WO2006046733A1 - Thiol compound, and photosensitive composition and black matrix resist composition using the compound - Google Patents

Thiol compound, and photosensitive composition and black matrix resist composition using the compound Download PDF

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Publication number
WO2006046733A1
WO2006046733A1 PCT/JP2005/019955 JP2005019955W WO2006046733A1 WO 2006046733 A1 WO2006046733 A1 WO 2006046733A1 JP 2005019955 W JP2005019955 W JP 2005019955W WO 2006046733 A1 WO2006046733 A1 WO 2006046733A1
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group
compound
meth
acrylate
formula
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French (fr)
Inventor
Hirotoshi Kamata
Mina Onishi
Katsumi Murofushi
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Resonac Holdings Corp
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Showa Denko KK
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Priority to CN2005800364238A priority Critical patent/CN101048372B/en
Priority to KR1020077007542A priority patent/KR101225527B1/en
Publication of WO2006046733A1 publication Critical patent/WO2006046733A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
    • H05K3/0076—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the composition of the mask
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Definitions

  • the present invention relates to a novel thiol compound having a bisphenol skeleton, a method of manufacturing the same, and an alkali-developable type photosensitive composition and a black matrix resist composition for color filters using the compound. More specifically, the present invention relates to a novel thiol compound having a bisphenol skeleton and to a photosensitive composition and a blackmatrix resist composition for color filters using the compound, which contain (A) aphotopolymerization initiator systemincluding such compound, (B) a binder resin having a carboxyl group and (C) a compound having an ethylenically unsaturated group and have high sensitivity and excellent property of retaining a line width in fine line patterns at the time of alkali development.
  • Photosensitive compositions are used invarious fields including such as printing plates, color proofs, color filters, solder resists and photo-curable ink.
  • the most characteristic properties of photocurable composition such as usability at room temperature, fast-drying property and solvent-free property, have received attention in various fields including those applications from the viewpoints of environmental concerns, energy saving, working safety, production costs and the like andmany studies and developments have been made on photosensitive compositions.
  • a photosensitive composition is mainly composed of a photopolymerization initiator, a binder resin, a compound having an ethylenicallyunsaturatedbondwhichiscuredbypolymerizationreaction and various kinds of additives, and the kinds of the components depend on use where the photosensitive composition is applied.
  • the photopolymerization initiator is selected by the photosensitive wavelengths and polymerization initiating properties.
  • Thebinderresin, thecompoundhavinganethylenicallyunsaturatedbond and the additives are selected by polymerizability and physical properties of the cured product as desired. These components are combined and used to constitute a photosensitive composition.
  • a color filter is usuallymanufacturedby forming a lattice-like black-colored matrix (black matrix) on the surface of a transparent substrate such as glass or a plastic sheet and then forming three or more different hue patterns of red, green, blue and the like with a precision of micrometers.
  • the black matrix is disposed to improve contrast and prevent malfunction of TFT.
  • a resist for forming such a black matrix black matrix resist
  • resists which can keep the line width of the fine pattern almost unchanged even when exposed to an alkali developer for a long period of time, i.e. which are excellent in development latitude.
  • Theobject ofthepresent inventionisto provide ahigh-sensitive photosensitive composition and a black matrix resist composition, excellent inpropertyof keepingthe linewidthconstant ina finepattern at the time of alkali development, i.e., excellent in the development latitude.
  • a thiol compound represented by formula (1) A thiol compound represented by formula (1) :
  • R 1 represents a straight- or branched-chain alkylene group having 1 to 6 carbon atoms
  • R 2 represents a straight- or branched-chain alkylene group having 2 to ⁇ carbon atoms
  • R 3 and R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen atom
  • X represents a single bond, -CO-, -SO 2 -, -CH 2 -, -C(CFs) 2 -, -C(CH 3 ) 2 - or -0-
  • n represents an integer of 1 to 5 .
  • R represents a linear orbranchedalkylene grouphaving 2 to 6 carbon atoms
  • R 3 and R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen ' atom
  • X represents a single bond, -CO-, -SO 2 -, -CH 2 -, -C(CF 3 ) 2 -, -C(CH 3 )J- or -0-, andnrepresents anintegerof 1to5) andamercaptogroup-containing carboxylic compound represented by formula (12)
  • R 1 represents a linear orbranchedalkylene grouphaving
  • R 2 represents a linear orbranchedalkylene grouphaving 2 to 6 carbon atoms
  • R 3 and R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen atom
  • X represents a single bond, -CO-, -SO 2 -, -CH 2 -, -C(CF 3 J 2 -, -C(CH 3 J 2 - or -O-
  • n represents an integer of 1 to 5
  • R 1 represents a linear orbranchedalkylene group having 1 to 6 carbon atoms
  • a photosensitive composition comprising (A) a photopolymerization initiator system containing the thiol compound according to any one of 1 to 5, (B) a binder resin containing a carboxyl group and (C) a compound having an ethylenically unsaturated group.
  • Y represents a halogen atom and R 5 represents an alkyl group or an alkoxy group, which may have a substituent
  • the sensitizer is one or more compounds selected from the group consisting of benzophenone-based compounds, thioxanthone-based compounds and ketocoumarin-based compounds.
  • Thephotosensitivecompositionaccordingto7, inwhichthebinder resin containing a carboxyl group (B) further contains an ethylenically unsaturated group.
  • Aresistcompositionforblackmatrixofcolorfilters containing (A) a photopolymerization initiator system containing the thiol compound according to any one of 1 to 5, (B) a binder resin having a carboxyl group, (C) a compound having an ethylenically unsaturated group, (D) black pigment and (E) an organic solvent. 14. Theresist compositionforblackmatrixofcolorfiltersaccording to 13, wherein the binder resin (B) having a carboxylic group further has an ethylenically unsaturated group.
  • (D) black pigment 40 to 80 % by mass.
  • the thiol compoundto be used in the present invention is a thiol compound having a bisphenol skeleton in molecule which is represented by the formula (1)
  • R 1 represents a straight- or branched-chain alkylene group having 1 to 6 carbon atoms
  • R 2 represents a straight- or branched-chain alkylene group having 2 to 6 carbon atoms
  • R 3 and R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen atom
  • X represents a single bond, -CO-, -SO 2 -, -CH 2 -, -C(CF 3 ) 2 -, -C(CH 3 )2- or -0-
  • n represents an integer of 1 to 5 .
  • radical polymerization of the thiol compound When radical polymerization of the thiol compound is carried out, radical polymerization inhibition with oxygen can be remarkably decreased and thus a photosensitive composition may show a remarkable increase in photosensitivity. Furthermore, as the thiol compound according to the present invention contains a bisphenol skeleton having high hydrophobic property, when the thiol compound is exposed and cured, such hydrophobic property will impart a high resistance against alkali developer to a cured product even if the curing degree is comparatively low.
  • R 1 is preferably a straight- or branched-chain alkylene group having 1 to 6 carbon atoms. If the number of carbon atoms exceeds 6, the developing latitude decreases as the hydrophobic property of the thiol compound molecule itself decreases. More preferred as R 1 is an alkylene group having a structure represented by any one of formulae (2) to (6) .
  • the thiol compound having an alkylene group with any one of the structures representedby formulae (4) to ( ⁇ ) , which forms a secondary or tertiary mercapto group is particularly preferable.
  • R 2 is preferably a straight- or branched-chain alkylene group having 2 to ⁇ carbon atoms. If the number of carbon atoms exceeds 6, the developing latitude decreases as the hydrophobic property of the thiol compound molecule itself decreases. More preferred are an alkylene group having a structure represented by any one of formulae (7) to (9) : H 2 H 2 ⁇ % ( 7 )
  • R 3 andR 4 eachindependentlyrepresentsahydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen atom
  • X represents a single bond, -CO-, -SO 2 -, -CH 2 -, -C(CF 3 ) 2 -, -C(CH 3 ) 2 - or -0-
  • n is preferably an integer of 1 to 5. If the value of n exceeds 5, the development latitude decreases as the hydrophobic property of the thiol compound molecule itself decreases.
  • the thiol compound represented by formula (1) is preferably a polyfunctional thiol compound for imparting high sensitivity to the black matrix resist composition of the present invention. Therefore, as an alcohol that is used in esterification reactionwith amercapto group-containing carboxylic acid represented by formula (12) , a diol representedby formula (11) , i.e. a diol having a bisphenol skeleton where two alcoholic hydroxyl groups are present in one molecule is preferred.
  • R 1 represents a straight- or branched-chain alkylene group having 1 to 6 carbon atoms.
  • R 2 represents a straight- or branched-chain alkylene grouphaving2to6carbonatoms
  • R 3 andR 4 eachindependentlyrepresents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen atom
  • X representsasinglebond, -CO-, -SO 2 -, -CH 2 -, -C(CF 3 ) 2 -, -C(CH 3 ) 2 - or -0-
  • n represents an integer of 1 to 5.
  • diol compound represented by formula (11) examples include compounds wherein an alkylene oxide such as ethylene oxide or propylene oxide is added to the phenolic hydroxyl group of the following compounds.
  • Examples of compound having a phenolic hydroxyl group include, in a case where X is a single bond, 4,4'-biphenol and 3,3'-biphenol.
  • examples thereof include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl) ketone and bis(4-hydroxy-3,5-dichlorophenyl) ketone.
  • Examples of the compound in a case where X is -SO 2 - include bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3,5-dimethylphenyl) sulfone and bis(4-hydroxy-3,5-dichlorophenyl)sulfone.
  • Examples of the compound in a case where X is -CH 2 - include bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl) methane and bis(4-hydroxy-3,5-dichlorophenyl)methane.
  • Examples of the compound in a case where X is -C(CF 3 ) 2 - include bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane and bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane.
  • Examples of the compound in a case where X is -C(CH 3 ) 2 - include 2,2-bis (4-hydroxyphenyl)propane,
  • examples of compound having a phenolic hydroxyl group are not limited to the compounds above mentioned.
  • examples of the mercapto group-containing carboxylic acid represented by formula (12) include thioglycol acid,
  • Particularly preferable specific examples of the thiol compound represented by formula (1) include compounds represented by formulae (10), (14) and (15) .
  • m is an integer of 1 or 2
  • p is an integer of 1 or 2.
  • k is an integer of 1 or 2.
  • a thiol compound represented by formula (10) is more preferable in view of its reactivity.
  • a method of manufacturing the thiol compound having a bisphenol skeleton of the present invention, which is represented by formula (1) , is not particularly limited but the thiol compound may be obtained by an esterification reaction between a mercapto group-containing carboxylicacidrepresentedbyformula (12) andadiol havingabisphenol skeleton represented by formula (11) .
  • the esterification reaction itself is known in the art, so that the esterification reaction can be carried out in the usual manner to form ester.
  • the conditions of the esterification reaction are not particularly limited and the conventional reaction conditions may be suitably selected.
  • the photosensitive composition and black matrix resist composition of the present invention contain, as essential components, (A) aphotopolymerizationinitiatorsystemcontainingthethiolcompound represented by formula (1) , (B) a binder resin having a carboxyl group, and (C) a compound having an ethylenically unsaturated bond and may optionally contain any of various additives including pigments and solvents.
  • Photopolymerization initiator system (A) used in the photosensitive composition of the present invention may contain, in addition to the above thiol compound having a bisphenol skeleton, any one of other components, such as those to be commonly used in general photopolymerization initiator systems, such as radical generators and sensitizers.
  • radical generator usable in the resist composition forblackmatrix of color filters of the present invention include known compounds such as acetophenone compounds, triazine compounds, titanocene compounds and ketoxime compounds. In the light of photosensitivity, biimidazole compound and/or aminoacetophenone are preferred.
  • Y 2 , Y 3 , and Y 4 represent each independently a halogen atom, a cyano group or a nitro group
  • R 6 , R 7 , R 8 , R 9 and R 10 each independently represents a hydrogen atom, an alkyl group whichmayhave a substituent, or an alkoxy group which may have a substituent.
  • the halogen atoms represented by the above Y 2 , Y 3 , and Y 4 include a chlorine atom, a bromine atom, and a fluorine atom.
  • R 8 , R 9 and R 10 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group. They may have substituents such as an alkoxy group and a halogen atom. Of those, preferable is a straight- or branched-chain alkyl group having 1 to 6 carbons and more preferable is a straight- or branched-chain alkyl group having 1 to 3 carbons.
  • Examples of the alkoxy groups represented by the above R 6 , R 7 , R 8 , R 9 , and R 10 include amethoxy group, an ethoxy group, a propoxy group, ann-butoxygroup, anisobutoxygroup, atert-butoxygroup, ann-pentyloxy group, and an n-hexyloxy group. They may have substituents such as an alkoxy group and a halogen atom. Of those, preferable is a straight- or branched-chain alkoxy group having 1 to 6 carbons andmorepreferable is a straight- or branched-chain alkoxy group having 1 to 3 carbons. Of those hexaarylbiimidazole compoounds, a compound having a structure represented by formula (13) is particularly preferable.
  • Y represents a halogen atom and R represents an alkyl group which may have a substituent or an alkoxy group which may have a substituent.
  • R 5 includes the same groups as those listed for R 6 to R 10 of the hexaarylbiimidazole compound represented by formula (16) but a methyl group or a methoxy group is particularly preferable.
  • a chlorine atom is particularly preferable as a halogen atom represented by the above Y.
  • Examples of an acetophenone-based compound used in the present invention include hydroxyacetophenone compounds and aminoacetophenone compounds. Of those, in terms of photosensitivity, aminoacetophenone compounds are particularly preferable.
  • hydroxyacetophenone compound ' examples include ⁇ -hydroxyacetophenones such as
  • aminoacetophenone compound 2-hydroxy-l- (4-(2-hydroxyethoxy) -phenyl)-2-methylpropan-l-one.
  • aminoacetophenone compound include ⁇ -a ' minoacetophenones such as
  • radical generators include benzoin methylether, benzoinethylether, benzoinisopropylether, benzylmethyl ketal, ⁇ -halogenoacetophenones, methylphenylglyoxylate, benzyl, anthraquinone, phenanthrenequinone, camphorquinoneisophthalophenone, acylphosphine oxide, ⁇ -acyloxime ester, benzyl, and camphor quinone.
  • the organic boron salt-based compound described in JP 2000-249822 A can be also used.
  • sensitizers commonlyusedinthegeneral photopolymerization initiator systems can be used.
  • one or more compounds selected fromthe group consisting ofbenzophenone-based compounds, thioxanthone-based compounds and ketocoumarin-based compounds are preferably used, as the sensitivity can be enhanced.
  • sensitizer examples include: a benzophenone-based compound such as benzophenone, 2, 4, ⁇ -trimethylbenzophenone, 4-phenylbenzophenone, 4-benzoyl-4' -methyldiphenyl sulfide, 4,4' -bis (dimethylamino)benzophenone or 4, 4' -bis (diethylamino)benzophenone; a thioxanthone-based compound such as thioxanthone, 2-methylthioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, isopropylthioxanthone, 2, 4-diisopropylthioxanthone or 2-chlorothioxanthone; and a ketocoumarin-based compound such as 3-acetylcoumarin, 3-acetyl-7-diethylaminocoumarin, 3-benzoylcoumarin, 3-benzoyl-7-diethylaminocoumarin
  • Thecompoundingratioofeachcomponentinthephotopolymerization initiator system (A) is as follows.
  • the content of the thiol compound having a bisphenol skeleton representedbyformula (1) is preferably20to70%bymass, morepreferably 30 to 60 % by mass. If the content is less than 20% by mass, the photosensitivity and development latitude may decrease. On the other hand, if the content exceeds 70 % by mass, the developability may i deteriorate.
  • the content of the radical generator is preferably 20 to '80 % by mass, more preferably 30 to 70%- by mass. If the content is less than 20% bymass, the photosensitivitymaydecrease. On the other hand, if the content exceeds 80% by mass, the line width tends to be larger than the line width of photomask.
  • the content of the sensitizer is preferably 5 to 40 % by mass, more preferably 10 to 30 % by mass. If the content is less than 5% bymass, the photosensitivity may decrease. The content exceeding 40% bymass is not preferred inthat the light transmission towardthebottom of the photosensitive composition is prevented, which causes the shape of cross-section of the resist to be reverse-trapezoidal, resulting in decrease in resolution.
  • the binder resin (B) used in the present invention has a carboxyl group on its side chain, which is a component that predominantly determines the properties of the resist, such as the film strength, thermal resistance, substrate adhesiveness, solubility to an aqueous alkaline solution and alkaline developability.
  • binder resin (B) examples include an 'acrylic copolymer (AP) having a carboxyl group, an epoxy (meth) acrylate resin (EA) having a carboxyl group and a urethane (meth)acrylate resin (UA) having a carboxyl group.
  • epoxy(meth)acrylate resin is preferable.
  • Particularly preferred is a bisphenol-type epoxy(meth) acrylate resin having a carboxylic acid.
  • Acrylic copolymer (AP) having carboxyl group t The acrylic copolymer having a carboxyl group can be obtained by copolymerizing:
  • the ethylenicallyunsaturatedmonomer (a) containing a carboxyl group is used for the purpose of imparting the acrylic copolymer (AP) with alkaline developability.
  • ethylenically unsaturated monomer (a) containing a carboxyl group examples include (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl phthalate, (meth)acryloyloxyethyl hexahydrophthalate, (meth)acrylic aciddimer, maleicacid, crotonicacid, itaconicacid, andfumaricacid.
  • the ethylenically unsaturated monomer (b) other than the above item (a) is used for the purpose of controlling the film strength and pigment dispersibility.
  • ethylenically unsaturated monomer (b) other than the above item (a) include: a vinyl compound such as styrene, ⁇ -methylstyrene,
  • (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl (meth)acrylate, tert-butyl(meth)acrylate, n-hexyl(meth)acrylate, cyclohexyl(meth)acrylate, benzyl(meth)acrylate, phenoxyethyl(meth)acrylate, isobornyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, (meth)acrylonitrile, glycidyl(meth)acrylate, allylglycidyl ether, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, i N,N-dimethylaminoethyl (meth) acrylate, trifluoroethyl
  • An acrylic copolymer having an ethylenically unsaturated group on ' the side chain which is obtained by reacting an epoxy group of a compound having an epoxy group and an ethylenically unsaturated group in one molecule (such as glycidyl (meth)acrylate, 3, 4-epoxycyclohexyl methyl (meth)acrylate, 4- (2, 3-epoxypropyl)butyl (meth) acrylate or allylglycidyl ether) with a carboxyl group as a part of the side chain ofanacryliccopolymerobtainedbycopolymerizationoftheabovemonomers or by reacting part or whole of hydroxy1 groups of an acrylic copolymer with an isocyanate group of a compound having the isocyanate group and an ethylenically unsaturated group in one molecule such as 2-methacryloyloxyethylisocyanate, canbealsousedwithoutanyproblem.
  • Thecopolymerizationratiobetweentheethylenicallyunsaturated monomer (a) containingacarboxylgroupandtheethylenicallyunsaturated monomer (b) other than the above item (a) is preferably from 5 : 95 to40 : 60, morepreferablyfrom10 : 90to50 : 50. Ifthecopolymerization ratio of the above item (a) is less than 5, the pattern formation may become difficult due to decrease in alkaline developability. If the copolymerization ratio of the above item (a) exceeds 60, alkali-development of photo-cured portions readily proceeds and therefore, it is difficult to keep the line width constant.
  • the molecular weight of the acrylic copolymer having a carboxyl i group and an ethylenically unsaturated group is preferably in the range of 1,000 to 500,000, more preferably 3,000 to 200,000 in terms of polystyrene as measured by GPC. If- the molecular weight is less than 1,000, the film strength may decrease markedly. On the other hand, if the molecular weight exceeds 500,000, the alkaline developability may decrease markedly.
  • the epoxy (meth)acrylate resin (EA) having a carboxyl group to be used in the present invention is not specifically limited, however, an ' epoxy (meth)acrylate resin obtained by reacting an acid anhydride with aproduct ofthe reactionbetweenan epoxyresinoranepoxycompound and an unsaturated group-containing monocarboxylic acid, is suitably used.
