CN103376654A - Color photosensitive resin composition - Google Patents

Color photosensitive resin composition Download PDF

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Publication number
CN103376654A
CN103376654A CN2013101470245A CN201310147024A CN103376654A CN 103376654 A CN103376654 A CN 103376654A CN 2013101470245 A CN2013101470245 A CN 2013101470245A CN 201310147024 A CN201310147024 A CN 201310147024A CN 103376654 A CN103376654 A CN 103376654A
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China
Prior art keywords
methyl
pigment
acid
multipolymer
resin
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Inventor
吉田雅子
松浦龙一
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
    • G03F7/2016—Contact mask being integral part of the photosensitive element and subject to destructive removal during post-exposure processing
    • G03F7/202—Masking pattern being obtained by thermal means, e.g. laser ablation

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a color photosensitive resin composition, which contains coloring agent, resin, polymerized compound and polymerization initiator, wherein, the coloring agent contains C. I. pigment green 36, yellow pigment and at least one pigment selected from a group which is composed of blue, red, purple pigment and orange pigments. The resin is a polymer, which contains at least one structural unit selected from a group which is composed of free unsaturated carboxylic acid and unsaturated carboxylic acid anhydride, and a astructural unit with alicyclic hydrocarbon strucutre.

Description

Photosensitive composition
Technical field
The present invention relates to a kind of photosensitive composition.
Background technology
Photosensitive composition is used for the manufacturing of the employed color filters of display device such as liquid crystal indicator, el display device, plasma scope.As such photosensitive composition, the known composition (JP2004-309537-A) that contains the multipolymer of methacrylic acid, methyl methacrylate, n-BMA and HEMA as resin.
With regard in the past known above-mentioned photosensitive composition, when forming colored pattern with photoetching process, sometimes can't fully remove by developing unexposed section, produce residue, film is residual.
Summary of the invention
The present invention includes following technical scheme.
[1] a kind of photosensitive composition, it contains colorant, resin, polymerizable compound and polymerization initiator, wherein,
Colorant contains C.I. pigment green 36, yellow uitramarine and is selected from least a in the group that is comprised of blue pigment, red pigment, violet pigment and orange pigment,
Resin is multipolymer, and this multipolymer contains: be derived from least a structural unit that is selected from the group that is formed by unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides, and, have the structural unit of ester ring type hydrocarbon structure.
[2] [1] described photosensitive composition, wherein, the structural unit with ester ring type hydrocarbon structure is the structural unit that is derived from following monomer, this monomer has, and can to have substituent carbon number be 3～18 ester ring type alkyl.
[3] [1] or [2] described photosensitive composition, wherein, polymerization initiator comprises O-acyl group oxime compound.
[4] each described photosensitive composition in [1] to [3] wherein, is selected from least a for C.I. paratonere 177 in the group that is comprised of blue pigment, red pigment, violet pigment and orange pigment.
[5] a kind of color filter, it is formed by each described photosensitive composition in [1]～[4].
[6] a kind of display device, it comprises the color filter of record in [5].
When adopting photosensitive composition of the present invention, the development when forming colored pattern with photoetching process is excellent.
Embodiment
Photosensitive composition of the present invention contains colorant (A), resin (B), polymerizable compound (C) and polymerization initiator (D).
Photosensitive composition of the present invention is preferred and then contain and be selected from least a in the group that is comprised of solvent (E), mercaptan compound (T), levelling agent (F) and driving fit promoter (G).
Photosensitive composition of the present invention and then can contain polymerization and cause auxiliary agent (D1).
＜colorant (A) 〉
Colorant (A) contains C.I. pigment green 36, yellow uitramarine and is selected from least a in the group that is comprised of blue pigment, red pigment, violet pigment and orange pigment.
As yellow uitramarine, for example can enumerate, C.I. pigment yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,137,138,139,147,148,150,153,154,166,173,194,214 etc., preferred C.I. pigment yellow 13 8,150.
As blue pigment, for example can enumerate C.I. pigment blue 15,15:3,15:4,15:6,60,80 etc.
As red pigment, for example can enumerate, C.I. Pigment Red 9,97,105,122,123,144,149,166,168,175,176,177,180,192,209,215,216,224,242,254,255,264,265 etc., preferred C.I. paratonere 177.
As violet pigment, for example can enumerate C.I. pigment violet 1,19,23,29,32,36,38 etc., preferred C.I. pigment Violet 23.
As orange pigment, for example can enumerate C.I. pigment violet 13,31,36,38,40,42,43,51,55,59,61,64,65,71,73 etc., preferred C.I. pigment violet 38.
In the middle of at least a in being selected from the group that is formed by blue pigment, red pigment, violet pigment and orange pigment, preferred C.I. paratonere 177 aspect the contrast raising of gained color filter.
The micronize that the pigment that uses in the photosensitive composition of the present invention can implement as required that the surface treatment that imports pigment derivative that acidic groups or basic group are arranged etc. has been processed, used to rosin, sulfuric acid micronize method is processed, used in the grafting of using macromolecular compound etc. to carry out to surface of pigments etc. process or use the organic solvent that is used for removing impurity or water etc. carrying out washing treatment, use that ion exchange process etc. removes ionic impurity remove processing etc.The particle diameter of pigment is preferably even separately.
These pigment carry out dispersion treatment by making it contain pigment dispersing agent, thereby can be made into the dispersible pigment dispersion of homodisperse state in the middle of the Pigments agent solution.Pigment can be distinguished independent dispersion treatment, also can mix the multiple dispersion treatment of coming.
As aforementioned pigment dispersing agent, for example can enumerate the pigment dispersing agents such as kation system, negative ion system, nonionic system, both sexes, polyester system, polyamines system, acrylic acid series etc.These pigment dispersing agents can also capable of being combinedly separately use more than 2 kinds.As pigment dispersing agent, can enumerate commodity KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system), Floren by name (common prosperity society chemistry (strain) system), Solsperse (ZENECA (strain) system), EFKA (BASF society system), Ajisper (Ajinomoto Fine-Techno Co., Inc. system), Disperbyk (Bi Ke chemical company system) etc.
When using pigment dispersing agent, with respect to pigment 100 mass parts, below preferred 100 mass parts of its use amount, more preferably below above 50 mass parts of 5 mass parts.The use amount of pigment dispersing agent has the trend of the dispersible pigment dispersion that can obtain uniform disperse state when aforementioned range.
With respect to the total amount of colorant (A), preferred 20～99 quality % of the content of C.I. pigment green 36, more preferably 30～95 quality %.
With respect to the total amount of colorant (A), preferred 0.1～79.9 quality % of the content of yellow uitramarine, more preferably 4.9～60 quality %.
With respect to the total amount of colorant (A), be selected from preferred 0.1～5 quality % of at least a content in the group that is formed by blue pigment, red pigment, violet pigment and orange pigment, more preferably 0.1～3 quality %.
With respect to the total amount of solid constituent, the above 50 quality % of the preferred 20 quality % of the containing ratio of colorant (A) are following, more preferably 28～45 quality %.In this instructions, " total amount of solid constituent " refers to the total amount of the composition that obtains from photosensitive composition desolventizing of the present invention (E).
＜resin (B) 〉
Resin (B) is multipolymer, this multipolymer contains: be derived from the structural unit that is selected from least a (below be sometimes referred to as " (a) ") in the group that is comprised of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides, with, have the structural unit of ester ring type hydrocarbon structure.
Structural unit with ester ring type hydrocarbon structure is to be obtained by the monomer with ester ring type hydrocarbon structure (below be sometimes referred to as " (x) ").
As resin (B), can enumerate for example following multipolymer [K1]～[K5].
Multipolymer [K1]: (a) with (x) multipolymer;
Multipolymer [K2]: (a), (x) and can (wherein,, (a) is different from (x) with the monomer (c) of (a) copolymerization.) multipolymer of (below be sometimes referred to as " (c) ");
Multipolymer [K3]: multipolymer [K1] or multipolymer [K2] and the resin that has the monomer (b) that carbon number is 2～4 cyclic ether structure and ethylenic unsaturated bond (below be sometimes referred to as " (b) ") reaction and obtain;
Multipolymer [K4]: the resin that multipolymer (b) and (x) and (a) reaction obtain;
Multipolymer [K5]: the resin that multipolymer (b) and (x) and (a) reaction obtain, and then the resin that obtains with the carboxylic acid anhydrides reaction.
As (a), specifically, for example can enumerate, acrylic acid, methacrylic acid, crotonic acid, neighbour,, to the unsaturated monocarboxylic class of vinyl benzoic acid etc.;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2, the unsaturated dicarboxylic classes such as 3,6-tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid, 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norborene-2,3-dicarboxylic acid, 5-carboxyl dicyclo [2.2.1] hept-2-ene", 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-6-methyl bicycle [2.2.1] hept-2-ene", the 5-carboxyl-carboxylic dicyclo unsaturated compound classes such as 6-ethyl dicyclo [2.2.1] hept-2-ene";
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrabydrophthalic anhydride, 1,2,3,6-tetrabydrophthalic anhydride, dimethyl tetrahydro phthalic anhydride, 5, the unsaturated dicarboxylic class acid anhydrides such as 6-dicarboxyl dicyclo [2.2.1] hept-2-ene" acid anhydride;
Unsaturated list ((methyl) acryloyloxyalkyl) the ester class of the polybasic carboxylic acids more than 2 yuan such as mono succinate (2-(methyl) acrylyl oxy-ethyl) ester, phthalic acid list (2-(methyl) acrylyl oxy-ethyl) ester;
Contain the unsaturated esters of acrylic acid of hydroxyl and carboxyl etc. in same a part of α-(hydroxymethyl) acrylic acid etc.
