor Electromagnetic wave energy or electron beam having a wavelength of 2000 angstrom to 7000 angstrom obtained from arc lamp, xenon arc lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, excimer lamp, germicidal lamp, light emitting diode, CRT light source, etc. Although high energy rays such as X-rays and radiation can be used, preferably, an ultra-high pressure mercury lamp that emits light having a wavelength of 300 to 450 nm, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, and the like. .
　更に、露光光源にレーザー光を用いることにより、マスクを用いずに、コンピューター等のデジタル情報から直接画像を形成するレーザー直接描画法が、生産性のみならず、解像性や位置精度等の向上も図れることから有用であり、そのレーザー光としては、３４０～４３０ｎｍの波長の光が好適に使用されるが、エキシマーレーザー、窒素レーザー、アルゴンイオンレーザー、ヘリウムカドミウムレーザー、ヘリウムネオンレーザー、クリプトンイオンレーザー、各種半導体レーザー及びＹＡＧレーザー等の可視から赤外領域の光を発するものも用いられる。これらのレーザーを使用する場合には、可視から赤外の当該領域を吸収する増感色素が加えられる。 Furthermore, by using laser light as the exposure light source, the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy. As the laser light, light having a wavelength of 340 to 430 nm is preferably used, but excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser. In addition, lasers that emit light in the visible to infrared region, such as various semiconductor lasers and YAG lasers, are also used. When these lasers are used, a sensitizing dye that absorbs the region from visible to infrared is added.
　本発明の硬化物はＢＣＳとして特に有用である。ＢＣＳは、（１）本発明のＢＣＳ用感光性組成物の塗膜を基板上に形成する工程、（２）該塗膜に所定のパターン形状を有するマスクを介して放射線を照射する工程、（３）露光後のベーク工程、（４）露光後の該被膜を現像する工程、（５）現像後の該被膜を加熱する工程により好ましく形成される。
　上記マスクとしては、ハーフトーンマスク又はグレースケールマスク等の多階調マスクを用いることもできる。 The cured product of the present invention is particularly useful as BCS. BCS is (1) a step of forming a coating film of the photosensitive composition for BCS of the present invention on a substrate, (2) a step of irradiating the coating film with radiation through a mask having a predetermined pattern shape, ( It is preferably formed by 3) a baking step after exposure, (4) a step of developing the coating after exposure, and (5) a step of heating the coating after development.
As the mask, a multi-tone mask such as a halftone mask or a gray scale mask can be used.
　本発明のディスプレイ表示装置は、本発明の硬化物（特にＢＣＳ）を備える以外は従来公知の表示装置と同じ構成であるが、ＢＣＳは、セルとセルの間に設けるのがよい。 The display device of the present invention has the same configuration as a conventionally known display device except that it includes the cured product (particularly BCS) of the present invention, but the BCS is preferably provided between cells.
　以下、実施例及び比較例を挙げて本発明を更に詳細に説明するが、本発明はこれらの実施例等に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and the like.
［製造例１］ラクタムブラック分散液Ｂ－１の調製　
　有機系の黒色顔料（ラクタムブラックとしてブラック５８２；ＢＡＳＦ社製）、分散剤（ＢＹＫ－１６７）及び分散物のためのポリマー（後述するアルカリ現像性化合物ＰＧＭＥＡ溶液Ｃ－１）を、それぞれ、１６質量部、３．２質量部及び３．６　質量部で混合した後で、この混合物にプロピレングリコールモノメチルエーテルアセタート（ＰＧＭＥＡ）を固形分濃度２５質量％となるよう秤量し、混合物を作成した。
　上記混合物をスターラーにより予備混合した後、直径０．３ｍｍのジルコニアビーズを分散物（溶剤：ＰＧＭＥＡ除く）と同じ重量で添加し、２５～６０℃の温度で６時間にわたってペイントシェーカーによる分散物処理にかけたのち、フィルタを用いてジルコニアビーズを取り除き、分散液を得た。得られた分散液にＰＧＭＥＡを追加し、分散物濃度が２０質量％となるように調整し、スターラーにより均一にした後、ラクタムブラック分散液Ｂ－１を得た。 [Production Example 1] Preparation of lactam black dispersion B-1
16 masses each of an organic black pigment (black 582 as lactam black; manufactured by BASF), a dispersant (BYK-167), and a polymer for dispersion (an alkali-developable compound PGMEA solution C-1 described later) Parts, 3.2 parts by weight, and 3.6 parts by weight, and then the mixture was weighed with propylene glycol monomethyl ether acetate (PGMEA) to a solid content concentration of 25% by weight to prepare a mixture.
After premixing the above mixture with a stirrer, zirconia beads having a diameter of 0.3 mm are added in the same weight as the dispersion (solvent: excluding PGMEA) and subjected to dispersion treatment with a paint shaker at a temperature of 25 to 60 ° C. for 6 hours. Thereafter, the zirconia beads were removed using a filter to obtain a dispersion. PGMEA was added to the obtained dispersion to adjust the dispersion concentration to 20% by mass, and the mixture was made uniform with a stirrer to obtain lactam black dispersion B-1.