  • Examples of the epoxy resin to react with an unsaturated- group-containing monocarboxylicacid include abisphenolAtype epoxy resin, a hydrogenated bisphenol A type epoxy resin, a brominated bisphenolAtypeepoxyresin, abisphenol Ftypeepoxyresin, abisphenol S type epoxy resin, a novolac type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a triphenylmethane type epoxy resin, a naphthalene type epoxy resin, an N-glycidyl type epoxy resin, a dicyclopentadiene phenolic epoxy resin, a diglycidylphthalate resin, a heterocyclic epoxy resin, a bixylenol type epoxy resin, and a biphenyl type epoxy resin. Each of them may be used alone, or two or more kinds thereof may be used in combination.
  • Examples of the epoxy compound to be reacted with the unsaturated group-containing monocarboxylic acid includeepoxycompounds suchasabisphenolAtypeepoxycompound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, aphenolnovolactypeepoxycompound, acresolnovolactypeepoxycompound i and an aliphatic epoxy compound. Each of them can be used alone, or two or more kinds thereof can be used in combination.
  • Examplesoftheunsaturatedgroup-containingmonocarboxylicacid tobereactedwiththeepoxyresinorepoxycompoundin include (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid,
  • Examples of such unsaturated group-containing monocarboxylic acid further include a half ester compound as a reaction product of a hydroxyl group-containing acrylate with a saturated or unsaturated dibasic anhydride, and a half ester compound as a reaction product of an unsaturated group-containing monoglycidyl ether with a saturated or unsaturated dibasic anhydride.
  • Each of the unsaturated group-containing monocarboxylic acids can be used alone or two or more kinds thereof can be used in combination.
  • the acid anhydride examples include: a dibasic anhydride such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride or methyltetrahydrophthalic anhydride; an aromatic polycarboxylic anhydride such as trimellitic anhydride, pyromelliticanhydrideorbenzophenonetetracarboxylicdianhydride; and a polycalboxylic anhydride derivative such as
  • the epoxy (meth) acrylate resin (EA) having a carboxyl group thus obtained has, but not specifically limited to, a molecular weight of preferably 1,000 to 40,000, more preferably 2,000 to 5,000 in terms of polystyrene as measured by GPC.
  • EA (means a solid acid value measured in accordance with JIS K0070, the same will be applied in the following description) is preferably 10 mgKOH/g or more, more preferably in the range of 45 to IGO mgKOH/g, furtherpreferably in the range of 50 to 140 mgKOH/g, which can establish a goodbalance between the alkali solubility andthe alkaline resistance of a cured film. If the acid value is less than 10 mgKOH/g, the alkaline solubility may decrease. On the other hand, an excessively large acid value may cause decrease in the characteristic features of the cured film such as alkaline resistance, in some cases of certain combinations of constituents of the photosensitive composition.
  • the urethane (meth) acrylate resin (UA) having a carboxyl group used in the present invention is a binder resin which is more flexible than the acrylic polymer (AP) or the epoxy (meth) acrylate resin (EA), and therefore, it is used in the applications where flexibility and bending resistance.
  • the urethane (meth) acrylate resin (UA) having a carboxyl group contains a unit originated from (meth) acrylate having a hydroxyl group, aunitoriginatedfrompolyol, andaunit originatedfrompolyisocyanate.
  • the repetitive structure of the urethane (meth)acrylate resin (UA) having a carboxyl group can be represented by formula (17) .
  • ORbO represents a dehydrogenation residue of polyol and Rc represents a deisocyanate residue of polyisocyanate.
  • the urethane (meth)acrylate resin (UA) having a carboxyl group can be produced by carrying out a reaction of at least (meth)acrylate having a hydroxyl group, polyol and polyisocyanate.
  • a compound having a carboxyl group should be used as at least one of the polyol and the polyisocyanate.
  • polyol having a carboxyl group is used. In this way, by the use of the compound having a carboxyl group as polyol and/orpolyisocyanate, theurethane (meth)acrylate resin (UA) in which a carboxyl group is present in Rb or Rc can be produced.
  • the integer n is preferably about 1 to 200, morepreferably2 to 30. Ifn iswithin suchranges, the flexibility of the cured film may be more excellent. Furthermore, if two or more kinds of at least one of polyol and polyisocyanate are used, the repeating unit represents multiple kinds.
  • the regularity of the units can be suitably selected from “complete random”, “block”, “localized” and the like, depending on the purpose.
  • Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, a caprolactone or alkylene oxide adduct of the above-described (meth) acrylates, glycerin mono(meth)acrylate, glycerindi (meth)acrylate, aglycidylmethacrylate-acrylicacidadduct, trimethylolpropanemono(meth) acrylate, trimethylol di (meth)acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth)acrylate and a trimethylolpropane-alkylene oxide adduct of di (meth)acrylate.
  • the (meth)acrylate (a) having a hydroxyl group can be used alone or two or more kinds thereof can be used in combination. Of those, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate and hydroxybutyl (meth) acrylate are preferable, and 2-hydroxyethyl (meth)acrylateismorepreferable. When2-hydroxyethyl (meth)acrylate is used, synthesis of a urethane (meth)acrylate (UA) resin containing a carboxyl group is easier.
  • Apolymer polyol and/or dihydroxyl compound canbe used as polyol to be used in the present invention.
  • the polymer polyol include: a polyether-based diol such as polyethylene glycol, polypropylene glycol, or polytetramethylene glycol; a polyester-based polyol obtained by a reaction between polyhydric alcohol and ester of polybasicacid; apolycarbonate-baseddiolhavingas a constituentunit, aunitderivedfromhexamethylenecarbonateorpentamethylenecarbonate; and a polylactone-based diol such as polycaprolactone diol or polybutyrolactone diol.
  • polymer polyol having a carboxyl group for example, a polymer polyol obtained by a synthesis process wherein a polybasic acid having 3 or higher valence such as (anhydrous) trimellitic acid isallowedtocoexisttotherebyprepareapolymerpolyolwhereacarboxyl group remains, can be employed.
  • a polymer polyol obtained by a synthesis process wherein a polybasic acid having 3 or higher valence such as (anhydrous) trimellitic acid isallowedtocoexisttotherebyprepareapolymerpolyolwhereacarboxyl group remains.
  • One kind of such a polymer polyol may beused, ortwoormore kinds ofpolymerpolyolmaybeusedincombination.
  • those polymer polyols those each having an average molecular weight of 200 to 2,000 are preferably used, which enhances the excellent flexibility of the cured film.
  • a branched- or straight-chain compound having two alcoholic hydroxyl groups canbe used as the above dihydroxyl compound.
  • Suchadihydroxycompound maybedimethylol propionic acid or dimethylol butanoic acid.
  • a carboxyl group can be easily present in a urethane (meth)acrylate resin (UA) .
  • U urethane
  • Each of those dihydroxyl compounds may be used singly or two or more of them may be used in combination.
  • the dihydroxyl compound may be used together with polymer polyol.
  • adihydroxylcompoundhaving no carboxyl group for example, ethylene glycol, diethylene glycol, propylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol, neopentyl glycol, 3-methyl-l, 5-pentanediol, 1, ⁇ -hexanediol or 1,4-cyclohexanedimethanol
  • polyisocyanate to be used in the present invention include diisocyanates such as 2,4-toluene diisocyanate, 2, ⁇ -toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, (o, m, or p)-xylene diisocyanate, methylene bis (cyclohexyl isocyanate) , trimethylhexamethylene diisocyanate, cyclohexane-1, 3-dimethylene diisocyanate, cyclohexane-1, 4-dimethylene diisocyanate and 1,5-naphthalene diisocyanate.
  • the polyisocyanate can be used alone or two or more kinds thereof can be in combination.
  • a polyisocyanate having a carboxyl group can be also used.
  • the molecular weight of the urethane (meth) acrylate resin (UA) havinga carboxyl groupusedinthepresent invention is not specifically limited, however, the mass average molecular weight in terms of polystyrene as measured by GPC is preferably 1,000 to 40,000, more preferably 8,000 to 30,000. If the mass average molecular weight of the urethane (meth) acrylate resin (UA) having a carboxyl group is less than 1,000, the elasticity and flexibility of the cured film may be deteriorated. On the other hand, a mass average molecular weight of more than 40,000 may lower the flexibility because the resin becomes too hard.
  • the acid value of the urethane (meth) acrylate resin (UA) is preferably 5 to 150 mgKOH/g, more preferably 30 to 120 mgKOH/g. Iftheacidvalueislessthan5mgKOH/g, thealkalinesolubility of the curable resin composition for resist may decrease. On the other hand, if the acid value exceeds 150 mgKOH/g, the alkaline resistance or ' the like of the cured film may deteriorate. 2-3.
  • the compound (C) havinganethylenicallyunsaturatedgroup which is included in the photosensitive composition of the present invention, is a compound other than the binder resin (B) described above and may be used for the purpose of adjusting the photosensitivity of the photosensitive composition or adjusting the physical properties of the cured product of the photosensitive composition, such as thermal resistance and flexibility.
  • (meth)acrylate is used.
  • Specific examples of the compound (C) having an ethylenically unsaturated group include: alkyl (meth) acrylate (such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth)acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate or stearyl (meth) acrylate) ; alicyclic (meth)acrylate (such as cyclohexyl (meth)acrylate, bornyl (meth)
  • (meth)acrylate having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, butanediol mono(meth) acrylate, glycerol (meth)acrylate, polyethyleneglycol (meth) acrylateorglycerol di(meth)acrylate) ;
  • (meth)acrylate having an amino group such as 2-dimethylaminoethyl (meth)acrylate, 2-diethylaminoethyl (meth)acrylate or 2-tert-butylaminoethyl (meth)acrylate
  • methacrylate having a phosphorus atom such as methacryloxyethyl phosphate, bis-methacryloxyethyl phosphate, or methacryloxyethyl phenyl acid phosphate
  • di (meth)acrylate suchas ethyleneglycol di (meth) acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylenedi(meth)acrylate, polyethyleneglycoldi (meth)acrylate, propyleneglycoldi (meth)acrylate, dipropyleneglycoldi (meth)acrylate, tripropyleneglycoldi (meth)acrylate
  • N-vinyl compound such as N-vinylpyrrolidone, N-vinylformaldehyde, orN-vinylacetamide
  • polyester (meth) acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, or the like can be suitablyused as a compound having an ethylenically unsaturated group.
  • preferable examples include poly(meth)acrylates such as di (meth)acrylate of 4-mol ethyleneoxide adduct of bisphenol A, di (meth)acrylate of 4-mol propyleneoxide adduct of bisphenol A or dimethylol tricyclodecane di (meth)acrylate with the object of the pattern configuration; and trimethylolpropane tri (meth)acrylate, pentaerythrytol tetra (meth)acrylate, or dipentaerythrytol hexa(meth)acrylate with the object of photosensitivity.
  • Pigment (D) may be blended in the photosensitive composition
  • C.I. Pigment Black 7 C.I. Pigment Black 7; and titanium black.
  • Each of the pigments may be used alone, or two or more of them may be used in combination.
  • black pigment (D) used in the resist composition for black matrix for color filters of the present invention include carbonblack, acetyleneblack, lampblack, graphite, ironblack, aniline black, cyanine black and titanium black.
  • a black pigment formed by mixing organic pigments of red, green and blue may be used.
  • carbon black and titanium black are particularly preferred in light of light-shielding and image property. Examples of commerciallyavailable carbonblacks include the followingproducts.
  • ManufacturedbyMitsubishiChemicalCorporation MA7, MA8, MAIl, MAlOO, MA220, MA230, #52, #50, #47, #45, #2700, #2650, #2200, #1000, #990, #900.
  • Manufactured by Degussa Printex 95, Printex 90, Printex 85, Printex 75, Printex 55, Printex 45, Printex 40, Printex 30, Printex 3, Printex A, Printex G, Special Black 4, Special Black 550, Special Black 350, Special Black 250, Special Black 100.
  • Manufactured by Cabot Corporation Monarch 460, Monarch 430, Monarch 280, Monarch 120, Monarch 800, Monarch 4630, REGAL 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL250R, REGAL 330, BLACK PEARL S480, PEARL S130.
  • Columbian Carbon Co Manufactured by Columbian Carbon Co.
  • Raven 11 Raven 15, Raven 30, Raven 35, Raven 40, Raven 410, Raven 420, Raven 450, Raven 500, Raven 780, Raven 850, Raven 890H, Raven 1000, Raven 1020, Raven 1040, Raven 1060, Raven 1080, Raven 1255.
  • the above-mentioned black pigments may be used in combination with each other.
  • a combination of a carbon black and a titanium black contributes to a higher light-shielding property. 2-5.
  • Solvent (E) Further, according to use of the product, various additives may be added to the photosensitive composition and the black matrix resist composition of the present invention in order to impart viscosity, operability, properties as cured product, and the like. Solvent (E) may be added- ' for the purposes of, for example, obtaining sufficient dispersibility of the components, improvement in operability and adhesion at the,time of coating and adjusting the viscosity.
  • volatile solvent examples include methanol, ethanol, toluene, xylene, ethylbenzene, cyclohexane, isophorone, cellosolve acetate, diethylene glycol dimethyl ether, ethyleneglycoldiethylether, ethyleneglycolmonoethylether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, isoamyl acetate,
  • ethyl lactate ⁇ -butyrolactone
  • methylethyl ketone acetone
  • cyclohexanone a reactive solvent (E) may be used.
  • reactive solvent examples include 2-hydroxyethyl (meth)acrylate, methyl (meth)acrylate, n-butyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl(meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N-acryloylmorpholine, N-acryloylpiperidine, N,N-dimethyl (meth)acrylamide, N-vinylpyrrolidone and N-vinylacetamide. Each of them can be used alone, or two or more kinds thereof can be used as a mixture.
  • the above-described volatile solvent may be further added to the reactive solvent when necessary.
  • the organic solvent (E) to be used in the black matrix resist composition of the present invention is not particularly limited as long as the organic solvent can dissolve and disperse each of the above-described components constituting the black matrix resist composition of the present invention.
  • Specific examples thereof include methanol, ethanol, isopropanol, toluene, xylene, ethylbenzene, cyclohexane, isophorone, cellosolve acetate, diethyleneglycol dimethyl ether, ethyleneglycoldiethylether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propyleneglycol monomethyl ether, propyleneglycol monomethyl ether acetate, propyleneglycol monoethyl ether acetate, diethyleneglycol ethyl ether acetate, methyl methoxypropionate, ethylmethoxypropionate, methyl ethoxypropionate, eth
  • the black matrix resist composition of the present invention by means of any of those organic solvents so as to be of a solid concentration of 5 to 30% by mass, preferably 10 to 25% by mass. 2-6.
  • Other optional components
  • a pigment dispersant in addition to the above essential components, a pigment dispersant, an adhesion-improving agent, a leveling agent, a development improver, anoxidationinhibitor, athermalpolymerization inhibitor or the like may be suitably added to the black matrix resist composition of the present invention.
  • the pigment dispersant in the coloring composition, it is preferable in some cases that the pigment dispersant be blended in, since it is important to finely disperse the coloring material and stabilize the dispersion state in light of quality stabilization.
  • the pigment dispersant has an affinity to each of the pigment and the binder resin, and examples thereof include nonionic, cationic, and anionic surfactants and polymer dispersants. Of those, polymer dispersants are preferable.
  • a polymer dispersant containing: abasicfunctionalgroup, forexampleanitrogen-containing heterocyclic group such as a primary, secondary, or tertiary amino group, pyridine, pyrimidine, or pyrazine; or a functional group, for example an amide group or a urethane group, maybe advantageouslyused.
  • the photosensitive composition and the black matrix resist composition of the present invention may further contain fluorescent whiteners, surfactants, plasticizers, flame-retardants, antioxidants, UV absorbents, foaming agents, fungicides, antistatic agents, magnetic materials, electrically conductive materials, antimicrobial/bactericidal agents, porous adsorbents, perfumes andthe
  • the photosensitive composition and the blackmatrix resist composition of the present invention may contain a heat polymerization inhibitor in order to prevent polymerization during storage.
  • a heat polymerization inhibitor include p-methoxyphenol, hydroquinone, catechol, tert-butylcatechol, phenothiazine and methoquinone. 2-7. Blendingratioofeachcomponentinthephotosensitivecomposition Thecompoundingratioofthephotopolymerizationinitiatorsystem
  • (A) in the photosensitive composition of the present invention is preferably 1 to 40 % by mass, more preferably 3 to 30 % by mass. If the compounding ratio is less than 1 % by mass, the photosensitivity may deteriorate. If the compounding ratio exceeds 40 % by mass, the mechanical strength of the cured product may decrease.
  • the blending ratio of each of the components in the blackmatrix resist compositionofthepresent invention is notparticularlylimited but the ratio of each component other than the organic solvent (E) to the total content (total solid content) is preferably within the following range .
  • the amount of the photopolymerization inhibitor system is preferably 2 to 15 % by mass, more preferably 5 to 10 % by mass. ' If the amount of the photopolymerization initiator system is too small, itisdisadvantageousinthatphotosensitivityanddevelopmentlatitude decrease. If the amount is too large, it is disadvantageous in that the line width of lines formed in the resist patterns are wider than that of the lines of the photomask.
  • the amount of the binder resin having a carboxyl group is preferably 10 to 30 % by mass, more preferably 15 to 25 % by mass.
  • Theamountofthecompoundhavinganethylenicallyunsaturated group is preferably 2 to 20 % by mass, more preferably 3 to 15 % by mass. Iftheamountofthecompoundhavinganethylenicallyunsaturated group is too small, it is disadvantageous in that photosensitivity decreases. If the amount is too large, it is disadvantageous in that the line width of lines formed in the resist patterns are wider than that of the lines of the photomask.
  • the amount of the black pigment is preferably 40 to 80 % by mass, more preferably 45 to 70 % by mass. If the amount of the blackpigmentistoosmall, itisdisadvantageousinthatlight-blocking effect decreases. If the amount is too large, it is disadvantageous inthatphotosensitivityandadhesivenesswiththe substratedecrease. 3. Manufacturingprocess anduses ofthephotosensitivecomposition
  • the photosensitive composition containing a pigment can be producedbymeansofvariouskindsofdispersingmeanssuchasathree-roll mill, a two-roll mill, a sand mill, an atoliter, a ball mill, a kneader
  • apolymerizationinhibitor may be added to prevent gelation caused by polymerization reactionorthelikeatthetimeofdispersing.
  • the monomer and photopolymerization initiator may be compounded after the pigment is dispersed.
  • a dispersion aid maybe addedas appropriate. The dispersion aid helps pigments be dispersed and also prevents reagglomeration after the dispersion.
  • anextender pigment such as barium sulfate, calcium carbonate, silica, titania, alumina, oraluminumpowdermaybeaddedtothephotosensitivecomposition of the present invention.
  • the photosensitive composition of the present invention may be applied onto a substrate, such as glass, aluminum, a PET film, or a polyesterfilmbyacoatingmethodsuchas spraycoating, spinnercoating, roll coating, screen coating, spread coating, dip coating, or calendar coating.
  • a substrate such as glass, aluminum, a PET film, or a polyesterfilmbyacoatingmethod suchas spraycoating, spinnercoating, roll coating, screen coating, spread coating, dip coating, or calendar coating.
  • a small amount of silicone- or fluorine-based surfactant as a leveling agent or defoaming agent may be added to the photosensitive composition of the present invention.
  • the photosensitive composition coated by means of any one of the above coating methods is dried when necessary by a hot-air oven or a hot plate generally under conditions of 60 to 100 0 C for 10 to 30 minutes to evaporate the volatile solvent. If the temperature in this instance is too high or the heating time is too long, polymerization orcross-linkingpartiallyoccurs, sothatthesolubilityofanunexposed portion in the developer is decreased to cause so-called burn, which is undesirable. Drying may be performed under reduced pressure.