In the middle of these, from aspect and the deliquescent aspect of gained resin aqueous alkali of copolyreaction, preferred acrylic acid, methacrylic acid, maleic anhydride etc.
(x) for example can have the monomer that substituent carbon number is 3～18 ester ring type alkyl for having.
Be 3～18 ester ring type alkyl as carbon number, for example can enumerate the naphthenic base such as cyclopentyl, cyclohexyl, suberyl, ring octyl group; The polycycle alicyclic hydrocarbon radicals such as three ring decyls, decahydro naphthyl, adamantyl, norborny etc., preferred polycycle alicyclic hydrocarbon radical, more preferably three ring decyls.
As the substituting group that these groups can have, can enumerate carbon number and be 1～18 aliphatic alkyl, carbon number and be 6～18 aromatic hydrocarbyl, hydroxyl, halogen atom, epoxy radicals etc.
Be 1～18 aliphatic alkyl as carbon number, for example can enumerate methyl, ethyl, propyl group, isopropyl, butyl, sec-butyl, the tert-butyl group, amyl group and hexyl etc.
Be 6～18 aromatic hydrocarbyl as carbon number, for example can enumerate phenyl, naphthyl, anthryl, toluyl, xylyl, cumenyl, a trimethylphenyl, xenyl, phenanthryl etc.
As halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms and iodine atom etc.
Have the monomer of ester ring type hydrocarbon structure for for example having the monomer of ester ring type hydrocarbon structure and ethylenic unsaturated bond, preferably have the monomer of ester ring type hydrocarbon structure and (methyl) acryloxy.
In addition, in this instructions, " (methyl) acryloyl group " expression is selected from least a in the group that is comprised of acryloyl group and methacryl.The statement of " (methyl) acrylic acid " and " (methyl) acrylate " etc. also has same implication.
As (x), for example can enumerate (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methyl cyclohexyl, three ring [5.2.1.0 2,6] decane-8-base (methyl) acrylate (in the art, is called habitual title " (methyl) acrylic acid two cyclopentyl (pentanyl) ester ".In addition, be sometimes referred to as " (methyl) acrylic acid three ring esters in the last of the ten Heavenly stems ".), three the ring [5.2.1.0 2,6] decene-8-base (methyl) acrylate (in the art, is called habitual title " (methyl) acrylic acid dicyclopentenyl (pentenyl) ester ".), (methyl) acrylic acid two ring penta oxygen ethyl ester, (methyl) isobornyl acrylate, (methyl) acrylic acid diamantane ester etc. have (methyl) esters of acrylic acid of ester ring type hydrocarbon structure;
Dicyclo [2.2.1] hept-2-ene", 5-methyl bicycle [2.2.1] hept-2-ene", 5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxyl dicyclo [2.2.1] hept-2-ene", 5-hydroxymethyl dicyclo [2.2.1] hept-2-ene", 5-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5-methoxyl dicyclo [2.2.1] hept-2-ene", 5-ethoxy dicyclo [2.2.1] hept-2-ene", 5,6-dihydroxy dicyclo [2.2.1] hept-2-ene", 5,6-two (hydroxymethyl) dicyclo [2.2.1] hept-2-ene", 5,6-two (2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5,6-dimethoxy dicyclo [2.2.1] hept-2-ene", 5,6-diethoxy dicyclo [2.2.1] hept-2-ene", 5-hydroxy-5-methyl base dicyclo [2.2.1] hept-2-ene", 5-hydroxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxymethyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-tert-butoxycarbonyl dicyclo [2.2.1] hept-2-ene", 5-cyclohexyl oxygen carbonyl dicyclo [2.2.1] hept-2-ene", 5-phenyloxycarbonyl dicyclo [2.2.1] hept-2-ene", 5, two (tert-butoxycarbonyl) dicyclo [2.2.1] hept-2-ene"s of 6-, the dicyclo unsaturated compound classes such as two (cyclohexyl oxygen carbonyl) dicyclo [2.2.1] hept-2-ene"s of 5,6-; N-N-cyclohexylmaleimide etc. has the N-substituted maleimide of ester ring type hydrocarbon structure; Deng.
In addition, (x) can be following monomer: the monomer of the structure that is replaced by epoxy radicals as 2 hydrogen atoms that the ester ring type hydrocarbon structure has with 2 adjacent carbon atoms of ester ring type hydrocarbon are combined respectively (below be sometimes referred to as " (x ') ").
(x) as such for example can enumerate, vinyl cyclohexene monoxide, 1,2-epoxy radicals-4-vinyl cyclohexane (for example, Celloxide2000; Co., Ltd.'s Daicel system), acrylic acid 3,4-epoxy radicals cyclohexyl methyl esters (for example, Cyclomer A400; Co., Ltd.'s Daicel system), methacrylic acid 3,4-epoxy radicals cyclohexyl methyl esters (for example, Cyclomer M100; Co., Ltd.'s Daicel system), compound shown in the compound shown in the formula (I) and the formula (II) etc.
[in formula (I) and the formula (II), R aAnd R bExpression hydrogen atom or carbon number are 1～4 alkyl, and the contained hydrogen atom of this alkyl can be replaced by hydroxyl.
X aAnd X bThe expression singly-bound ,-R c-, *-R c-O-, *-R c-S-or *-R c-NH-.
R cThe expression carbon number is 1～6 alkane 2 basis.
* represent the connecting key with O.]
Be 1～4 alkyl as carbon number, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group etc.
As the alkyl that hydrogen atom is replaced by hydroxyl, can enumerate hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyl-1-Methylethyl, 2-hydroxyl-1-Methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl etc.
As R aAnd R b, preferably enumerate hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, more preferably enumerate hydrogen atom, methyl.
As alkane 2 basis, can enumerate methylene, ethylidene, propane-1,2-two bases, propane-1,3-two bases, butane-Isosorbide-5-Nitrae-two base, pentane-1,5-two bases, hexane-1,6-two bases etc.
As X aAnd X b, preferably enumerate singly-bound, methylene, ethylidene, *-CH 2-O-and *-CH 2CH 2-O-, more preferably singly-bound, *-CH 2CH 2-O-(* represents the connecting key with O).
As the compound shown in the formula (I), but compound shown in arbitrary formula etc. in enumerative (I-1)～formula (I-15).Wherein, compound shown in preferred formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11)～formula (I-15), the more preferably compound shown in formula (I-1), formula (I-7), formula (I-9) or the formula (I-15).
Figure BDA00003101888300081
As the compound shown in the formula (II), but compound shown in arbitrary formula etc. in enumerative (II-1)～formula (II-15).Wherein, compound shown in preferred formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11)～formula (II-15), the more preferably compound shown in formula (II-1), formula (II-7), formula (II-9) or the formula (II-15).
Figure BDA00003101888300091
Compound shown in compound shown in the formula (I) and the formula (II) can be distinguished separately use, also can be also with the compound shown in the formula (I) and the compound shown in the formula (II).And during with these compounds, in molar basis, the compound shown in the compound shown in the formula (I) and the formula (II) contain ratio preferred 5: 95～95: 5, more preferably 10: 90～90: 10 and then preferred 20: 80～80: 20.
(c) so long as can from (a) copolymerization and with (a) and (x) different monomer then be not particularly limited.
As (c), for example can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) dodecylacrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) allyl acrylate, (methyl) acrylic acid alkynes propyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid naphthyl ester, (methyl) esters of acrylic acids such as (methyl) acrylic acid benzyl ester;
(methyl) esters of acrylic acid of the hydroxyls such as (methyl) HEA, (methyl) acrylic acid 2-hydroxy-propyl ester;
The dicarboxylic diesters such as diethyl maleate, DEF, diethyl itaconate;
The dicarbapentaborane imide derivative classes such as N-phenylmaleimide, N-benzyl maleimide, N-succinimido-3-maleimide benzoic ether, N-succinimido-4-maleimide butyric ester, N-succinimido-6-maleimide capronate, N-succinimido-3-maleimide propionic ester, N-(9-acridinyl) maleimide;
Styrene, α-methyl styrene, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxy styrene, vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc.
In the middle of these, from copolyreaction and stable on heating aspect, optimization styrene, vinyltoluene, (methyl) acrylic acid benzyl ester, N-phenylmaleimide, N-benzyl maleimide etc.