［製造例２］ぺリレンブラック分散液Ｂ－２の調製
　有機系の黒色顔料［ペリレンブラックとしてＣ．Ｉ．ピグメントブラック３１（ＰａｌＩｏｇｅｎＢｌａｃｋＳ００８４；ＢＡＳＦ社製）］、分散剤（ＢＹＫ－１６７）及び分散物のためのポリマー（後述するアルカリ現像性化合物ＰＧＭＥＡ溶液Ｃ－１）を、それぞれ、１２質量部、３．６質量部及び８質量部で混合した後で、この混合物にプロピレングリコールモノメチルエーテルアセタート（ＰＧＭＥＡ）を固形分濃度２５質量％となるよう秤量し、混合物を作成した。
　上記混合物をスターラーにより予備混合した後、直径０．３ｍｍのジルコニアビーズを分散物（溶剤：ＰＧＭＥＡ除く）と同じ重量で添加し、２５～６０℃の温度で６時間にわたってペイントシェーカーによる分散物処理にかけたのち、フィルタを用いてジルコニアビーズを取り除き、分散液を得た。得られた分散液にＰＧＭＥＡを追加し、分散物濃度が２０質量％となるように調整し、スターラーにより均一にした後、ペリレンブラック分散液Ｂ－２を得た。 [Production Example 2] Preparation of Perylene Black Dispersion B-2 Organic black pigment [C. I. Pigment Black 31 (PalIogenBlackS0084; manufactured by BASF)], a dispersant (BYK-167), and a polymer for the dispersion (an alkali-developable compound PGMEA solution C-1 described later) are each 12 parts by mass, 3.6 After mixing in parts by mass and 8 parts by mass, propylene glycol monomethyl ether acetate (PGMEA) was weighed into this mixture to a solid content concentration of 25% by mass to prepare a mixture.
After premixing the above mixture with a stirrer, zirconia beads having a diameter of 0.3 mm are added in the same weight as the dispersion (solvent: excluding PGMEA) and subjected to dispersion treatment with a paint shaker at a temperature of 25 to 60 ° C. for 6 hours. Thereafter, the zirconia beads were removed using a filter to obtain a dispersion. PGMEA was added to the obtained dispersion to adjust the dispersion concentration to 20% by mass, and the mixture was made uniform with a stirrer to obtain a perylene black dispersion B-2.
［製造例３］ラクタムブラック／ぺリレンブラック共分散液Ｂ－３の調製　
　上記ラクタムブラック分散液Ｂ－１及びぺリレンブラック分散液Ｂ－２をそれぞれ５０質量部ずつ加え、スターラーにより室温で２時間撹拌し、ラクタムブラック／ぺリレンブラック共分散液Ｂ－３を得た。 [Production Example 3] Preparation of lactam black / perylene black co-dispersion B-3
50 parts by mass of each of the above lactam black dispersion B-1 and perylene black dispersion B-2 were added and stirred with a stirrer at room temperature for 2 hours to obtain lactam black / perylene black co-dispersion B-3.
［製造例４］カーボンブラック分散液Ｂ－４の調製
　カーボンブラックとしてＭＡ１００（三菱化学社製）を２０質量部、分散剤としてＢＹＫ１６１（ビックケミー（ＢＹＫ）社製）１２．５質量部（固形分濃度４０質量％）、溶媒としてプロピレングリコールモノメチルエーテルアセテート６７．５質量部を混合し、ビーズミルにより処理して、カーボンブラック分散液Ｂ―４を調製した。 [Production Example 4] Preparation of carbon black dispersion B-4 20 parts by mass of MA100 (manufactured by Mitsubishi Chemical) as carbon black and 12.5 parts by mass of BYK161 (by BYK (BYK)) as a dispersant (solid content concentration) 40 mass%) and 67.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent were mixed and treated with a bead mill to prepare a carbon black dispersion B-4.
