CN103838084A - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

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Publication number
CN103838084A
CN103838084A CN201310589020.2A CN201310589020A CN103838084A CN 103838084 A CN103838084 A CN 103838084A CN 201310589020 A CN201310589020 A CN 201310589020A CN 103838084 A CN103838084 A CN 103838084A
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methyl
parts
solvent
resin
acrylic acid
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CN201310589020.2A
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CN103838084B (en
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三浦洋之
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
    • G03F7/027—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
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/23—Photochromic filters
    • 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
    • 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

Abstract

The invention relates to a photosensitive resin composition, containing binder resin (A), a polymerized compound (B), a polymerization initiator (C), a body pigment (D), and a solvent (E). The solvent (E) comprises a solvent (E1) having a 70-99 mass% solubility parameter of 8.0-9.1 (cal/cm<3>)<1/2> with respect to the solvent (E) and a solvent (E2) having a 1-30 mass% solubility parameter of 9.2-11.0 (cal/cm<3>)<1/2> with respect to the solvent (E). According to the invention, a drying film with a satisfactory low viscidity can be produced and provided, and the patterned photosensitive resin composition with a satisfactory hardness can be produced.

Description

Photosensitive polymer combination
Technical field
The present invention relates to photosensitive polymer combination.
Background technology
The pattern use sense photosensitive resin composition manufacture of the color filter using in the display device such as display panels, electroluminescence panel, plasma display panel, Electronic Paper etc.Particularly, after photosensitive polymer combination is coated on substrate, dry, by after the desciccator diaphragm selectivity exposure obtaining, by developing, form pattern.
As such photosensitive polymer combination, for example, in TOHKEMY 2011-221310 communique, record the photosensitive polymer combination that contains resin glue, polymerizable compound, polymerization initiator, extender pigment and solvent, recorded the example that uses propylene glycol methyl ether acetate as above-mentioned solvent.
Summary of the invention
The desciccator diaphragm being obtained by above-mentioned photosensitive polymer combination in the past sometimes differs and meets surely its low viscosity, and in addition, the pattern being obtained by above-mentioned photosensitive polymer combination in the past sometimes differs and meets surely its hardness.
In order to solve above-mentioned problem, the invention provides following [1].
[1] a kind of photosensitive polymer combination, it contains resin glue (A), polymerizable compound (B), polymerization initiator (C), extender pigment (D) and solvent (E), wherein, to contain 70～99 quality % solubility parameters with respect to described solvent (E) be 8.0～9.1 (cal/cm to described solvent (E) 3) 1/2solvent (E1), and to contain 1～30 quality % solubility parameter with respect to described solvent (E) be 9.2～11.0 (cal/cm 3) 1/2solvent (E2).
In addition, the invention provides following [2]～[10].
[2] according to the photosensitive polymer combination [1] described, wherein, described polymerization initiator (C) is oxime compound.
[3] according to the photosensitive polymer combination [1] or [2] described, wherein, the acid number of described resin glue (A) is 50～180mg-KOH/g.
[4] according to the photosensitive polymer combination described in any one of [1]～[3], wherein, with respect to total amount 100 mass parts of described resin glue (A) and described polymerizable compound (B), the content of described resin glue (A) is 30～80 mass parts.
[5] according to the photosensitive polymer combination described in any one of [1]～[4], wherein, described extender pigment (D) is monox.
[6] according to the photosensitive polymer combination described in any one of [1]～[5], wherein, also contain colorant.
[7] according to photosensitive polymer combination claim [6] Suo Shu, wherein,
Described colorant is the colorant that contains pigment.
[8] according to claim [6] or [7] described photosensitive polymer combination, wherein,
Described colorant is the colorant that contains dyestuff.
[9] pattern, it is formed by the photosensitive polymer combination described in any one of [1]～[8].
[10] display device, it contains [9] described pattern.
According to the present invention, can provide preparation to there is the low-viscosity desciccator diaphragm that can meet, and preparation have the photosensitive polymer combination of the pattern of hardness that can be satisfied.
Embodiment
Photosensitive polymer combination of the present invention contains resin glue (A), polymerizable compound (B), polymerization initiator (C), extender pigment (D) and solvent (E).
Resin glue (A) preferably contains that to make to have the addition polymer (a) of the structural unit that is derived from unsaturated carboxylic acid (following, be sometimes referred to as " (a) ") react with the unsaturated compound (b) (following, to be sometimes referred to as " (b) ") with epoxy radicals the resin glue (Aa) forming.
As (a), can enumerate as: make unsaturated carboxylic acid (a1) (following, be sometimes referred to as " (a1) ") and there is the addition polymer that can obtain with the monomer (a2) of the unsaturated link of (a1) addition polymerization (following, to be sometimes referred to as " (a2) ") addition polymerization.
As (a1), can list (methyl) acrylic acid, crotonic acid, adjacent vinyl benzoic acid, a vinyl benzoic acid, to unsaturated monocarboxylic classes such as vinyl benzoic acids;
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, Isosorbide-5-Nitrae-cyclohexene dicarboxylic acid;
Methyl-5-norborene-2,3-dicarboxylic acid, 5-carboxyl dicyclo [2.2.1] hept-2-ene", 5, the dicyclo unsaturated compound class that 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", 5-carboxyl-6-ethyl dicyclo [2.2.1] hept-2-ene" etc. contain carboxyl;
Unsaturated list ((methyl) acryloxyalkyl) the ester class of 2 yuan of above polybasic carboxylic acids such as mono succinate (2-(methyl) acryloxy ethyl) ester, phthalic acid list (2-(methyl) acryloxy ethyl) ester;
The unsaturated compound class that α-(methylol) acrylic acid etc. contains hydroxyl and carboxyl in same a part etc.
Among them, from copolyreaction aspect, alkali dissolubility aspect preferably uses (methyl) acrylic acid.
Herein, in this manual, " (methyl) acrylic acid " expression is selected from acrylic acid and methacrylic acid at least a kind." (methyl) acryloyl group " and " (methyl) acrylate " etc. are recorded too.
As (a2), can list (methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate;
(methyl) cyclohexyl acrylate, (methyl) acrylic acid-2-methyl cyclohexyl, (methyl) acrylic acid three encircle [5.2.1.0 2,6] last of the ten Heavenly stems-8-base ester (in this technical field, as popular name, is referred to as (methyl) acrylic acid dicyclo pentyl ester.), (methyl) acrylic acid cyclic alkyl ester class such as (methyl) acrylic acid dicyclo amoxy ethyl ester, (methyl) isobornyl acrylate;
(methyl) aryl acrylate or the aralkyl ester classes such as (methyl) phenyl acrylate, (methyl) benzyl acrylate;
The dicarboxylic diesters such as diethyl maleate, DEF, diethyl itaconate;
The hydroxy alkyl ester classes such as (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate;
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-methylol 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-bis-(methylol) dicyclo [2.2.1] hept-2-ene", 5,6-bis-(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-methylol-5-methyl bicycle [2.2.1] hept-2-ene", 5-tert-butoxycarbonyl dicyclo [2.2.1] hept-2-ene", 5-cyclohexyloxy carbonyl dicyclo [2.2.1] hept-2-ene", 5-phenyloxycarbonyl dicyclo [2.2.1] hept-2-ene", 5,6-bis-(tert-butoxycarbonyl) dicyclo [2.2.1] hept-2-ene", the dicyclo unsaturated compound classes such as 5,6-bis-(cyclohexyloxy carbonyl) dicyclo [2.2.1] hept-2-ene",
The dicarbapentaborane imide derivative classes such as N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, 3-maleimide yl benzoic acid-N-succinimide ester, 4-dimaleoyl imino butyric acid-N-succinimide ester, 6-maleimide caproic acid-N-succinimide ester, 3-maleimide propionic acid-N-succinimide 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.
(a2) be particularly preferably to have and be selected from least a kind of skeleton of tricyclodecane skeleton and tricyclo decene skeleton and the compound (a2-1) (being referred to as below " (a2-1) ") of olefinic unsaturated link.(a2), while being (a2-1), the film of the pattern that can suppress to be caused by development reduces.
Herein, " tricyclodecane skeleton " in this instructions and " tricyclo decene skeleton " refer to respectively following structure (it has respectively bonding end at an arbitrary position).
Figure BDA0000418769070000041
As (a2-1), can list (methyl) acrylic acid dicyclo pentyl ester, (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate, (methyl) acrylic acid dicyclo amoxy ethyl ester, (methyl) acrylic acid dicyclo amylene oxygen base ethyl ester.They can be used alone or in combination of two or more respectively.
As (b), can enumerate as: have structure that chain type alkene epoxidation is formed and olefinic unsaturated link monomer (b-1) (have below and be referred to as " (b-1) "), there is structure that cycloolefin epoxidation is formed and the monomer (b-2) (being referred to as below " (b-2) ") of ethylenic unsaturated bond.As (b), consider to be preferably (b-1) from reactive viewpoint.