In addition, (c) in the middle of, as have carbon number be 2～4 cyclic ether structure (for example, be selected from by the oxirane ring, in the group that oxetanes ring and tetrahydrofuran ring form at least-kind) monomer (below be sometimes referred to as " (c ') "), for example can enumerate, (methyl) acrylic acid glycidyl esters, (methyl) acrylic acid Beta-methyl glycidyl esters, (methyl) propenoic acid beta-ethyl glycidyl esters, the glycidyl vinyl ether, adjacent vinyl benzyl glycidyl ether, between the vinyl benzyl glycidyl ether, to the vinyl benzyl glycidyl ether, Alpha-Methyl-adjacent vinyl benzyl glycidyl ether, an Alpha-Methyl-vinyl benzyl glycidyl ether, Alpha-Methyl-to the vinyl benzyl glycidyl ether, 2, two (diglycidyl yloxymethyl) styrene of 3-, 2, two (diglycidyl yloxymethyl) styrene of 4-, 2, two (diglycidyl yloxymethyl) styrene of 5-, 2, two (diglycidyl yloxymethyl) styrene of 6-, 2,3,4-three (diglycidyl yloxymethyl) styrene, 2,3,5-three (diglycidyl yloxymethyl) styrene, 2,3,6-three (diglycidyl yloxymethyl) styrene, 3,4,5-three (diglycidyl yloxymethyl) styrene, 2,4,6-three (diglycidyl yloxymethyl) styrene etc. has the monomer of Oxyranyle and ethylenic unsaturated bond;
3-methyl-3-methacryloxypropyl methyl oxetanes, 3-methyl-3-acryloyl-oxy methyl oxetanes, 3-ethyl-3-methacryloxypropyl methyl oxetanes, 3-ethyl-3-acryloyl-oxy methyl oxetanes, 3-methyl-3-methylacryoyloxyethyl oxetanes, 3-methyl-3-acrylyl oxy-ethyl oxetanes, 3-ethyl-3-methylacryoyloxyethyl oxetanes, 3-ethyl-3-acrylyl oxy-ethyl oxetanes etc. has the monomer of oxetanyl and ethylenic unsaturated bond;
Acrylic acid tetrahydro furfuryl ester (for example, VISCOAT V#150, Osaka organic chemistry industry (strain) system), methacrylic acid tetrahydro furfuryl ester etc. have the monomer of tetrahydrofuran base and ethylenic unsaturated bond; Deng.
In the multipolymer [K1], in all structural units that consist of multipolymer [K1], the ratio that is derived from the structural unit of each monomer is,
Preferably:
Be derived from the structural unit of (a): 2～60 % by mole
Be derived from the structural unit of (x): 40～98 % by mole
More preferably:
Be derived from the structural unit of (a): 10～50 % by mole
Be derived from the structural unit of (x): 50～90 % by mole.
The ratio of the structural unit of multipolymer [K1] has the trend of the solvent resistance excellence of development when forming colored pattern and gained color filter when above-mentioned scope.
Multipolymer [K1] but the citing document put down in writing in the method for record and the document in reference example such as the document " experimental method of Polymer Synthesizing " (the grand row work sale room in large Tianjin (strain) chemistry is with the distribution on March 1st, 1972 of the 1st edition the 1st brush of people) make.
Specifically, can be listed below method: with (a) and (x) ormal weight, polymerization initiator, solvent etc. put into reaction vessel, for example, replace oxygen to make deoxidation atmosphere by nitrogen, stir on the limit, the method for limit heating and insulation.In addition, polymerization initiator used herein and solvent etc. are not particularly limited, and can use material usually used in this field.For example, as polymerization initiator, can enumerate azo-compound (2,2 '-azoisobutyronitrile, 2,2 '-azo two (2,4-methyl pentane nitrile) etc.), organic peroxide (benzoyl peroxide etc.), as solvent, get final product so long as dissolve the solvent of each monomer, can enumerate solvent described later etc. as the solvent (E) of photosensitive composition of the present invention.
In addition, the gained multipolymer can directly use reacted solution, also can use solution concentrated or that dilution forms, also can use by the material of the methods such as precipitation again as solid (powder) taking-up.Particularly, solvent by as this polymerization the time uses the contained solvent of photosensitive composition of the present invention, reacted solution can be directly used in the preparation of photosensitive composition of the present invention, therefore, the manufacturing process of photosensitive composition of the present invention is simplified.
In the multipolymer [K2], in all structural units that consist of multipolymer [K2], the ratio that is derived from the structural unit of each monomer is,
Preferably:
Be derived from the structural unit of (a): 2～45 % by mole
Be derived from the structural unit of (x): 2～95 % by mole
Be derived from the structural unit of (c): 1～65 % by mole
More preferably:
Be derived from the structural unit of (a): 5～40 % by mole
Be derived from the structural unit of (x): 5～80 % by mole
Be derived from the structural unit of (c): 5～60 % by mole.
The ratio of the structural unit of multipolymer [K2] has the trend of solvent resistance, thermotolerance and the physical strength excellence of development when forming colored pattern and gained color filter when above-mentioned scope.
Multipolymer [K3] can be made by making (b) and multipolymer [K1] or multipolymer [K2] addition.As (b), can enumerate above-mentioned (c ') and (x ').The multipolymer [K1] that uses in the manufacturing of multipolymer [K3] and multipolymer [K2] preferably do not have and are derived from the structural unit of (x ') and be derived from the multipolymer of the structural unit of (c ').
Make multipolymer [K1] or multipolymer [K2] such as above-mentioned manufacturing, make the part of the carboxylic acid and/or the carboxylic acid anhydrides that are derived from (a) in this multipolymer, the carbon number that has with (b) is 2～4 cyclic ether reaction.
Can be after the manufacturing of multipolymer [K1] or multipolymer [K2], atmosphere in the flask is substituted by air by nitrogen, the catalysts (such as three (dimethylaminomethyl) phenol etc.) of (b), carboxylic acid or carboxylic acid anhydrides and cyclic ether and polymerization inhibitor (such as p-dihydroxy-benzene etc.) etc. are put into flask, by for example reaction reaction in 1～10 hour under 60～130 ℃, thereby make multipolymer [K3].
With respect to 100 moles (a), preferred 5～80 moles, more preferably 10～75 moles of use amounts (b).By in this scope, the trend that has the balance of solvent resistance, thermotolerance, physical strength and light sensitivity of storage stability, the development when forming pattern and the gained pattern of photosensitive composition to improve.Be difficult to residual angle from reactive high, unreacted (b) of cyclic ether, (b) that uses in the manufacturing as multipolymer [K3] preferably has the monomer of Oxyranyle and ethylenic unsaturated bond.
The all monomers that use in the manufacturing with respect to multipolymer [K1] or multipolymer [K2] and total metering 100 mass parts (b), preferred 0.001～5 mass parts of the use amount of previous reaction catalyzer.The all monomers that use in the manufacturing with respect to multipolymer [K1] or multipolymer [K2] and total metering 100 mass parts (b), preferred 0.001～5 mass parts of the use amount of aforementioned polymerization inhibitor.
The reaction conditionss such as charging process, temperature of reaction and time can consider that thermal value that manufacturing equipment, polymerization bring etc. suitably adjusts.In addition, thermal value that manufacturing equipment, polymerization bring etc. be can consider equally with polymerizing condition, charging process, temperature of reaction suitably adjusted.
For multipolymer [K4], as the phase one, obtain (b) and (x) multipolymer with the same operation of the manufacture method of above-mentioned multipolymer [K1].With above-mentioned same, the gained multipolymer can directly use reacted solution, also can use solution concentrated or that dilution forms, also can use by the material of the methods such as precipitation again as solid (powder) taking-up.(b) that uses in the manufacturing as multipolymer [K4] preferably has the monomer of Oxyranyle and ethylenic unsaturated bond.
With respect to the total molal quantity of all structural units that consist of aforesaid multipolymer, the ratio that is derived from (b) and structural unit (x) is respectively,
Preferably:
Be derived from the structural unit of (b): 5～95 % by mole
Be derived from the structural unit of (x): 5～95 % by mole
More preferably:
Be derived from the structural unit of (b): 10～90 % by mole
Be derived from the structural unit of (x): 10～90 % by mole.
And then, can by with the same condition of the manufacture method of multipolymer [K4] under, make the cyclic ether that is derived from (b) that (b) and (x) multipolymer have, with the carboxylic acid that (a) has or carboxylic acid anhydrides reaction, thereby obtain multipolymer [K4].
With respect to 100 moles (b), with preferred 5～80 moles of the use amount of (a) of aforesaid copolymer reaction.
Multipolymer [K5] is that multipolymer [K4] reacts the resin that obtains with carboxylic acid anhydrides again.Make the hydroxyl that produces by cyclic ether and carboxylic acid or carboxylic acid anhydrides reaction, react with carboxylic acid anhydrides.
As carboxylic acid anhydrides, can enumerate maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrabydrophthalic anhydride, 1,2,3,6-tetrabydrophthalic anhydride, dimethyl tetrahydro phthalic anhydride, 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene" acid anhydride etc.With respect to the use amount of 1 mole (a), preferred 0.5～1 mole of the use amount of carboxylic acid anhydrides.