  • the methods of forming a pattern of a certain configuration with the photosensitive composition of the present invention are roughly classified into two types. One is a method involving coating the photosensitive composition in a desired configuration and then curing it by irradiation with light.
  • the other is a method involving applying the photosensitive composition evenly onto a substrate, irradiating the photosensitive composition with light so that the exposed portion forms a desired configuration to cure the photosensitive composition and then removing an unexposed portion by means of washing, peeling, physical polishing, chemical polishing, or the like to form a pattern with the photo-cured product.
  • a suitable pattern can be formed by the latter method of pattern formation.
  • examples of a solventforadeveloperin includeN-methylpyrrolidone, methanol, ethanol, toluene, cyclohexane, isophorone, cellosolve acetate, diethylene i glycol dimethyl ether, ethylene glycol diethyl ether, xylene, ethylbenzene, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, isoamyl acetate, ethyl lactate, methylethyl ketone, acetone, cyclohexanone, N,N-dimethyl formamide, acetonitrile, and an alkali aqueous solution. Each of themmay be used alone, or
  • alkali aqueous solution examples include: an aqueous solution of an inorganic salt such as sodium hydroxide, potassium hydroxide, sodium carbonate, or potassium carbonate; and an aqueous solution of an organic salt such as hydroxytetramethyl ammonium or hydroxytetraethyl ammonium. Each of them may be used alone, or two or more kinds thereof can be used in combination.
  • an inorganic salt such as sodium hydroxide, potassium hydroxide, sodium carbonate, or potassium carbonate
  • organic salt such as hydroxytetramethyl ammonium or hydroxytetraethyl ammonium.
  • the photosensitive composition of the present invention can be suitably used particularly for a development type resist that forms finepatterns.
  • a development type resist that forms finepatterns.
  • Specificexamplesthereofin includeopticalplatemaking, solder resists, etching resists, color filter resists, holograms, optical sculpturing and UV ink. 4. Manufacturing method of the black matrix resist composition
  • the production of the black matrix resist composition of the present invention is carried out by: mixing or premixing (B) a binder resin having a carboxyl group, (E) an organic solvent, (D) a black pigment, and optionally a pigment dispersant; subjecting the mixture to dispersion treatment; and mixing in and dissolving (C) a compound havinganethylenicallyunsaturatedgroupand (A) aphotopolymerization initiator system into the resultant.
  • a disperser for carrying out the dispersion treatment may be
  • roll mills such as a two-roll mill and a three-roll mill
  • ball mills such as a ball mill and a vibration ball mill
  • be'ads mills such as a paint conditioner, a continuous disk type beads mill, and a continuous annular-stirred bead mill.
  • acontinuousannular-stirredbeadmill whichcanperformpulverization and dispersion within a short time and attains a sharp distribution ofparticle diameters afterdispersionandinwhichtemperature control during pulverization and dispersion is easy so that deterioration of the dispersion solution can be prevented.
  • Acontinuous annular-stirredbeadmill is constituted such that a rotor (bodyof rotation) havinggrooves for stirringbeads is inserted into a vessel (cylindrical body) having an inlet and an outlet for the material.
  • thebeads areallowedtomovearoundbythe rotation of the rotor, to thereby pulverize, shear and grind to effectively pulverize and disperse the black pigment.
  • the sample is introduced throughtheendportionofthevesselandthenformedintofineparticles, andthendischargedfromthe opposite sideofthe inlet. This treatment is repeated until the desired particle size distribution is obtained.
  • the term "residence time” refers to a time period in which the 1 sample is actually pulverized and dispersed in the vessel.
  • Suchacontinuous annular-stirredbeadsmill maybe, forexample, SPIKE MILL (trade name) manufactured by Inoue Manufacturing, Inc., or OB-MILL (trade name) manufactured by Turbo Kogyo Co., Ltd.
  • Preferable dispersion conditions for using the continuous annular-stirred bead mill are as follows.
  • the bead size (diameter) used is preferably 0.2 to 1.5 mm, more preferably 0.4 to 1.0 mm. If the bead size is less than 0.2 mm, the weight of a single bead is too small and the pulverization energy of the single bead is then reduced i and the pulverization of the pigment does not proceed. If the bead size exceeds 1.5 mm, the collision frequency between the beads becomes low and performing the pulverization of carbon black within a short time is difficult.
  • ceramics such as zirconia and alumina and stainless steel, which have a specific gravity of 4 or more, are preferable in light of high pulverization efficiency.
  • the peripheral speed of the rotor is preferably 5 to 20 m/second, more preferably 8 to 15 m/second. If the peripheral speed is less than 5 m/second, the pigment cannot be pulverized and dispersed sufficiently. If the peripheral speed exceeds 20 m/second, it is not preferable in that the pigment dispersion solution has an excessively increased temperature due to frictional heat and that denaturation such as thickening may occur.
  • the temperature at dispersion is preferably within the range of 10 to ⁇ O°C, more preferably within the range of room temperature to 50°C. A temperature lower than 10 0 C is not preferable in that atmospheric moisture may be mixed into the dispersion solution due to dew condensation. Atemperature in excess of 60 0 C is not preferable in that changes such as thickening may occur.
  • the residencetime is preferably 1 to 30minutes, morepreferably 3 to 20 minutes. If the residence time is shorter than 1 minute, the pulverization and dispersion treatments may be insufficient. If the residence time exceeds 30 minutes, the dispersion solution may be deteriorated and thickened.
  • a method of manufacturing a color filter using the black matrix resist composition of the present invention will be described.
  • the description will be made with reference to a color filter for a liquidcrystaldisplaydevice, whereablackmatrixresistcomposition, pixels and a protective film are laminated in this order.
  • the black matrix resist composition of the present invention is applied on a transparent substrate. Then, after a solvent is dried in an oven or the like, black matrix patterns are formed by exposure/ development through a photomask and post baking is then carried out, thereby completing the formation of a black matrix.
  • the transparent substrate examples include, but not particularly limited to: inorganic glass such as quartz glass, borosilicate glass and lime soda glass having a silica-coated surface; andfilms and sheets of polyesters such as polyethylene terephthalate, polyolefins such as polypropylene and polyethylene, polycarbonate, polymethylmethacrylate, and thermoplastics of polysulfone, an epoxy resin, and thermosetting plastics such as a polyester resin.
  • Those transparent substrates may be previously subjected to any one of a coronadischargetreatment, anozonetreatment, orathinfilmtreatment with various polymers such as a silane-coupling agent and a urethane polymer.
  • Coating methods include, in addition to methods of dip coating, a role coater, a wire bar, a flow coater, a die coater and a spray coating, spin coating such as a method using a spinner.
  • Drying of a solvent is carried in a drying device such as a hot plate, an IR oven, or a convection oven.
  • a drying device such as a hot plate, an IR oven, or a convection oven.
  • Preferable drying conditions include a temperature of 40 to 150°C and a drying time period within 10 seconds to 60 minutes.
  • the solvent may be dried in a vacuum.
  • An exposure method involves: providing a 50-200 urn space (gap) above the sample/ placing a photomask thereon; and carrying out an image exposure.
  • light sourcewhich canbeusedforexposure include: lamplight sources suchas axenon lamp, ahighpressuremercury lamp, anultra-highpressuremercurylamp, ametalhalidelamp, amoderate pressuremercury lamp, anda low-pressuremercury lamp; and laser light sources such as an argon ion laser, a YAG laser, an excimer laser and a nitrogen laser. When only light having a specific irradiation wavelength is used, an optical filter may be used.
  • the developing process is carried out using a liquid developer to develop a resist by a dipping, shower, or paddle method or the like.
  • the liquid developer is not particularly limited as far as it is capable of dissolving a resist film on an unexposed portion.
  • organic solvents including acetone, methylene chloride, trichlene, and cyclohexanone can be used.
  • many of the organic solvents may causeenvironmentalpollution, havetoxicitytothehumanbodyorinclude fire hazard. Therefore, it is preferable to use an alkali liquid developerhavingno suchrisks.
  • the alkali liquiddeveloper examples include aqueous solutions containing: inorganic alkali agents such as sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide andpotassiumhydroxide; and organic alkali agents such as diethanolamine, triethanolamine and tetra-alkyl-ammonium hydroxide.
  • a surfactant, a water-solubleorganicsolvent, alowmolecularcompoundhavingahydroxy1 group or a carboxyl group or the like may be added to the alkali liquid developer.
  • a surfactant which has effects of improving developability and resolution and reducing scumming.
  • surfactants used in the liquid developer include: anionic surfactants each having a sodium naphthalenesulfonate group or a sodium benzenesulfonate group; nonionic surfactants each having a polyalkyleneoxy group; and cationic surfactants each having a tetraalkylammoniumgroup. Amethod ofdevelopment is notparticularly
  • the development is carried out at a development temperature of preferably 15 to 50 0 C, more preferably 15 to 45 0 C by means of a method such as immersion development, spray development, brush development or ultrasonic wave development.
  • Post bake is performed at temperatures ranging from 150 to 300 0 C for a time period of 1 to 120 minutes using the same apparatus as one used in drying the solvent.
  • the black matrix thus obtained has a film thickness preferably in the range of 0.1 to 1.5 urn, more preferably in the range of 0.2 to1.2urn. Furthermore, forattainingthefunctionsoftheblackmatrix, in those filmthicknesses, the optical density is preferably 3 ormore.
  • pixels of mutiple colors are formed in the spaces of the black matrix.
  • the colors of the respective pixels usually are three colors, red (R) , green (G) andblue (B) , andaphotosensitivecomposition iscoloeredwithapigmentoradye.
  • thecoloredphotosensitive composition is appliedon a transparent substrate onwhichblackmatrix patterns are placed.
  • the solvent is dried in an oven or the like to form a colored layer of the first color all over the entire surface of the black matrix.
  • unnecessary portions of the first color layer may be removed by photolithography to form a desired first-color pixel pattern.
  • the pixel film thickness is about 0.5 to 3 ⁇ m.
  • a protective film is laminated.
  • the materials of the protective film include, but not particularly limited to, an acryl resin, an epoxy resin, a silicone resin, and a polyimide resin.
  • the so-called backside exposure method involving: previously forming pixels in patterns on a transparent substrate; applying a black matrix resist composition; exposing from the transparent substrate; and using pixels as masks to forma blackmatrix between the pixels.
  • an ITO transparent electrode may be laminated and patterned using any conventional method.
  • Fig. 1 shows the 1 H-NMR chart of a thiol compound (BAEMB) manufactured in Synthesis Example 1.
  • Fig. 2 shows the 13 C-NMR chart of the thiol compound (BAEMB) manufactured in Synthesis Example 1.
  • the contents were heated at an oil bath temperature of 140 0 C.
  • the reaction mixture was left to cool and neutralized with 200 ml of a 10% aqueous solution of sodium hydrogen carbonate. Further, the reaction mixture was washed with deionized water three times, and then dehydrated and dried over anhydrous magnesium sulfate (manufactured by Junsei Chemicals Co., Ltd.) . Then, toluene was distilled off to obtain 64.4 g of BAEMB (98.9% yield) with a purity of 97.2% measured by high-performance liquid chromatography. The resulting BAEMBwas a highly viscous, colorless and transparent liquid.
  • BAPMB 2,2-bis [4- ⁇ 2- ( 3-mercaptobutyloyloxy) -1-methylethoxy ⁇ phenyl]propa ne
  • EGMB was synthesized according to the method described in JP 2004-149755 A.
  • TPMB was synthesized according to the method described in JP 2004-149755 A.
  • EGMIB was synthesized according to the method described in JP 2004-149755 A.
  • UV detector SPD-MlOAVP manufactured by Shimadzu Corp.
  • the 1 H-NMR chart of BAEMB (Synthesis Example 1) was shown in Fig. 1.
  • the 1 H-NMR was measured in deuterated chloroform using JNM-AL400 manufactured by JEOL, Ltd. and assignment of the major peak of each chemical shift was performed.
  • the 13 C-NMR chart of BAEMB (Synthesis Example 1) was shown in Fig.2.
  • Epicoat 1004 bisphenol Atype epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent of 925
  • 14.4 g of acrylic acid, 0.20 g of hydroquinone, and 197 g of diethyleneglycol i monoethyletheracetate (hereinafter, abbreviatedas DGEA, manufactured by Daicel Chemical Industries, Ltd.) were charged and heated to 9'5°C.
  • DGEA diethyleneglycol i monoethyletheracetate
  • MA (manufactured by Kyoeisha Chemical Co. , Ltd. ) , 19.0 g of methyl methacrylate (MMA) (manufacturedbyKyoeisha Chemical Co. , Ltd. ) , 18.5 g of n-butyl methacrylate (BMA) (manufactured by Kyoeisha Chemical
  • the flask was heated up to 9O 0 C in an oil bath, and a mixture solution of 37.5 g of MA, 19.0 g of MMA, 18.5 g of BMA, 0.75 g of 2-mercaptoethanol, 225.0 g of PGM, and 3.2 g of 2,2'-azobis isobutyronitrile (AIBN) (manufactured by Wako Pure Chemical Industry, Co. , Ltd. ) was then graduallydroppedover one hour.
  • AIBN 2,2'-azobis isobutyronitrile
  • GMA glycidyl methacrylate
  • TBAB tetra-n-butylammonium bromide
  • methoquinone manufactured by Junsei Chemical, Co., Ltd.
  • the solid concentration of AP-I was 30.5 %, the sold acid value thereof was 116mgKOH/g, and the weight averagemolecular weight thereof in terms of polystyrene as measured by GPC was 14,000.
  • Ajisper PB822 pigment dispersant, manufacturedbyAjinomoto-Fine-Techno Co. , Inc.
  • PMA propyleneglycol monomethylethylacetate
  • PMA propyleneglycol monomethylethylacetate
  • Special Black 350 carbon black, manufactured by Degussa Co., Ltd.
  • 15.0 gof 13M-C titaniumblack, manufacturedbyMitsubishiMaterialCorp.
  • Dispersion solution 2 In a mixture solvent of 1,874 g of cyclohexane (CH) and 1,874 g of PMA, 57 g of a dispersant Ajisper PB822 (manufactured by Ajinomoto-Fine-TechnoCo., Inc.) was dissolvedand 317 gofEP-I (solid content: 19Og) was thenmixedin. Subsequently, 439 g of carbonblack Special Black 350 (SB 350) (manufactured by Degussa Co., Ltd.) and 439 g of titanium black 13M-C (manufactured by Mitsubishi Material
  • a dispersion solution 2 was obtained according to the above method.
  • Dispersion solutions 3 and 4 Dispersion solutions 3 and 4 were prepared fromthe compositions shown in Table 1 by the same method as that of the dispersion solution 2.
  • Photosensitive compositions of Examples 1 to 3 andComparative Examples 1 to 2 were prepared from the compositions listed in Tables 2 and 3.
  • Black matrix resist compositions of Examples 4 to 9 and ComparativeExamples 3to 5 werepreparedfromthe compositions listed in Tables 4 to 6.
  • Each of the photosensitive compositions of Examples 1 to 3 and Comparative Examples 1 to 2 and blackmatrix resist compositions of Examples 4 to 9 and Comparative Examples 3 to 5 was applied onto a glass substrate (dimensions: 100 x 100 x 1mm) toa dry filmthickness of about 1 ⁇ m by means of a spin coater and left alone for 5 minutes at room temperature, followed by drying the solvent for 3 minutes at 90 0 C. Furthermore, the glass substrate was exposed at 50 mj/cm 2 with an exposure device equipped with a super-high pressure mercury lamp (trade name: MultiLight ML-251A/B, manufactured by Ushio Inc.) through a photomask made of quartz, to thereby photo-cure the composition.
  • a super-high pressure mercury lamp trade name: MultiLight ML-251A/B, manufactured by Ushio Inc.
  • the exposure value was measured using a UV light integrator (tradename: UIT-150, manufacturedbyUsio Inc., detector: UVD-S365) .
  • the quartz photomask had a line/space pattern of 4, 6, 8, 10, 20, 50, and 100 ⁇ m and a pattern with lines of 4, ⁇ , 8, 10, 20, 50 and 100 urn and spaces of all 50 um.
  • the film of the exposed and cured photosensitive composition was further subjected to alkali development with time variation by using an aqueous solution (21 0 C) containing 0.25% Developer 9033 (manufactured by Shipley Far East., Co., Ltd.) which is an alkali developer containing potassium carbonate and 0.03% dodecylbenzenesulfonate (manufacturedbyTokyoKaseiKogyoCo. , Ltd. ) , and a spin developer (AD-1200, manufactured by Takizawa Industries, Co., Ltd.) .
  • the linewidthof each line formedbyexposure wasmeasuredbyanopticalmicroscope (VH-Z250, manufacturedbyKeyence Corp. ) .
  • EachoftheresistcompositionsofExamples4to 9andComparative Examples 3 to 5 was spin-coated on a glass substrate (100 x 100 mm in dimensions) and then dried at room temperature for 5 minutes, followed by drying a solvent at 90 0 C for 3 minutes. The resultant was exposed at 50 mj/cm 2 by an ultra-high pressure mercury lamp and thenpost-bakedat230 0 Cfor60minutes. Theresultingglasssubstrate on which the resist was applied was used for the OD value measurement. The OD value was determined from a standard curve made by measuring a transmission factor at 550 nm on a standard substrate with a known OD value. Subsequently, the resist-applied glass substrate of each of Examples and Comparative Examples was subjected to the measurement oftransmissionfactorat 550nmtocalculatetheODvalue. Theresults are shown in Tables 4 to 6.
  • each of the photosensitive compositions of Example 1 using a thiol compound having a bisphenol skeleton has high sensitivity that allows photo-curing even by a low exposure value of 50 mj/cm 2 and is simultaneously excellent in development latitudecomparedwithotherthiolcompounds. Therefore, the thiol compound and the photosensitive composition using the same of the present invention can be advantageously used in alkali development type resists such as solder resists, etching resists, and color filter resists.
  • each of the black matrix resist compositions of Example 4 to 9 using a thiol compound having a bisphenol skeleton has high sensitivity that allows photo-curing evenbya lowexposurevalueof50mj/cm 2 andis simultaneouslyexcellent indevelopmentlatitudecomparedwithotheraliphaticthiolcompounds. Therefore, the black matrix resist composition containing the thiol compound of the present invention can be advantageously used in large-size substrates.
  • the novel thiol compound having a bisphenol skeleton and the photosensitive compositionusingthe compound have a high sensitivity and are excellent in the development latitude, so that they can be suitablyusedforetchingresists, solderresists, colorfilterresists and the like, which form patterns in photolithography and alkali development.
  • the resist composition for black matrix of color filters using a novel thiol compound having a bisphenol skeleton has a high light-shielding property, a high sensitivity and is excellent in the development latitude, so that the composition can be suitably used for large substrates for color filters.

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Abstract

The invention is related to a thiol compound represented by formula (1), production method thereof, and a photosensitive composition and a resist composition for black matrix for color filters which use the thiol compound and are excellent in sensitivity and can keep the line width in patterns unchanged, i. e. attain an excellent developing latitude. (All the symbols have the same meanings as defined in the Description.)

Description

DESCRIPTION
THIOL COMPOUND, AND PHOTOSENSITIVE COMPOSITION AND BLACK MATRIX RESIST COMPOSITION USING THE COMPOUND
CROSS-REFERENCE TO RELATED APPLICATIONS
This is an application filedpursuant to 35 U.S.C. Section 111 (a) with claiming the benefit of U.S. provisional application Serial No.
60/624,530 filed November 4, 2004 and U.S. provisional application Serial No. 60/624,531 filed November 4, 2004 under the provision of
35-U.S.C. lll(b), pursuant to 35 U.S.C. Section 119(e) (l) .
