WO2006046733A1 - Composé thiol, composition photosensible et composition de réserve à matrice noire utilisant ledit composé - Google Patents

Composé thiol, composition photosensible et composition de réserve à matrice noire utilisant ledit composé Download PDF

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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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PCT/JP2005/019955
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English (en)
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Hirotoshi Kamata
Mina Onishi
Katsumi Murofushi
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Showa Denko K.K
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Priority to KR1020077007542A priority Critical patent/KR101225527B1/ko
Priority to CN2005800364238A priority patent/CN101048372B/zh
Publication of WO2006046733A1 publication Critical patent/WO2006046733A1/fr

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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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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)

Abstract

La présente invention concerne un composé thiol représenté par la formule (1), son procédé de fabrication, une composition photosensible et une composition de réserve pour la matrice noire de filtres de couleur qui utilisent le composé thiol, qui présentent une excellente sensibilité et qui peuvent garder inchangée la largeur de ligne dans des motifs, c'est-à-dire atteindre une excellente latitude de développement. (Tous les symboles ont les mêmes significations que celles définies dans la description.)
PCT/JP2005/019955 2004-10-26 2005-10-25 Composé thiol, composition photosensible et composition de réserve à matrice noire utilisant ledit composé WO2006046733A1 (fr)

Priority Applications (2)

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KR1020077007542A KR101225527B1 (ko) 2004-10-26 2005-10-25 티올 화합물 및 이를 사용한 감광성 조성물과 블랙매트릭스 레지스트 조성물
CN2005800364238A CN101048372B (zh) 2004-10-26 2005-10-25 硫醇化合物和使用该化合物的光敏组合物与黑色基质抗蚀剂组合物

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008127036A2 (fr) * 2007-04-11 2008-10-23 Lg Chem, Ltd. Composition de résine photosensible comprenant un polymère préparé en utilisant un macromonomère en tant que résine soluble dans l'alkali
CN112051710A (zh) * 2020-09-02 2020-12-08 之江实验室 一种基于巯基烯光点击聚合高折射率飞秒激光光刻胶
CN113039216A (zh) * 2018-11-08 2021-06-25 昭和电工株式会社 共聚物及包含该共聚物的树脂组合物

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 (fr) * 1979-06-26 1981-01-07 Rhone-Poulenc Specialites Chimiques Procédé de stabilisation de polymères à base de chlorure de polyvinyle et polymères ainsi stabilisés
FR2492391A1 (fr) * 1980-10-20 1982-04-23 Rhone Poulenc Ind Compositions stabilisantes pour polymeres a base de chlorure de polyvinyle. procede de stabilisation desdits polymeres et polymeres ainsi stabilises
FR2552440A1 (fr) * 1983-09-28 1985-03-29 Rhone Poulenc Spec Chim Procede de stabilisation de polymeres a base de chlorure de vinyle, compositions stabilisantes pour la mise en oeuvre du procede et polymeres ainsi stabilises
WO2003072614A2 (fr) * 2002-02-28 2003-09-04 Showa Denko K.K. Compose thiol, composition d'initiateur de photopolymerisation et composition photosensible
JP2004149755A (ja) * 2002-02-28 2004-05-27 Showa Denko Kk チオール化合物、光重合開始剤組成物および感光性組成物
WO2004055596A1 (fr) * 2002-12-16 2004-07-01 Showa Denko K. K. Composition de reserve a matrice noire pour filtres colores

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 (fr) * 1979-06-26 1981-01-07 Rhone-Poulenc Specialites Chimiques Procédé de stabilisation de polymères à base de chlorure de polyvinyle et polymères ainsi stabilisés
FR2492391A1 (fr) * 1980-10-20 1982-04-23 Rhone Poulenc Ind Compositions stabilisantes pour polymeres a base de chlorure de polyvinyle. procede de stabilisation desdits polymeres et polymeres ainsi stabilises
FR2552440A1 (fr) * 1983-09-28 1985-03-29 Rhone Poulenc Spec Chim Procede de stabilisation de polymeres a base de chlorure de vinyle, compositions stabilisantes pour la mise en oeuvre du procede et polymeres ainsi stabilises
WO2003072614A2 (fr) * 2002-02-28 2003-09-04 Showa Denko K.K. Compose thiol, composition d'initiateur de photopolymerisation et composition photosensible
JP2004149755A (ja) * 2002-02-28 2004-05-27 Showa Denko Kk チオール化合物、光重合開始剤組成物および感光性組成物
WO2004055596A1 (fr) * 2002-12-16 2004-07-01 Showa Denko K. K. Composition de reserve a matrice noire pour filtres colores

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 (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008127036A2 (fr) * 2007-04-11 2008-10-23 Lg Chem, Ltd. Composition de résine photosensible comprenant un polymère préparé en utilisant un macromonomère en tant que résine soluble dans l'alkali
WO2008127036A3 (fr) * 2007-04-11 2008-12-04 Lg Chemical Ltd Composition de résine photosensible comprenant un polymère préparé en utilisant un macromonomère en tant que résine soluble dans l'alkali
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 (zh) * 2018-11-08 2021-06-25 昭和电工株式会社 共聚物及包含该共聚物的树脂组合物
CN113039216B (zh) * 2018-11-08 2023-08-22 株式会社力森诺科 共聚物及包含该共聚物的树脂组合物
CN112051710A (zh) * 2020-09-02 2020-12-08 之江实验室 一种基于巯基烯光点击聚合高折射率飞秒激光光刻胶

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