［製造例５］アルカリ現像性化合物ＰＧＭＥＡ溶液Ｃ－１の調製
　１，１－ビス〔４－（２，３－エポキシプロピルオキシ）フェニル〕インダンの１８４ｇ、アクリル酸５８ｇ、２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール０．２６ｇ、テトラ－ｎ－ブチルアンモニウムブロミド０．１１ｇ及びＰＧＭＥＡ１０５ｇを仕込み、１２０℃で１６時間撹拌した。反応液を室温まで冷却し、ＰＧＭＥＡ１６０ｇ、ビフタル酸無水物５９ｇ及びテトラ－ｎ－ブチルアンモニウムブロミド０．２４ｇを加えて、１２０℃で４時間撹拌した。更に、テトラヒドロ無水フタル酸２０ｇを加え、１２０℃で４時間、１００℃で３時間、８０℃で４時間、６０℃で６時間、４０℃で１１時間撹拌した後、ＰＧＭＥＡ１２８ｇを加えて、ＰＧＭＥＡ溶液としてアルカリ現像性化合物Ｃ－１を得た（Ｍｗ＝５０００、Ｍｎ＝２１００、酸価（固形分）９２．７ｍｇＫＯＨ／ｇ）。アルカリ現像性化合物ＰＧＭＥＡ溶液Ｃ－１におけるアルカリ現像性化合物の含有率は４５質量％であった。 [Production Example 5] Preparation of alkali-developable compound PGMEA solution C-1 184 g of 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane, 58 g of acrylic acid, 2,6-di-tert -0.26 g of butyl-p-cresol, 0.11 g of tetra-n-butylammonium bromide and 105 g of PGMEA were charged and stirred at 120 ° C. for 16 hours. The reaction solution was cooled to room temperature, 160 g of PGMEA, 59 g of biphthalic anhydride and 0.24 g of tetra-n-butylammonium bromide were added, and the mixture was stirred at 120 ° C. for 4 hours. Further, 20 g of tetrahydrophthalic anhydride was added, and after stirring at 120 ° C. for 4 hours, at 100 ° C. for 3 hours, at 80 ° C. for 4 hours, at 60 ° C. for 6 hours, and at 40 ° C. for 11 hours, PGMEA 128 g was added to obtain a PGMEA solution As an alkali developable compound C-1 (Mw = 5000, Mn = 2100, acid value (solid content) 92.7 mgKOH / g). The content of the alkali developable compound in the alkali developable compound PGMEA solution C-1 was 45% by mass.
［製造例６］アルカリ現像性化合物ＰＧＭＥＡ溶液Ｃ－２の製造
　９，９－ビス（４－グリシジルオキシフェニル）フルオレン７５．０ｇ、アクリル酸２３．８ｇ、２，６－ジ－ｔ－ブチル－ｐ－クレゾール０．２７３ｇ、テトラブチルアンモニウムクロリド０．５８５ｇ、及びＰＧＭＥＡ６５．９ｇを仕込み、９０℃で１時間、１００℃で１時間、１１０℃で１時間及び１２０℃で１４時間撹拌した。室温まで冷却し、無水コハク酸２５．９ｇ、テトラブチルアンモニウムクロリド０．４２７ｇ、及びＰＧＭＥＡ１．３７ｇを加えて、１００℃で５時間撹拌した。更に、９，９－ビス（４－グリシジルオキシフェニル）フルオレン３０．０ｇ、２，６－ジ－ｔ－ブチル－ｐ－クレゾール０．２６９ｇ、及びＰＧＭＥＡ１．５０ｇを加えて、９０℃で９０分、１２０℃で４時間撹拌後、ＰＧＭＥＡ１２２．２ｇを加えて、ＰＧＭＥＡ溶液として目的物であるアルカリ現像性化合物Ｃ－２を得た（Ｍｗ＝４１９０、Ｍｎ＝２１７０，酸価（固形分）５２ｍｇ・ＫＯＨ／ｇ）。アルカリ現像性化合物ＰＧＭＥＡ溶液Ｃ－２におけるアルカリ現像性化合物の含有率は４５質量％であった。 [Production Example 6] Production of alkali developable compound PGMEA solution C-2 9,9-bis (4-glycidyloxyphenyl) fluorene 75.0 g, acrylic acid 23.8 g, 2,6-di-t-butyl-p -0.273 g of cresol, 0.585 g of tetrabutylammonium chloride and 65.9 g of PGMEA were charged and stirred for 1 hour at 90 ° C, 1 hour at 100 ° C, 1 hour at 110 ° C and 14 hours at 120 ° C. The mixture was cooled to room temperature, 25.9 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride and 1.37 g of PGMEA were added, and the mixture was stirred at 100 ° C. for 5 hours. Further, 90.0 g of 9,9-bis (4-glycidyloxyphenyl) fluorene, 0.269 g of 2,6-di-t-butyl-p-cresol, and 1.50 g of PGMEA were added, and 90 minutes at 90 ° C. After stirring at 120 ° C. for 4 hours, 122.2 g of PGMEA was added to obtain the target alkali-developable compound C-2 as a PGMEA solution (Mw = 4190, Mn = 2170, acid value (solid content) 52 mg · KOH / G). The content of the alkali developable compound in the alkali developable compound PGMEA solution C-2 was 45% by mass.