TECHNICAL FIELD
The present invention relates to a novel thiol compound having a bisphenol skeleton, a method of manufacturing the same, and an alkali-developable type photosensitive composition and a black matrix resist composition for color filters using the compound. More specifically, the present invention relates to a novel thiol compound having a bisphenol skeleton and to a photosensitive composition and a blackmatrix resist composition for color filters using the compound, which contain (A) aphotopolymerization initiator systemincluding such compound, (B) a binder resin having a carboxyl group and (C) a compound having an ethylenically unsaturated group and have high sensitivity and excellent property of retaining a line width in fine line patterns at the time of alkali development.
BACKGROUND ART
Photosensitive compositions are used invarious fields including such as printing plates, color proofs, color filters, solder resists and photo-curable ink. In particular, in recent years, the most characteristic properties of photocurable composition, such as usability at room temperature, fast-drying property and solvent-free property, have received attention in various fields including those applications from the viewpoints of environmental concerns, energy saving, working safety, production costs and the like andmany studies and developments have been made on photosensitive compositions.
A photosensitive composition is mainly composed of a photopolymerization initiator, a binder resin, a compound having an ethylenicallyunsaturatedbondwhichiscuredbypolymerizationreaction and various kinds of additives, and the kinds of the components depend on use where the photosensitive composition is applied.
The photopolymerization initiator is selected by the photosensitive wavelengths and polymerization initiating properties. Thebinderresin, thecompoundhavinganethylenicallyunsaturatedbond and the additives are selected by polymerizability and physical properties of the cured product as desired. These components are combined and used to constitute a photosensitive composition.
However, in cases of using some binder resins, some compounds each having an ethylenically unsaturated bond and some additives,
(1) sufficient energy for initiatingphotopolymerization cannot be obtained;
(2) storage stability cannot be obtained;
(3) irradiation light does not reach deep enough in a desired cured product owing to the thickness thereof, which results in insufficient curing;
(4) oxygen inhibition occurs at the portion where the photosensitive composition contacts the air; and
(5) property of retaining a line width of fine line patterns at alkali development is low.
Forthoseproblems, variousmeasureshavebeentaken; forexample, irradiation with greater light energy, use of an excess amount ,of a photopolymerization initiator, and provision of an oxygen shielding membrane. However, for energy saving and reduction inproduction cost, a photosensitive composition having a higher photosensitivity has been desired.
Of those, in developments of color filters to be used for color televisions, liquid crystal display devices, solid-state image sensing devices, cameras and the like, pigment-dispersing resists for color filters are being considered for improvement in productivity and higher definition. In such applications, there have been growing demands for photosensitive compositions which can be cured at lower energy andmore quickly , can achieve a higher definition in forming a pattern and have an excellent curing depth.
A color filter is usuallymanufacturedby forming a lattice-like black-colored matrix (black matrix) on the surface of a transparent substrate such as glass or a plastic sheet and then forming three or more different hue patterns of red, green, blue and the like with a precision of micrometers. Of those, the black matrix is disposed to improve contrast and prevent malfunction of TFT. However, a resist for forming such a black matrix (black matrix resist) has a high light-shielding effect and therefore, it is inherently hard to be photo-cured. However, with increase in size of glass substrate, there is an increasing demand for higher sensitivity. Also, there is a strong demand for resists which can keep the line width of the fine pattern almost unchanged even when exposed to an alkali developer for a long period of time, i.e. which are excellent in development latitude.
Recently, since liquid crystal displays have come into use for television sets, demands have risen for color filters having excellent chromatic contrasts and it has been desired that pigments have higher concentrations. However, sincehighlyconcentratedpigmentsmaycause decrease in sensitivity, use ofpolyfunctional thiol compounds has been proposed for the purpose of improving sensitivity of photosensitive composition or a black matrix resist composition (JP 10-253815 A, JP 10-253816 A, JP 10-253817 A and JP 2004-149755 A) .
However, inpolyfunctional thiol compounds heretoforeproposed , sincepolyolcomponentscontainedthereinasbasicskeletonarealiphatic, there remains a problem in photo-cured products obtained by using such compounds that line width of fine line patterns gets smaller due to poor resistance against alkali development, that is, a problem of an insufficient development latitude, although sensitivity of the composition can be enhanced. In particular, for a black matrix resist on which lattice-like patterns are to be formed, such a phenomenon that the line width of fine line patterns becomes small is critical.
DISCLOSURE OF THE INVENTION
Theobject ofthepresent inventionistoprovide ahigh-sensitive photosensitive composition and a black matrix resist composition, excellent inpropertyof keepingthe linewidthconstant ina finepattern at the time of alkali development, i.e., excellent in the development latitude.
As a result of intensive studies, the inventors of the present invention have completed the present invention by finding out that the above problems can be solvedby a photosensitive composition or a black matrixresistcompositionusinganovelthiol compoundhavingabisphenol skeleton.
That is, the present inventionpertains to a novel thiol compound according to any one of items 1 to 20 described below, a production method thereof, and a photosensitive composition and a black matrix resist composition using the compound. 1. A thiol compound represented by formula (1) :
Figure imgf000006_0001
(in the formula, R1 represents a straight- or branched-chain alkylene group having 1 to 6 carbon atoms, R2 represents a straight- or branched-chain alkylene group having 2 to β carbon atoms, R3 and R4 each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen atom, X represents a single bond, -CO-, -SO2-, -CH2-, -C(CFs)2-, -C(CH3)2- or -0-, and n represents an integer of 1 to 5) .
2. The thiol compoundaccording to 1, wherein R1 is an alkylene group represented by any one of formulae (2) to (6) .
-CH2CH2- * (2)
-CH CH2- * (3) CH3
-CH2CH- * (4) CH3
-CH- * (5) CH3
CH3
-C- * (6) CH3 (The symbol "*" shows a position bonding with a mercapto group.) 3. The thiol compoundaccording to 1, wherein R is an alkylene group represented by any one of formulae (7) to (9) .
-CH2CH2- (7)
-CH CH2- (8) CH3
-CH2CH- (9) CH3
4. ■ Thethiolcompoundaccordingto 1, whichisrepresentedbyformula (10) .
Figure imgf000007_0001
(In the formula, m represents an integer of 1 or 2.) 5. The thiol compound according to 1, which is a compound obtained through esterification reaction between a diol compound represented by formula (11)
Figure imgf000007_0002
(inthe formula, R" represents a linear orbranchedalkylene grouphaving 2 to 6 carbon atoms, R3 and R4 each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen' atom, X represents a single bond, -CO-, -SO2-, -CH2-, -C(CF3)2-, -C(CH3)J- or -0-, andnrepresents anintegerof 1to5) andamercaptogroup-containing carboxylic compound represented by formula (12)
Figure imgf000008_0001
(inthe formula, R1 represents a linear orbranchedalkylene grouphaving
1 to 6 carbon atoms) . β. Amethod of producing a thiol compound as represented by formula
(D,
Figure imgf000008_0002
(all the symbols in the formula have the same meaning as defined above) comprising esterification reaction of a diol compound represented by formula (11)
Figure imgf000008_0003
(inthe formula, R2 represents a linear orbranchedalkylene grouphaving 2 to 6 carbon atoms, R3 and R4 each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen atom, X represents a single bond, -CO-, -SO2-, -CH2-, -C(CF3J2-, -C(CH3J2- or -O-, and n represents an integer of 1 to 5) and a mercapto group-containing carboxylic compound represented by formula (12)
1
HS-R
^CH (12)
(in the formula, R1 represents a linear orbranchedalkylene group having 1 to 6 carbon atoms) .
7. A photosensitive composition comprising (A) a photopolymerization initiator system containing the thiol compound according to any one of 1 to 5, (B) a binder resin containing a carboxyl group and (C) a compound having an ethylenically unsaturated group.
8. The photosensitive composition according to I1 wherein the photopolymerization initiator system (A) contains a hexaarylbiimidazole compound and/or an aminoacetophenone compound.
9. The photosensitive composition according to 8, wherein the hexaarylbiimidazole compound is represented by formula (13)
Figure imgf000009_0001
(in the formula, Y represents a halogen atom and R5 represents an alkyl group or an alkoxy group, which may have a substituent) . 10. The photosensitive composition according to 7, wherein the photopolymerization initiator system (A) contains a sensitizer. 11. The photosensitive composition according to 10, wherein the sensitizer is one or more compounds selected from the group consisting of benzophenone-based compounds, thioxanthone-based compounds and ketocoumarin-based compounds. 12. Thephotosensitivecompositionaccordingto7, inwhichthebinder resin containing a carboxyl group (B) further contains an ethylenically unsaturated group.
13. Aresistcompositionforblackmatrixofcolorfilters, containing (A) a photopolymerization initiator system containing the thiol compound according to any one of 1 to 5, (B) a binder resin having a carboxyl group, (C) a compound having an ethylenically unsaturated group, (D) black pigment and (E) an organic solvent. 14. Theresist compositionforblackmatrixofcolorfiltersaccording to 13, wherein the binder resin (B) having a carboxylic group further has an ethylenically unsaturated group.
15. Theresistcompositionforblackmatrixofcolorfiltersaccording to 14, wherein the binder resin (B) having a carboxylic group is a bisphenol-type epoxy acrylate resin, lβ. Theresist compositionforblackmatrixofcolorfiltersaccording to 13, wherein the photopolymerization initiator system (A) contains a hexaarylbiimidazole compound and/or an aminoacetophenone compound. 17. Theresist compositionforblackmatrixofcolorfiltersaccording to16, whereinthehexaarylbiimidazolecompoundisacompoundrepresented by formula (13)
Figure imgf000011_0001
(all the symbols have the same meanings as defined in 9) . 18. Theresistcompositionforblackmatrixofcolorfiltersaccording tolβor17, whereinthephotopolymerizationinitiatorsystem (A) contains asasensitizer, oneormorecompounds selectedfromthegroupconsisting of benzophenone-based compounds, thioxanthone-based compounds and ketocoumarin-based compounds.
19. Theresistcompositionforblackmatrixofcolorfiltersaccording to 13, wherein the blackpigment (D) is a carbon black and/or a titanium black.
20. Theresistcompositionforblackmatrixofcolorfiltersaccording to 13, wherein the components other than the organic solvent (E) are contained at the following ratios:
(A) photopolymerization initiator system; 2 to 15 % mass, (B) binder resin having a carboxyl group; 10 to 30 % by mass,
(C) compound having an ethylenically unsaturated group;
2 to 20 % by mass, and
(D) black pigment; 40 to 80 % by mass.
21. Theresistcompositionforblackmatrixofcolorfiltersaccording to 20, wherein the thiol compound of formula (1) is contained at 20 to 70 % by mass in the photopolymerization initiator system (A) . BEST MODE POR CARRYING OtFT THE INVENTION
1. Thiol compound having a bisphenol skeleton
The thiol compoundto be used in the present invention is a thiol compound having a bisphenol skeleton in molecule which is represented by the formula (1)
Figure imgf000012_0001
(In the formula, R1 represents a straight- or branched-chain alkylene group having 1 to 6 carbon atoms, R2 represents a straight- or branched-chain alkylene group having 2 to 6 carbon atoms, R3 and R4 each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen atom, X represents a single bond, -CO-, -SO2-, -CH2-, -C(CF3)2-, -C(CH3)2- or -0-, and n represents an integer of 1 to 5) . When radical polymerization of the thiol compound is carried out, radical polymerization inhibition with oxygen can be remarkably decreased and thus a photosensitive composition may show a remarkable increase in photosensitivity. Furthermore, as the thiol compound according to the present invention contains a bisphenol skeleton having high hydrophobic property, when the thiol compound is exposed and cured, such hydrophobic property will impart a high resistance against alkali developer to a cured product even if the curing degree is comparatively low.
In formula (1) , R1 is preferably a straight- or branched-chain alkylene group having 1 to 6 carbon atoms. If the number of carbon atoms exceeds 6, the developing latitude decreases as the hydrophobic property of the thiol compound molecule itself decreases. More preferred as R1 is an alkylene group having a structure represented by any one of formulae (2) to (6) .
Figure imgf000013_0001
H2 H -C -C- (4)
CH,
H
■c- 5)
CH,
CH3
-C * (6)
CH3
(The symbol "*" represents a site bonded with a mercapto group.) In consideration of storage stability of the composition, the thiol compound having an alkylene group with any one of the structures representedby formulae (4) to (β) , which forms a secondary or tertiary mercapto group, is particularly preferable.
In formula (1) , R2 is preferably a straight- or branched-chain alkylene group having 2 to β carbon atoms. If the number of carbon atoms exceeds 6, the developing latitude decreases as the hydrophobic property of the thiol compound molecule itself decreases. More preferred are an alkylene group having a structure represented by any one of formulae (7) to (9) : H2 H2 ^% ( 7 )
H H2
V. L> ( 8 )
I \
CH3
H2 H C — -C ( 9 )
CH-,
Informula (1) , R3andR4 eachindependentlyrepresentsahydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen atom, X represents a single bond, -CO-, -SO2-, -CH2-, -C(CF3)2-, -C(CH3)2- or -0-, and n is preferably an integer of 1 to 5. If the value of n exceeds 5, the development latitude decreases as the hydrophobic property of the thiol compound molecule itself decreases.
In addition, the thiol compound represented by formula (1) is preferably a polyfunctional thiol compound for imparting high sensitivity to the black matrix resist composition of the present invention. Therefore, as an alcohol that is used in esterification reactionwith amercapto group-containing carboxylic acid represented by formula (12) , a diol representedby formula (11) , i.e. a diol having a bisphenol skeleton where two alcoholic hydroxyl groups are present in one molecule is preferred.
Figure imgf000014_0001
(In the formula, R1 represents a straight- or branched-chain alkylene group having 1 to 6 carbon atoms.)
Figure imgf000015_0001
(In the formula, R2 represents a straight- or branched-chain alkylene grouphaving2to6carbonatoms, R3andR4 eachindependentlyrepresents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen atom, Xrepresentsasinglebond, -CO-, -SO2-, -CH2-, -C(CF3)2-, -C(CH3)2- or -0-, and n represents an integer of 1 to 5.)
Specific examples of the diol compound represented by formula (11) include compounds wherein an alkylene oxide such as ethylene oxide or propylene oxide is added to the phenolic hydroxyl group of the following compounds.
Examples of compound having a phenolic hydroxyl group include, in a case where X is a single bond, 4,4'-biphenol and 3,3'-biphenol.
In a case where X is -CO-, examples thereof include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl) ketone and bis(4-hydroxy-3,5-dichlorophenyl) ketone.
Examples of the compound in a case where X is -SO2- include bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3,5-dimethylphenyl) sulfone and bis(4-hydroxy-3,5-dichlorophenyl)sulfone.
Examples of the compound in a case where X is -CH2- include bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl) methane and bis(4-hydroxy-3,5-dichlorophenyl)methane.
Examples of the compound in a case where X is -C(CF3)2- include bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane and bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane.
Examples of the compound in a case where X is -C(CH3)2- include 2,2-bis (4-hydroxyphenyl)propane,
2,2-bis (4-hydroxy-3,5-dimethylphenyl)propane, '
2,2-bis (4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis (4-hydroxy-3-methylphenyl)propane and 2,2-bis (4-hydroxy-3-chlorophenyl)propane.
Needless to say, in the present invention, examples of compound having a phenolic hydroxyl group are not limited to the compounds above mentioned.
On the other hand, examples of the mercapto group-containing carboxylic acid represented by formula (12) include thioglycol acid,
3-mercaopto propionic acid, 2-mercapto propionic acid, 3-mercapto butyric acid and 2-mercapto isobutyric acid. In view of the storage stabilityofthephotosensitivecomposition, 2-mercaptopropionicacid,
3-mercapto butyric acid and 2-mercapto isobutyric acid each of which forms secondaryortertiarymercaptogroupareparticularlypreferable .
Particularly preferable specific examples of the thiol compound represented by formula (1) include compounds represented by formulae (10), (14) and (15) .
Figure imgf000016_0001
JIn the formula, m is an integer of 1 or 2,
Figure imgf000017_0001
(In the formula, p is an integer of 1 or 2.
Figure imgf000017_0002
(In the formula, k is an integer of 1 or 2.) Among them, a thiol compound represented by formula (10) is more preferable in view of its reactivity.
A method of manufacturing the thiol compound having a bisphenol skeleton of the present invention, which is represented by formula (1) , is not particularly limited but the thiol compound may be obtained by an esterification reaction between a mercapto group-containing carboxylicacidrepresentedbyformula (12) andadiol havingabisphenol skeleton represented by formula (11) . The esterification reaction itself is known in the art, so that the esterification reaction can be carried out in the usual manner to form ester. The conditions of the esterification reaction are not particularly limited and the conventional reaction conditions may be suitably selected. 2. Photosensitive composition and black matrix resist composition
The photosensitive composition and black matrix resist composition of the present invention contain, as essential components, (A) aphotopolymerizationinitiatorsystemcontainingthethiolcompound represented by formula (1) , (B) a binder resin having a carboxyl group, and (C) a compound having an ethylenically unsaturated bond and may optionally contain any of various additives including pigments and solvents.
2-1. Photopolymerization initiator system (A) The photopolymerization initiator system (A) used in the photosensitive composition of the present invention may contain, in addition to the above thiol compound having a bisphenol skeleton, any one of other components, such as those to be commonly used in general photopolymerization initiator systems, such as radical generators and sensitizers.
(1) Radical generator
Examples of radical generator usable in the resist composition forblackmatrix of color filters of the present invention include known compounds such as acetophenone compounds, triazine compounds, titanocene compounds and ketoxime compounds. In the light of photosensitivity, biimidazole compound and/or aminoacetophenone are preferred.
(1-1) Biimidazole-based compound and/or acetophenone-based compound Anyoneofthosecommonlyusedintheordinaryphotopolymerization initiator system may be used as a biimidazole-based compound used in the present invention but a hexaarylbiimidazole compound having a structure represented by formula (16) is preferable.
(16)
Figure imgf000018_0001
In formula (16), Y2, Y3, and Y4 represent each independently a halogen atom, a cyano group or a nitro group, R6, R7, R8, R9 and R10 each independently represents a hydrogen atom, an alkyl group whichmayhave a substituent, or an alkoxy group which may have a substituent. Examples of the halogen atoms represented by the above Y2, Y3, and Y4 include a chlorine atom, a bromine atom, and a fluorine atom.
Examples of the alkyl groups represented by the above R6, R7,
R8, R9 and R10 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group. They may have substituents such as an alkoxy group and a halogen atom. Of those, preferable is a straight- or branched-chain alkyl group having 1 to 6 carbons and more preferable is a straight- or branched-chain alkyl group having 1 to 3 carbons. Examples of the alkoxy groups represented by the above R6, R7, R8, R9, and R10 include amethoxy group, an ethoxy group, a propoxy group, ann-butoxygroup, anisobutoxygroup, atert-butoxygroup, ann-pentyloxy group, and an n-hexyloxy group. They may have substituents such as an alkoxy group and a halogen atom. Of those, preferable is a straight- or branched-chain alkoxy group having 1 to 6 carbons andmorepreferable is a straight- or branched-chain alkoxy group having 1 to 3 carbons. Of those hexaarylbiimidazole compoounds, a compound having a structure represented by formula (13) is particularly preferable.
Figure imgf000020_0001
In the formula, Y represents a halogen atom and R represents an alkyl group which may have a substituent or an alkoxy group which may have a substituent. Specific examples of the alkyl and alkoxy groups of R5 include the same groups as those listed for R6 to R10 of the hexaarylbiimidazole compound represented by formula (16) but a methyl group or a methoxy group is particularly preferable. A chlorine atom is particularly preferable as a halogen atom represented by the above Y. Examples of an acetophenone-based compound used in the present invention include hydroxyacetophenone compounds and aminoacetophenone compounds. Of those, in terms of photosensitivity, aminoacetophenone compounds are particularly preferable.