As resin (B), specifically, can enumerate 3,4-epoxy radicals cyclohexyl methyl (methyl) acrylate/(methyl) acrylic copolymer, 3,4-epoxy radicals three ring [5.2.1.0 2.6] decyl (methyl) acrylate/(methyl) acrylic copolymer, three the ring [5.2.1.0 2.6] decyl (methyl) acrylate/multipolymers [K1] such as (methyl) acrylic copolymer;
3,4-epoxy radicals, three ring [5.2.1.0 2.6] decyl (methyl) acrylate/(methyl) acrylic acid/N-N-cyclohexylmaleimide multipolymer, 3,4-epoxy radicals three ring [5.2.1.0 2.6] decyl (methyl) acrylate/(methyl) acrylic acid/vinyl toluene copolymer, three the ring [5.2.1.0 2.6] decyl (methyl) acrylate/(methyl) acrylic copolymer/multipolymers [K2] such as (methyl) benzyl acrylate;
The multipolymers such as resin [K3] that the resin that (methyl) acrylic acid three ring ester/styrene in the last of the ten Heavenly stems/(methyl) acrylic copolymers and the addition of (methyl) glycidyl acrylate obtain, (methyl) acrylic acid three ring ester in the last of the ten Heavenly stems/(methyl) benzyl acrylate/(methyl) acrylic copolymers and the addition of (methyl) glycidyl acrylate obtain;
The multipolymer of (methyl) acrylic acid three ring ester in the last of the ten Heavenly stems/(methyl) glycidyl acrylates reacts the resin that obtains, the multipolymer of (methyl) acrylic acid three ring ester/styrene in the last of the ten Heavenly stems/(methyl) glycidyl acrylates and the multipolymers such as resin [K4] that the reaction of (methyl) acrylic acid obtains with (methyl) acrylic acid;
The multipolymers such as resin [K5] that the resin that the multipolymer of (methyl) acrylic acid three ring ester in the last of the ten Heavenly stems/(methyl) glycidyl acrylates and the reaction of (methyl) acrylic acid obtain obtains with the tetrabydrophthalic anhydride reaction again etc.
Resin (B) is preferably selected from a kind of in the group that is comprised of multipolymer [K1] and multipolymer [K2].During for these resins, the development of photosensitive composition is excellent.On the viewpoint of the adaptation of colored pattern and substrate, more preferably multipolymer [K2].
The weight-average molecular weight of the polystyrene conversion of resin (B) preferred 3,000～100,000, more preferably 5,000～50,000, and then preferred 5,000～30,000.Molecular weight has that hardness of film improves, also high, unexposed portion trend that the resolution of the favorable solubility of developer solution and colored pattern is improved of residual film ratio when aforesaid scope.
The molecular weight distribution of resin (B) [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] preferred 1.1～6, more preferably 1.2～4.
Preferred 50～the 170mg-KOH/g of acid number of resin (B), more preferably 60～150mg-KOH/g and then preferred 70～135mg-KOH/g.Here, acid number is the value of measuring with the amount (mg) of the necessary potassium hydroxide of 1g resin (B) in the conduct, can be by obtaining with for example potassium hydroxide aqueous solution titration.
With respect to the total amount of solid constituent, preferred 7～65 quality % of the content of resin (B), more preferably 13～60 quality % and then preferred 17～55 quality %.The content of resin (B) has the resolution of colored pattern and the trend that residual film ratio improves in aforementioned range the time.
＜polymerizable compound (C) 〉
Polymerizable compound (C) is the compound that can carry out polymerization under the effect of the living radical that is produced by polymerization initiator (D) and/or acid, for example can enumerate, compound etc. with ethylenic unsaturated bond of polymerism, preferred (methyl) acrylate compounds.
Wherein, polymerizable compound (C) preferably has the polymerizable compound of the ethylenic unsaturated bond more than 3.As such polymerizable compound, for example can enumerate trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, tripentaerythritol eight (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, the four seasons penta tetrol ten (methyl) acrylate, the four seasons penta tetrol nine (methyl) acrylate, three (2-(methyl) acrylyl oxy-ethyl) isocyanuric acid ester, glycol-modified pentaerythrite four (methyl) acrylate, glycol-modified dipentaerythritol six (methyl) acrylate, propylene glycol modified pentaerythrite four (methyl) acrylate, propylene glycol modified dipentaerythritol six (methyl) acrylate, caprolactone modification pentaerythrite four (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate etc.
Wherein, preferred dipentaerythritol five (methyl) acrylate and dipentaerythritol six (methyl) acrylate.
The weight-average molecular weight of polymerizable compound (C) is preferred more than 150 below 2,900, more preferably 250～1, below 500.
With respect to the total amount of solid constituent, preferred 7～65 quality % of the content of polymerizable compound (C), more preferably 13～60 quality % and then preferred 17～55 quality %.
In addition, in quality criteria, the content of resin (B) and polymerizable compound (C) is than (resin (B): polymerizable compound (C)) preferred 20: 80～80: 20, more preferably 35: 65～80: 20 and then preferred 50: 50～75: 25, especially preferred 55: 50～70: 30.
The content of polymerizable compound (C) is in aforementioned range the time, the trend that the residual film ratio when having colored pattern to form and the chemical proofing of color filter improve.
＜polymerization initiator (D) 〉
Polymerization initiator (D) but so long as under the effect of light or heat, produce living radical, acid etc., the compound of initiated polymerization also, then be not particularly limited, can use known polymerization initiator.
As polymerization initiator (D), can enumerate alkyl phenones compound, triaizine compounds, acylphosphine oxide compound, O-acyl group oxime compound and double imidazole compound etc.
Aforementioned O-acyl group oxime compound is for having the compound of the part-structure shown in the formula (d1).Below, * represents connecting key.
As aforementioned O-acyl group oxime compound; for example can enumerate; N-benzoyloxy-1-(4-phenyl sulfydryl (ス Le Off ア ニ Le) phenyl) butane-1-ketone-2-imines; N-benzoyloxy-1-(4-phenyl sulfydryl phenyl) octane-1-ketone-2-imines; N-benzoyloxy-1-(4-phenyl sulfydryl phenyl)-3-cyclopentyl propane-1-ketone-2-imines; N-acetoxyl group-1-[9-ethyl-6-(2-toluyl)-9H-carbazole-3-yl] ethane-1-imines; N-acetoxyl group-1-[9-ethyl-6-{2-methyl-4-(3; 3-dimethyl-2,4-dioxy cyclopentyl-methyl oxygen base) benzoyl }-9H-carbazole-3-yl] ethane-1-imines; N-acetoxyl group-1-[9-ethyl-6-(2-toluyl)-9H-carbazole-3-yl]-3-cyclopentyl propane-1-imines; N-benzoyloxy-1-[9-ethyl-6-(2-toluyl)-9H-carbazole-3-yl]-3-cyclopentyl propane-1-ketone-2-imines etc.Can use the commercially available products such as Irgacure OXE01, OXE02 (more than, BASF society system), N-1919 (ADEKA society system).Wherein, O-acyl group oxime compound is preferably selected from least a kind in N-benzoyloxy-1-(4-phenyl sulfydryl phenyl) butane-1-ketone-2-imines, N-benzoyloxy-1-(4-phenyl sulfydryl phenyl) octane-1-ketone-2-imines and the N-benzoyloxy-1-group that (4-phenyl sulfydryl phenyl)-3-cyclopentyl propane-1-ketone-the 2-imines forms, more preferably N-benzoyloxy-1-(4-phenyl sulfydryl phenyl) octane-1-ketone-2-imines.
Aforesaid alkyl benzophenone compound is for having the compound of the part-structure shown in the part-structure shown in the formula (d2) or the formula (d3).In these part-structures, phenyl ring can have Dai Ji.
As the compound with the part-structure shown in the formula (d2), for example can enumerate 2-methyl-2-morpholine-1-(4-methyl mercapto phenyl) propane-1-ketone, 2-dimethylamino-1-(4-morpholinyl phenyl)-2-benzyl butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholine) phenyl] butane-1-ketone etc.Can use the commercially available products such as Irgacure369,907,379 (more than, BASF society system).
As the compound with the part-structure shown in the formula (d3), for example can enumerate, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-hydroxy-2-methyl-1-(4-(2-hydroxyl-oxethyl) phenyl) propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(the 4-isopropenyl phenyl) propane-oligomer of 1-ketone, α, α-diethoxy acetophenone, benzil (ベ Application ジ Le) dimethyl ketal etc.
Aspect light sensitivity, as the alkyl phenones compound, preferably has the compound of the part-structure shown in the formula (d2).
Aforementioned double imidazole compound is the compound shown in the formula (d5) for example.
Figure BDA00003101888300181
[in the formula (d5), R 3～R 8Expression can have the aryl of substituent carbon number 6～10.]
As the aryl of carbon number 6～10, for example can enumerate phenyl, toluyl, xylyl, ethylphenyl and naphthyl etc., preferred phenyl.
As substituting group, for example can enumerate the alkoxy of halogen atom, carbon number 1～4 etc.As halogen atom, for example can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom etc., preferred chlorine atom.As the alkoxy of carbon number 1～4, for example can enumerate methoxyl, ethoxy, propoxyl group, butoxy etc., preferred methoxyl.