［実施例１～２４及び比較例１～４］重合性組成物の調製
　［表１］～［表４］の配合に従って各成分を混合し、重合性組成物（実施例１～２４及び比較例１～４）を得た。尚、表中の配合の数値は質量部を表す。
　また、表中の各成分の符号は、下記の成分を表す。
Ａ－１　ＵＡ－３０６Ｈ（ウレタン（メタ）アクリレート化合物；共栄社化学社製）
Ａ－２　ＥＢＥＣＲＹＬ８８１０　
（ウレタンアクリレート化合物；ダイセル社製）
Ｂ－１　ラクタムブラック分散液Ｂ－１
Ｂ－２　ぺリレンブラック分散液Ｂ－２
Ｂ－３　ラクタムブラック／ぺリレンブラック共分散液Ｂ－３
Ｂ－４　カーボンブラック分散液Ｂ－４ 
Ｃ－１　アルカリ現像性化合物ＰＧＭＥＡ溶液Ｃ－１
Ｃ－２　アルカリ現像性化合物ＰＧＭＥＡ溶液Ｃ－２
Ｃ－３　ＳＰＲＲ－６Ｘ
（アルカリ現像性化合物；５１．５質量％ＰＧＭＥＡ溶液　；昭和電工社製）
Ｃ－４　ＳＰＣ－３０００
（アルカリ現像性化合物；５１．５質量％ＰＧＭＥＡ溶液　；昭和電工社製）
Ｃ－５　ＣＣＲ－１１７１Ｈ
（アルカリ現像性化合物；６７質量％ＰＧＭＥＡ溶液　；日本化薬社製）
Ｄ－１　カヤラッドＤＰＨＡ　（アクリル化合物　；日本化薬） 
Ｄ－２　カヤラッドＲ－６８４　（アクリル化合物　；日本化薬） 
Ｅ－１　化合物Ｎｏ．Ｅ１ 
Ｅ－２　化合物Ｎｏ．Ｅ２ 
Ｅ－３　化合物Ｎｏ．Ｅ４ 
Ｆ－１　ＥＨＰＥ－３１５０　（エポキシ化合物　；ダイセル社製） 
Ｆ－２　１５７Ｓ７０　（エポキシ化合物　；三菱化学社製） 
Ｆ－３　ＪＰ－２００　（エポキシ化合物　；日本曹達社製）
Ｆ－４　γ－グリシドキシプロピルトリメトキシシラン（カップリング剤）
Ｆ－５　カレンズＰＥ－１（チオール化合物　；昭和電工社製）
Ｇ－１　ＰＧＭＥＡ
Ｇ－２　３－メトキシブチルアセテート  [Examples 1 to 24 and Comparative Examples 1 to 4] Preparation of Polymerizable Composition Each component was mixed in accordance with the formulation of [Table 1] to [Table 4] to obtain a polymerizable composition (Examples 1 to 24 and Comparative Example). 1-4) were obtained. In addition, the numerical value of the mixing | blending in a table | surface represents a mass part.
Moreover, the code | symbol of each component in a table | surface represents the following component.
A-1 UA-306H (urethane (meth) acrylate compound; manufactured by Kyoeisha Chemical Co., Ltd.)
A-2 EBECRYL8810
(Urethane acrylate compound; manufactured by Daicel)
B-1 Lactam black dispersion B-1
B-2 Perylene black dispersion B-2
B-3 Lactam black / perylene black co-dispersion B-3
B-4 Carbon black dispersion B-4
C-1 Alkali developable compound PGMEA solution C-1
C-2 Alkali developable compound PGMEA solution C-2
C-3 SPRR-6X
(Alkali developable compound; 51.5 mass% PGMEA solution; Showa Denko KK)
C-4 SPC-3000
(Alkali developable compound; 51.5 mass% PGMEA solution; Showa Denko KK)
C-5 CCR-1171H
(Alkali developable compound; 67 mass% PGMEA solution; manufactured by Nippon Kayaku Co., Ltd.)
D-1 Kayalad DPHA (acrylic compound; Nippon Kayaku)
D-2 Kayalad R-684 (acrylic compound; Nippon Kayaku)
E-1 Compound No. E1
E-2 Compound No. E2
E-3 Compound No. E4
F-1 EHPE-3150 (Epoxy compound; manufactured by Daicel)
F-2 157S70 (epoxy compound; manufactured by Mitsubishi Chemical Corporation)
F-3 JP-200 (epoxy compound; manufactured by Nippon Soda Co., Ltd.)
F-4 γ-Glycidoxypropyltrimethoxysilane (coupling agent)
F-5 Karenz PE-1 (thiol compound; Showa Denko)
G-1 PGMEA
G-2 3-Methoxybutyl acetate
［重合性組成物から得られる硬化物の評価］
　実施例１～２４及び比較例１～４の重合性組成物から得られる硬化物について、弾性率回復率、遮光性（ＯＤ値）、誘電率、液晶汚染性（ＶＨＲ）の評価を、下記の手順で行った。結果を［表１］～［表４］に併記する。 [Evaluation of cured product obtained from polymerizable composition]
The cured products obtained from the polymerizable compositions of Examples 1 to 24 and Comparative Examples 1 to 4 were evaluated for the elastic modulus recovery rate, light shielding property (OD value), dielectric constant, and liquid crystal contamination (VHR) as follows. I went by the procedure. The results are also shown in [Table 1] to [Table 4].