Specific examples of the hydroxyacetophenone compound'include α-hydroxyacetophenones such as
2-hydroxy-2-methyl-l-phenylpropan-l-one,
2-hydroxy-2-methyl-l-phenylbutan-l-one,
1- (4-methylphenyl) -2-hydroxy-2-methylpropan-l~one,
1- (4-isopropylphenyl) -2-methylpropan-l-one, 1- (4-butylphenyl) -2-hydroxy-2-methylpropan-l-one, 2-hydroxy-2-methyl-l- (4-octylphenyl)propan-1-one, 1- (4-dodecylphenyl) -2-methylpropan~l-one, 1- (4-methoxyphenyl) -2-methylpropan-l-one, i 1- (4-methylthiophenyl) -2-methylpropan-l-one,
1- (4-chlorophenyl)-2-hydroxy-2-methylpropan-l-one, 1- (4-bromophenyl) -2-hydroxy-2-methylpropan-l-one, 2-hydroxy-l- (4-hydroxyphenyl) -2-methylpropan-l-one,
1- (4-dimethylaminophenyl) -2-hydroxy-2-methylpropan-l-one,
1- (4-carboethoxyphenyl) -2-hydroxy-2-methylpropan-l-one,
1-hydroxycyclohexylphenyl ketone and
2-hydroxy-l- (4-(2-hydroxyethoxy) -phenyl)-2-methylpropan-l-one. Specific examples of the aminoacetophenone compound include α-a'minoacetophenones such as
2-dimethylamino-2-methyl-l-phenylpropan-l-one, 2-diethylamino-2-methyl-l-phenylpropan-l-one, 2-methyl-2-morphorino-l-phenylpropan-l-one, 2-dimethylamino-2-methyl-l- (4-methylphenyl)propan-1-one, 2-dimethylamino-l-(4-ethylphenyl) -2-methylpropan-l-one, 2-dimethylamino-l-(4-isopropylphenyl) -2-methylpropan-l-one, 1- (4-butylphenyl)-2-dimethylamino-2-methylpropan-l-one, 2-dimethylamino-l- (4-methoxyphenyl) -2-methylpropan-l-one, 2-dimethylamino-2-methyl-l- (4-methylthiophenyl)propan-1-one, 2-methyl-l-[4- (methylthio)phenyl]-2-morphorinopropan-l-one> 2-benzyl-2-dimethylamino-l- (4-morphorinophenyl) -butan-1-one, and 2-benzyl-2-dimethylamino-l- (4-dimethylaminophenyl)butan-1-one.
Specific examples of other radical generators include benzoin methylether, benzoinethylether, benzoinisopropylether, benzylmethyl ketal, α-halogenoacetophenones, methylphenylglyoxylate, benzyl, anthraquinone, phenanthrenequinone, camphorquinoneisophthalophenone, acylphosphine oxide, α-acyloxime ester, benzyl, and camphor quinone. The organic boron salt-based compound described in JP 2000-249822 A can be also used.
J (2) Sensitizer
Inthepresent invention, sensitizers commonlyusedinthegeneral photopolymerization initiator systems can be used. Of those, one or more compounds selected fromthe group consisting ofbenzophenone-based compounds, thioxanthone-based compounds and ketocoumarin-based compounds are preferably used, as the sensitivity can be enhanced.
Specific examples of such sensitizer include: a benzophenone-based compound such as benzophenone, 2, 4, β-trimethylbenzophenone, 4-phenylbenzophenone, 4-benzoyl-4' -methyldiphenyl sulfide, 4,4' -bis (dimethylamino)benzophenone or 4, 4' -bis (diethylamino)benzophenone; a thioxanthone-based compound such as thioxanthone, 2-methylthioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, isopropylthioxanthone, 2, 4-diisopropylthioxanthone or 2-chlorothioxanthone; and a ketocoumarin-based compound such as 3-acetylcoumarin, 3-acetyl-7-diethylaminocoumarin, 3-benzoylcoumarin, 3-benzoyl-7-diethylaminocoumarin, 3-benzoyl-7-methoxycoumarin,
3, 3' -carbonylbiscoumarin, 3, 3' -carbonylbis (7-methoxycoumarin) or 3, 3' -carbonylbis (5, 7-dimethoxycoumarin) . Each of them may be used alone, or two or more kinds thereof may be used as a mixture.
Thecompoundingratioofeachcomponentinthephotopolymerization initiator system (A) is as follows.
The content of the thiol compound having a bisphenol skeleton representedbyformula (1) ispreferably20to70%bymass, morepreferably 30 to 60 % by mass. If the content is less than 20% by mass, the photosensitivity and development latitude may decrease. On the other hand, if the content exceeds 70 % by mass, the developability may i deteriorate.
The content of the radical generator is preferably 20 to '80 % by mass, more preferably 30 to 70%- by mass. If the content is less than 20% bymass, the photosensitivitymaydecrease. On the other hand, if the content exceeds 80% by mass, the line width tends to be larger than the line width of photomask.
The content of the sensitizer is preferably 5 to 40 % by mass, more preferably 10 to 30 % by mass. If the content is less than 5% bymass, the photosensitivity may decrease. The content exceeding 40% bymass is not preferred inthat the light transmission towardthebottom of the photosensitive composition is prevented, which causes the shape of cross-section of the resist to be reverse-trapezoidal, resulting in decrease in resolution. 2-2. Binder resin having a carboxyl group (B)
The binder resin (B) used in the present invention has a carboxyl group on its side chain, which is a component that predominantly determines the properties of the resist, such as the film strength, thermal resistance, substrate adhesiveness, solubility to an aqueous alkaline solution and alkaline developability.
Specific examples of the binder resin (B) include an 'acrylic copolymer (AP) having a carboxyl group, an epoxy (meth) acrylate resin (EA) having a carboxyl group and a urethane (meth)acrylate resin (UA) having a carboxyl group. In consideration for adhesion with glass substrate, epoxy(meth)acrylate resin is preferable. Particularly preferred is a bisphenol-type epoxy(meth) acrylate resin having a carboxylic acid.
Two or more of those binder resins having a carboxylic acid may be used in combination. (1) Acrylic copolymer (AP) having carboxyl group t The acrylic copolymer having a carboxyl group can be obtained by copolymerizing:
(a) an ethylenically unsaturatedmonomer containing a carboxyl group; and
(b) an ethylenically unsaturated monomer other than the above item (a) .
The ethylenicallyunsaturatedmonomer (a) containing a carboxyl group is used for the purpose of imparting the acrylic copolymer (AP) with alkaline developability.
Specific examples of the ethylenically unsaturated monomer (a) containing a carboxyl group include (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl phthalate, (meth)acryloyloxyethyl hexahydrophthalate, (meth)acrylic aciddimer, maleicacid, crotonicacid, itaconicacid, andfumaricacid. The ethylenically unsaturated monomer (b) other than the above item (a) is used for the purpose of controlling the film strength and pigment dispersibility.
Specific examples of the ethylenically unsaturated monomer (b) other than the above item (a) include: a vinyl compound such as styrene, α-methylstyrene,
(o,m,p-)hydroxystyrene or vinyl acetate;
(meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl (meth)acrylate, tert-butyl(meth)acrylate, n-hexyl(meth)acrylate, cyclohexyl(meth)acrylate, benzyl(meth)acrylate, phenoxyethyl(meth)acrylate, isobornyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, (meth)acrylonitrile, glycidyl(meth)acrylate, allylglycidyl ether, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, i N,N-dimethylaminoethyl (meth) acrylate, trifluoroethyl acrylate,
2,2,3, 3-tetrafluoropropyl (meth)acrylate or ' perfluorooctylethyl (meth) acrylate; a compound having an amide group such as (meth) acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-isopropyl(meth)acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam or N- (meth) acryloyl morpholine. An acrylic copolymer having an ethylenically unsaturated group on'the side chain which is obtained by reacting an epoxy group of a compound having an epoxy group and an ethylenically unsaturated group in one molecule (such as glycidyl (meth)acrylate, 3, 4-epoxycyclohexyl methyl (meth)acrylate, 4- (2, 3-epoxypropyl)butyl (meth) acrylate or allylglycidyl ether) with a carboxyl group as a part of the side chain ofanacryliccopolymerobtainedbycopolymerizationoftheabovemonomers or by reacting part or whole of hydroxy1 groups of an acrylic copolymer with an isocyanate group of a compound having the isocyanate group and an ethylenically unsaturated group in one molecule such as 2-methacryloyloxyethylisocyanate, canbealsousedwithoutanyproblem.
Thecopolymerizationratiobetweentheethylenicallyunsaturated monomer (a) containingacarboxylgroupandtheethylenicallyunsaturated monomer (b) other than the above item (a) is preferably from 5 : 95 to40 : 60, morepreferablyfrom10 : 90to50 : 50. Ifthecopolymerization ratio of the above item (a) is less than 5, the pattern formation may become difficult due to decrease in alkaline developability. If the copolymerization ratio of the above item (a) exceeds 60, alkali-development of photo-cured portions readily proceeds and therefore, it is difficult to keep the line width constant. The molecular weight of the acrylic copolymer having a carboxyl i group and an ethylenically unsaturated group is preferably in the range of 1,000 to 500,000, more preferably 3,000 to 200,000 in terms of polystyrene as measured by GPC. If- the molecular weight is less than 1,000, the film strength may decrease markedly. On the other hand, if the molecular weight exceeds 500,000, the alkaline developability may decrease markedly. (2) Epoxy (meth)acrylate resin (EA) having carboxyl group
The epoxy (meth)acrylate resin (EA) having a carboxyl group to be used in the present invention is not specifically limited, however, an'epoxy (meth)acrylate resin obtained by reacting an acid anhydride with aproduct ofthe reactionbetweenan epoxyresinoranepoxycompound and an unsaturated group-containing monocarboxylic acid, is suitably used. Examples of the epoxy resin to react with an unsaturated- group-containing monocarboxylicacid include abisphenolAtype epoxy resin, a hydrogenated bisphenol A type epoxy resin, a brominated bisphenolAtypeepoxyresin, abisphenol Ftypeepoxyresin, abisphenol S type epoxy resin, a novolac type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a triphenylmethane type epoxy resin, a naphthalene type epoxy resin, an N-glycidyl type epoxy resin, a dicyclopentadiene phenolic epoxy resin, a diglycidylphthalate resin, a heterocyclic epoxy resin, a bixylenol type epoxy resin, and a biphenyl type epoxy resin. Each of them may be used alone, or two or more kinds thereof may be used in combination.
Examples of the epoxy compound to be reacted with the unsaturated group-containing monocarboxylic acid, although not particularly limited, includeepoxycompoundssuchasabisphenolAtypeepoxycompound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, aphenolnovolactypeepoxycompound, acresolnovolactypeepoxycompound i and an aliphatic epoxy compound. Each of them can be used alone, or two or more kinds thereof can be used in combination.
Examplesoftheunsaturatedgroup-containingmonocarboxylicacid tobereactedwiththeepoxyresinorepoxycompoundinclude (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid,
2- (meth)acryloyloxyethyl phthalic acid, (meth)acryloyloxyethyl hexahydrophthalic acid, (meth)acrylic dimer, β-furfuryl acrylic acid, β-styryl acrylicacid, cinnamicacid, crotonicacidandα-cyanocinnamic acid. Examples of such unsaturated group-containing monocarboxylic acid further include a half ester compound as a reaction product of a hydroxyl group-containing acrylate with a saturated or unsaturated dibasic anhydride, and a half ester compound as a reaction product of an unsaturated group-containing monoglycidyl ether with a saturated or unsaturated dibasic anhydride. Each of the unsaturated group-containing monocarboxylic acids can be used alone or two or more kinds thereof can be used in combination.
Examples of the acid anhydride include: a dibasic anhydride such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride or methyltetrahydrophthalic anhydride; an aromatic polycarboxylic anhydride such as trimellitic anhydride, pyromelliticanhydrideorbenzophenonetetracarboxylicdianhydride; and a polycalboxylic anhydride derivative such as
5- (2,5-dioxotetrahydrofurfuryl) -3-methyl-3-cyclohexene-l,2-dicarbo xylic anhydride or endobicyclo-[2,2, 1]-hept-5-ene-2, 3-dicarboxylic anhydride. Each of them can be used alone or two or more kinds thereof i can be used in combination.
The epoxy (meth) acrylate resin (EA) having a carboxyl group thus obtained has, but not specifically limited to, a molecular weight of preferably 1,000 to 40,000, more preferably 2,000 to 5,000 in terms of polystyrene as measured by GPC.
In addition, the acid value of the epoxy (meth) acrylate resin
(EA) (means a solid acid value measured in accordance with JIS K0070, the same will be applied in the following description) is preferably 10 mgKOH/g or more, more preferably in the range of 45 to IGO mgKOH/g, furtherpreferably in the range of 50 to 140 mgKOH/g, which can establish a goodbalance between the alkali solubility andthe alkaline resistance of a cured film. If the acid value is less than 10 mgKOH/g, the alkaline solubility may decrease. On the other hand, an excessively large acid value may cause decrease in the characteristic features of the cured film such as alkaline resistance, in some cases of certain combinations of constituents of the photosensitive composition.
(3) Urethane (meth) acrylate resin (UA) having carboxyl group
The urethane (meth) acrylate resin (UA) having a carboxyl group used in the present invention is a binder resin which is more flexible than the acrylic polymer (AP) or the epoxy (meth) acrylate resin (EA), and therefore, it is used in the applications where flexibility and bending resistance.
The urethane (meth) acrylate resin (UA) having a carboxyl group contains a unit originated from (meth) acrylate having a hydroxyl group, aunitoriginatedfrompolyol, andaunit originatedfrompolyisocyanate.
More specifically, it is constituted by a unit originated from
(meth) acrylate having hydroxyl groups on its both terminals, between the terminals are repeating units consisting of a polyol-derived unit and a polyisocyanate-derived unit which are linked by a urethane bond,
J and a carboxyl group is present in the repetitive unit.
That is, the repetitive structure of the urethane (meth)acrylate resin (UA) having a carboxyl group can be represented by formula (17) .
- (ORbO-OCNHRcNHC O) n- (17)
In formula (17), ORbO represents a dehydrogenation residue of polyol and Rc represents a deisocyanate residue of polyisocyanate.
The urethane (meth)acrylate resin (UA) having a carboxyl group can be produced by carrying out a reaction of at least (meth)acrylate having a hydroxyl group, polyol and polyisocyanate. Here, a compound having a carboxyl group should be used as at least one of the polyol and the polyisocyanate. Preferably, polyol having a carboxyl group is used. In this way, by the use of the compound having a carboxyl group as polyol and/orpolyisocyanate, theurethane (meth)acrylate resin (UA) in which a carboxyl group is present in Rb or Rc can be produced.
Here, in formula (17), the integer n is preferably about 1 to 200, morepreferably2 to 30. Ifn iswithin suchranges, the flexibility of the cured film may be more excellent. Furthermore, if two or more kinds of at least one of polyol and polyisocyanate are used, the repeating unit represents multiple kinds.
The regularity of the units can be suitably selected from "complete random", "block", "localized" and the like, depending on the purpose.
Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, a caprolactone or alkylene oxide adduct of the above-described (meth) acrylates, glycerin mono(meth)acrylate, glycerindi (meth)acrylate, aglycidylmethacrylate-acrylicacidadduct, trimethylolpropanemono(meth) acrylate, trimethylol di (meth)acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth)acrylate and a trimethylolpropane-alkylene oxide adduct of di (meth)acrylate. The (meth)acrylate (a) having a hydroxyl group can be used alone or two or more kinds thereof can be used in combination. Of those, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate and hydroxybutyl (meth) acrylate are preferable, and 2-hydroxyethyl (meth)acrylateismorepreferable. When2-hydroxyethyl (meth)acrylate is used, synthesis of a urethane (meth)acrylate (UA) resin containing a carboxyl group is easier.
Apolymer polyol and/or dihydroxyl compound canbe used as polyol to be used in the present invention. Examples of the polymer polyol include: a polyether-based diol such as polyethylene glycol, polypropylene glycol, or polytetramethylene glycol; a polyester-based polyol obtained by a reaction between polyhydric alcohol and ester of polybasicacid; apolycarbonate-baseddiolhavingas a constituentunit, aunitderivedfromhexamethylenecarbonateorpentamethylenecarbonate; and a polylactone-based diol such as polycaprolactone diol or polybutyrolactone diol.
Furthermore, in a case where polymer polyol having a carboxyl group is used as the above polyol having a carboxyl group, for example, a polymer polyol obtained by a synthesis process wherein a polybasic acid having 3 or higher valence such as (anhydrous) trimellitic acid isallowedtocoexisttotherebyprepareapolymerpolyolwhereacarboxyl group remains, can be employed. One kind of such a polymer polyol may beused, ortwoormore kinds ofpolymerpolyolmaybeusedincombination. In addition, for those polymer polyols, those each having an average molecular weight of 200 to 2,000 are preferably used, which enhances the excellent flexibility of the cured film.
A branched- or straight-chain compound having two alcoholic hydroxyl groups canbe used as the above dihydroxyl compound. However, it is particularly preferable to use a dihydroxy aliphatic carboxylic
J acidhavingacarboxylgroup. Suchadihydroxycompoundmaybedimethylol propionic acid or dimethylol butanoic acid. By using the dihydroxy aliphatic carboxylic acid having a carboxyl group, a carboxyl group can be easily present in a urethane (meth)acrylate resin (UA) . Each of those dihydroxyl compounds may be used singly or two or more of them may be used in combination. In addition, the dihydroxyl compound may be used together with polymer polyol.
In addition, in the case of using the polymer polyol having a carboxyl group in combination or using polyisocyanate having a carboxyl groupasthepolyisocyanatedescribedbelow, adihydroxylcompoundhaving no carboxyl group (for example, ethylene glycol, diethylene glycol, propylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol, neopentyl glycol, 3-methyl-l, 5-pentanediol, 1, β-hexanediol or 1,4-cyclohexanedimethanol) may be used.
Specific examples of the polyisocyanate to be used in the present invention include diisocyanates such as 2,4-toluene diisocyanate, 2,β-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, (o, m, or p)-xylene diisocyanate, methylene bis (cyclohexyl isocyanate) , trimethylhexamethylene diisocyanate, cyclohexane-1, 3-dimethylene diisocyanate, cyclohexane-1, 4-dimethylene diisocyanate and 1,5-naphthalene diisocyanate. The polyisocyanate can be used alone or two or more kinds thereof can be in combination. A polyisocyanate having a carboxyl group can be also used.