As double imidazole compound, for example can enumerate 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2,3-dichlorophenyls)-4,4 ', 5,5 '-tetraphenyl double imidazole is (for example, with reference to JPH06-75372-A, JPH06-75373-A etc.), 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2-chlorphenyls)-4, the two imidazoles of 4 ', 5,5 '-four (alkoxyl phenyls), 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (dialkoxy phenyl) two imidazoles, 2,2 '-two (2-chlorphenyl)-4,4 ', the two imidazoles of 5,5 '-four (tri-alkoxy phenyls) are (for example, with reference to JPS48-38403-B, JPS62-174204-A etc.), the phenyl of 4,4 ' 5,5 '-position replaced the imidazolium compounds form (for example, with reference to JPH07-10913-A etc.) etc. by the carbonyl alkoxy.Wherein, the compound shown in the preferred following formula and these potpourri.
As aforementioned triaizine compounds, two (the trichloromethyl)-6-(4-methoxyphenyl)-1 of 2,4-are for example arranged, 3, the 5-triazine, two (the trichloromethyl)-6-(4-methoxyl naphthyl)-1,3 of 2,4-, the 5-triazine, 2, two (the trichloromethyl)-6-piperonyl-1,3,5-triazines of 4-, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1 of 4-, 3,5-triazine, two (the trichloromethyl)-6-(2-(5-methylfuran-2-yl) vinyl (ethenyl))-1 of 2,4-, 3, the 5-triazine, two (the trichloromethyl)-6-(2-(furans-2-yl) vinyl (ethenyl))-1,3 of 2,4-, the 5-triazine, 2, two (the trichloromethyl)-6-(2-(4-diethylamino-2-aminomethyl phenyl) vinyl (ethenyl)) of 4--1,3,5-triazines, 2, (2-(3 for two (the trichloromethyl)-6-of 4-, the 4-Dimethoxyphenyl) vinyl (ethenyl))-1,3,5-triazines etc.
As aforementioned acylphosphine oxide compound, can enumerate 2,4,6-trimethylbenzene formyl diphenyl phosphine oxide, two (2,4,6-trimethylbenzene formyl)-phenyl phosphine oxides etc.Also can use the commercially available products such as Lucirin (registered trademark) TPO (BASF AG's system), Irgacure (registered trademark) 819 (BASF AG's system).
And then as polymerization initiator (D), can enumerate the benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether, benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl base sulfide, 3,3 ', 4,4 '-four (t-butylperoxy carbonyl) benzophenone, 2, the benzophenone cpds such as 4,6-tri-methyl benzophenone; The quinone compounds such as 9,10-phenanthrenequione, 2-EAQ, camphorquinone; 10-butyl-2-chloro-acridine ketone, benzil, phenyl glyoxalic acid methylester, two cyclopentadiene titanium compounds etc.Preferably these and polymerization described later initiation auxiliary agent (D1) (particularly amine) are used in combination.
With respect to the total amount of solid constituent, preferred 1～30 quality % of the content of polymerization initiator (D), more preferably 5～20 quality %.
In addition, with respect to total metering 100 mass parts of resin (B) and polymerizable compound (C), preferred 1～50 mass parts of the content of polymerization initiator (D), more preferably 10～45 mass parts and then preferred 20～40 mass parts.
＜polymerization causes auxiliary agent (D1) 〉
It is compound or the sensitizer that is used by the polymerization of the polymerizable compound of polymerization initiator initiated polymerization in order to promote that polymerization causes auxiliary agent (D1).When containing polymerization initiation auxiliary agent (D1), common and polymerization initiator (D) is used in combination.
Cause auxiliary agent (D1) as polymerization, can enumerate amines, alkoxy anthracene compound, thioxanthones compound, carboxylic acid compound etc.
As aforementioned amines, can enumerate triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl esters, EDMAB, 4-dimethylaminobenzoic acid isopentyl ester, benzoic acid 2-dimethylamino ethyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, N, the N-dimethyl-p-toluidine, 4,4 '-two (dimethylamino) benzophenone (common name Michler's keton), 4,4 '-two (diethylamino) benzophenone, 4,4 '-two (ethylmethylamino) benzophenone etc., wherein, preferred 4,4 '-two (diethylamino) benzophenone.Can use the commercially available products such as EAB-F (hodogaya chemical industry (strain) system).
As aforementioned alkoxy anthracene compound, can enumerate 9,10-dimethoxy anthracene, EDMO, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene, 9,10-dibutoxy anthracene, 2-ethyl-9,10-dibutoxy anthracene etc.
As aforementioned thioxanthones compound, can enumerate ITX, ITX, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones etc.
As aforementioned carboxylic acid compound, can enumerate phenyl sulfydryl (ス Le Off ア ニ Le) acetic acid, aminomethyl phenyl mercaptoacetic acid, ethylphenyl mercaptoacetic acid, Methylethyl phenyl mercaptoacetic acid, 3,5-dimethylphenyl mercaptoacetic acid, methoxyphenyl mercaptoacetic acid, Dimethoxyphenyl mercaptoacetic acid, chlorphenyl mercaptoacetic acid, dichlorophenyl mercaptoacetic acid, N-phenylglycine, phenoxyacetic acid, naphthyl thioacetic acid, N-naphthyl glycocoll, naphthoxy acetic acid etc.
When using these polymerizations to cause auxiliary agents (D1), with respect to total metering 100 mass parts of resin (B) and polymerizable compound (C), preferred 0.1～30 mass parts of its content, more preferably 1～20 mass parts.The amount that polymerization causes auxiliary agent (D1) has the trend that can form colored pattern with higher light sensitivity, improve the throughput rate of color filter in this scope the time.
＜mercaptan compound (T) 〉
Mercaptan compound (T) is for having in the molecule-compound of SH.
As the compound that has 1-SH in the molecule, for example can enumerate, 2-sulfydryl (ス Le Off ア ニ Le) oxazole, the 2-thyroidan, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, the 2-mercaptobenzoxazole, 2-sulfydryl nicotinic acid, the 2-mercaptopyridine, 2-mercaptopyridine-3-alcohol, pyrithione, 4-Amide-6-hydroxy-2--mercaptopyrimidine, 4-Amide-6-hydroxy-2--mercaptopyrimidine, 4-amino-2-mercapto phenyl formic pyrimidine, 6-amino-5-nitroso--2-deracil, 4,5-diamido-6-hydroxyl-2-mercaptopyrimidine, 4,6-diamido-2-mercaptopyrimidine, 2,4-diamido-6-mercaptopyrimidine, 4,6-dihydroxy-2-mercaptopyrimidine, 4,6-dimethyl-2-mercaptopyrimidine, 4-hydroxyl-2-sulfydryl-6-methylpyrimidine, 4-hydroxyl-2-sulfydryl-6-propyl group pyrimidine, 2-sulfydryl-4-methylpyrimidine, the 2-mercaptopyrimidine, the 2-deracil, 3,4,5,6-tetrahydropyrimidine-2-mercaptan, 4,5-diphenyl-imidazole-2-mercaptan, the 2-mercaptoimidazole, 2-sulfydryl-1-methylimidazole, 4-amino-3-diazanyl-5-sulfydryl-1,2, the 4-triazole, 3-amino-5-sulfydryl-1,2, the 4-triazole, 2-methyl-4H-1,2,4-triazole-3-mercaptan, 4-methyl-4H-1,2,4-triazole-3-mercaptan, 3-sulfydryl 1H-1,2,4-triazole-3-mercaptan, 2-amino-5-sulfydryl-1,3, the 4-thiadiazoles, 5-amino-1,3,4-thiadiazoles-2-mercaptan, 2,5-dimercapto-1,3, the 4-thiadiazoles, (furans-2-yl) methyl mercaptan, 2-sulfydryl-5-thiazolidone, 2-mercaptothiazoline, 2-sulfydryl-4 (3H)-quinazolinone (キ Na ゾ リ ノ Application), 1-phenyl-1H-TETRAZOLE-5-mercaptan, 2-quinoline mercaptan, 2-sulfydryl-5-tolimidazole, 2-sulfydryl-5-nitrobenzimidazole, 6-amino-2-mercapto phenyl formic benzothiazole, 5-chloro-2-mercaptobenzothiazole, 6-ethoxy-2-mercaptobenzothiazole, nitrocaptax, 2-mercaptonaphthalene imidazoles, 2-sulfydryl naphthoxazole, 3-sulfydryl-1,2, the 4-triazole, 4-amino-6-sulfydryl pyrazolo [2,4-d] pyridine, 2-amino-6-purine mercaptan, Ismipur, 4-sulfydryl-1H-pyrazolo [2,4-d] pyrimidine etc.
As having in the molecule more than 2-compound of SH, can enumerate hexane two mercaptan, decane two mercaptan, 1, two (methyl mercapto) benzene of 4-, butylene glycol two (3-mercaptopropionic acid ester), butylene glycol two (3-mercaptoacetate), ethylene glycol bis (3-mercaptoacetate), trimethylolpropane tris (3-mercaptoacetate), butylene glycol two (3-mercaptopropionic acid ester), trimethylolpropane tris (3-mercaptopropionic acid ester), trimethylolpropane tris (3-mercaptoacetate), pentaerythrite four (3-mercaptopropionic acid ester), pentaerythrite four (3-mercaptoacetate), trihydroxy ethyl three (3-mercaptopropionic acid ester), pentaerythrite four (3-sulfydryl butyric ester), Isosorbide-5-Nitrae-two (3-sulfydryl butyl oxygen) butane etc.