As (b-1), can list (methyl) glycidyl acrylate, (methyl) acrylic acid Beta-methyl ethylene oxidic ester, (methyl) propenoic acid beta-ethyl ethylene oxidic ester, glycidyl vinyl ether, adjacent vinyl benzyl glycidol ether, between vinyl benzyl glycidol ether, to vinyl benzyl glycidol ether, Alpha-Methyl-adjacent vinyl benzyl glycidol ether, an Alpha-Methyl-vinyl benzyl glycidol ether, Alpha-Methyl-to vinyl benzyl glycidol ether, 2,3-bis-(glycidyl oxygen ylmethyl) styrene, 2,4-bis-(glycidyl oxygen ylmethyl) styrene, 2,5-bis-(glycidyl oxygen ylmethyl) styrene, 2,6-bis-(glycidyl oxygen ylmethyl) styrene, 2,3,4-tri-(glycidyl oxygen ylmethyl) styrene, 2,3,5-tri-(glycidyl oxygen ylmethyl) styrene, 2,3,6-tri-(glycidyl oxygen ylmethyl) styrene, 3,4,5-tri-(glycidyl oxygen ylmethyl) styrene, 2,4,6-tri-(glycidyl oxygen ylmethyl) styrene, the compound of recording in Japanese kokai publication hei 7-248625 communique etc.
As (b-2), can list vinyl cyclohexene monoxide, 1,2-epoxy radicals-4-vinyl cyclohexane (for example, Celloxide 2000; (strain) Daicel system), 3,4-epoxycyclohexyl methacrylate (for example, Cyclomer A400; (strain) Daicel system), 3,4-epoxycyclohexyl methyl acrylate (for example, Cyclomer M100; (strain) Daicel system), the represented compound of represented compound, the formula (II) of formula (I) etc.
Figure BDA0000418769070000051
[in formula (I) and formula (II), R 1and R 2the alkyl that represents independently of each other hydrogen atom or carbon number 1～4, the hydrogen atom comprising in this alkyl can be replaced by hydroxyl.
X 1and X 2represent independently of each other singly-bound ,-R 3-, *-R 3-O-, *-R 3-S-, *-R 3-NH-.
R 3represent the alkylidene of carbon number 1～6.
* represent the bonding end with O.]
Resin glue (Aa) can be through the operation manufacture of for example two-stage.Now, can reference example as the manufacture resin glue such as method and the method for recording in TOHKEMY 2001-89533 communique (Aa) of recording in document " high point son closes into experiment method (experimental method of Polymer Synthesizing) " (the large grand row work sale room in Tianjin (strain) chemistry is with the 1st edition the 1st printing distribution on March 1st, 1972 of people).
In the manufacture of resin glue (Aa), first, as the first stage, make (a1) and addition polymer (a) (a2).Can concrete example illustrate (a1) of ormal weight and (a2), polymerization initiator and solvent etc. drop in reaction vessel, by use nitrogen replacement oxygen, in the atmosphere of deoxidation, stir, heating, the method that is incubated.Polymerization initiator used herein and solvent etc. are not particularly limited, and also can use the arbitrary substance conventionally being used in the art.As polymerization initiator, can enumerate as azo-compound (2,2 '-azoisobutyronitrile, 2,2 '-azo two (2,4-methyl pentane nitrile) etc.) or organic peroxide (benzoyl peroxide etc.), as solvent, as long as dissolving the solvent of each monomer, can be used as the solvent of photosensitive composition and solvent described later etc.
In addition, the addition polymer making can directly use with the state of reacted solution, also can use with the state of the solution that concentrates or diluted, also can use the solid (powder) proposing by methods such as precipitations again.
With respect to the total mole number of entire infrastructure unit that forms addition polymer, preferred source from the ratio of (a1) and structural unit (a2) in following scope.
Be derived from the structural unit of (a1): 5～50 % by mole, more preferably 10～45 % by mole
Be derived from the structural unit of (a2): 50～95 % by mole, more preferably 55～90 % by mole
Then,, as subordinate phase, a part for the carboxyl in the structural unit that is derived from (a1) that the addition polymer making has is reacted with (b).Because reactivity is high, unreacted (b) is difficult for residual, pretends as (b) and is preferably (b-1).
Particularly, and then, be air by the atmosphere in flask by nitrogen replacement, in flask, input is (b) of 5～80 % by mole with respect to the molal quantity of (a1), with respect to (a1), (b) total amount and (a2) is the catalysts (for example three (dimethylamino methyl) phenol etc.) of 0.001～5 quality % and with respect to (a1), (b) total amount and (a2) is the polymerization inhibitor (such as p-dihydroxy-benzene etc.) of 0.001～5 quality %, conventionally, it is reacted 1～10 hour at 60～130 DEG C, can make resin (Aa).And, with polymerizing condition similarly, the thermal values that can consider manufacturing equipment, caused by polymerization etc. are suitably adjusted feeding method, temperature of reaction.
In addition, now, the molal quantity that with respect to the molal quantity of (a1), preferably makes (b) is 10～75 % by mole, more preferably 15～70 % by mole.By making the molal quantity of (b) within the scope of this, there are storage stability, solvent resistance and stable on heating balance to become good tendency.
As resin glue (Aa), the multipolymer that can enumerate (methyl) acrylic acid of sening as an envoy to/(methyl) acrylic acid dicyclo pentyl ester reacts with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of (methyl) acrylic acid/(methyl) benzyl acrylate react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of (methyl) acrylic acid/(methyl) cyclohexyl acrylate react with (methyl) glycidyl acrylate the resin forming; Make (methyl) acrylic acid/cinnamic multipolymer react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of (methyl) acrylic acid/(methyl) methyl acrylate react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of (methyl) acrylic acid/N-N-cyclohexylmaleimide react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of crotonic acid/(methyl) acrylic acid dicyclo pentyl ester react with (methyl) glycidyl acrylate the resin forming;
Make the multipolymer of crotonic acid/(methyl) benzyl acrylate react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of crotonic acid/(methyl) cyclohexyl acrylate react with (methyl) glycidyl acrylate the resin forming; Make crotonic acid/cinnamic multipolymer react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of crotonic acid/ethyl crotonate react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of crotonic acid/N-N-cyclohexylmaleimide react with (methyl) glycidyl acrylate the resin forming;
Make the multipolymer of maleic acid/(methyl) acrylic acid dicyclo pentyl ester react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of maleic acid/(methyl) benzyl acrylate react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of maleic acid/(methyl) cyclohexyl acrylate react with (methyl) glycidyl acrylate the resin forming; Make maleic acid/cinnamic multipolymer react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of maleic acid/maleic acid methyl esters react the resin forming with (methyl) glycidyl acrylate, the multipolymer that makes maleic acid/N-N-cyclohexylmaleimide reacts with (methyl) glycidyl acrylate the resin forming;
Make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) benzyl acrylate react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) cyclohexyl acrylate react with (methyl) glycidyl acrylate the resin forming; Make (methyl) acrylic acid/maleic anhydride/cinnamic multipolymer react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) methyl acrylate react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of (methyl) acrylic acid/maleic anhydride/N-N-cyclohexylmaleimide react with (methyl) glycidyl acrylate the resin forming;
Make the multipolymer and 3 of (methyl) acrylic acid/(methyl) acrylic acid dicyclo pentyl ester, 4-epoxy radicals cyclohexyl methyl methacrylate reacts the resin forming, the multipolymer and 3 that makes (methyl) acrylic acid/(methyl) benzyl acrylate, the resin that the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, the multipolymer that makes (methyl) acrylic acid/(methyl) cyclohexyl acrylate and 3,4-epoxycyclohexyl methyl acrylate reactions form; The resin that (methyl) acrylic acid/cinnamic multipolymer and 3,4-epoxycyclohexyl methyl acrylate reactions are formed; Make the multipolymer and 3 of (methyl) acrylic acid/(methyl) methyl acrylate, the resin that the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, the multipolymer that makes (methyl) acrylic acid/N-N-cyclohexylmaleimide and 3,4-epoxycyclohexyl methyl acrylate reactions form;
Make the multipolymer of crotonic acid/(methyl) acrylic acid dicyclo pentyl ester and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; Make the multipolymer of crotonic acid/(methyl) benzyl acrylate and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; Make the multipolymer of crotonic acid/(methyl) cyclohexyl acrylate and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; The resin that crotonic acid/cinnamic multipolymer and 3,4-epoxycyclohexyl methyl acrylate reactions are formed; Make the multipolymer of crotonic acid/ethyl crotonate and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; Make the multipolymer of crotonic acid/N-N-cyclohexylmaleimide and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms;
Make the multipolymer of maleic acid/(methyl) acrylic acid dicyclo pentyl ester and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; Make the multipolymer of maleic acid/(methyl) benzyl acrylate and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; Make the multipolymer of maleic acid/(methyl) cyclohexyl acrylate and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; The resin that maleic acid/cinnamic multipolymer and 3,4-epoxycyclohexyl methyl acrylate reactions are formed; Make the multipolymer of maleic acid/maleic acid methyl esters and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; Make the multipolymer of maleic acid/N-N-cyclohexylmaleimide and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms;
Make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; Make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) benzyl acrylate and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; Make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) cyclohexyl acrylate and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; The resin that (methyl) acrylic acid/maleic anhydride/cinnamic multipolymer and 3,4-epoxycyclohexyl methyl acrylate reactions are formed; Make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) methyl acrylate and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; Make the multipolymer of (methyl) acrylic acid/maleic anhydride/N-N-cyclohexylmaleimide and resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms etc.