The molecular weight of the urethane (meth) acrylate resin (UA) havinga carboxyl groupusedinthepresent inventionis not specifically limited, however, the mass average molecular weight in terms of polystyrene as measured by GPC is preferably 1,000 to 40,000, more preferably 8,000 to 30,000. If the mass average molecular weight of the urethane (meth) acrylate resin (UA) having a carboxyl group is less than 1,000, the elasticity and flexibility of the cured film may be deteriorated. On the other hand, a mass average molecular weight of more than 40,000 may lower the flexibility because the resin becomes too hard. Furthermore, the acid value of the urethane (meth) acrylate resin (UA) is preferably 5 to 150 mgKOH/g, more preferably 30 to 120 mgKOH/g. Iftheacidvalueislessthan5mgKOH/g, thealkalinesolubility of the curable resin composition for resist may decrease. On the other hand, if the acid value exceeds 150 mgKOH/g, the alkaline resistance or 'the like of the cured film may deteriorate. 2-3. Compound (C) having ethylenically unsaturated group
The compound (C) havinganethylenicallyunsaturatedgroup, which is included in the photosensitive composition of the present invention, is a compound other than the binder resin (B) described above and may be used for the purpose of adjusting the photosensitivity of the photosensitive composition or adjusting the physical properties of the cured product of the photosensitive composition, such as thermal resistance and flexibility. Preferably, (meth)acrylate is used. ■ Specific examples of the compound (C) having an ethylenically unsaturated group include: alkyl (meth) acrylate (such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth)acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate or stearyl (meth) acrylate) ; alicyclic (meth)acrylate (such as cyclohexyl (meth)acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth)acrylate or dicyclopentenyloxyethyl (meth)acrylate) ; aromatic (meth) acrylate (such as benzyl(meth) acrylate, phenyl (meth)acrylate, phenylcarbitol (meth) acrylate, nonylphenyl (meth)acrylate, nonylphenylcarbitol (meth)acrylate or nonylphenoxy(meth)acrylate) ;
(meth)acrylate having a hydroxyl group (such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, butanediol mono(meth) acrylate, glycerol (meth)acrylate, polyethyleneglycol (meth) acrylateorglycerol di(meth)acrylate) ;
(meth)acrylate having an amino group (such as 2-dimethylaminoethyl (meth)acrylate, 2-diethylaminoethyl (meth)acrylate or 2-tert-butylaminoethyl (meth)acrylate) ; methacrylate having a phosphorus atom (such as methacryloxyethyl phosphate, bis-methacryloxyethyl phosphate, or methacryloxyethyl phenyl acid phosphate) ; di (meth)acrylate (suchas ethyleneglycol di (meth) acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylenedi(meth)acrylate, polyethyleneglycoldi (meth)acrylate, propyleneglycoldi (meth)acrylate, dipropyleneglycoldi (meth)acrylate, tripropyleneglycoldi (meth)acrylate, 1, 4-butanedioldi (meth)acrylate, 1,3-butanediol di (meth)acrylate, neopentyl glycol di (meth) acrylate, 1, β-hexanediol di(meth)acrylate, bis-glycidyl (meth)acrylate or dimethylol tricyclodecane di (meth)acrylate) ; poly(meth)acrylate (such as trimethylolpropane tri (meth)acrylate, pentaerythritol tri (meth) acrylate, or dipentaerythritol hexa (meth)acrylate) ; modifiedpolyolpoly(meth)acrylate (suchas a di (meth)acrylate of 4-mol ethyleneoxideadductofbisphenolS, adi (meth)acrylateof4-molethylene j oxide adduct of bisphenol A, aliphatic-modified pentaerythritol di (meth)acrylate, a tri (meth) acrylate of 3-mol propylene oxide adduct of trimethylolpropane, or a tri(meth)acrylate of β-mol propylene oxide adduct of trimethylolpropane) ; polyacrylate having an isocyanuric acid skeleton (such as bis (acryloyloxyethyl) monohydroxyethyl isocyanurate, tris (acryloyloxyethyl) isocyanurate, or tris (acryloyloxyethyl) isocyanurate of ε-caprolactone adduct) ; polyester acrylate (such as α,ώ-diacryloyl- (bisethyleneglycol)-phthalate or α,ω-tetraacryloyl- (bistrimethylolpropane) -tetrahydrophthalate) ; glycidyl (meth)acrylate; allyl (meth)acrylate; ω-hydroxyhexanoyloxyethyl (meth)acrylate; polycaprolactone (meth)acrylate; (meth)acryloyloxyethyl phthalate; (meth)acryloyloxyethyl succinate; 2-hydroxy-3-phenoxypropylacrylate; and phenoxyethyl acrylate.
In addition, an N-vinyl compound (such as N-vinylpyrrolidone, N-vinylformaldehyde, orN-vinylacetamide) , polyester (meth) acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, or the like can be suitablyused as a compound having an ethylenically unsaturated group.
Of those, preferable examples include poly(meth)acrylates such as di (meth)acrylate of 4-mol ethyleneoxide adduct of bisphenol A, di (meth)acrylate of 4-mol propyleneoxide adduct of bisphenol A or dimethylol tricyclodecane di (meth)acrylate with the object of the pattern configuration; and trimethylolpropane tri (meth)acrylate, pentaerythrytol tetra (meth)acrylate, or dipentaerythrytol hexa(meth)acrylate with the object of photosensitivity. 2-4. Pigment (D) Pigment (D) may be blended in the photosensitive composition
J of the present invention. Examples thereof include the followings
(represented by color index numbers, respectively) : C.I. Pigment Yellow 12, 13, 14, 17, 20, 24, 55, 83, 86, 93, 109, 110, 117, 125, 137, 139, 147, 148, 153, 154, 166, or 168; C.I. Pigment Orange 36, 43, 51, 55, 59, or 61;
C.I. Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, or 240; C.I. Pigment Violet 19, 23, 29, 30, 37, 40, or 50; C.I. Pigment Blue 15, 15:1, 15:4, 15:6, 22, 60, or 64; C.I. Pigment Green 7 or 36; C.I. Pigment Brown 23, 25, or 26;
C.I. Pigment Black 7; and titanium black. Each of the pigments may be used alone, or two or more of them may be used in combination. Examples of black pigment (D) used in the resist composition for black matrix for color filters of the present invention include carbonblack, acetyleneblack, lampblack, graphite, ironblack, aniline black, cyanine black and titanium black. Also, a black pigment formed by mixing organic pigments of red, green and blue may be used. Among these, carbon black and titanium black are particularly preferred in light of light-shielding and image property. Examples of commerciallyavailable carbonblacks include the followingproducts. ManufacturedbyMitsubishiChemicalCorporation: MA7, MA8, MAIl, MAlOO, MA220, MA230, #52, #50, #47, #45, #2700, #2650, #2200, #1000, #990, #900.
Manufactured by Degussa: Printex 95, Printex 90, Printex 85, Printex 75, Printex 55, Printex 45, Printex 40, Printex 30, Printex 3, Printex A, Printex G, Special Black 4, Special Black 550, Special Black 350, Special Black 250, Special Black 100. Manufactured by Cabot Corporation: Monarch 460, Monarch 430, Monarch 280, Monarch 120, Monarch 800, Monarch 4630, REGAL 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL250R, REGAL 330, BLACK PEARL S480, PEARL S130. Manufactured by Columbian Carbon Co. : Raven 11, Raven 15, Raven 30, Raven 35, Raven 40, Raven 410, Raven 420, Raven 450, Raven 500, Raven 780, Raven 850, Raven 890H, Raven 1000, Raven 1020, Raven 1040, Raven 1060, Raven 1080, Raven 1255.
As a titanium black, 13M-C manufactured by Mitsubishi Material Corporation may be mentioned.
The above-mentioned black pigments may be used in combination with each other. In particular, a combination of a carbon black and a titanium black contributes to a higher light-shielding property. 2-5. Solvent (E) Further, according to use of the product, various additives may be added to the photosensitive composition and the black matrix resist composition of the present invention in order to impart viscosity, operability, properties as cured product, and the like. Solvent (E) may be added- 'for the purposes of, for example, obtaining sufficient dispersibility of the components, improvement in operability and adhesion at the,time of coating and adjusting the viscosity.
Specific examples of the volatile solvent (E) which may be added to the photosensitive composition of the present invention include alcohols, ketonesandesters. Examples ofsuchvolatile solventinclude methanol, ethanol, toluene, xylene, ethylbenzene, cyclohexane, isophorone, cellosolve acetate, diethylene glycol dimethyl ether, ethyleneglycoldiethylether, ethyleneglycolmonoethylether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, isoamyl acetate,
) ethyl lactate, γ-butyrolactone, methylethyl ketone, acetone, and cyclohexanone. Each of them can be used alone, or two or more kinds thereof can be used as a mixture. Further, when it is difficult to employ the above-described volatile solvent in consideration for the use of the product, a reactive solvent (E) may be used. Specific examples of such reactive solvent include 2-hydroxyethyl (meth)acrylate, methyl (meth)acrylate, n-butyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl(meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N-acryloylmorpholine, N-acryloylpiperidine, N,N-dimethyl (meth)acrylamide, N-vinylpyrrolidone and N-vinylacetamide. Each of them can be used alone, or two or more kinds thereof can be used as a mixture. The above-described volatile solvent may be further added to the reactive solvent when necessary.
The organic solvent (E) to be used in the black matrix resist composition of the present invention is not particularly limited as long as the organic solvent can dissolve and disperse each of the above-described components constituting the black matrix resist composition of the present invention. Specific examples thereof includemethanol, ethanol, isopropanol, toluene, xylene, ethylbenzene, cyclohexane, isophorone, cellosolve acetate, diethyleneglycol dimethyl ether, ethyleneglycoldiethylether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propyleneglycol monomethyl ether, propyleneglycol monomethyl ether acetate, propyleneglycol monoethyl ether acetate, diethyleneglycol ethyl ether acetate, methyl methoxypropionate, ethylmethoxypropionate, methyl ethoxypropionate, ethylethoxypropionate, ethylacetate, isoamylacetate, ethyl lactate, acetone, methyl ethyl ketone, cyclohexanone, N,N-dimethylformamide, and N-methylpyrrolidone. Each of them is used alone, or two or more i kinds thereof are used in combination.
It is desirable to prepare the black matrix resist composition of the present invention by means of any of those organic solvents so as to be of a solid concentration of 5 to 30% by mass, preferably 10 to 25% by mass. 2-6. Other optional components
In addition to the above essential components, a pigment dispersant, an adhesion-improving agent, a leveling agent, a development improver, anoxidationinhibitor, athermalpolymerization inhibitor or the like may be suitably added to the black matrix resist composition of the present invention. In particular, in the coloring composition, it is preferable in some cases that the pigment dispersant be blended in, since it is important to finely disperse the coloring material and stabilize the dispersion state in light of quality stabilization.
The pigment dispersant has an affinity to each of the pigment and the binder resin, and examples thereof include nonionic, cationic, and anionic surfactants and polymer dispersants. Of those, polymer dispersants are preferable. In particular, a polymer dispersant containing: abasicfunctionalgroup, forexampleanitrogen-containing heterocyclic group such as a primary, secondary, or tertiary amino group, pyridine, pyrimidine, or pyrazine; or a functional group, for example an amide group or a urethane group, maybe advantageouslyused. The photosensitive composition and the black matrix resist composition of the present invention may further contain fluorescent whiteners, surfactants, plasticizers, flame-retardants, antioxidants, UV absorbents, foaming agents, fungicides, antistatic agents, magnetic materials, electrically conductive materials, antimicrobial/bactericidal agents, porous adsorbents, perfumes andthe
J like, depending on the purpose.
Also, the photosensitive composition and the blackmatrix resist composition of the present invention may contain a heat polymerization inhibitor in order to prevent polymerization during storage. Specific examples of the heat polymerization inhibitor include p-methoxyphenol, hydroquinone, catechol, tert-butylcatechol, phenothiazine and methoquinone. 2-7. Blendingratioofeachcomponentinthephotosensitivecomposition Thecompoundingratioofthephotopolymerizationinitiatorsystem
(A) in the photosensitive composition of the present invention is preferably 1 to 40 % by mass, more preferably 3 to 30 % by mass. If the compounding ratio is less than 1 % by mass, the photosensitivity may deteriorate. If the compounding ratio exceeds 40 % by mass, the mechanical strength of the cured product may decrease.
Thecompoundingratiobetweenthebinderresin (B) andthecompound (C) having an ethylenicallyunsaturated group is (B) : (C) = from 50 :50 to 95 : 5, preferably from 60 : 40 from 90 : 10, more preferably from 85 : 15 to 70 : 30 in mass ratio. If the compounding ratio of the binder resin (B) exceeds 95 or more, the photosensitivity may deteriorate. On the other hand, a compounding ratio of the binder resin (B) 'of less than 50 is not preferable in that the line width of patterns is apt to be wider. 2-8. Blending ratio of each component in the black matrix resist composition
The blending ratio of each of the components in the blackmatrix resist compositionofthepresent inventionis notparticularlylimited but the ratio of each component other than the organic solvent (E) to the total content (total solid content) is preferably within the following range .
I
(A) The amount of the photopolymerization inhibitor system is preferably 2 to 15 % by mass, more preferably 5 to 10 % by mass. ' If the amount of the photopolymerization initiator system is too small, itisdisadvantageousinthatphotosensitivityanddevelopmentlatitude decrease. If the amount is too large, it is disadvantageous in that the line width of lines formed in the resist patterns are wider than that of the lines of the photomask.
(B) The amount of the binder resin having a carboxyl group is preferably 10 to 30 % by mass, more preferably 15 to 25 % by mass.
If the amount of the binder resin is too small, it is disadvantageous inthatadhesivenesswithasubstrateordevelopmentlatitudedecreases. Iftheamountistoolarge, it isdisadvantageous inthat light-blocking effect decreases. (C) Theamountofthecompoundhavinganethylenicallyunsaturated group is preferably 2 to 20 % by mass, more preferably 3 to 15 % by mass. Iftheamountofthecompoundhavinganethylenicallyunsaturated group is too small, it is disadvantageous in that photosensitivity decreases. If the amount is too large, it is disadvantageous in that the line width of lines formed in the resist patterns are wider than that of the lines of the photomask.
(D) The amount of the black pigment is preferably 40 to 80 % by mass, more preferably 45 to 70 % by mass. If the amount of the blackpigmentistoosmall, itisdisadvantageousinthatlight-blocking effect decreases. If the amount is too large, it is disadvantageous inthatphotosensitivityandadhesivenesswiththe substratedecrease. 3. Manufacturingprocess anduses ofthephotosensitivecomposition
The photosensitive composition containing a pigment can be producedbymeansofvariouskindsofdispersingmeanssuchasathree-roll mill, a two-roll mill, a sand mill, an atoliter, a ball mill, a kneader
J and a paint shaker. To prevent gelation caused by polymerization reactionorthelikeatthetimeofdispersing, apolymerizationinhibitor may be added. The monomer and photopolymerization initiator may be compounded after the pigment is dispersed. In addition, in order to disperse the pigment well, a dispersion aidmaybe addedas appropriate. The dispersion aid helps pigments be dispersed and also prevents reagglomeration after the dispersion. For the purpose of obtaining appropriate fluidity or obtaining the light-shielding property and mechanicalandphysicalcharacteristicsofthecuredproduct, anextender pigment such as barium sulfate, calcium carbonate, silica, titania, alumina, oraluminumpowdermaybeaddedtothephotosensitivecomposition of the present invention.
The photosensitive composition of the present invention may be applied onto a substrate, such as glass, aluminum, a PET film, or a polyesterfilmbyacoatingmethodsuchas spraycoating, spinnercoating, roll coating, screen coating, spread coating, dip coating, or calendar coating. Here, inordertoobtainappropriate coatingcharacteristics, a small amount of silicone- or fluorine-based surfactant as a leveling agent or defoaming agent may be added to the photosensitive composition of the present invention.
The photosensitive composition coated by means of any one of the above coating methods is dried when necessary by a hot-air oven or a hot plate generally under conditions of 60 to 1000C for 10 to 30 minutes to evaporate the volatile solvent. If the temperature in this instance is too high or the heating time is too long, polymerization orcross-linkingpartiallyoccurs, sothatthesolubilityofanunexposed portion in the developer is decreased to cause so-called burn, which is undesirable. Drying may be performed under reduced pressure. The methods of forming a pattern of a certain configuration with the photosensitive composition of the present invention are roughly classified into two types. One is a method involving coating the photosensitive composition in a desired configuration and then curing it by irradiation with light. The other is a method involving applying the photosensitive composition evenly onto a substrate, irradiating the photosensitive composition with light so that the exposed portion forms a desired configuration to cure the photosensitive composition and then removing an unexposed portion by means of washing, peeling, physical polishing, chemical polishing, or the like to form a pattern with the photo-cured product. In the case of the photosensitive composition of thepresent invention, inparticular, a suitable pattern can be formed by the latter method of pattern formation.
Anyoneofinorganicmaterials suchas glassandsilicon, metallic materialssuchasaluminum, stainlesssteel, andcopper, resinmaterials such as PET, polyester, polyimide, epoxy resin, polyethylene and polycarbonate, and paper may be used for the substrate used in the pattern formation of the present invention. The surface of the substrate may be subjected to oxidation treatment, acid treatment, plasma treatment, discharge treatment or the like to improve adhesion of the photosensitive composition. Since the photosensitive composition is usually present on the surface of a substrate, the thickness of the substrate can be selected optionally. A resin layer orthelikethatdoesnotparticipateinthephotoreactionmaybeprovided between the photosensitive composition and the substrate.
Intheabove-describedpatternformation, whenanuncuredportion of the photosensitive composition after light irradiation is dissolved and removed to be subjected to development treatment, examples of a solventforadeveloperincludeN-methylpyrrolidone, methanol, ethanol, toluene, cyclohexane, isophorone, cellosolve acetate, diethylene i glycol dimethyl ether, ethylene glycol diethyl ether, xylene, ethylbenzene, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, isoamyl acetate, ethyl lactate, methylethyl ketone, acetone, cyclohexanone, N,N-dimethyl formamide, acetonitrile, and an alkali aqueous solution. Each of themmay be used alone, or two or more kinds thereof can be used in combination. A basic substance such as trimethylamine or triethylamine or a surfactant may be further added to the solvent.
Examples of the alkali aqueous solution include: an aqueous solution of an inorganic salt such as sodium hydroxide, potassium hydroxide, sodium carbonate, or potassium carbonate; and an aqueous solution of an organic salt such as hydroxytetramethyl ammonium or hydroxytetraethyl ammonium. Each of them may be used alone, or two or more kinds thereof can be used in combination.
The photosensitive composition of the present invention can be suitably used particularly for a development type resist that forms finepatterns. Specificexamplesthereofincludeopticalplatemaking, solder resists, etching resists, color filter resists, holograms, optical sculpturing and UV ink. 4. Manufacturing method of the black matrix resist composition
The production of the black matrix resist composition of the present invention is carried out by: mixing or premixing (B) a binder resin having a carboxyl group, (E) an organic solvent, (D) a black pigment, and optionally a pigment dispersant; subjecting the mixture to dispersion treatment; and mixing in and dissolving (C) a compound havinganethylenicallyunsaturatedgroupand (A) aphotopolymerization initiator system into the resultant. A disperser for carrying out the dispersion treatment may be
) any one of: roll mills such as a two-roll mill and a three-roll mill; ball mills such as a ball mill and a vibration ball mill; and be'ads mills such as a paint conditioner, a continuous disk type beads mill, and a continuous annular-stirred bead mill. Of those, in particular, acontinuousannular-stirredbeadmill, whichcanperformpulverization and dispersion within a short time and attains a sharp distribution ofparticle diameters afterdispersionandinwhichtemperature control during pulverization and dispersion is easy so that deterioration of the dispersion solution can be prevented.
Acontinuous annular-stirredbeadmill is constituted such that a rotor (bodyof rotation) havinggrooves for stirringbeads is inserted into a vessel (cylindrical body) having an inlet and an outlet for the material. In the gap portion between the double cylinders of the vesselandtherotor, thebeads areallowedtomovearoundbythe rotation of the rotor, to thereby pulverize, shear and grind to effectively pulverize and disperse the black pigment. The sample is introduced throughtheendportionofthevesselandthenformedintofineparticles, andthendischargedfromthe opposite sideofthe inlet. This treatment is repeated until the desired particle size distribution is obtained. The term "residence time" refers to a time period in which the1 sample is actually pulverized and dispersed in the vessel.
Suchacontinuous annular-stirredbeadsmillmaybe, forexample, SPIKE MILL (trade name) manufactured by Inoue Manufacturing, Inc., or OB-MILL (trade name) manufactured by Turbo Kogyo Co., Ltd.
Preferable dispersion conditions for using the continuous annular-stirred bead mill are as follows. The bead size (diameter) used is preferably 0.2 to 1.5 mm, more preferably 0.4 to 1.0 mm. If the bead size is less than 0.2 mm, the weight of a single bead is too small and the pulverization energy of the single bead is then reduced i and the pulverization of the pigment does not proceed. If the bead size exceeds 1.5 mm, the collision frequency between the beads becomes low and performing the pulverization of carbon black within a short time is difficult. As a material for beads, ceramics such as zirconia and alumina and stainless steel, which have a specific gravity of 4 or more, are preferable in light of high pulverization efficiency.