As mercaptan compound (T), has the compound of 1-SH in the preferred molecule.
With respect to polymerization initiator (D) 100 mass parts, preferred 0.5～20 mass parts of the content of mercaptan compound (T), more preferably 1～15 mass parts.The content of mercaptan compound (T) is in this scope the time, has light sensitivity to uprise and trend that the development change is good.
＜solvent (E) 〉
Solvent (E) is not particularly limited, and can use the normally used solvent in this area.For example can enumerate, ester solvent (molecule contains-COO-, do not contain-O-solvent), ether solvents (molecule contains-O-, do not contain-COO-solvent), ether-ether solvent (molecule contains-COO-and-solvent of O-), ketone solvent (molecule contains-CO-, do not contain-COO-solvent), alcoholic solvent (molecule contains OH, do not contain-O-,-CO-and-solvent of COO-), aromatic hydrocarbon solvents, amide solvent, dimethyl sulfoxide etc.
As ester solvent, can enumerate methyl lactate, ethyl lactate, butyl lactate, 2-hydroxy-methyl isobutyl acid, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, butyric acid isopropyl ester, butyric acid ethyl ester, butyric acid butyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, adnoral acetate, gamma-butyrolacton etc.
As ether solvents, can enumerate the glycol monomethyl methyl ether, ethylene glycol monomethyl ether, the glycol monomethyl propyl ether, ethylene glycol monobutyl ether, the diglycol monotertiary methyl ether, carbiphene, the diglycol monotertiary butyl ether, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list propyl ether, the propylene glycol single-butyl ether, 3-methoxyl-n-butyl alcohol, 3-methoxyl-3-methyl butanol, tetrahydrofuran, oxinane, Isosorbide-5-Nitrae-dioxs, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, the diglycol methyl ethyl ether, the diglycol dipropyl ether, the diglycol dibutyl ethers, methyl phenyl ethers anisole, phenetol, methylanisole etc.
As the ether-ether solvent, can enumerate methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, the 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, the 2-methoxy methyl propionate, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester, 3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butylacetic acid ester, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, propylene glycol list propyl ether acetic acid esters, the ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diglycol monotertiary butyl ether acetic acid esters, dipropylene glycol methyl ether acetic acid esters etc.
As ketone solvent, can enumerate 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-HEPTANONE, 3-heptanone, 4-heptanone, 4-methyl-2 pentanone, cyclopentanone, cyclohexanone, isophorone etc.
As alcoholic solvent, can enumerate methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerine etc.
As aromatic hydrocarbon solvents, can enumerate benzene,toluene,xylene, sym-trimethyl benzene etc.
As amide solvent, can enumerate DMF, DMA, 1-METHYLPYRROLIDONE etc.
These solvents can use separately, also can and with more than 2 kinds.
In the middle of the above-mentioned solvent, from the aspect of coating, drying property, the boiling point under the preferred 1atm is the organic solvent below 180 ℃ more than 120 ℃.Wherein, preferred propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl ether, the 3-ethoxyl ethyl propionate, the glycol monomethyl methyl ether, ethylene glycol monobutyl ether, the diglycol monotertiary methyl ether, carbiphene, 3-methoxyl butylacetic acid ester, 3-methoxyl-n-butyl alcohol, the 4-hydroxy-4-methyl-2-pentanone, N, dinethylformamide, more preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, the dipropylene glycol methyl ether acetic acid esters, ethyl lactate, 3-methoxyl butylacetic acid ester, 3-methoxyl-n-butyl alcohol, the 3-ethoxyl ethyl propionate.
With respect to the total amount of photosensitive composition, preferred 70～95 quality % of the content of solvent (E), more preferably 75～92 quality %.In other words, preferred 5～30 quality % of the solid constituent of photosensitive composition, more preferably 8～25 quality %.
The content of solvent (E) is when aforementioned range, and the flatness when coating is arranged becomes good and because colour saturation can be enough so that the good trend of display characteristic when forming color filter.
＜levelling agent (F) 〉
As levelling agent (F), can enumerate the silicon-type surfactant, fluorine is surfactant and the silicon-type surfactant with fluorine atom etc.These can have polymerizable group at side chain.
As the silicon-type surfactant, can enumerate surfactant that has siloxane bond in the molecule etc.Specifically, can enumerate TORAY SILICONE DC3PA, TORAYSILICONE SH7PA, TORAY SILICONE DC11PA, TORAYSILICONE SH21PA, TORAY SILICONE SH28PA, TORAYSILICONE SH29PA, TORAY SILICONE SH30PA, TORAYSILICONE SH8400 (trade name: Dow Corning Toray Company, Limited system), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (Momentive Performance Materials (Japan) Inc. system) etc.
Be surfactant as aforesaid fluorine, can enumerate surfactant that has fluorocarbon chain in the molecule etc.Particularly, can enumerate Fluorad (registered trademark) FC430, Fluorad FC431 (Sumitomo3M Limited system), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC R S-718-K (DIC (strain) system), EFTOP (registered trademark) EF301, EFTOP EF303, EFTOP EF351, EFTOPEF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd. (strain) system), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass (strain) system) and E5844 ((strain) Da Jin fine chemistry institute system) etc.
As aforesaid silicon-type surfactant with fluorine atom, can enumerate surfactant that has siloxane bond and fluorocarbon chain in the molecule etc.Particularly, can enumerate MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477 and MEGAFAC F443 (DIC (strain) system) etc.
With respect to the total amount of photosensitive composition, below the above 0.2 quality % of the preferred 0.001 quality % of the content of levelling agent (F), below the above 0.1 quality % of preferred 0.002 quality %, more preferably below the above 0.05 quality % of 0.005 quality %.The content of levelling agent (F) can make the flatness of color filter good in aforesaid scope the time.
＜driving fit promoter (G) 〉
As driving fit promoter (G), for example can enumerate, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, 3-glycidyl oxygen base キ シ propyl trimethoxy silicane, 3-glycidoxy propyl group methyl dimethoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-methyl allyl acyloxypropyl trimethoxysilane, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl trimethoxy silicane, 3-isocyanates propyl-triethoxysilicane, N-2-(amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-aminopropyl methyldiethoxysilane, N-2-(amino-ethyl)-3-TSL 8330, N-2-(amino-ethyl)-3-aminopropyl methyldiethoxysilane, the 3-TSL 8330, APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES etc.
With respect to the total amount of solid constituent, below the above 5 quality % of the preferred 0.1 quality % of the content of driving fit promoter (G), below the above 2 quality % of preferred 0.2 quality %.The content of driving fit promoter (G) can make with the adaptation of substrate good in aforesaid scope the time.
＜other composition 〉
Photosensitive composition of the present invention can contain filling agent, other the adjuvant well-known in the art such as macromolecular compound, driving fit promoter, antioxidant, light stabilizer, chain-transferring agent as required.
The manufacture method of＜photosensitive composition 〉
Photosensitive composition of the present invention for example can cause auxiliary agent (D1), driving fit promoter (G) and other the preparation that becomes to assign to by mixed colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D) and the solvent (E) that uses as required, mercaptan compound (T), levelling agent (F), polymerization.
Pigment preferably in advance with one one of solvent (E) or all mix, and to use ball mill etc. to make its mean grain size that is dispersed into pigment be the following degree of 0.2 μ m.At this moment, can cooperate as required aforementioned pigment dispersing agent, resin (B) one one or all.By in the dispersible pigment dispersion that operation obtains like this, mixing remaining composition with the concentration of regulation, can prepare the target photosensitive composition.
Preferably filter mixed photosensitive composition with the filtrator about 0.1～10 μ m of aperture.
The manufacture method of＜color filter 〉
As making the method that colored pattern is filmed by photosensitive composition of the present invention, can enumerate photoetching process, ink-jet method, print process etc.Wherein, preferred photoetching process.Photoetching process is following method: aforementioned photosensitive composition is coated with at substrate, and makes its drying with formation coloured composition layer, and by photomask this coloured composition layer is exposed, develops.In the photoetching process, by not using photomask and/or do not develop when exposing, the hardening thing that can form above-mentioned coloured composition layer is painted filming.The colored pattern that forms is like this filmed or painted filming is color filter of the present invention.
The thickness of the color filter of made is not particularly limited, can suitably adjust according to purpose or purposes etc., for example, 0.1～30 μ m, preferred 0.1～20 μ m and then preferred 0.5～6 μ m.
As substrate, can use quartz glass, pyrex, alumina silicate glass, surface-coated that the resin plate such as the glass plates such as soda-lime glass, polycarbonate, polymethylmethacrylate, polyethylene terephthalate, silicon of silicon dioxide arranged, be formed with the substrate of aluminium, silver, silver/copper/palldium alloy film etc. at aforesaid base plate.Can form at these substrates other color-filter layer, resin bed, transistor, circuit etc.