Further, as resin glue (Aa), the resin that more preferably makes addition polymer react with (b) and to make, wherein, described addition polymer makes (a1), (a2-1) and (a2) copolymerization except (a2-1).Be above-mentioned formation by resin glue (A1), have the pattern and the adaptation of substrate and the tendency of solvent resistance excellence that obtain.
When addition polymer (a) is made by (a1), (a2-1) and (a2) except (a2-1), preferred source is 10: 90～60: 40 from the ratio (being derived from the structural unit of (a2-1): the structural unit that is derived from (a2) except (a2-1)) of the structural unit of (a2-1) and (a2) except (a2-1), more preferably 10: 90～40: 60, more preferably 10: 90～30: 70.
As making (b) and make (a1) and (a2) copolymerization (a2-1) and except (a2-1) addition polymer react and must resin, the multipolymer that can enumerate (methyl) acrylic acid of sening as an envoy to/(methyl) acrylic acid dicyclo pentyl ester/(methyl) benzyl acrylate reacts the resin forming with (methyl) glycidyl acrylate; Make the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) cyclohexyl acrylate react with (methyl) glycidyl acrylate the resin forming; Make (methyl) acrylic acid/(methyl) acrylic acid dicyclo pentyl ester/cinnamic multipolymer react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) methyl acrylate react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid dicyclo pentyl ester/N-N-cyclohexylmaleimide react with (methyl) glycidyl acrylate the resin forming;
Make the multipolymer of crotonic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) benzyl acrylate react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of crotonic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) cyclohexyl acrylate react with (methyl) glycidyl acrylate the resin forming; Make crotonic acid/(methyl) acrylic acid dicyclo pentyl ester/cinnamic multipolymer react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of crotonic acid/(methyl) acrylic acid dicyclo pentyl ester/ethyl crotonate react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of crotonic acid/(methyl) acrylic acid dicyclo pentyl ester/N-N-cyclohexylmaleimide react with (methyl) glycidyl acrylate the resin forming;
Make the multipolymer of maleic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) benzyl acrylate react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of maleic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) cyclohexyl acrylate react with (methyl) glycidyl acrylate the resin forming; Make maleic acid/(methyl) acrylic acid dicyclo pentyl ester/cinnamic multipolymer react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of maleic acid/(methyl) acrylic acid dicyclo pentyl ester/maleic acid methyl esters react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of maleic acid/(methyl) acrylic acid dicyclo pentyl ester/N-N-cyclohexylmaleimide react with (methyl) glycidyl acrylate the resin forming;
Make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester/(methyl) benzyl acrylate react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester/(methyl) cyclohexyl acrylate react with (methyl) glycidyl acrylate the resin forming; Make (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester/cinnamic multipolymer react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester/(methyl) methyl acrylate react with (methyl) glycidyl acrylate the resin forming; Make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester/N-N-cyclohexylmaleimide react with (methyl) glycidyl acrylate the resin forming;
Make the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) benzyl acrylate and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; Make the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) cyclohexyl acrylate and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; The resin that (methyl) acrylic acid/(methyl) acrylic acid dicyclo pentyl ester/cinnamic multipolymer and 3,4-epoxycyclohexyl methyl acrylate reactions are formed; Make the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) methyl acrylate and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; Make the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid dicyclo pentyl ester/N-N-cyclohexylmaleimide and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms;
Make the multipolymer of crotonic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) benzyl acrylate and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; Make the multipolymer of crotonic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) cyclohexyl acrylate and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; The resin that crotonic acid/(methyl) acrylic acid dicyclo pentyl ester/cinnamic multipolymer and 3,4-epoxycyclohexyl methyl acrylate reactions are formed; Make the multipolymer of crotonic acid/(methyl) acrylic acid dicyclo pentyl ester/ethyl crotonate and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; Make the multipolymer of crotonic acid/(methyl) acrylic acid dicyclo pentyl ester/N-N-cyclohexylmaleimide and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms;
Make the multipolymer of maleic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) benzyl acrylate and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; Make the multipolymer of maleic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) cyclohexyl acrylate and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; The resin that maleic acid/(methyl) acrylic acid dicyclo pentyl ester/cinnamic multipolymer and 3,4-epoxycyclohexyl methyl acrylate reactions are formed; Make the multipolymer of maleic acid/(methyl) acrylic acid dicyclo pentyl ester/maleic acid methyl esters and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; Make the multipolymer of maleic acid/(methyl) acrylic acid dicyclo pentyl ester/N-N-cyclohexylmaleimide and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms;
Make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester/(methyl) benzyl acrylate and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; Make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester/(methyl) cyclohexyl acrylate and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; The resin that (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester/cinnamic multipolymer and 3,4-epoxycyclohexyl methyl acrylate reactions are formed; Make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester/(methyl) methyl acrylate and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms; Make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester N-N-cyclohexylmaleimide and resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms etc.
These resin glues (A) can be used alone or in combination of two or more respectively.
The weight-average molecular weight (Mw) of the polystyrene conversion of resin glue (A) is preferably 8 × 10 3～100 × 10 3, more preferably 10 × 10 3～50 × 10 3.If the weight-average molecular weight (Mw) of resin glue (A) is in above-mentioned scope, there are the coating of photosensitive polymer combination and the viscosity of desciccator diaphragm to become better tendency, in the time developing, being difficult for that in addition film occurs reduces, further, in the time developing, there is the good tendency of removability of non-pixel portion.
The acid number of preferred binder resin (A) is 30～200mg-KOH/g, more preferably 40～190mg-KOH/g, more preferably 50～180mg-KOH/g.Acid number be measure as for and the amount (mg) of the required potassium hydroxide of 1g resin glue (A) and value, can obtain by carrying out titration with potassium hydroxide aqueous solution.
Although preferred binder resin (A) is only made up of above-mentioned resin glue (Aa), also can contain other resins.As such resin, can enumerate as epoxy resin, acryl resin, urethane resin, vibrin, polyimide resin, polyolefin resin, linear phenol-aldehyde resin, polyamines resin etc.
When resin glue (A) contains the resin except resin glue (Aa), with respect to resin glue (A), the content of resin glue (Aa) is preferably 20～99 quality %, more preferably 50～99 quality %.
As long as polymerizable compound (B) is to utilize the living radical or the acid etc. that are produced by the effect of light or heat by polymerization initiator (C) and compound that can initiated polymerization is just not particularly limited.As polymerizable compound (B), can list compound having polymerism carbon-to-carbon unsaturated bond etc., preferably use the polyfunctional monomer that monofunctional monomer, bifunctional monomer, 3 officials can be above.In addition, as polymerizable compound (B), preferably use does not have the compound of acidic groups.
As monofunctional monomer, can list (methyl) acrylic acid nonyl phenyl carbitol ester, (methyl) acrylic acid-2-hydroxyl-3-phenoxy group propyl ester, (methyl) acrylic acid-2-ethyl hexyl carbitol ester, (methyl) acrylic acid-2-hydroxyl ethyl ester, NVP etc.
As bifunctional monomer, can list two (acryloxy ethyl) ethers, 3-methyl pentanediol two (methyl) acrylate etc. of 1,6-hexanediol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, bisphenol-A.
Polyfunctional monomer that can be above as 3 officials, can list product, Osaka organic chemistry industry (strain) V#1000 processed, V#802, the STAR-501 of product, dipentaerythritol five (methyl) acrylate and the acid anhydrides of trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, pentaerythrite three (methyl) acrylate and acid anhydrides; Common prosperity society chemistry (strain) UA-306H processed, UA-306T, UA-306I; The urethane acrylates such as the first industrial pharmacy (strain) New frontier processed R-1150 etc.Wherein, preferably use the polyfunctional monomer that bifunctional monomer, 3 officials can be above.
In addition, as polymerizable compound (B), can use following polymerizable compound.
Figure BDA0000418769070000131
Figure BDA0000418769070000141
Figure BDA0000418769070000151
Figure BDA0000418769070000161
Figure BDA0000418769070000171
Figure BDA0000418769070000181
Figure BDA0000418769070000191
Figure BDA0000418769070000201
Figure BDA0000418769070000211
Figure BDA0000418769070000221
Figure BDA0000418769070000231
Figure BDA0000418769070000241
Figure BDA0000418769070000251
Figure BDA0000418769070000271
These polymerizable compounds (B) can be distinguished use separately, also two or more use capable of being combined.
With respect to the solid state component of photosensitive polymer combination, the content of preferred polymeric compound (B) is 1～50 quality %, more preferably 5～30 quality %.In addition, with respect to total amount 100 mass parts of resin glue (A) and polymerizable compound (B), the content of resin glue (A) is preferably 30～80 mass parts.
Herein, solid state component refers to, removes whole compositions of the solvent containing in photosensitive polymer combination.
