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WO2018159265A1 - Composition polymérisable, et composition photosensible pour élément d'espacement de colonne noire - Google Patents

Composition polymérisable, et composition photosensible pour élément d'espacement de colonne noire 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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Prior art keywords
group
compound
carbon atoms
meth
represented
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English (en)
Japanese (ja)
Inventor
翔 六谷
祐也 中田
桂典 松平
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Adeka Corp
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Adeka Corp
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Priority to CN201880006925.3A priority Critical patent/CN110177817A/zh
Priority to KR1020197019534A priority patent/KR20190123259A/ko
Priority to JP2019502845A priority patent/JPWO2018159265A1/ja
Publication of WO2018159265A1 publication Critical patent/WO2018159265A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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.

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Abstract

L'invention a pour objet de fournir une composition polymérisable qui comprend un composé uréthane (méth)acrylate (A), un colorant (B), un composé à développement alcalin (C) (le composé uréthane (méth)acrylate (A) étant exclu), un composé éthyléniquement insaturé (D) ) (le composé uréthane (méth)acrylate (A) et le composé à développement alcalin (C) étant exclus), et un initiateur de polymérisation (E). De préférence, le colorant (B) consiste en un pigment de couleur noire. En outre, l'invention concerne une composition photosensible pour élément d'espacement de colonne noire constitué de ladite composition polymérisable, un article durci de cette composition, et un dispositif d'affichage comprenant cet article durci.
PCT/JP2018/004626 2017-03-01 2018-02-09 Composition polymérisable, et composition photosensible pour élément d'espacement de colonne noire Ceased WO2018159265A1 (fr)

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JP2021173971A (ja) * 2020-04-30 2021-11-01 サカタインクス株式会社 ブラックマトリックス用顔料分散組成物、ブラックマトリックス用レジスト組成物、及び、ブラックマトリックス
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CN114068070A (zh) * 2020-08-10 2022-02-18 天材创新材料科技(厦门)有限公司 透明导电薄膜及其制备方法

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