Use the formation of photolithographic each color pixel under known or habitual device, condition, to carry out.For example, can make by following operation.
At first, photosensitive composition is coated with at substrate, and comes the volatile ingredients such as desolventizing so that its drying obtains smooth coloured composition layer by heat drying (prebake) and/or drying under reduced pressure.
As coating process, can enumerate spin-coating method, slot coated method, slit and spin-coating method etc.
Preferred 30～120 ℃, more preferably 50～110 ℃ of temperature when carrying out heat drying.In addition, as heat time heating time, preferred 10 seconds～60 minutes, more preferably 30 seconds～30 minutes.
When carrying out drying under reduced pressure, preferably under the pressure of 50～150Pa, carry out in 20～25 ℃ the temperature range.
The thickness of coloured composition layer is not particularly limited, and suitably selects to get final product according to the thickness of target color filter.
Then, film in order to form the target colored pattern, across photomask the coloured composition layer is exposed.Pattern on this photomask is not particularly limited, and can use the pattern corresponding to the target purposes.
As the light source that is used for exposure, preferably produce the light source of light of the wavelength of 250～450nm.For example, the light that is lower than 350nm can be sheared with the wave filter of shearing this wavelength region may, perhaps with near near near the light the 436nm, the 408nm, the 365nm, use can be taken out the bandpass filter selectivity of these wavelength region may and be taken out.Particularly, can enumerate mercury lamp, light emitting diode, metal halide lamp, halogen lamp etc.
Owing to can maybe can carry out photomask and the accurately contraposition that is formed with the substrate of coloured composition layer to the whole uniform irradiation parallel rays of plane of exposure, therefore, preferably use the exposure devices such as mask aligner (mask aligner) and litho machine (stepper).
Contact to develop with developer solution by the coloured composition layer after will exposing, film thereby form colored pattern at substrate.By developing, the unexposed section of coloured composition layer dissolves in developer solution and is removed.
As developer solution, for example, the aqueous solution of the alkali compounds such as preferred potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethyl ammonium hydroxide.Preferred 0.01～10 quality % of concentration in the aqueous solution of these alkali compounds, more preferably 0.03～5 quality %.And then developer solution can contain surfactant.
Developing method can be any in oar formula method, infusion process and the spray-on process etc.And then, can be with substrate to arbitrarily angle inclination when developing.
Preferred washing after developing.
And then, preferably the gained colored pattern is filmed and cure (postbaking) after carrying out.Preferred 150～250 ℃, more preferably 160～235 ℃ of rear stoving temperatures.After cure preferred 1～120 minute of time, more preferably 10～60 minutes.
According to photosensitive composition of the present invention, because particularly the residual generation of residue, film is less, but thereby the few color filter of manufacturing defect.This color filter is useful as being used for display device (for example, liquid crystal indicator, organic El device, Electronic Paper etc.) and the color filter of solid-state imager.
Embodiment
Then, enumerate embodiment and then specify the present invention." % " in the example and " part " then are quality % and mass parts as long as no special record.
Synthesis example 1
In the flask that possesses stirring machine, thermometer, reflux cooler and tap funnel, make nitrogen add propylene glycol monomethyl ether 257 mass parts so that 0.02L/ minute speed is mobile to make nitrogen atmosphere, be heated to while stirring 70 ℃.Then, with 70 parts in 8 parts in acrylic acid, N-N-cyclohexylmaleimide, 3,4-epoxy radicals three ring [5.2.1.0 2.6] decane-8-base acrylate and 3,4-epoxy radicals, three ring [5.2.1.0 2.6] decane-9-base acrylate potpourri (contain than take molar ratio computing as 50: 50) thus 32 mass parts are dissolved in preparation solution in propylene glycol monomethyl ether 140 mass parts, use tap funnel dripped through 4 hours this solution to insulation to 70 ℃ flask.
On the other hand, with polymerization initiator 2,2 '-azo two (2,4-methyl pentane nitrile), 15 mass parts are dissolved in propylene glycol monomethyl ether 225 mass parts and obtain solution, use another tap funnel through 4 hours this solution to be dropped in the flask.After the dropping of the solution that finishes polymerization initiator, kept 4 hours at 70 ℃, be cooled to thereafter room temperature, obtaining solid constituent is resin B 1 solution of 26.7 quality %.The weight-average molecular weight of resin B 1 is 6.8 * 10 3, molecular weight distribution is 2.23, the acid number that converts take solid constituent is as 114mg-KOH/g.Resin B 1 has following structural unit.
Figure BDA00003101888300291
Synthesis example 2
In the flask with reflux cooler, tap funnel and stirring machine, make an amount of flow of nitrogen gas, be replaced as nitrogen atmosphere, add 371 parts of propylene glycol monomethyl ether, be heated to while stirring 85 ℃.Then, with 54 parts in acrylic acid, 3,4-epoxy radicals three ring [5.2.1.0 2.6] decane-8-base acrylate and 3,4-epoxy radicals, three ring [5.2.1.0 2.6] 81 parts of 225 parts in potpourri (contain than take molar ratio computing as 50: 50), the vinyltoluenes (isomer mixture) of decane-9-base acrylate be dissolved in 80 parts of propylene glycol monomethyl ether, make mixed solution, this mixed solution was dropped in the flask through 4 hours.
On the other hand, with polymerization initiator 2,30 parts of 2-azos two (2,4-methyl pentane nitrile) were dissolved in 160 parts of propylene glycol monomethyl ether and obtain solution, dripped this solution through 5 hours.After the dropping of initiator solution finishes, after 4 hours, be cooled to room temperature 85 ℃ of lower maintenances, obtain copolymer solution.With this multipolymer as resin B 2.The viscosity that the solid constituent of resin B 2 solution is 37.5%, measure with Brookfield viscometer (23 ℃) is 246mPas.The weight-average molecular weight of resin B 2 is 1.06 * 10 4, molecular weight distribution is 2.01, the acid number that converts take solid constituent is as 115mg-KOH/g.Resin B 2 has following structural unit.
Figure BDA00003101888300301
Synthesis example 3
In the flask with stirring machine, thermometer, backflow cooling tube, tap funnel and gas introduction tube, import 200 parts of propylene glycol monomethyl ether., by gas introduction tube nitrogen imported flask in, atmosphere in the flask is replaced into nitrogen thereafter.After the solution in the flask is warming up to 70 ℃, use tap funnel to drip by 144 parts of benzyl methacrylates, three ring [5.2.1.0 in flask through 2 hours 2.6] potpourri of 30 parts of decyl methacrylates, 35 parts of methacrylic acids, 5.2 parts of azoisobutyronitriles and 213 parts of compositions of propylene glycol monomethyl ether, drip finish after so that 100 ℃ of lower stirrings 5 hours.After the dropping of polymerization initiator solution finishes, kept 4 hours at 70 ℃, be cooled to thereafter room temperature, obtain solid constituent and be 33.6% resin B 3 solution.The weight-average molecular weight of resin B 3 is 1.03 * 10 4, molecular weight distribution is 2.16, the acid number that converts take solid constituent is as 110.4mg-KOH/g.Resin B 3 has following structural unit.
Figure BDA00003101888300302
Synthesis example 4
In the flask with stirring machine, thermometer, backflow cooling tube, tap funnel and gas introduction tube, import 200 parts of propylene glycol monomethyl ether., by gas introduction tube nitrogen imported flask in, atmosphere in the flask is replaced into nitrogen thereafter.After the solution in the flask is warming up to 70 ℃, use tap funnel to drip by 144 parts of benzyl methacrylates, three ring [5.2.1.0 in flask through 2 hours 2.6] potpourri of 30 parts of decyl methacrylates, 42 parts in acrylic acid, 5.2 parts of azoisobutyronitriles and 213 parts of compositions of propylene glycol monomethyl ether, drip finish after so that 100 ℃ of lower stirrings 5 hours.After the dropping of polymerization initiator solution finishes, kept 4 hours at 70 ℃, be cooled to thereafter room temperature, obtain solid constituent and be 34.1% resin B 4 solution.The weight-average molecular weight of resin B 4 is 1.13 * 10 4, molecular weight distribution is 2.18, the acid number that converts take solid constituent is as 108.5mg-KOH/g.Resin B 4 has following structural unit.
Figure BDA00003101888300311
The mensuration of the weight-average molecular weight of the polystyrene conversion of resin (Mw) and number-average molecular weight (Mn) is carried out under the following conditions by the GPC method.
Device: HLC-8120GPC (TOSOH CORPORATION system)
Post: TSK-GELG2000HXL
Column temperature: 40 ℃
Solvent: THF
Flow velocity: 1.0mL/min
Test solution solid component concentration: 0.001～0.01 quality %
Injection rate IR: 50 μ L
Detecting device: RI
Proofread and correct and use standard substance: TSK STANDARD POLYSTYRENE
F-40、F-4、F-288、A-2500、A-500
(TOSOH CORPORATION system)
With the ratio (Mw/Mn) of the weight-average molecular weight of polystyrene conversion obtained above and number-average molecular weight as molecular weight distribution.