If the content of resin glue (A), in above-mentioned scope, because the viscosity of desciccator diaphragm is further suppressed, has to make not exist the tendency of the inhomogeneous color filter of color so preferably.
Polymerization initiator (C) is the compound that produces polymerization living radical, the acid etc. used of initiated polymerization compound (B), although can be the Photoepolymerizationinitiater initiater that produces living radical, acid etc. by the effect of light, also can be the thermal polymerization that produces living radical, acid etc. by hot effect, but be preferably Photoepolymerizationinitiater initiater, more preferably produce the optical free radical polymerization initiator of living radical by the effect of light.
Polymerization initiator (C) is preferably oxime compound.By using such polymerization initiator, the sensitivity of photosensitive polymer combination uprises, and uses in addition the exploring degree of film of its formation and solvent resistance excellence and pattern becomes good.Further, by and cause auxiliary agent (C-1) with polymerization, the photosensitive polymer combination sensitivity obtaining becomes higher, the productivity while using it to form color filter improves so preferably.
As oxime compound; can list N-benzoyloxy-1-(4-thiophenyl phenyl) butane-1-ketone-2-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-{2-methyl-4-(3; 3-dimethyl-2,4-dioxane amyl group methoxyl) benzoyl }-9H-carbazole-3-yl] ethane-1-imines etc.Can use the commercially available products such as IRGACURE (registered trademark) OXE01, OXE02 (more than, BASF Japan (strain) system), N-1919 ((strain) Ai Dike system) etc.Wherein preferred N-benzoyloxy-1-(4-thiophenyl phenyl) butane-1-ketone-2-imines.
Figure BDA0000418769070000281
In addition, as the polymerization initiator except oxime compound, can list united imidazole, alkyl phenones compound, triaizine compounds, acylphosphine oxide compound etc.
As united imidazole, can list 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2,3-dichlorophenyls)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline is (for example,, with reference to Japanese kokai publication hei 6-75372 communique, Japanese kokai publication hei 6-75373 communique etc.), 2,2 '-bis-(2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2-chlorphenyls)-4,4 ', 5,5 '-tetra-(alkoxyl phenyl) bisglyoxaline, 2,2 '-bis-(2-chlorphenyls)-4,4 ', 5,5 '-tetra-(dialkoxy phenyl) bisglyoxaline, 2,2 '-bis-(2-chlorphenyls)-4,4 ', 5,5 '-tetra-(tri-alkoxy phenyl) bisglyoxaline is (for example,, with reference to Japanese Patent Publication 48-38403 communique, Japanese Patent Publication 62-174204 communique etc.), the imidazolium compounds that replaced by alkoxy carbonyl group of the phenyl of 4,4 ' 5,5 '-position is (for example,, with reference to Japanese kokai publication hei 7-10913 communique etc.) etc.Can preferably list 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2,3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline.
As alkyl phenones compound, can list diethoxy acetophenone, 2-methyl-2-morpholino-1-(4-methyl mercapto phenyl) propane-1-ketone, 2-dimethylamino-1-(4-morpholino phenyl)-2-benzyl butane-1-ketone, 2-dimethylamino-1-(4-morpholino phenyl)-2-(4-aminomethyl phenyl methyl) butane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzil dimethyl ketal, 2-hydroxy-2-methyl-1-(4-(2-hydroxyl-oxethyl) phenyl) propane-1-ketone, 1-hydroxycyclohexylphenylketone, the oligomer of 2-hydroxy-2-methyl-1-(4-isopropenyl phenyl) propane-1-ketone etc., can preferably list 2-methyl-2-morpholino-1-(4-methyl mercapto phenyl) propane-1-ketone, 2-dimethylamino-1-(4-morpholino phenyl)-2-benzyl butane-1-ketone etc.Can use the commercially available products such as IRGACURE (registered trademark) 369,907 (more than, BASF Japan (strain) system).
As triaizine compounds, can list 2, two (the trichloromethyl)-6-(4-methoxyphenyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl naphthyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-of 4-piperonyl-1, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1 of 4-, 3, 5-triazine, 2, two (trichloromethyl)-6-[2-(5-methylfuran-2-yl) vinyl of 4-]-1, 3, 5-triazine, 2, two (trichloromethyl)-6-[2-(furans-2-yl) vinyl of 4-]-1, 3, 5-triazine, 2, two (trichloromethyl)-6-[2-(4-lignocaine-2-aminomethyl phenyl) vinyl of 4-]-1, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(3 of 4-, 4-Dimethoxyphenyl) vinyl]-1, 3, 5-triazine etc.
As acylphosphine oxide compound, can list TMDPO etc.Can use the commercially available products such as IRGACURE (registered trademark) 819 (BASF Japan (strain) system).
Further, as the polymerization initiator (C) except oxime compound, united imidazole, alkyl phenones compound, triaizine compounds and acylphosphine oxide compound, can list the benzoin compounds such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether; Benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 3,3 ', 4,4 '-tetra-(t-butyl peroxy carbonyl) benzophenone, 2, the benzophenone cpds such as 4,6-tri-methyl benzophenone; The naphtoquinone compounds such as 9,10-phenanthrenequione, 2-EAQ, camphorquinone; 10-butyl-2-chloro-acridine ketone, benzyl, phenylacetaldehyde acid methyl esters, two cyclopentadiene titanium compounds etc.
These polymerization initiators (C) can be distinguished use separately, also two or more use capable of being combined.
With respect to total amount 100 mass parts of resin (A) and polymerizable compound (B), the content of polymerization initiator (C) is preferably 0.1～80 mass parts, more preferably 1～60 mass parts.If the total amount of polymerization initiator, within the scope of this, can form pattern with high sensitivity, figuratum chemical resistance, physical strength, surface smoothness become good tendency.
Polymerization initiator (C) preferably causes auxiliary agent (C-1) (particularly amine) with polymerization and is used in combination.Polymerization to cause auxiliary agent (C-1) and to have caused the polymerization of polymerizable compound of polymerization and the compound that uses in order promoting by polymerization initiator (C), or sensitizer.
Cause auxiliary agent (C-1) as polymerization, can list amines, thiazoline compound, alkoxy anthracene compound, thioxanthones compound, carboxylic acid compound, mercaptan compound etc.
As amines, can list triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl esters, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid isopentyl ester, benzoic acid-2-dimethylaminoethyl, 4-dimethylaminobenzoic acid-2-Octyl Nitrite, N, N-dimethyl-p-toluidine, 4, 4 '-bis-(dimethylamino) benzophenone (common name Michler's keton), 4, 4 '-bis-(lignocaine) benzophenone, 4, 4 '-bis-(ethylmethylamino) benzophenone etc., wherein be preferably 4, 4 '-bis-(lignocaine) benzophenone.Can use the commercially available products such as EAB-F (hodogaya chemical industry (strain) system).
As thiazoline compound, can list the represented compound of formula (III-1)～formula (III-3) etc.
Figure BDA0000418769070000311
As alkoxy anthracene compound, can list 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 thioxanthones compound, can list ITX, ITX, 2,4-diethyl thioxanthone, 2,4-bis-clopenthixal ketones, the chloro-4-propoxyl group of 1-thioxanthones etc.
As carboxylic acid compound, can list thiophenyl acetic acid, methylbenzene ethyl thioglycollic acid, ethylbenzene ethyl thioglycollic acid, ethyl methyl benzene ethyl thioglycollic acid, dimethyl benzene ethyl thioglycollic acid, methoxybenzene ethyl thioglycollic acid, dimethoxy benzene ethyl thioglycollic acid, chlorobenzene ethyl thioglycollic acid, dichloro-benzenes ethyl thioglycollic acid, N-phenylglycine, phenoxyacetic acid, naphthalene ethyl thioglycollic acid, N-naphthyl glycocoll, naphthoxy acetic acid etc.
As mercaptan compound, can list 2-Qiu Ji oxazole, 2-thyroidan, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-sulfydryl nicotinic acid, 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, 2-mercaptopyrimidine, 2-deracil, 3,4,5,6-tetrahydropyrimidine-2-mercaptan, 4,5-diphenyl-imidazole-2-mercaptan, 2-mercaptoimidazole, 2-sulfydryl-1-methylimidazole, 4-amino-3-diazanyl-5-sulfydryl-1,2,4-triazole, 3-amino-5-sulfydryl-1,2,4-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-1,3,4-thiadiazoles, 5-amido-1,3,4-thiadiazoles-2-mercaptan, 2,5-dimercapto-1,3,4-thiadiazole, (furans-2-yl) methyl mercaptan, 2-sulfydryl-5-thiazolidone, 2-sulfydryl thiazoline, 2-sulfydryl-4 (3H)-quinazolinone, 1-phenyl-1H-TETRAZOLE-5-mercaptan, 2-quinoline mercaptan, 2-sulfydryl-5-tolimidazole, 2-sulfydryl-5-nitrobenzimidazole, 6-amino-2-mercapto phenyl formic benzothiazole, the chloro-2-mercaptobenzothiazole of 5-, 6-ethoxy-2-mercaptobenzothiazole, nitrocaptax, 2-sulfydryl naphtho-imidazoles, 2-sulfydryl naphtho-oxazole, 3-sulfydryl-1,2,4-triazole, 4-amino-6-sulfydryl pyrazolo [2,4-d] pyridine, 2-amino-6-purine mercaptan, Ismipur, 4-sulfydryl-1H-pyrazolo [2,4-d] pyrimidine, ethanthiol, the last of the ten Heavenly stems two mercaptan, Isosorbide-5-Nitrae-bis-(methyl mercapto) benzene, 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), trihydroxyethyl three (3-mercaptopropionic acid ester), pentaerythrite four (3-sulfydryl butyric ester), Isosorbide-5-Nitrae-bis-(3-sulfydryl butyl oxygen base) butane etc.