（弾性率回復率）
　ガラス基板上に実施例１～２４の重合性組成物及び比較例１～４の比較重合性組成物をスピンコート（３μｍ厚，３００ｒｐｍ×７秒）により塗布し、乾燥した後９０℃において１００秒間プリベークを行い、溶剤を除去した後、フォトマスクを使用して高圧水銀ランプにて１００ｍＪ／ｃｍ２露光後、０．０４ｗｔ％ＫＯＨ水溶液を用いてで現像を行った後、２３０℃にて３０分加熱し、パターンを作成した。得られたパターンの２０μｍ部分で、島津社ダイナミック微小硬度計ＤＵＨ－２１１を用いて、４０ｍＮにて荷重を負荷－除荷試験を行なった。弾性率回復率（％）下記の計算式によって算出した。
 
 弾性回復率（％）＝［（回復距離／圧縮変位）×１００］
 
　弾性回復率（％）が、６０％以上の硬化物はＢＣＳとして使用することができ、弾性回復率（％）が、７０％以上の硬化物はＢＣＳとして好ましく使用することができ、弾性回復率（％）が、８０％以上の硬化物はＢＣＳとして特に好ましく使用することができる。 (Elastic modulus recovery rate)
The polymerizable compositions of Examples 1 to 24 and the comparative polymerizable compositions of Comparative Examples 1 to 4 were applied on a glass substrate by spin coating (3 μm thickness, 300 rpm × 7 seconds), dried, and then 90 ° C. for 100 seconds. After pre-baking and removing the solvent, after exposure to 100 mJ / cm 2 with a high-pressure mercury lamp using a photomask and development with an aqueous 0.04 wt% KOH solution, 30 minutes at 230 ° C. Heated to create a pattern. A load-unloading test was performed on the 20 μm portion of the obtained pattern using a Shimadzu dynamic microhardness meter DUH-211 at 40 mN. Elastic modulus recovery rate (%) was calculated by the following formula.

Elastic recovery rate (%) = [(recovery distance / compression displacement) × 100]

A cured product having an elastic recovery rate (%) of 60% or more can be used as a BCS, and a cured product having an elastic recovery rate (%) of 70% or more can be preferably used as a BCS. A cured product having (%) of 80% or more can be particularly preferably used as BCS.
（ＯＤ値）
　ガラス基板上に実施例１～２４の重合性組成物及び比較例１～４の比較重合性組成物をスピンコート（３００ｒｐｍ、７秒間）し乾燥させた後、９０℃で１００秒間プリベークを行った。光源として超高圧水銀ランプを用いて露光後した後、２３０℃で３０分間ベークして硬化物を作成した。得られた膜のＯＤ値を、マクベス透過濃度計を用いて測定し、該ＯＤ値をポストベイク後の膜厚で割って、膜厚あたりのＯＤ値を算出した。
　膜厚あたりのＯＤ値が１.０以上の硬化物はＢＣＳとして使用することができ、膜厚あたりのＯＤ値が１．５以上の硬化物はＢＣＳとして好ましく使用することができ、膜厚あたりのＯＤ値が２．０以上の硬化物はＢＣＳとして特に好まし使用できる。膜厚あたりのＯＤ値が１．０未満の硬化物はＢＣＳとして使用できない。 (OD value)
The polymerizable compositions of Examples 1 to 24 and the comparative polymerizable compositions of Comparative Examples 1 to 4 were spin-coated (300 rpm, 7 seconds) and dried on a glass substrate, and then prebaked at 90 ° C. for 100 seconds. . After exposure using an ultrahigh pressure mercury lamp as a light source, the cured product was prepared by baking at 230 ° C. for 30 minutes. The OD value of the obtained film was measured using a Macbeth transmission densitometer, and the OD value per film thickness was calculated by dividing the OD value by the film thickness after post-baking.
A cured product having an OD value of 1.0 or more per film thickness can be used as BCS, and a cured product having an OD value of 1.5 or more per film thickness can be preferably used as BCS. A cured product having an OD value of 2.0 or more can be particularly preferably used as BCS. A cured product having an OD value per film thickness of less than 1.0 cannot be used as BCS.
（比誘電率）
　ガラス基板上に実施例１～２４の重合性組成物及び比較例１～４の比較重合性組成物をスピンコート（３μｍ厚，３００ｒｐｍ×７秒間）し、乾燥させた後、９０℃で１００秒間プリベークを行ない、マスクを使用せず高圧水銀ランプにて１００ｍＪ／ｃｍ２露光した後、２３０℃×１８０分間加熱し、上記評価サンプルを作成した。
（評価法）
　上記評価サンプルについて、ＬＣＲメーター、アジレント社４２８４Ａを用いて、ＡＣ１Ｖ、１ｋＨｚ印加し測定を行った。
　比誘電率が５．０未満の硬化物はＢＣＳとして使用することができ、比誘電率が４．５以下の硬化物はＢＣＳとして好まし使用でき、比誘電率が４．０以下の硬化物はＢＣＳとして特に好ましく使用できる。比誘電率が５．０以上の硬化物はＢＣＳとして使用できない。 (Relative permittivity)
The polymerizable compositions of Examples 1 to 24 and the comparative polymerizable compositions of Comparative Examples 1 to 4 were spin-coated (3 μm thickness, 300 rpm × 7 seconds) on a glass substrate, dried, and then 90 ° C. for 100 seconds. Pre-baking was performed, 100 mJ / cm 2 exposure was performed with a high-pressure mercury lamp without using a mask, and then heating was performed at 230 ° C. for 180 minutes to prepare the evaluation sample.