The peripheral speed of the rotor is preferably 5 to 20 m/second, more preferably 8 to 15 m/second. If the peripheral speed is less than 5 m/second, the pigment cannot be pulverized and dispersed sufficiently. If the peripheral speed exceeds 20 m/second, it is not preferable in that the pigment dispersion solution has an excessively increased temperature due to frictional heat and that denaturation such as thickening may occur. The temperature at dispersion is preferably within the range of 10 to βO°C, more preferably within the range of room temperature to 50°C. A temperature lower than 100C is not preferable in that atmospheric moisture may be mixed into the dispersion solution due to dew condensation. Atemperature in excess of 600C is not preferable in that changes such as thickening may occur.
The residencetime ispreferably 1 to 30minutes, morepreferably 3 to 20 minutes. If the residence time is shorter than 1 minute, the pulverization and dispersion treatments may be insufficient. If the residence time exceeds 30 minutes, the dispersion solution may be deteriorated and thickened.
5. Method of manufacturing a color filter
A method of manufacturing a color filter using the black matrix resist composition of the present invention will be described. Here, the description will be made with reference to a color filter for a liquidcrystaldisplaydevice, whereablackmatrixresistcomposition, pixels and a protective film are laminated in this order.
The black matrix resist composition of the present invention is applied on a transparent substrate. Then, after a solvent is dried in an oven or the like, black matrix patterns are formed by exposure/ development through a photomask and post baking is then carried out, thereby completing the formation of a black matrix.
Examples of the transparent substrate include, but not particularly limited to: inorganic glass such as quartz glass, borosilicate glass and lime soda glass having a silica-coated surface; andfilms and sheets of polyesters such as polyethylene terephthalate, polyolefins such as polypropylene and polyethylene, polycarbonate, polymethylmethacrylate, and thermoplastics of polysulfone, an epoxy resin, and thermosetting plastics such as a polyester resin. Those transparent substrates may be previously subjected to any one of a coronadischargetreatment, anozonetreatment, orathinfilmtreatment with various polymers such as a silane-coupling agent and a urethane polymer.
Coating methods include, in addition to methods of dip coating, a role coater, a wire bar, a flow coater, a die coater and a spray coating, spin coating such as a method using a spinner.
Drying of a solvent is carried in a drying device such as a hot plate, an IR oven, or a convection oven. Preferable drying conditions include a temperature of 40 to 150°C and a drying time period within 10 seconds to 60 minutes. Alternatively, the solvent may be dried in a vacuum.
An exposure method involves: providing a 50-200 urn space (gap) above the sample/ placing a photomask thereon; and carrying out an image exposure. Examples of light sourcewhich canbeusedforexposure include: lamplight sources suchas axenon lamp, ahighpressuremercury lamp, anultra-highpressuremercurylamp, ametalhalidelamp, amoderate pressuremercury lamp, anda low-pressuremercury lamp; and laser light sources such as an argon ion laser, a YAG laser, an excimer laser and a nitrogen laser. When only light having a specific irradiation wavelength is used, an optical filter may be used.
The developing process is carried out using a liquid developer to develop a resist by a dipping, shower, or paddle method or the like. The liquid developer is not particularly limited as far as it is capable of dissolving a resist film on an unexposed portion. For instance, organic solvents including acetone, methylene chloride, trichlene, and cyclohexanone can be used. However, many of the organic solvents may causeenvironmentalpollution, havetoxicitytothehumanbodyorinclude fire hazard. Therefore, it is preferable to use an alkali liquid developerhavingno suchrisks. Examples ofthe alkali liquiddeveloper include aqueous solutions containing: inorganic alkali agents such as sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide andpotassiumhydroxide; and organic alkali agents such as diethanolamine, triethanolamine and tetra-alkyl-ammonium hydroxide. If required, a surfactant, a water-solubleorganicsolvent, alowmolecularcompoundhavingahydroxy1 group or a carboxyl group or the like may be added to the alkali liquid developer. In particular, it is preferable to add a surfactant, which has effects of improving developability and resolution and reducing scumming.
Examples of surfactants used in the liquid developer include: anionic surfactants each having a sodium naphthalenesulfonate group or a sodium benzenesulfonate group; nonionic surfactants each having a polyalkyleneoxy group; and cationic surfactants each having a tetraalkylammoniumgroup. Amethod ofdevelopment is notparticularly
] limited but in general the development is carried out at a development temperature of preferably 15 to 500C, more preferably 15 to 450C by means of a method such as immersion development, spray development, brush development or ultrasonic wave development.
Post bake is performed at temperatures ranging from 150 to 3000C for a time period of 1 to 120 minutes using the same apparatus as one used in drying the solvent.
The black matrix thus obtained has a film thickness preferably in the range of 0.1 to 1.5 urn, more preferably in the range of 0.2 to1.2urn. Furthermore, forattainingthefunctionsoftheblackmatrix, in those filmthicknesses, the optical density is preferably 3 ormore.
In this step, black matrix patterns with spaces of about 20 to
200 μm among the blackmatrices are formed. In the subsequent process, pixels will be formed in those spaces.
Next, pixels of mutiple colors are formed in the spaces of the black matrix. The colors of the respective pixels usually are three colors, red (R) , green (G) andblue (B) , andaphotosensitivecomposition iscoloeredwithapigmentoradye. Atfirst, thecoloredphotosensitive composition is appliedon a transparent substrate onwhichblackmatrix patterns are placed. Subsequently, the solvent is dried in an oven or the like to form a colored layer of the first color all over the entire surface of the black matrix. In general, since a color filter is composed of pixels of multiple colors, unnecessary portions of the first color layer may be removed by photolithography to form a desired first-color pixel pattern. The pixel film thickness is about 0.5 to 3 μm. This procedure is repeated for pixels for required colors to form pixels of multiple colors, thereby forming a color filter. Apparatuses and agents used in the process of forming each pixel are preferably the same as those used in the formation of the blackmatrix, i but if they are different from each other, there is no problem.
After that, if required, a protective film is laminated. 'The materials of the protective filminclude, but not particularly limited to, an acryl resin, an epoxy resin, a silicone resin, and a polyimide resin.
In addition, as amethod other than those described above, there is a method, the so-called backside exposure method, involving: previously forming pixels in patterns on a transparent substrate; applying a black matrix resist composition; exposing from the transparent substrate; and using pixels as masks to forma blackmatrix between the pixels.
Finally, if required, an ITO transparent electrode may be laminated and patterned using any conventional method.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 shows the 1H-NMR chart of a thiol compound (BAEMB) manufactured in Synthesis Example 1.
Fig. 2 shows the 13C-NMR chart of the thiol compound (BAEMB) manufactured in Synthesis Example 1.
EXAMPLES
Hereinafter, the present invention will be described in further detail with reference to the synthesis examples of the thiol compounds, radical generators and binder resins having a carboxyl group on its side chain, preparation of a black pigment dispersion solution, and Examples and Comparative examples of the photosensitive composition and black matrix resist composition of the present invention will be given to further describe the present invention. However, thepresent inventionisnotlimitedtotheseexamples. Inaddition, intheexamples below, "part" represents "part bymass" and "%" represents "% bymass". j
(1) Synthesis examples of thiol compounds Synthesis Example 1: Synthesis of •
2,2-bis{4- (3-mercaptobutyloyloxyethoxy)phenyl}propane (the compound of the formula (10) wherein m is 1) (BAEMB)
Figure imgf000050_0001
In a 200-ml volume eggplant-shaped flask, 40 g (hydroxyl group equivalent:246 meq) of 2,2-bis{4-(2-hydroxyethoxy)phenyl}propane
(BA-2, manufactured by Nippon Nyukazai Co. , Ltd. , hydroxyl group value of 345 mgKOH/g) , 32.24 g (268 mmol) of 3-mercapto butyric acid (manufacturedby Yodo Chemical Co. , Ltd.), 0.98 g (5.2 mmol) op-toluene sulfonic acidmonohydrate (manufactured by Junsei Chemicals Co. , Ltd. ) and 40 g (2.6 mmol) of toluene (manufactured by Junsei Chemicals Co., Ltd. ) were placed, and a Dean-Stark apparatus and a condenser tube were attached to the flask. While being stirred, the contents were heated at an oil bath temperature of 140 0C. After 4 hours from the start of the reaction, the reaction mixture was left to cool and neutralized with 200 ml of a 10% aqueous solution of sodium hydrogen carbonate. Further, the reaction mixture was washed with deionized water three times, and then dehydrated and dried over anhydrous magnesium sulfate (manufactured by Junsei Chemicals Co., Ltd.) . Then, toluene was distilled off to obtain 64.4 g of BAEMB (98.9% yield) with a purity of 97.2% measured by high-performance liquid chromatography. The resulting BAEMBwas a highly viscous, colorless and transparent liquid.
Synthesis Example 2: Synthesis of
2,2-bis [4-{2- ( 3-mercaptobutyloyloxy) -1-methylethoxy}phenyl]propa ne (BAPMB) (the compound of the formula (14))
Figure imgf000051_0001
In a 50-ml volume eggplant-shaped flask, 40.0Og (hydroxy1 group equivalent: 234 meq.)of 2,2-bis{4-(2-hydroxy-1-methylethoxy)phenyl}propane (RikaresinPO-20, hydroxyl group value: 328 mgKOH/g) , 29.51 g (245 mmol) of
3-mercaptobutyric acid (manufacturedbyYodo Chemical Co. , Ltd. ) , 0.98 g (5.2 mmol) of p-toluene sulfonic acid monohydrate (manufactured by Junsei Chemicals Co. , Ltd. ) and 40 g of toluene (manufactured by Junsei Chemicals Co., Ltd.) were charged, and a Dean-Stark apparatus and a condenser tube were attached to the flask. While being stirred, the content was heated at an oil bath temperature of 14O0C. After 4 hours from the start of the reaction, the reaction mixture was left to cool and neutralized with 50 ml of a 10% aqueous solution of sodiumhydrogen carbonate. Further, the reaction mixture was washed with deionized waterthreetimes, andthendehydratedanddriedoveranhydrousmagnesium sulfate (manufactured by Junsei Chemicals Co. , Ltd.) . Then, toluene was distilled off and 64.68 g of BAPMB (95.1 % yield) with a purity of 96.6% was obtained through high-performance liquid chromatography. The obtained BAPMB was a highlyviscous, colorless transparent liquid. Synthesis Example 3: Synthesis of i ethyleneglycol bis (3-mercaptobutyrate) (EGMB)
EGMB was synthesized according to the method described in JP 2004-149755 A.
Synthesis Example 4: Synthesis of trimethylolpropane tris(3-mercaptobutyrate) (TPMB)
TPMB was synthesized according to the method described in JP 2004-149755 A.
Synthesis Example 5: Synthesis of ethyleneglycol bis (2-mercaptoisobutyrate) (EGMIB)
EGMIB was synthesized according to the method described in JP 2004-149755 A.
[Analytical conditions]
The purity of the product obtained by the synthesis was analyzed using high-performance liquid chromatography. The analytical conditions are shown below. Column: Shodex 5C84E (manufactured by Showa Denko K.K.),
Eluent composition: acetonitrile/water = 3/1 (volume1ratio) , 2 mM tetra-n-butylammonium perchlorate,
Pump: LC-IOAD (manufactured by Shimadzu Corp.), Eluent flow rate: 1.0 ml/min, Temperature: 4O0C,
Detector: UV detector SPD-MlOAVP (manufactured by Shimadzu Corp. ) , and
Detection wavelength: 210 run. [Structural analysis]
• 1H-NMR
The 1H-NMR chart of BAEMB (Synthesis Example 1) was shown in Fig. 1. The 1H-NMR was measured in deuterated chloroform using JNM-AL400 manufactured by JEOL, Ltd. and assignment of the major peak of each chemical shift was performed.
1H-NMR:
1.353, 1.371 ppm: hydrogen atoms of methyl groups at 15 and 15', 1.617 ppm: hydrogen atoms of methyl groups at 1 and 3, 1.828, 1.845 ppm: hydrogen atoms of mercapto groups
2.6' ppm: hydrogen atoms of methylene groups of 13 and 13', and 3.3 ppm: hydrogen atoms of methine groups of 14 and 14'.
• 13C-NMR
The 13C-NMR chart of BAEMB (Synthesis Example 1) was shown in Fig.2. The13C-NMRwasmeasuredindeuteratedchloroformusingJNM-AL400 manufactured by JEOL, Ltd. and assignment of the major peak of each chemical shift was performed.
13C-NMR:
24.74 ppm: carbon atoms of methyl groups at 15 and 15', 30.98 ppm: carbon atoms of methyl groups at 1 and 3,
31.18 ppm: carbon atoms of methine groups at 14 and 14', and 45.64 ppm: carbon atoms of methylene groups at 13 and 13', and 170.86 ppm: carbon atoms of carbonyl groups at 12 and 12'.
(2) Synthesis of radical generator Synthesis Example 6: Synthesis of
2,2'-bis (2-chlorophenyl) -4, 4 ' ,5, 5'-tetrakis (4-methylphenyl) -1,2'-b iimidazole (hereinafter, abbreviated as MHABI)
In a 1-L volume eggplant-shaped flask, 27.50 g (115 mmol) of 4, 4'-dimethylbenzyl (manufacturedbyTokyoKaseiKogyoCo. , Ltd.), 16.25 i g (116 πimol) ofo-chlorobenzaldehyde (manufacturedbyTokyoKaseiKogyo
Co., Ltd.), 69.45 g (901 iranol) of ammonium acetate (manufactured by Junsei Chemicals Co., Ltd.), and 450 g of acetic acid (manufactured by Junsei Chemicals Co., Ltd.) were placed. While being stirred, the contents were heated at 117 °C and reacted for 5 hours. After having beencooled, thereactionliquidwasgraduallypouredinto2Lofdeionized water being stirred, causing precipitation of 2- (2-chlrophenyl) -4, 5-bis (4-methylphenyl) imidazole. Subsequently, 2-(2-chlorophenyl) -4,5-bis (4-methylphenyl) imidazole was filtrated andwashed with water, and then dissolved in 500 g of methylene chloride
(manufactured by Junsei Chemicals Co., Ltd.). Then the resultant mixture was placed in a 2-L volume four-neck flask and cooled to 5 to
1O0C. Tothis, amixtureof117.6g (357 mmol) ofpotassiumferricyanide (manufacturedby Junsei Chemicals Co. , Ltd. ) , 44.7 g of sodiumhydroxide
(manufactured by Junsei Chemicals Co., Ltd.) and 600 g of deionized water was gradually added over 1 hour while stirring, and then reacted for 18 hours at room temperature. The reaction mixture was washed with deionized water three times, and then dehydrated over about 50 g of anhydrousmagnesiumsulfate (manufacturedbyJunseiChemicalsCo. , Ltd.) . Then, methylene chloride was distilled off under reduced pres'sure, to thereby produce crystals of MHABI. The MHABI was re-crystallized from ethanol (manufacturedby Junsei Chemicals Co. , Ltd. ) and then filtrated anddried, to thereby obtain 36.5 g ofpale yellow crystal (88.7% yield) .
(3) Synthesis of binder resin having carboxyl group on side chain Synthesis Example 7: Synthesis of EP-I
185 g of Epicoat 1004 (bisphenol Atype epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent of 925), 14.4 g of acrylic acid, 0.20 g of hydroquinone, and 197 g of diethyleneglycol i monoethyletheracetate (hereinafter, abbreviatedas DGEA, manufactured by Daicel Chemical Industries, Ltd.) were charged and heated to 9'5°C. After confirming uniform dissolution of the mixture solution, 2.O g of triphenylphosphine was added and the whole was heated to 100 0C to react for about 30 hours, to thereby obtain a reaction product having an acid value of 0.5 mgKOH/g. To the reaction product, 96.0 g of tetrahydrophthalic anhydride (manufactured by New Japan Chemical Co. , Ltd. ) was added and the whole was heated to 900C to react for 6 hours. After the disappearance of absorption by acid anhydride in an infrared absorption spectrum (IR) was confirmed, epoxyacrylate resinEP-Ihaving a solid acid value of 119 mgKOH/g and a solid concentration of 60 % was obtained.
Synthesis Example 8: Synthesis of EP-2
185 g of Epicoat 1004 (bisphenol A type epoxy resin, epoxy equivalent of 925; manufactured by Japan Epoxy Resin Co. , Ltd. ) , 14.4 g of acrylic acid, 0.20 g of hydroquinone, and 181 g of diethyleneglycol monoethylether acetate (DGEA) (manufactured by Daicel Chemical Industries, Ltd.) were charged and heated to 95°C. After confirming that the mixture was dissolved uniformly, 2.0 g of triphenylphosphine was charged and the whole was heated to 1000C to react for about 30 hours, thereby obtaining a reaction product having an acid value of 0.5 mgKOH/g. To the reaction product, 70.0 g of tetrahydrophthalic anhydride (manufactured by New Japan Chemical Co., Ltd.) was added and the whole was heated to 900C to react for about 6 hours, followed by confirming the disappearance of absorption of the acid anhydride in an infrared absorption spectrum (IR) . As a result, epoxy acrylate resin EP-2 having a solid acid value of 95 mgKOH/g and a solid concentration of 60 % was obtained.
Synthesis Example 9: Synthesis of AP-I
In a four-neck flask attached with a dropping funnel, a thermometer, a cooling pipe, and a stirrer, 37.5 g of methacrylic acid
(MA) (manufactured by Kyoeisha Chemical Co. , Ltd. ) , 19.0 g of methyl methacrylate (MMA) (manufacturedbyKyoeisha Chemical Co. , Ltd. ) , 18.5 g of n-butyl methacrylate (BMA) (manufactured by Kyoeisha Chemical
Co., Ltd.), 0.75 g of 2-mercaptoethanol (manufactured by Wako Pure Chemical IndustryCo. , Ltd.), and225.0gofpropyleneglycolmethylether (PGM) (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were charged, and the inside of the four-neck flask was then replaced with nitrogen gas for one hour. Furthermore, the flask was heated up to 9O0C in an oil bath, and a mixture solution of 37.5 g of MA, 19.0 g of MMA, 18.5 g of BMA, 0.75 g of 2-mercaptoethanol, 225.0 g of PGM, and 3.2 g of 2,2'-azobis isobutyronitrile (AIBN) (manufactured by Wako Pure Chemical Industry, Co. , Ltd. ) was then graduallydroppedover one hour. After 3 hours of polymerization, the resultant was heated up to 1000C and then mixed with a mixture solution of 1.0 g of AIBN and 15.O g of propyleneglycol methyletheracetate (PMA) (manufactured by Daicel Chemical Industries, Ltd.), followed by carrying out additional 1.5-hourpolymerizationandthen left standing to cool. Subsequently, the inside of the four-neck flask was replaced with fresh air and then into the flask, 61.5 parts by mass of glycidyl methacrylate (GMA) (manufactured by Mitsubishi Rayon Co., Ltd.), 3.6 g of tetra-n-butylammonium bromide (TBAB) (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 0.15 g of methoquinone (manufactured by Junsei Chemical, Co., Ltd.) were added, to thereby carry out a reaction for 8 hours at 8O0C, thereby adding GMA to the carboxyl group of acrylic copolymer. Consequently, GMA-added acrylic copolymer (AP-I) was
J obtained. The solid concentration of AP-I was 30.5 %, the sold acid value thereof was 116mgKOH/g, and the weight averagemolecular weight thereof in terms of polystyrene as measured by GPC was 14,000.
(4) Preparation of pigment dispersion solution 1 to be used in the photosensitive composition
In a 300-ml volume stainless steel can, 1.98 g of Ajisper PB822 (pigment dispersant, manufacturedbyAjinomoto-Fine-Techno Co. , Inc.) was dissolved with 113.5 g propyleneglycol monomethylethylacetate (hereinafter, abbreviated as PMA, manufactured by Daicel Chemical Industries, Ltd. ) , andthenmixedwith 12.54 gofEP-I, 15.0 g of Special Black 350 (carbon black, manufactured by Degussa Co., Ltd.), and 15.0 gof 13M-C (titaniumblack, manufacturedbyMitsubishiMaterialCorp.) . Subsequently, 200 g of zirconiumbeads of 0.65 mm in diameter was added to the reaction mixture and the whole was then subjected to dispersion treatment for 3 hours with a paint conditioner (manufactured by Asada Iron Works Co., Ltd.). The above pigment dispersion solution was filtrated through filter paper having a pore size of 0.8 urn, to thereby prepare a black pigment dispersion solution 1.