While using polymerization to cause auxiliary agent (C-1), with respect to total amount 100 mass parts of resin (A) and polymerizable compound (B), its content is preferably 0.01～50 mass parts, more preferably 0.1～40 mass parts.In addition, every 1 mole of polymerized initiating agent (C), is preferably 0.01～10 mole, more preferably 0.01～5 mole.If polymerization causes the content of auxiliary agent (C-1) within the scope of this, can further form pattern with high sensitivity, the tendency that the productivity in pattern improves.
Extender pigment (D), although be not particularly limited, can use at least one that is selected from monox, barium sulphate, titanium dioxide, zinc paste, aluminium oxide, magnesium oxide and calcium carbonate.In addition, from the viewpoint of transparent, the mean grain size of extender pigment is preferably below 500nm.Wherein consider preferential oxidation silicon from the low-viscosity viewpoint of reliability and desciccator diaphragm.
With respect to total amount 100 mass parts of resin (A) and polymerizable compound (B), the content of extender pigment (D) is preferably 0.1～80 mass parts, more preferably 1～30 mass parts.If the content of extender pigment within the scope of this, has the low viscosity of desciccator diaphragm and solvent resistance to become good tendency.
It is 8.0～9.1 (cal/cm that photosensitive polymer combination of the present invention contains solubility parameter 3) 1/2solvent (E1) and solubility parameter be 9.2～11.0 (cal/cm 3) 1/2solvent (E2).The photosensitive composite of the solvent that contains such regulation by use, can obtain having the low-viscosity desciccator diaphragm that can meet, and can obtain having the pattern of hardness that can be satisfied.
Be 8.0～9.1 (cal/cm as solubility parameter 3) 1/2solvent (E1), if mark its solubility parameter ((cal/cm with bracket 3) 1/2) examples, can list ethylene glycol list isobutyl ether (8.9), diethylene glycol list-2-ethylhexyl ether (8.4), dipropylene glycol list positive propyl ether (8.8), dipropylene glycol mono-n-butyl ether (8.5), tripropylene glycol list positive propyl ether (8.5), tripropylene glycol mono-n-butyl ether (8.2), glycol dimethyl ether (8.6), diethylene glycol dimethyl ether (8.6), diethylene glycol diethyl ether (8.6), diethylene glycol di-n-butyl ether (8.3), TRIGLYME (8.4), diethylene glycol ethyl-methyl ether (8.6), diethylene glycol mono-n-butyl ether acetic acid esters (9.0), propylene glycol methyl ether acetate (9.0), dipropylene glycol monomethyl ether acetic acid esters (8.1), ethyl-3-ethoxy-c acid esters (9.1), n-propyl acetate (8.6), n propyl propionate (8.6), n-butyl propionate (8.3), propionic acid n-pentyl ester (8.4), ethyl acetate (9.1), butyl acetate (8.3) etc.Wherein consider the acylate of the monoether that is preferably the glycol as propylene glycol methyl ether acetate from deliquescent viewpoint, the more preferably alkanoate of the monoalky lether of aklylene glycol, two aklylene glycols or three aklylene glycols.
Be 9.2～11.0 (cal/cm as solubility parameter 3) 1/2solvent (E2), if mark its solubility parameter ((cal/cm with bracket 3) 1/2) examples, can list ethylene glycol ether (10.6), ethylene glycol list isopropyl ether (9.2), ethylene glycol mono-n-butyl ether (10.2), ethylene glycol ether (9.4), ethyleneglycol monophenylether (10.9), ethylene glycol monobenzyl ether (10.8), ethylene glycol monoallyl ether (9.8), diethylene glycol monomethyl ether (10.7), diethylene glycol mono-n-butyl ether (10.0), diethylene glycol monohexyl ether (9.7), diethylene glycol list-2-ethylhexyl ether (9.2), diethylene glycol list benzyl oxide (9.6), triethylene glycol monomethyl ether (10.2), Triethylene glycol ethyl ether (9.9), triethylene glycol mono-n-butyl ether (9.3), poly glycol monomethyl ether (9.2), propylene glycol monomethyl ether (10.7), propylene glycol list positive propyl ether (9.7), propylene glycol mono-n-butyl ether (9.3), the tertiary butyl ether of propylene glycol list (9.7), propylene glycol monophenyl ether (11.0), dipropylene glycol monomethyl ether (9.6), Tripropylene glycol monomethyl Ether (9.4), ethylene glycol mono-n-butyl ether acetic acid esters (10.3), propylene-glycol diacetate (9.6), methyl-3-methoxy propyl acid esters (9.5), methyl lactate (10.7), butyl lactate (9.8), cyclohexanone (9.9), 4-hydroxy-4-methyl-2-pentanone (another name diacetone alcohol) (10.2), n-butyl alcohol (11.4), diox (10.0), chloroform (9.3), acetone (9.9), 1,1,2,2-tetrachloroethane (9.7) etc.Wherein consider to be preferably hydroxyl compound from deliquescent viewpoint, the more preferably monoether of the glycol as propylene glycol monomethyl ether or the hydroxy-ketone as 4-hydroxy-4-methyl-2-pentanone, the more preferably monoalky lether of aklylene glycol, two aklylene glycols or three aklylene glycols or hydroxy alkyl ketone.
With respect to solvent (E), solubility parameter is 8.0～9.1 (cal/cm 3) 1/2the content of solvent (E1) be 70～99 quality %, be preferably 70～97 quality %, with respect to solvent (E), solubility parameter is 9.2～11.0 (cal/cm 3) 1/2the content of solvent (E2) be 1～30 quality %, be preferably 3～30 quality %.If the flatness when ratio of the quality % of solvent has dissolubility, coating in above-mentioned scope becomes good tendency.It should be noted that, solvent (E) although can contain desolventizes (E1) and (E2) solvent in addition, and its content is generally below 20 quality % with respect to solvent (E), is preferably below 10 quality %.
It should be noted that solubility parameter utilizes following formula to obtain.
Solubility parameter=(Δ E/V) 1/2
Δ E: cohesive energy (enthalpy of vaporization), V: molar volume
Solvent (E) can use in the time of resin glue (A) synthetic.
With respect to photosensitive polymer combination, the content of solvent (E) is preferably 60～95 quality %, more preferably 70～90 quality %.In other words, the solid state component of photosensitive polymer combination is preferably 5～40 quality %, more preferably 10～30 quality %.If the flatness when content of solvent (E) in above-mentioned scope, has coating becomes good tendency.
Photosensitive polymer combination of the present invention preferably also contains colorant (F).As such colorant (F), although can list pigment and dyestuff, aspect the thermotolerance and photostability of pattern, preferably contain pigment, aspect the photopermeability of pattern, preferred coloring agent, more preferably contains pigment and dyestuff.
As pigment, can list organic pigment and inorganic pigment, can list in Colour Index (The Society of Dyers and Colourists publication) and be sorted in the compound in pigment.
As organic pigment, can list the yellow uitramarines such as 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;
C.I. pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65,71, the orange pigments such as 73;
C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,209,215,216,224,242,254,255,264, the red pigments such as 265;
C.I. pigment blue 15,15:3,15:4,15:6, the blue pigments such as 60;
C.I. pigment violet 1,19,23,29,32,36, the violet pigments such as 38;
C.I. pigment Green 7,36, the viridine greens such as 58;
C.I. the brown such as pigment brown 23,25;
C.I. black pigment such as pigment black 1,7 etc.
Wherein, preferred C.I. pigment yellow 13 8,139,150; C.I. paratonere 177,242,254; C.I. pigment Violet 23; C.I. pigment blue 15: 3,15:6; C.I. pigment Green 7,36,58.
These pigment can independent or two or more mixing uses.
As required, the grafting processing of can implement rosin processing to above-mentioned pigment, used the surface treatment of pigment derivative or the pigment dispersing agent etc. of having introduced acidic-group or basic group, by macromolecular compound etc., surface of pigments being carried out, the micronize of being undertaken by sulfuric acid micronize method etc. are processed or are removed processing etc. by what remove that carrying out washing treatment that organic solvent or water etc. that impurity uses carries out, ion exchange process by ionic impurity etc. carry out.In addition, the particle diameter of preferred pigments is even.Then carry out dispersion treatment by containing pigment dispersing agent, can make pigment and be dispersed in the dispersible pigment dispersion of the state in solution.