(Evaluation method)
About the said evaluation sample, AC1V and 1kHz were applied and measured using the LCR meter and Agilent 4284A.
A cured product having a relative dielectric constant of less than 5.0 can be used as a BCS, a cured product having a relative dielectric constant of 4.5 or less can be preferably used as a BCS, and a cured product having a relative dielectric constant of 4.0 or less. Can be particularly preferably used as BCS. A cured product having a relative dielectric constant of 5.0 or more cannot be used as BCS.
（ＶＨＲ）
　実施例１～２４で得られた重合性組成物及び比較例１～４で得られた比較重合性組成物を、ガラス基板（１００ｍｍ×１００ｍｍ）上にスピンコーターを用いて塗布し、９０℃で１００秒間プリベークを行い、膜厚３．０μｍの塗膜を形成した。次いで、ミラープロジェクションアライナー（製品名：ＴＭＥ－１５０ＲＴＯ、株式会社トプコン製）を使用し、マスクを介さず塗膜に紫外線を照射量２００ｍＪ／ｃｍ２で照射した。その後、２３０℃で３０分間、ポストベークを行った。
　ポストベーク後の塗膜の１質量部を４０質量部のＡＤＥＫＡ社製の液晶「ＲＳ－１８２」と混合し、１２０℃で１時間保存した。これを室温に取り出し静置後、上澄み液を採取した。採取した液晶組成物について、上記液晶を混合する前後でのＶＨＲ（電圧保持率）を比較し、ＶＨＲの低下率を求め、下記基準により評価を行った。評価は、液晶組成物を液晶評価用ＴＮセル（セル厚５μｍ、電極面積８ｍｍ×８ｍｍ配向膜ＪＡＬＳ２０９６）に注入し、ＶＨＲをＶＨＲ－１Ａ（東陽テクニカ製）を用い測定した。（測定条件：パルス電圧幅６０μｓ、フレーム周期１６．７ｍｓ、波高±５Ｖ、測定温度６０℃）
　ＶＨＲが、９０％以上の硬化物は、ＢＣＳとして使用することができ、ＶＨＲが、９５％以上の硬化物は、ＢＣＳとして好ましく使用することができ、ＶＨＲが、９８％以上の硬化物は、ＢＣＳとして特に好ましく使用することができる。ＶＨＲが９０％未満の硬化物は、ＢＣＳとして使用できない。 (VHR)
The polymerizable composition obtained in Examples 1 to 24 and the comparative polymerizable composition obtained in Comparative Examples 1 to 4 were applied onto a glass substrate (100 mm × 100 mm) using a spin coater, and the coating composition was applied at 90 ° C. Pre-baking was performed for 100 seconds to form a coating film having a thickness of 3.0 μm. Next, using a mirror projection aligner (product name: TME-150 RTO, manufactured by Topcon Co., Ltd.), the coating film was irradiated with ultraviolet rays at a dose of 200 mJ / cm 2 without using a mask. Thereafter, post-baking was performed at 230 ° C. for 30 minutes.
1 part by mass of the post-baked coating film was mixed with 40 parts by mass of ADEKA liquid crystal “RS-182” and stored at 120 ° C. for 1 hour. This was taken out to room temperature and allowed to stand, and then the supernatant was collected. The collected liquid crystal compositions were compared for VHR (voltage holding ratio) before and after mixing the liquid crystal, to determine the reduction rate of VHR, and evaluated according to the following criteria. The liquid crystal composition was injected into a TN cell for liquid crystal evaluation (cell thickness 5 μm, electrode area 8 mm × 8 mm alignment film JALS2096), and VHR was measured using VHR-1A (manufactured by Toyo Technica). (Measurement conditions: pulse voltage width 60 μs, frame period 16.7 ms, wave height ± 5 V, measurement temperature 60 ° C.)
A cured product having a VHR of 90% or more can be used as a BCS, a cured product having a VHR of 95% or more can be preferably used as a BCS, and a cured product having a VHR of 98% or more is It can be particularly preferably used as a BCS. A cured product having a VHR of less than 90% cannot be used as a BCS.
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000023
　［表１］～［表４］から明らかなように、本発明の重合性組成物及びＢＣＳ用感光性組成物より得られる硬化物は、遮光性（ＯＤ値）、誘電率、低液晶汚染性（ＶＨＲ）を高いレベルで満たしたうえで、弾性率回復率に優れるため、ＢＣＳとして有用なものである。 As is clear from [Table 1] to [Table 4], the cured product obtained from the polymerizable composition of the present invention and the photosensitive composition for BCS has a light shielding property (OD value), a dielectric constant, and low liquid crystal contamination. Since (VHR) is satisfied at a high level and the elastic modulus recovery rate is excellent, it is useful as a BCS.
　本発明の重合性組成物又はＢＣＳ用感光性組成物より得られる硬化物は、弾性回復に優れ、誘電率が低く、電気特性が良好な硬化物（特にＢＣＳ）である。該硬化物はディスプレイ表示装置等に、特に有用である。 The cured product obtained from the polymerizable composition of the present invention or the photosensitive composition for BCS is a cured product (particularly BCS) having excellent elastic recovery, low dielectric constant, and good electrical properties. The cured product is particularly useful for a display device or the like.