(5) Preparation of black pigment dispersion solution 2 to be used in the black matrix resist composition
Dispersion solution 2: In a mixture solvent of 1,874 g of cyclohexane (CH) and 1,874 g of PMA, 57 g of a dispersant Ajisper PB822 (manufactured by Ajinomoto-Fine-TechnoCo., Inc.) was dissolvedand 317 gofEP-I (solid content: 19Og) was thenmixedin. Subsequently, 439 g of carbonblack Special Black 350 (SB 350) (manufactured by Degussa Co., Ltd.) and 439 g of titanium black 13M-C (manufactured by Mitsubishi Material
J Corporation.) as black pigments were mixed in, followed by premixing with a disperser. Furthermore, the mixture solution was dispersed using a continuous annular-stirred bead mill (trade name: Spike Mill Type: SHG-4C, manufactured by Inoue Manufacturing Co., Ltd.) . The beads used were zirconium beads of 0.40 mm in diameter and the packing rate of the beads in the vessel was 80% by volume. The peripheral speed of a rotor was set to 12 m/second, the amount of the black pigment dispersion solution discharged was set to 1 litter/minute and temperature was set to about 300C. The residence time of the black pigment dispersion solutionwas set to 6minutes (driving time: 1 hour) . A dispersion solution 2 was obtained according to the above method.
Dispersion solutions 3 and 4: Dispersion solutions 3 and 4 were prepared fromthe compositions shown in Table 1 by the same method as that of the dispersion solution 2.
Table1
Figure imgf000059_0001
+1: carbon black manufactured by Degussa AG
■*2: titanium black manufactured by Mitsubishi Materials Corporation
*3: pigment dispersant manufactured by Ajinomoto-Fine-Techno Co., Inc.
*4: propylene glycol mono methyl ether acetate manufactured by Daicel Chemical Industries, Ltd.
*5: cyclohexanone manufactured by Wako Pure Chemical Industries, Ltd.
(6) Preparation of photosensitive composition
I
Photosensitive compositions of Examples 1 to 3 andComparative Examples 1 to 2 were prepared from the compositions listed in Tables 2 and 3.
(7) Preparation of black matrix resist composition
Black matrix resist compositions of Examples 4 to 9 and ComparativeExamples 3to 5werepreparedfromthe compositions listed in Tables 4 to 6.
(8) Evaluationofphotosensitive compositions andblackmatrixresist compositions
[Proper developing time]
Each of the photosensitive compositions of Examples 1 to 3 and Comparative Examples 1 to 2 and blackmatrix resist compositions of Examples 4 to 9 and Comparative Examples 3 to 5 was applied onto a glass substrate (dimensions: 100 x 100 x 1mm) toa dry filmthickness of about 1 μm by means of a spin coater and left alone for 5 minutes at room temperature, followed by drying the solvent for 3 minutes at 900C. Furthermore, the glass substrate was exposed at 50 mj/cm2 with an exposure device equipped with a super-high pressure mercury lamp (trade name: MultiLight ML-251A/B, manufactured by Ushio Inc.) through a photomask made of quartz, to thereby photo-cure the composition. The exposure value was measured using a UV light integrator (tradename: UIT-150, manufacturedbyUsio Inc., detector: UVD-S365) . The quartz photomask had a line/space pattern of 4, 6, 8, 10, 20, 50, and 100 μm and a pattern with lines of 4, β, 8, 10, 20, 50 and 100 urn and spaces of all 50 um.
The film of the exposed and cured photosensitive composition was further subjected to alkali development with time variation by using an aqueous solution (21 0C) containing 0.25% Developer 9033 (manufactured by Shipley Far East., Co., Ltd.) which is an alkali developer containing potassium carbonate and 0.03% dodecylbenzenesulfonate (manufacturedbyTokyoKaseiKogyoCo. , Ltd. ) , and a spin developer (AD-1200, manufactured by Takizawa Industries, Co., Ltd.) . Afterthat, the linewidthof each line formedbyexposure wasmeasuredbyanopticalmicroscope (VH-Z250, manufacturedbyKeyence Corp. ) . The proper developing time was defined as a time periodwhere a line width of about 20 μm was obtained in the photo-curing of a portionhavingalinewidthof20μmandaspaceof50urninthephotomask. The results are shown in Tables 2 to 6. [Resolution]
Each of the photosensitive compositions of Examples 1 to 3 and Comparative Examples 1 to 2 and black matrix resist compositions of Examples 4 to 9 and Comparative Examples 3 to 5 was subjected to alkali development in the same manner as that of the above, including drying of the solvent , exposure and then alkali development over the proper developing time. The minimum line width among lines in line/space patterns corresponding to those of photomasks formed through exposure, was read using an optical microscope (VH-Z250, manufactured by Keyence Corp.) . The results are shown in Tables 2 to 6. [Development latitude] Each of the photosensitive compositions of Examples 1 to 3 and Comparative Examples 1 to 2 and black matrix resist compositions of Examples 4 to 9 and Comparative Examples 3 to 5 was subjected to alkali development in the same manner as above, including drying of the solvent, exposure to light, alkali development over the proper developing time and further alkali development over the developing time plus 20 seconds. The minimum line width on a part where the lines in patterns of the photomask were 4, 6, 8, 10, 20, 50, and 100 urn and all the spaces were 50 um was read using an optical microscope (VH-Z250, manufactured by Keyence Corp.) . The results are shown in Tables 2 and β. [OD value (optical density) ]
EachoftheresistcompositionsofExamples4to 9andComparative Examples 3 to 5 was spin-coated on a glass substrate (100 x 100 mm in dimensions) and then dried at room temperature for 5 minutes, followed by drying a solvent at 900C for 3 minutes. The resultant was exposed at 50 mj/cm2 by an ultra-high pressure mercury lamp and thenpost-bakedat2300Cfor60minutes. Theresultingglasssubstrate on which the resist was applied was used for the OD value measurement. The OD value was determined from a standard curve made by measuring a transmission factor at 550 nm on a standard substrate with a known OD value. Subsequently, the resist-applied glass substrate of each of Examples and Comparative Examples was subjected to the measurement oftransmissionfactorat 550nmtocalculatetheODvalue. Theresults are shown in Tables 4 to 6.
Table 2
Figure imgf000063_0001
*1: carbon black manufactured by Degussa AG
*2: titanium black manufactured by Mitsubishi Materials Corporation
*3: pigment dispersing agent manufactured by Ajinomoto-Fine-Techno
Co. , Inc. *4: propylene glycolmonomethyl ether acetatemanufacturedby Daicel
Chemical Industries, Ltd.
*5: diethyleneglycolmonomethyletheracetatemanufacturedbyDaicel
Chemical Industries, Ltd.
*β: diacrylate of 4-mol EOadduct bisphenolAmanufacturedbyKyoeisha Chemical Co., ltd.
*7: dipentaerythritolhexaacrylatemanufacturedbyToagoseiCo. , ltd.
*8: tricyclo decanediacrylatemanufacturedby Kyoeisha Chemical Co. , ltd.
*9: 4,4 '-Bis (N,N-diethylamino)benzophenonemanufacturedbyHODOGAYA CHEMICAL Co.,Ltd.
*10: 2-methyl-l- [4- (methylthio)phenyl] -2-morpholinopropane-l-one manufactured by Ciba Specialty Chemicals K. K.
+11: fluorine compound manufactured by DAINIPPON INK AND CHEMICALS,
INC.
Table 3
Figure imgf000065_0001
Table4
Figure imgf000066_0001
*β: diethyleneglycolmonomethyletheracetatemanufacturedbyDaicel Chemical Industries, Ltd.
*7: propyleneglycolmonomethyl etheracetatemanufacturedbyDaicel Chemical Industries, Ltd.
*8: diacrylateof 4-molEOadductbisphenolAmanufacturedbyKyoeisha
Chemical Co., ltd.
*9: dipentaerythritol hexaacrylate manufactured by Toagosei Co., ltd. *10: 4, 4 '-Bis (N,N-diethylamino)benzophenone manufactured by HODOGAYA CHEMICAL Co.,Ltd. ,
*11: fluorine compound manufactured by DAINIPPON INK AND CHEMICALS, INC.
Table 5
Figure imgf000067_0001
*12: dimethylol tricyclo decanediacrylate manufactured by Kyoeisha Chemical Co., ltd. *13: 2-methyl-l- [4- (methylthio)phenyl]-2-morpholinopropane-1-one manufactured by Ciba Specialty Chemicals K. K. j
Table 6
Figure imgf000068_0001
As is evident from Table 2, each of the photosensitive compositions of Example 1 using a thiol compound having a bisphenol skeleton has high sensitivity that allows photo-curing even by a low exposure value of 50 mj/cm2 and is simultaneously excellent in development latitudecomparedwithotherthiolcompounds. Therefore, the thiol compound and the photosensitive composition using the same of the present invention can be advantageously used in alkali development type resists such as solder resists, etching resists, and color filter resists.
As is evident from Tables 4 and 5, each of the black matrix resist compositions of Example 4 to 9 using a thiol compound having a bisphenol skeleton has high sensitivity that allows photo-curing evenbya lowexposurevalueof50mj/cm2andis simultaneouslyexcellent indevelopmentlatitudecomparedwithotheraliphaticthiolcompounds. Therefore, the black matrix resist composition containing the thiol compound of the present invention can be advantageously used in large-size substrates.
INDUSTRIAL APPLICABILITY
The novel thiol compound having a bisphenol skeleton and the photosensitive compositionusingthe compoundhave a high sensitivity and are excellent in the development latitude, so that they can be suitablyusedforetchingresists, solderresists, colorfilterresists and the like, which form patterns in photolithography and alkali development. The resist composition for black matrix of color filters using a novel thiol compound having a bisphenol skeleton has a high light-shielding property, a high sensitivity and is excellent in the development latitude, so that the composition can be suitably used for large substrates for color filters.

Claims

CIAIMS
1. A thiol compound represented by formula (1) :
Figure imgf000070_0001
wherein R1 represents a straight- or branched-chain alkylene group having 1 to β carbon atoms, R2 represents a straight- orbranched-chain alkylene grouphaving 2 to 6 carbon atoms, R3 andR4 each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen atom, X represents a single bond, -CO-, -SO2-, -CH2-,
-C(CFs)2-, -C(CHs)2- or -0-, and n represents an integer of 1 to 5.
2. Thethiol compoundaccordingtoclaim1, whereinR1 isanalkylene group represented by any one of formulae (2) to (β) .
-CH2CH2- * (2)
-CH CH2- * (3) CH3
-CH2CH- * (4) CH3
-CH- * (5) CH3
CH3
-C- * (6) CH3 wherein the symbols "*" each shows a position bonding with a mercapto group.
3. Thethiolcompoundaccordingtoclaim1, whereinR2is analkylene group represented by any one of formulae (7) to (9) :
CH2CH2- (7)
CH CH2- (8) CH3
CH2 CH - (9) CH,
4. The thiol compound according to claim 1, which is represented by formula (10)
Figure imgf000071_0001
wherein m represents an integer of 1 or 2.
5. The thiol compound according to claim 1, which is a compound obtained through esterification reaction between a diol compound represented by formula (11)
Figure imgf000072_0001
wherein R2 represents a linear or branched alkylene group having 2 to β carbon atoms, R3 and R4 each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen atom, X represents a single bond, -CO-, -SO2-, -CH2-, -C(CF3)2-, -C(CH3)2- or -0-, and n represents an integer of 1 to 5) and a mercapto group-containing carboxylic compound represented by formula (12)
Figure imgf000072_0002
wherein R1 represents a linear or branched alkylene group having 1 to β carbon atoms.
6. Amethodofproducinga thiol compoundas representedby formula
(D,
Figure imgf000072_0003
wherein all the symbols in formula (1) have the samemeaning as defined in claim 1, comprising esterification reaction of a diol compound represented by formula (11)
Figure imgf000073_0001
wherein R2 represents a linear or branched alkylene group having 2 to 6 carbon atoms, R3 and R4 each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen atom, X represents a single bond, -CO-, -SO2-, -CH2-, -C (CF3)2~, -C (CH3)2- or -0-, and n represents an integer of 1 to 5, and a mercapto group-containing carboxylic compound represented by formula (12)
Figure imgf000073_0002
wherein R1 represents a linear or branched alkylene group having 1 to 6 carbon atoms.
7. A photosensitive composition comprising (A) a photopolymerization initiator system containing the thiol compound according to any one of claims 1 to 5, (B) a binder resin containing a carboxylgroupand (C) acompoundhavinganethylenicallyunsaturated group.
8. The photosensitive composition according to claim 7, wherein the photopolymerization initiator system (A) contains a hexaarylbiimidazole compound and/or an aminoacetophenone compound.
9. The photosensitive composition according to claim 8, wherein the hexaarylbiimidazole compound is represented by formula (13)
Figure imgf000074_0001
wherein Y represents a halogen atom and R represents an alkyl group or an alkoxy group, which may have a substituent.
10. The photosensitive composition according to claim 7, wherein the photopolymerization initiator system (A) contains a sensitizer.
11. The photosensitive composition according to claim 10, wherein the sensitizer is one or more compounds selected from the group consisting of benzophenone-based compounds, thioxanthone-based compounds and ketocoumarin-based compounds.
12. The photosensitive composition according to claim 7, in which the binder resin containing a carboxyl group (B) further contains an ethylenically unsaturated group.
13. A resist composition for black matrix of color filters, containing (A) a photopolymerization initiator system containing the thiol compound according to any one of claims 1 to 5, (B) a binder resin having a carboxyl group, (C) a compound having an ethylenically unsaturated group, (D) black pigment and (E) an organic solvent.
14. The resist composition for black matrix of color filters accordingtoclaim13, whereinthebinderresin (B) havingacarboxylic group further has an ethylenically unsaturated group.
15. The resist composition for black matrix of color filters accordingtoclaim14, whereinthebinderresin (B) isabisphenol-type epoxy acrylate resin.
16. The resist composition for black matrix of color filters according to claim 13, wherein the photopolymerization initiator system (A) contains a hexaarylbiimidazole compound and/or an aminoacetophenone compound.
17. The resist composition for black matrix of color filters according to claim 16, wherein the hexaarylbiimidazole compound is a compound represented by formula (13)
Figure imgf000075_0001
wherein all the symbols have the same meanings as defined in claim 9.
18. The resist composition for black matrix of color filters accordingtoclaim16or17, whereinthephotopolymerizationinitiator system (A) contains as a sensitizer, one or more compounds selected from the group consisting of benzophenone-based compounds, thioxanthone-based compounds and ketocoumarin-based compounds.
19. The resist composition for black matrix of color filters according to claim 13, whereinthe blackpigment (D) is a carbonblack and/or a titanium black.
20. The resist composition for black matrix of color filters according to claim 13, wherein the components other than the organic solvent (E) are contained at the following ratios:
(A) photopolymerization initiator system; 2 to 15 % mass,
(B) binder resin having a carboxyl group; 10 to 30 % by mass, (C) compound having an ethylenically unsaturated group;
2 to 20 % by mass, and (D) black pigment; 40 to 80 % by mass.
21. The resist composition for black matrix of color filters according to claim 20, wherein the thiol compound of formula (1) is contained at 20 to 70 % by mass in the photopolymerization initiator system (A) .
PCT/JP2005/019955 2004-10-26 2005-10-25 Thiol compound, and photosensitive composition and black matrix resist composition using the compound Ceased WO2006046733A1 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008127036A3 (en) * 2007-04-11 2008-12-04 Lg Chemical Ltd Photosensitive resin composition comprising a polymer prepared by using macromonomer as alkali soluble resin
CN112051710A (en) * 2020-09-02 2020-12-08 之江实验室 A high-refractive-index femtosecond laser photoresist based on mercaptoene photo-click polymerization
CN113039216A (en) * 2018-11-08 2021-06-25 昭和电工株式会社 Copolymer and resin composition comprising the same

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4048218A (en) * 1975-02-24 1977-09-13 W. R. Grace & Co. Flame retardant mercaptocarboxylic acid esters of halogenated aromatic polyols
EP0022047A1 (en) * 1979-06-26 1981-01-07 Rhone-Poulenc Specialites Chimiques Stabilization process for polymers made of PVC and polymers so stabilized
FR2492391A1 (en) * 1980-10-20 1982-04-23 Rhone Poulenc Ind Synergistic heat stabilisers for PVC - contg. organo-zinc cpd., organic deriv. of Gp.=IIA metal and thioglycolic acid ester
FR2552440A1 (en) * 1983-09-28 1985-03-29 Rhone Poulenc Spec Chim Process for stabilisation of vinyl chloride-based polymers, stabilising compositions for making use of the process and polymers thus stabilised.
WO2003072614A2 (en) * 2002-02-28 2003-09-04 Showa Denko K.K. Thiol compound, photopolymerization initiator composition and photosensitive composition
JP2004149755A (en) * 2002-02-28 2004-05-27 Showa Denko Kk Thiol compound, photopolymerization initiator composition and photosensitive composition
WO2004055596A1 (en) * 2002-12-16 2004-07-01 Showa Denko K. K. Color filter black matrix resist composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4048218A (en) * 1975-02-24 1977-09-13 W. R. Grace & Co. Flame retardant mercaptocarboxylic acid esters of halogenated aromatic polyols
EP0022047A1 (en) * 1979-06-26 1981-01-07 Rhone-Poulenc Specialites Chimiques Stabilization process for polymers made of PVC and polymers so stabilized
FR2492391A1 (en) * 1980-10-20 1982-04-23 Rhone Poulenc Ind Synergistic heat stabilisers for PVC - contg. organo-zinc cpd., organic deriv. of Gp.=IIA metal and thioglycolic acid ester
FR2552440A1 (en) * 1983-09-28 1985-03-29 Rhone Poulenc Spec Chim Process for stabilisation of vinyl chloride-based polymers, stabilising compositions for making use of the process and polymers thus stabilised.
WO2003072614A2 (en) * 2002-02-28 2003-09-04 Showa Denko K.K. Thiol compound, photopolymerization initiator composition and photosensitive composition
JP2004149755A (en) * 2002-02-28 2004-05-27 Showa Denko Kk Thiol compound, photopolymerization initiator composition and photosensitive composition
WO2004055596A1 (en) * 2002-12-16 2004-07-01 Showa Denko K. K. Color filter black matrix resist composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
A. ZOCHNIAK, ET AL.: "Products of polyaddition of 1,1'-isopropylidene- bis(p-phenylene-oxy)di- .beta.-ethanol thioglycolate with 4,4'-diphenylmethane diisocyanate and Desmodur L", JOURNAL OF MACROMOLECULAR SCIENCE : PART A - CHEMISTRY, vol. A18, no. 7, 1982, MARCEL DEKKER, NEW YORK, NY, US, pages 1021 - 1029, XP008057373 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008127036A3 (en) * 2007-04-11 2008-12-04 Lg Chemical Ltd Photosensitive resin composition comprising a polymer prepared by using macromonomer as alkali soluble resin
US8357483B2 (en) 2007-04-11 2013-01-22 Lg Chem, Ltd. Photosensitive resin composition comprising a polymer prepared by using macromonomer as alkali soluble resin
CN113039216A (en) * 2018-11-08 2021-06-25 昭和电工株式会社 Copolymer and resin composition comprising the same
CN113039216B (en) * 2018-11-08 2023-08-22 株式会社力森诺科 Copolymer and resin composition containing the same
CN112051710A (en) * 2020-09-02 2020-12-08 之江实验室 A high-refractive-index femtosecond laser photoresist based on mercaptoene photo-click polymerization

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