As above-mentioned pigment dispersing agent, can use commercially available surfactant, can enumerate as surfactants such as silicone-based, fluorine system, ester system, kation system, negative ion system, nonionic system, both sexes, polyester system, polyamines system, acrylic acid series etc.As above-mentioned surfactant, except polyoxyethylene alkyl ether class, polyoxyethylene alkyl phenyl ether class, polyethylene glycol di class, sorbitan fatty ester class, fatty acid modified polyesters, tertiary amine modified polyurethane, beyond polyethylene imine based class etc., can list commodity KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system) by name, Flowlen (common prosperity society chemistry (strain) system), Solsperse (Jie Likang (strain) system), EFKA (EFKA) (BASF system), Ajisper (registered trademark) (aginomoto fine chemistry (strain) system), Disperbyk (Bi Ke chemical company system) etc.They can be used alone or in combination of two or more respectively.
While using pigment dispersing agent, with respect to pigment, preferably its consumption is below 100 quality %, more preferably 5～50 quality %.If the consumption of pigment dispersing agent is in above-mentioned scope, in making the tendency of dispersible pigment dispersion of uniform disperse state.
As colorant (F), also can use known dyestuff, as dyestuff, can list oil-soluble dyes, acid dyes etc.
These dyestuffs can be according to the solubleness to solvent, fast light fadedness, spectrophotometric spectra while forming the pattern of color filter with the colored curable resin composition that contain this dyestuff carrys out suitable selection.
Dyestuff is not particularly limited and can uses known dyestuff, can enumerate as solvent dye, acid dyes, direct dyes, mordant dye etc.As dyestuff, can enumerate as being classified except pigment in Colour Index (The Society of Dyers and Colourists publication) in the compound of material or the known dyestuff of record in Dyeing Note (Se Ran society) with form and aspect.In addition, according to chemical constitution, can list azo dyes, cyanine dye, kiton colors, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dyestuff, quinoneimine dye, methine dyes, azo methine dyes, squaraine dye, acridine dye, styryl dye, coumarine dye, quinoline dye and nitro dye etc.Among them, be preferably organic solvent soluble dye
Particularly, can list C.I. solvent yellow 4,14,15,23,24,38,62,63,68,82,94,98,99,117,162,163,167,189;
C.I. solvent red 45,49,111,125,130,143,145,146,150,151,155,168,169,172,175,181,207,218,222,227,230,245,247;
C.I. solvent orange 2,7,11,15,26,56,77,86;
C.I. solvent violet 11,13,14,26,31,36,37,38,45,47,48,51,59,60;
C.I. solvent blue 4,5,14,18,35,36,37,45,58,59,59:1,63,67,68,69,70,78,79,83,90,94,97,98,100,101,102,104,105,111,112,122,128,132,136,139;
C.I. the C.I. solvent dye such as solvent green 1,3,4,5,7,28,29,32,33,34,35;
C.I. Indian yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251,
C.I. azogeramine, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426,
C.I. acid orange 6,7,8,10,12,26,50,51,52,56,62,63,64,74,75,94,95,107,108,169,173;
C.I. acid violet 6B, 7,9,15,16,17,19,21,23,24,25,30,34,38,49,72,102;
C.I. Blue VRS, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340,
C.I. acid green 1,3,5,6,7,8,9,11,13,14,15,16,22,25,27,28,41,50,50:1,58,63,65,80,104,105,106, the C.I. acid dyess such as 109;
C.I. direct Huang 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129,136,138,141;
C.I. directly red 79,82,83,84,91,92,96,97,98,99,105,106,107,172,173,176,177,179,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246,250;
C.I. direct orange 26,34,39,41,46,50,52,56,57,61,64,65,68,70,96,97,106,107;
C.I. direct purple 47,52,54,59,60,65,66,79,80,81,82,84,89,90,93,95,96,103,104;
C.I. direct indigo plant 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293,
C.I. the C.I. direct dyes such as direct green 25,27,31,32,34,37,63,65,66,67,68,69,72,77,79,82;
C.I. disperse yellow 51,54,76;
C.I. disperse violet 26,27;
C.I. the C.I. disperse dyes such as disperse blue 1,14,56,60;
C.I. alkali red 1:1,10;
C.I. alkali blue 1,3,5,7,9,19,21,22,24,25,26,28,29,40,41,45,47,54,58,59,60,64,65,66,67,68,81,83,88,89;
C.I. alkalescence purple 2;
C.I. alkaline red 9;
C.I. Viride Nitens 1; Deng C.I. basic-dyeable fibre;
C.I. reactive yellow 2,76,116;
C.I. reactive orange 16;
C.I. reactive red 36; Deng C.I. reactive dye;
C.I. mordant yellow 5,8,10,16,20,26,30,31,33,42,43,45,56,61,62,65;
C.I. mordant rouge 1,2,3,4,9,11,12,14,17,18,19,22,23,24,25,26,27,29,30,32,33,36,37,38,39,41,42,43,45,46,48,52,53,56,62,63,71,74,76,78,85,86,88,90,94,95;
C.I. mordant dyeing orange 3,4,5,8,12,13,14,20,21,23,24,28,29,32,34,35,36,37,42,43,47,48;
C.I. mordant dyeing purple 1,1:1,2,3,4,5,6,7,8,10,11,14,15,16,17,18,19,21,22,23,24,27,28,30,31,32,33,36,37,39,40,41,44,45,47,48,49,53,58;
C.I. mordant dyeing indigo plant 1,2,3,7,8,9,12,13,15,16,19,20,21,22,23,24,26,30,31,32,39,40,41,43,44,48,49,53,61,74,77,83,84;
C.I. the C.I. mordant dye such as viridon 1,3,4,5,10,13,15,19,21,23,26,29,31,33,34,35,41,43,53;
C.I. vat green 1 reducing dye such as C.I. such as grade etc.
These dyestuffs are as long as carry out suitable selection according to the spectrophotometric spectra of desirable color filter.
Dyestuff preferably contains the compound in molecule with xanthene skeleton.
With respect to the solid state component of photosensitive polymer combination, the content of colorant (F) is preferably 5～60 quality %, more preferably 5～45 quality %.If the content of colorant (F) is above-mentioned scope, can obtain desirable spectrum, color density.
Photosensitive polymer combination of the present invention can contain surfactant.As surfactant, can to list silicone-based surfactant, fluorine be surfactant, have silicone-based surfactant of fluorine atom etc.By containing surfactant, the flatness while having coating becomes good tendency.
As silicone-based surfactant, can list the surfactant with siloxane bond.Particularly, can list TORAY SILICONE DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DC11PA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA, polyether modified silicon oil SH8400 (eastern beautiful DOW CORNING (strain) 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, TSF4460 (stepping contract commercial firm of figure new high-tech material Japan system) etc.
Be surfactant as fluorine, can list the surfactant with fluorocarbon chain.Particularly, can list Fluorinert (registered trademark) FC430, Fluorinert FC431 (Sumitomo 3M (strain) system), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac R30 (large Japanese ink chemistry (strain) system), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (Mitsubishi Materials electronics changes into (strain) system), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass (strain) system), E5844 (Daikin Industries (strain) system) etc.
As the silicone-based surfactant with fluorine atom, can list the surfactant with siloxane bond and fluorocarbon chain.Particularly, can list Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, Megafac F443 (large Japanese ink chemistry (strain) system) etc.Can preferably list Megafac (registered trademark) F475.
With respect to photosensitive polymer combination, preferred surfactant is 0.001～0.2 quality %, and more preferably 0.002～0.1 quality %, is particularly preferably 0.01～0.05 quality %.By containing the surfactant of this scope, can make the flatness of film good.
As required, photosensitive polymer combination of the present invention can contain the various adjuvants such as filling agent, other macromolecular compounds, adhesion promoter, antioxidant, ultraviolet light absorber, light stabilizer, chain-transferring agent.
Photosensitive polymer combination of the present invention can assign to obtain by hybrid adhesive resin (A), polymerizable compound (B), polymerization initiator (C), extender pigment (D), solvent (E) and colorant as required (F), other one-tenth.
In addition, during as colorant (F) hybrid pigment, for example, preferably preparation in the following order.
First, in advance pigment is mixed with solvent (E), use ball mill etc. makes Pigments until the mean grain size of pigment fades to the degree below 0.2 μ m.Now, as required, can hybrid pigment spreading agent, resin glue (A) part or all.Can in the dispersible pigment dispersion obtaining, add the remainder, polymerizable compound (B), polymerization initiator (C), extender pigment (D) of resin glue (A), as required use other compositions, further the solvent (E) added as required, to the concentration of regulation, makes photosensitive polymer combination.
Coating process as photosensitive polymer combination of the present invention to substrate, can list extrusion coated method, direct intaglio plate rubbing method, reverse intaglio plate rubbing method, CAP rubbing method, mould rubbing method etc.In addition, also can use the apparatus for coating such as dip coaterd, roll coater, rod coater, spin coater, slit and spin coater, slit coater (sometimes also referred to as mould coating machine, showering curtain type coating machine, sol evenning machine (Spinless coater)), ink-jet printer to be coated with.Wherein, preferably use slit coater, spin coater, roll coater etc. to be coated with.