Claims (9)

  1. 　ウレタン（メタ）アクリレート化合物（Ａ）、着色剤（Ｂ）、アルカリ現像性化合物（Ｃ）[但し、ウレタン（メタ）アクリレート化合物（Ａ）を除く]、エチレン性不飽和化合物（Ｄ）[但し、ウレタン（メタ）アクリレート化合物（Ａ）及びアルカリ現像性化合物
    （Ｃ）を除く]及び重合開始剤（Ｅ）を含有する重合性組成物。     Urethane (meth) acrylate compound (A), colorant (B), alkali developable compound (C) [excluding urethane (meth) acrylate compound (A)], ethylenically unsaturated compound (D) [provided that A polymerizable composition containing a urethane (meth) acrylate compound (A) and an alkali developable compound (C)] and a polymerization initiator (E).
  2. 　着色剤（Ｂ）が黒色顔料である請求項１に記載の重合性組成物。 The polymerizable composition according to claim 1, wherein the colorant (B) is a black pigment.
  3. 　アルカリ現像性化合物（Ｃ）が、
    　下記一般式（Ｉ）で表されるエポキシ化合物に不飽和一塩基酸を付加させた構造を有するエポキシ付加化合物と、
    　多塩基酸無水物とのエステル化反応により得られる構造を有する不飽和化合物である請求項１又は２に記載の重合性組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｍは直接結合、炭素原子数１～２０の炭化水素基、－Ｏ－、－Ｓ－、－ＳＯ2－、－ＳＳ－、－ＳＯ－、－ＣＯ－、－ＯＣＯ－又は下記式（ａ）、（ｂ）、（ｃ）又は（ｄ）で表される群から選ばれる置換基を表し、
    　Ｍで表される炭素原子数１～２０の炭化水素基中の水素原子はハロゲン原子で置換される場合があり、
    　Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８（以下、Ｒ１～Ｒ８とも記載）は、それぞれ独立に、水素原子、炭素原子数１～２０の炭化水素基、又はハロゲン原子を表し、
    　Ｒ１～Ｒ８で表される基中のメチレン基は、不飽和結合、－Ｏ－又は－Ｓ－で置換される場合があり、
    　ｎは０～１０の数であり、
    　ｎ≧１の場合、複数存在するＲ１～Ｒ８及びＭは、それぞれ、同一である場合もあり、異なる場合もある。）
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ９は、炭素原子数１～２０の炭化水素基を表し、
    　Ｒ１０、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９、Ｒ２０、Ｒ２１、Ｒ２２、Ｒ２３、Ｒ２４、Ｒ２５、Ｒ２６、Ｒ２７、Ｒ２８、Ｒ２９、Ｒ３０、Ｒ３１、Ｒ３２、Ｒ３３、Ｒ３４、Ｒ３５、Ｒ３６、Ｒ３７及びＲ３８（以下、Ｒ１０～Ｒ３８とも記載）は、それぞれ独立に、水素原子、炭素原子数１～２０の炭化水素基、複素環を含有する炭素原子数２～２０の基、又はハロゲン原子を表し、
    　Ｒ１０～Ｒ３８で表される基中のメチレン基は、不飽和結合、－Ｏ－又は－Ｓ－で置換される場合があり、
    　Ｒ１０とＲ１１、Ｒ１１とＲ１２、Ｒ１２とＲ１３、Ｒ１３とＲ１４、Ｒ２２とＲ１５、Ｒ１５とＲ１６、Ｒ３０とＲ２３、Ｒ２３とＲ２４、Ｒ２４とＲ２５、Ｒ３８とＲ３１、Ｒ３１とＲ３２、Ｒ３２とＲ３３、Ｒ３４とＲ３５、Ｒ３５とＲ３６及びＲ３６とＲ３７は結合して環を形成する場合があり、
    　式（ａ）、（ｂ）、（ｃ）及び（ｄ）で表される基中の＊は、結合手を表す。）     Alkali developable compound (C)
    An epoxy addition compound having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the following general formula (I);
    The polymerizable composition according to claim 1 or 2, which is an unsaturated compound having a structure obtained by an esterification reaction with a polybasic acid anhydride.