(preparation of dispersible pigment dispersion A1)
With 15.0 parts of C.I. pigment green 36s
3.0 parts of acrylic acid series pigment dispersing agents
78.0 parts of propylene glycol monomethyl ether
Mix, use ball mill that pigment is fully disperseed, thereby obtain dispersible pigment dispersion A1.
(preparation of dispersible pigment dispersion A2)
With 150 11.9 parts of C.I. pigment yellows
5.4 parts of acrylic acid series pigment dispersing agents
77.3 parts of propylene glycol monomethyl ether
Mix, use ball mill that pigment is fully disperseed, thereby obtain dispersible pigment dispersion A2.
(preparation of dispersible pigment dispersion A3)
With 9 15.0 parts of C.I. pigment yellow 13s
4.5 parts of acrylic acid series pigment dispersing agents
80.6 parts of propylene glycol monomethyl ether
Mix, use ball mill that pigment is fully disperseed, thereby obtain dispersible pigment dispersion A3.
(preparation of dispersible pigment dispersion A4)
With 177 14.2 parts of C.I. paratoneres
2.8 parts of acrylic acid series pigment dispersing agents
77.3 parts of propylene glycol monomethyl ether
Mix, use ball mill that pigment is fully disperseed, thereby obtain dispersible pigment dispersion A4.
(preparation of dispersible pigment dispersion A5)
With 254 11.1 parts of C.I. paratoneres
6.4 parts of acrylic acid series pigment dispersing agents
80.0 parts of propylene glycol monomethyl ether
Mix, use ball mill that pigment is fully disperseed, thereby obtain dispersible pigment dispersion A5.
Embodiment 1～7 and comparative example 1
(preparation of photosensitive composition)
Mixture table 1 described composition obtains photosensitive composition.
[table 1]
Figure BDA00003101888300331
In the table 1, " resin (B) " hurdle represents the content (part) with the solid constituent conversion.
Colorant (A) is made in advance dispersible pigment dispersion A1～A5 and is used for mixing." colorant (A) " hurdle in the table 1 represents the content (part) of the colorant that employed dispersible pigment dispersion is contained.
" dispersant containing acrylic " hurdle represents total metering (part) of the dispersant containing acrylic that employed dispersible pigment dispersion is contained.
" solvent (E) " hurdle represents total metering (part) of each solvent that photosensitive composition is contained.
In the table 1, each composition is as follows.
Colorant (A): A1:C.I. pigment green 36 (dispersible pigment dispersion A1)
Colorant (A): A2:C.I. pigment yellow 150 (dispersible pigment dispersion A2)
Colorant (A): A3:C.I. pigment yellow 13 9 (dispersible pigment dispersion A3)
Colorant (A): A4:C.I. paratonere 177 (dispersible pigment dispersion A4)
Colorant (A): A5:C.I. paratonere 254 (dispersible pigment dispersion A5)
Resin (B): B1: resin B 1
Resin (B): B2: resin B 2
Resin (B): B3: resin B 3
Resin (B): B4: resin B 4
Resin (B): B5: methacrylic acid/methyl methacrylate/n-BMA/2-hydroxyl-metacrylate multipolymer (copolymerization ratio with quality criteria count 20/10/55/15, weight-average molecular weight: about 40000, synthesize according to the embodiment of TOHKEMY 2004-309537 communique)
Polymerizable compound (C): C1: dipentaerythritol acrylate (KAYARAD (registered trademark) DPHA; Japan's chemical drug (strain) system)
Polymerizable compound (C): C2: trimethylolpropane acrylates (NK ester ATMPT: Xin Zhong village chemistry society system)
Polymerization initiator (D): D1:N-benzoyloxy-1-(4-phenyl sulfydryl phenyl) octane-1-ketone-2-imines (Irgacure (registered trademark) OXE01:BASF society system: O-acyl group oxime compound)
Polymerization initiator (D): D2:2-methyl-2-morpholine-1-(4-methyl mercapto phenyl) propane-1-ketone (Irgacure (registered trademark) 907; BASF society system; The alkyl phenones compound)
Polymerization initiator (D): D3: the potpourri of the compound shown in the following formula (CHEMCURE-TCDM:Cambrige, Ltd. system: double imidazole compound)
Figure BDA00003101888300341
Polymerization causes auxiliary agent (D1): 4,4 '-two (diethylamino) benzophenone (EAB-F; Hodogaya chemical industry (strain) system)
Mercaptan compound (T): D1a:2-mercaptobenzothiazoler (ソ Network シ ノ one Le (registered trademark) M; Sumitomo Chemical (strain) system: the compound shown in the following formula)
Figure BDA00003101888300351
Driving fit promoter (G): D1b:3-methyl allyl acyloxypropyl trimethoxysilane (KBM-503; SHIN-ETSU HANTOTAI's chemical industry (strain) system)
Solvent (E): E1: propylene glycol monomethyl ether
Solvent (E): E2: ethyl lactate
Solvent (E): E3: cyclohexanone
Surfactant (F): organic silicon modified by polyether oil (Dow Corning Toray Company, Limited system; SH8400)
(making of patterned coating film)
At 2 square inches glass substrates (EAGLE XG; Corning Incorporated system) on, behind spin-coating method coating photosensitive composition, 100 ℃ of lower prebake 3 minutes to form the coloured composition layer.Naturally after the cooling, will be formed with the substrate of this coloured composition layer and the interval of quartz glass photomask processed and be made as 100 μ m, use exposure machine (TME-150RSK; TOPCON CORPORATION system), under air atmosphere with 30mJ/cm 2Exposure (365nm benchmark) carry out irradiation.As photomask, used the photomask that is formed with 50 μ m lines and space (line and space) pattern.Behind the irradiation, the above-mentioned 24 ℃ of lower dippings of filming in containing the water system developer solution that nonionic is surfactant 0.12% and sodium carbonate 2% were developed in 60 seconds, after the washing, in baking oven, after carrying out 30 minutes under 230 ℃, cure, obtain colored pattern and film.
(development evaluation)
Be formed with the glass substrate that colored pattern is filmed with observation by light microscope, if unexposed unconfirmed residual to residue or film, then be zero, if confirm residue or film is residual, then be *.The results are shown in table 2.
(adaptation evaluation)
Film with the observation by light microscope colored pattern, if unconfirmed to peeling off, then be zero, peel off if confirm the part that colored pattern films, be △ then, if filming, all peels off colored pattern, then be *.The results are shown in table 2.
(determining film thickness)
Film for the gained colored pattern, use determining film thickness device (DEKTAK3; Japan's vacuum technique (strain) system) measured thickness.The results are shown in table 2.
(chromaticity evaluation)
Film for the gained colored pattern, use colour examining machine (OSP-SP-200; Olympus Co., Ltd's system) measures light splitting, xy chromaticity coordinate (x, y) and tristimulus values Y (tristimulus values) in the XYZ colorimetric system of the characteristic function mensuration CIE of use illuminant-C.The value of Y is larger to represent that then brightness is higher.The results are shown in table 2.
[contrast evaluation]
Do not use during except exposure the photomask, carry out being coated with the same operation of film production with colored pattern, make colored pattern and film.Film for the gained colored pattern, use contrast meter (CT-1; Kettle Ban Dianjishe system, color colour difference meter BM-5A; TOPCONCORPORATION system, light source; F-10, polarization film; Kettle slope motor (strain) system), measure contrast with 30000 as blank value.
The results are shown in the table 2.When also using in the situation of colorant A1 and colorant A4, the contrast that colored pattern is filmed has the trend that uprises.
[table 2]
When adopting photosensitive composition of the present invention, the development when the formation colored pattern is filmed is excellent.

Claims (6)

1. photosensitive composition, it contains colorant, resin, polymerizable compound and polymerization initiator, wherein,
Colorant contains C.I. pigment green 36, yellow uitramarine and is selected from least a in the group that is comprised of blue pigment, red pigment, violet pigment and orange pigment,
Resin is multipolymer, and this multipolymer contains: be derived from the structural unit that is selected from least a structural unit in the group that is comprised of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides and has the ester ring type hydrocarbon structure.
2. photosensitive composition according to claim 1, wherein, the structural unit with ester ring type hydrocarbon structure is the structural unit that is derived from following monomer, this monomer has, and can to have substituent carbon number be 3～18 ester ring type alkyl.
3. photosensitive composition according to claim 1 and 2, wherein, polymerization initiator comprises O-acyl group oxime compound.
4. each described photosensitive composition according to claim 1～3 wherein, is selected from least a for C.I. paratonere 177 in the group that is comprised of blue pigment, red pigment, violet pigment and orange pigment.
5. color filter, it is formed by each described photosensitive composition in the claim 1～4.
6. display device, it comprises color filter claimed in claim 5.
CN2013101470245A 2012-04-27 2013-04-25 Color photosensitive resin composition Pending CN103376654A (en)

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CN105974733A (en) * 2015-03-11 2016-09-28 东友精细化工有限公司 Negative-type photosensitive resin composition, pattern formed by using the same and image display device
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CN108459467A (en) * 2017-02-17 2018-08-28 住友化学株式会社 Red colored composition
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