As photosensitive polymer combination is coated to substrate the drying means of film, can list the methods such as heat drying, natural drying, aeration-drying, drying under reduced pressure.Several different methods can be combined to carry out.
As baking temperature, be preferably 10～120 DEG C, more preferably 25～100 DEG C.In addition, as the heat time, be preferably 10 second～60 minute, more preferably 30 second～30 minute.
Preferably under the pressure of 50～150Pa, carry out drying under reduced pressure in the temperature range of 20～25 DEG C.
By dried coating film and the thickness of desciccator diaphragm be not particularly limited, can suitably adjust according to the material, the purposes etc. that use, be generally 0.1～20 μ m, be preferably 1～6 μ m.
Across the photomask that is used to form target pattern, desciccator diaphragm is exposed.Now the pattern form on photomask is not particularly limited, and can use the pattern form corresponding to target purposes.It should be noted that, while using thermal polymerization as polymerization initiator (C), by exposure, desciccator diaphragm is heated, this hotwork is for thermal polymerization.
As the light source for exposing, preferably send the light source of the light of the wavelength of 250～450nm.For example, can block less than the light of 350nm with the wave filter that blocks this wavelength coverage, use the bandpass filter that intercepts these wavelength coverages optionally to intercept near near near light 436nm, 408nm, 365nm.As light source, can list mercury lamp, light emitting diode, metal halide lamp, Halogen lamp LED etc.
Because irradiating equably parallel rays to plane of exposure entirety, make mask and base material in correct aligned in position, therefore preferably use the devices such as mask aligning machine, stepper.
The desciccator diaphragm exposed film obtaining of exposing is contacted with developer solution by making, make established part, for example unexposed portion dissolves, develops, and can obtain pattern.As developer solution, although also can be with an organic solvent, because of developer solution be difficult for that the exposed portion of exposed film is dissolved, swelling, can obtain the pattern of good shape, therefore preferably use the aqueous solution of alkali compounds.
Developing method can be to revolve any one that covers immersion method, infusion process, spray-on process etc.Further in the time developing, substrate can be tilted to arbitrarily angled.
Preferably after development, wash.
As above-mentioned alkali compounds, can list the inorganic alkaline compounds such as NaOH, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, sal tartari, sodium bicarbonate, saleratus, sodium borate, potassium borate, ammonia;
The organic basic compounds such as Tetramethylammonium hydroxide, 2-hydroxyethyl trimethylammonium hydroxide, monomethyl amine, dimethylamine, trimethylamine, monoethyl amine, diethylamine, triethylamine, Mono Isopropylamine, diisopropylamine, monoethanolamine.
Wherein, preferred potassium hydroxide, sodium bicarbonate, Tetramethylammonium hydroxide.
Preferably these inorganic and organic basic compound concentration in aqueous solution are 0.01～10 quality %, more preferably 0.03～5 quality %.
The aqueous solution of above-mentioned alkali compounds can contain surfactant.
As surfactant, can list the nonionics such as polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other polyoxyethylene derivs, ethylene oxide/propylene oxide segmented copolymer, sorbitan fatty ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, fatty acid glyceride, polyoxyethylene fatty acid ester, polyoxyethylene alkyl amine is surfactant;
The negative ion such as lauryl alcohol sodium sulfovinate, oleyl alcohol sodium sulfovinate, NaLS, Texapon Special, neopelex, dodecyl sodium naphthalene sulfonate are surfactant;
The kations such as octadecylamine hydrochloride, lauryl trimethyl ammonium chloride are surfactant etc.
Preferably the concentration of the surfactant of alkali compounds in aqueous solution is 0.01～10 quality %, and more preferably 0.05～8 quality %, is particularly preferably 0.1～5 quality %.
By the pattern as above obtaining is further cured, can obtain the pattern after heat curing.As stoving temperature, more than being generally 25 DEG C and below 230 DEG C, more than being preferably 25 DEG C and below 200 DEG C, more preferably more than 25 DEG C and below 160 DEG C, more preferably more than 25 DEG C and below 120 DEG C.As the time of curing, be generally 1～300 minute, be preferably 1～180 minute, more preferably 1～60 minute.
The pattern that obtains of operation is for example as the light pad (Photo spacer) using in liquid crystal indicator, the protective seam that can form pattern, color filter and useful like this.In addition, photosensitive polymer combination of the present invention can be aptly for becoming film or the pattern etc. of pixel of liquid crystal indicator, imageing sensor, these films or pattern color filter, the array base palte as a part for its member of formation can possessed, further, in the display device that possesses these color filters and/or array base palte etc., such as, in liquid crystal indicator, organic El device, device for solid photography etc., be used.
Embodiment
Below, utilize embodiment to be described in more detail photosensitive composition of the present invention." % " in example and " part " unless otherwise specified, are quality % and mass parts.
The synthetic > of < resin glue (A1) solution
In the flask that possesses stirring apparatus, tap funnel, condenser, thermometer, gas introduction tube, get 67 parts of propylene glycol methyl ether acetates, 33 parts of propylene glycol monomethyl ethers, stir on displacement nitrogen limit, limit, is warming up to 120 DEG C.Then, in the monomer mixture that comprises 11 parts of acrylic acid dicyclo pentyl esters, 31 parts of benzyl methacrylates, 23 parts of methacrylic acids, add Perbutyl O with respect to 100 parts of monomer mixtures with the ratio of 1 part.Splashed into flask with 2 hours from tap funnel, further, at 120 DEG C, stir and within 2 hours, make multipolymer.Then, air will be replaced in flask, in the solution of above-mentioned multipolymer, drop into 0.08 part of 10 parts of glycidyl methacrylate, 0.46 part of triphenylphosphine and methylnaphthohydroquinone, sustained response at 120 DEG C is until solid state component acid number finishes reaction while becoming 150mg-KOH/g, add 75 parts of propylene glycol methyl ether acetates, 5 parts of propylene glycol monomethyl ethers, making thus the weight-average molecular weight (Mw) that contains 30 quality % is 30 × 10 3, the acid number resin glue (A1) that is 150mg-KOH/g solution.Resin glue (A1) has following structural unit.
The synthetic > of < resin glue (A2) solution
In the flask that possesses stirring apparatus, tap funnel, condenser, thermometer, gas introduction tube, get 67 parts of propylene glycol methyl ether acetates, 33 parts of propylene glycol monomethyl ethers, stir on displacement nitrogen limit, limit, is warming up to 120 DEG C.Then, in the monomer mixture that comprises 10 parts of acrylic acid dicyclo pentyl esters, 34 parts of benzyl methacrylates, 20 parts of methacrylic acids, add Perbutyl O with respect to monomer mixture 100 weight portions with the ratio of 1 part.Splashed into flask with 2 hours from tap funnel, further, at 120 DEG C, stir and within 2 hours, make multipolymer.Then, air will be replaced in flask, in the solution of above-mentioned multipolymer, drop into 0.08 part of 10 parts of glycidyl methacrylate, 0.44 part of triphenylphosphine and methylnaphthohydroquinone, sustained response at 120 DEG C is until solid state component acid number finishes reaction while becoming 130mg-KOH/g, add 74 parts of propylene glycol methyl ether acetates, 5 parts of propylene glycol monomethyl ethers, making thus the weight-average molecular weight (Mw) that contains 30 quality % is 30 × 10 3, the acid number resin glue (A2) that is 130mg-KOH/g solution.Resin glue (A2) has following structural unit.
The synthetic > of < resin glue (A3) solution
In the flask that possesses stirring machine, thermometer, reflux condensing tube, tap funnel and gas introduction tube, import 413 parts of propylene glycol methyl ether acetates., by gas introduction tube nitrogen imported flask in, atmosphere in flask is replaced into nitrogen, add 5.2 parts of 144 parts of benzyl methacrylates, 30 parts of acrylic acid dicyclo pentyl esters, 35 parts of methacrylic acids and azoisobutyronitriles, stir 5 hours at 100 DEG C thereafter.Thereafter be cooled to room temperature, making the weight-average molecular weight (Mw) that contains 33.6 quality % is 10 × 10 3, the acid number resin glue (A3) that is 110mg-KOH/g solution.Resin (A3) has following structural unit.
Figure BDA0000418769070000442
The synthetic > of < resin glue (A4) solution
In the flask of 1L that possesses reflux condenser, tap funnel and stirring machine, pass into appropriate nitrogen and be replaced into nitrogen atmosphere, add 371 parts of propylene glycol methyl ether acetates, be heated to while stirring 85 DEG C.Then, splash into 54 parts, acrylic acid, acrylic acid-3 with 4 hours, 4-epoxy three encircles [5.2.1.0 2,6] last of the ten Heavenly stems-8-base ester and acrylic acid-3,4-epoxy three encircles [5.2.1.0 2,6] 225 parts, potpourri, 81 parts of the vinyltoluenes (isomer mixture) of the last of the ten Heavenly stems-9-base ester, the mixed solution of 80 parts of propylene glycol methyl ether acetates.On the other hand, splash into polymerization initiator 2 with 5 hours, two (2, the 4-methyl pentane nitriles) 30 parts of 2-azo are dissolved in 160 parts of solution that form of propylene glycol methyl ether acetate.After initiator solution dropwises, keep at the same temperature, after 4 hours, being cooled to room temperature, make that to contain 37.5 quality % weight-average molecular weight (Mw) be 10 × 10 3and the resin glue that acid number is 115mg-KOH/g (A4), and Type B viscosity (23 DEG C) is the solution of 246mPas.Resin glue (A4) has following structural unit.