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, M is a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, —O—, —S—, —SO 2 —, —SS—, —SO—, —CO—, —OCO— or Represents a substituent selected from the group represented by formula (a), (b), (c) or (d);
    The hydrogen atom in the hydrocarbon group having 1 to 20 carbon atoms represented by M may be substituted with a halogen atom,
    R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 (hereinafter also referred to as R 1 to R 8 ) are each independently a hydrogen atom or a carbon atom having 1 to 20 carbon atoms. Represents a hydrocarbon group or a halogen atom,
    The methylene group in the group represented by R 1 to R 8 may be substituted with an unsaturated bond, —O— or —S—,
    n is a number from 0 to 10,
    When n ≧ 1, a plurality of R 1 to R 8 and M may be the same or different. )
    Figure JPOXMLDOC01-appb-C000002
     (Wherein R 9 represents a hydrocarbon group having 1 to 20 carbon atoms,
    R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 and R 38 (hereinafter also referred to as R 10 to R 38 ) are respectively Independently, it represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 2 to 20 carbon atoms containing a heterocyclic ring, or a halogen atom,
    The methylene group in the group represented by R 10 to R 38 may be substituted with an unsaturated bond, —O— or —S—,
    R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 22 and R 15 , R 15 and R 16 , R 30 and R 23 , R 23 and R 24 , R 24 And R 25 , R 38 and R 31 , R 31 and R 32 , R 32 and R 33 , R 34 and R 35 , R 35 and R 36, and R 36 and R 37 may combine to form a ring. ,
    * In the groups represented by the formulas (a), (b), (c) and (d) represents a bond. )
  4. 　重合開始剤（Ｅ）が、下記一般式（ＩＩ）で表される基を有する重合開始剤である請求項１～３の何れか一項に記載の重合性組成物。
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ４１及びＲ４２は、それぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素原子数１～２０の炭化水素基又は複素環を含有する炭素原子数２～２０の基を表し、
    　Ｒ４１及びＲ４２で表される炭素原子数１～２０の炭化水素基又はＲ４１及びＲ４２で表される複素環を含有する炭素原子数２～２０の基の水素原子はハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、ビニルエーテル基、メルカプト基、イソシアネート基又は複素環を含有する炭素原子数２～２０の基で置換される場合があり、
    　Ｒ４１及びＲ４２で表される炭素原子数１～２０の炭化水素基又はＲ４１及びＲ４２で表される複素環を含有する炭素原子数２～２０の基中のメチレン基は－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ４３－、－ＮＲ４３ＣＯ－、－Ｓ－、－ＣＳ－、－ＳＯ２－、－ＳＣＯ－、－ＣＯＳ－、－ＯＣＳ－又はＣＳＯ－で置換される場合もあり、
    　Ｒ４３は、水素原子、炭素原子数１～２０の炭化水素基を表し、
    　ｍは０又は１を表し、
    　式中の＊は、結合手を表す。）     The polymerizable composition according to any one of claims 1 to 3, wherein the polymerization initiator (E) is a polymerization initiator having a group represented by the following general formula (II).
    Figure JPOXMLDOC01-appb-C000003
     (In the formula, each of R 41 and R 42 independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring. Represents
    Hydrogen atoms of the hydrocarbon group, or R 41 and having 2 to 20 carbon atoms containing heterocyclic ring represented by R 42 of R 41 and having 1 to 20 carbon atoms represented by R 42 is a halogen atom, a nitro Substituted with a group having 2 to 20 carbon atoms containing a group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group or heterocyclic ring There is a case,
    Methylene groups in the group having 2 to 20 carbon atoms having a hydrocarbon group or a heterocyclic ring represented by R 41 and R 42 having 1 to 20 carbon atoms represented by R 41 and R 42 -O- , —CO—, —COO—, —OCO—, —NR 43 —, —NR 43 CO—, —S—, —CS—, —SO 2 —, —SCO—, —COS—, —OCS— or CSO -May be replaced by-
    R 43 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
    m represents 0 or 1;
    * In the formula represents a bond. )
  5. 　重合開始剤（Ｅ）が、水酸基を有する重合開始剤である請求項１～４の何れか一項に記載の重合性組成物。 The polymerizable composition according to any one of claims 1 to 4, wherein the polymerization initiator (E) is a polymerization initiator having a hydroxyl group.
  6. 　請求項１～５の何れか一項に記載の重合性組成物からなるブラックカラムスペーサー用感光性組成物。 A photosensitive composition for a black column spacer, comprising the polymerizable composition according to any one of claims 1 to 5.
  7. 　請求項１～５の何れか一項に記載の重合性組成物又は請求項６に記載のブラックカラムスペーサー用感光性組成物を用いて硬化物を製造する方法。 A method for producing a cured product using the polymerizable composition according to any one of claims 1 to 5 or the photosensitive composition for a black column spacer according to claim 6.
  8. 　請求項１～５の何れか一項に記載の重合性組成物又は請求項６に記載のブラックカラムスペーサー用感光性組成物の硬化物。 A cured product of the polymerizable composition according to any one of claims 1 to 5 or the photosensitive composition for a black column spacer according to claim 6.
  9. 　請求項８に記載の硬化物を含有するディスプレイ表示装置。  A display device containing the cured product according to claim 8.
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JP7006358B2 (en) 2018-02-21 2022-01-24 三菱ケミカル株式会社 Photosensitive coloring composition, cured product, coloring spacer, and image display device
JP2021032943A (en) * 2019-08-19 2021-03-01 東京応化工業株式会社 Photosensitive resin composition, production method of patterned cured film, and patterned cured film
JP7282631B2 (en) 2019-08-19 2023-05-29 東京応化工業株式会社 Photosensitive resin composition, method for producing patterned cured film, and patterned cured film

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