Figure BDA0000418769070000451
The mensuration of the weight-average molecular weight (Mw) of the resin obtaining in synthesis example and number mean molecular weight (Mn) is used GPC method to carry out under following condition.
Device: K2479 ((strain) Shimadzu Seisakusho Ltd. system)
Chromatographic column: SHIMADZUShim-packGPC-80M
Column temperature: 40 DEG C
Solvent: THF (tetrahydrofuran)
Flow velocity: 1.0mL/min
Detecting device: RI
The synthetic > of the represented compound of < formula (F1)
60.5 parts of 40.5 parts of the compounds that hybrid under lucifuge condition (IV-1) is represented and 2,6-xylidins (Tokyo changes into (strain) system), in 200 parts of N-methylpyridones, stir 8 hours at 150 DEG C.The reactant liquor obtaining is cooled to after room temperature, is added in the mixed liquor of 1200 parts, water, 75 parts of 35% hydrochloric acid and at room temperature stirs 1 hour, result crystal is separated out.The crystal suction filtration of separating out is obtained to residue, after cleaning with 100 parts of methyl alcohol, 60 DEG C of 1 evenings of drying under reduced pressure, obtain 49 parts of the represented compounds of formula (IV-2).Yield is 85%.
Figure BDA0000418769070000461
Then, 24.2 parts, 28.8 parts of compounds represented formula (IV-2), 21.6 parts of 1-N-Propyl Bromides and sal tartari is added in 144 parts of N-methylpyridones, stir 4 hours at 90 DEG C.The reactant liquor obtaining is cooled to after room temperature concentrated, is added in 560 parts, water and stirs 1 hour at 10～15 DEG C, result crystal is separated out.The crystal suction filtration of generation is obtained after residue dryly, after cleaning with 1000 parts of ion exchange waters, 60 DEG C of 1 evenings of drying under reduced pressure, obtained 30.0 parts of the represented compounds of formula (F1).Yield is 91%.
Figure BDA0000418769070000462
The qualification of the represented compound of formula (F1)
(mass spectrophotometry) ionization mode=ESI+:m/z=[M+H] +659.3
Accurate mass: 658.3
Embodiment 1
[preparation of photosensitive polymer combination 1]
Mix
Colorant (F): 242 15 parts of C.I. paratoneres,
Colorant (F): 177 20 parts of C.I. paratoneres,
14 parts of acrylic acid series pigment dispersing agents,
33.3 parts of resin glue (A1) solution (10 parts of resin glues (A1))
And solvent (E): 191 parts of propylene glycol methyl ether acetates,
Use ball mill pigment is fully disperseed and obtain dispersible pigment dispersion;
By described dispersible pigment dispersion with
254 parts of resin glue (A1) solution (76.2 parts of resin glues (A1));
Polymerizable compound (B): glycerine 1,3-bis-glycerine alkyd diacrylates
(GDDA; Aldrich company system) 37 parts;
Polymerization initiator (C): N-benzoyloxy-1-(4-thiophenyl phenyl) octane-1-ketone-2-imines (IRGACURE (registered trademark) OXE-01; BASF Japan (strain) system) 3.7 parts;
Polymerization initiator (C): two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide (IRGACURE (registered trademark) 819; BASF Japan (strain) system) 7.4 parts;
Polymerization causes auxiliary agent (C): diethyl thioxanthone (KAYACURE (registered trademark) DETX-S; Japan's chemical drug (strain) system) 3.7 parts;
Extender pigment (D) dispersion liquid: PMA-ST; 41 parts of daily output chemistry (strain) systems (monox 30 quality %, propylene glycol monoethyl ether acetate 69.5 quality % and methyl alcohol 0.5 quality %) (lower same);
Solvent (E): 398 parts of propylene glycol methyl ether acetates;
And surfactant: polyether modified silicon oil (TORAY SILICONE SH8400; The beautiful DOW CORNING in east (strain) system) 0.5 part
Mix, make photosensitive polymer combination 1.
In whole solvents (E) in the photosensitive polymer combination 1 making, propylene glycol methyl ether acetate (solvent (E1)) proportion is that 93.3 quality %, propylene glycol monomethyl ether (solvent (E2)) proportion are 6.7 quality %.In addition, resin glue (A1) is 70/30 with the quality ratio (resin glue (A1)/polymerizable compound (B)) of polymerizable compound (B).
Embodiment 2
[preparation of photosensitive polymer combination 2]
Mix
Colorant (F): 58 43 parts of C.I. naphthol greens,
Colorant (F): 8 24 parts of C.I. pigment yellow 13s,
12 parts of acrylic acid series pigment dispersing agents,
86.7 parts of resin glue (A1) solution (26 parts of resin glues (A1))
And solvent (E): 390 parts of propylene glycol methyl ether acetates,
Use ball mill pigment is fully disperseed and obtain dispersible pigment dispersion;
By described dispersible pigment dispersion with
117 parts of resin glue (A1) solution (35.1 parts of resin glues (A1));
Polymerizable compound (B): dipentaerythritol acrylate (KAYARAD (registered trademark) DPHA; (Japanese chemical drug (strain) system)) 41 parts;
Polymerization initiator (C): N-benzoyloxy-1-(4-thiophenyl phenyl) octane-1-ketone-2-imines (IRGACURE (registered trademark) OXE-01; BASF Japan (strain) system) 10 parts;
Polymerization initiator (C): two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide
(IRGACURE (registered trademark) 819; BASF Japan (strain) system) 8.1 parts;
Polymerization causes auxiliary agent (C): diethyl thioxanthone (KAYACURE (registered trademark) DETX-S; Japan's chemical drug (strain) system) 10 parts;
Extender pigment (D) dispersion liquid: PMA-ST; 34 parts of daily output chemistry (strain) systems;
Solvent (E): 307 parts of propylene glycol methyl ether acetates; And
Surfactant: polyether modified silicon oil (TORAY SILICONE SH8400; The beautiful DOW CORNING in east (strain) system) 0.5 part
Mix, make photosensitive polymer combination 2.
In whole solvents (E) in the photosensitive polymer combination 2 making, propylene glycol methyl ether acetate (solvent (E1)) proportion is 96.9 quality %, and propylene glycol monomethyl ether (solvent (E2)) proportion is 3.1 quality %.In addition, resin glue (A1) is 60/40 with the quality ratio (resin glue (A1)/polymerizable compound (B)) of polymerizable compound (B).
Embodiment 3
[preparation of photosensitive polymer combination 3]
Mix
Colorant (F): C.I. pigment blue 15: 6 27 parts,
Colorant (F): 0.5 part of C.I. pigment Violet 23,
10 parts of acrylic acid series pigment dispersing agents,
27.7 parts of resin glue (A1) solution (8.3 parts of resin glues (A1))
And 140 parts of solvent (E) propylene glycol methyl ether acetates,
Use ball mill pigment is fully disperseed and obtain dispersible pigment dispersion;
By described dispersible pigment dispersion with
227 parts of resin glue (A1) solution (68.1 parts of resin glues (A1));
Polymerizable compound (B): dipentaerythritol acrylate (KAYARAD (registered trademark) DPHA; (Japanese chemical drug (strain) system)) 32 parts;
Polymerization initiator (C): N-benzoyloxy-1-(4-thiophenyl phenyl) octane-1-ketone-2-imines (IRGACURE (registered trademark) OXE-01; BASF Japan (strain) system) 5.4 parts;
Polymerization initiator (C): two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide
(IRGACURE (registered trademark) 819; BASF Japan (strain) system) 8.6 parts;
Polymerization causes auxiliary agent (C): diethyl thioxanthone (KAYACURE (registered trademark) DETX-S; Japan's chemical drug (strain) system) 4.3 parts;
Extender pigment (D) dispersion liquid: PMA-ST; 36 parts of daily output chemistry (strain) systems;
Solvent (E): 497 parts of propylene glycol methyl ether acetates; And
Surfactant: polyether modified silicon oil (TORAY SILICONE SH8400; The beautiful DOW CORNING in east (strain) system) 0.5 part
Mix, make photosensitive polymer combination 3.
In whole solvents (E) in the photosensitive polymer combination 3 making, propylene glycol methyl ether acetate (solvent (E1)) proportion is 94.2 quality %, and propylene glycol monomethyl ether (solvent (E2)) proportion is 5.8 quality %.In addition, resin glue (A1) is 70/30 with the quality ratio (resin glue (A1)/polymerizable compound (B)) of polymerizable compound (B).
Embodiment 4
[preparation of photosensitive polymer combination 4]
Mix
Colorant (F): C.I. pigment blue 15: 6 27 parts,
Colorant (F): 0.5 part of C.I. pigment Violet 23,
10 parts of acrylic acid series pigment dispersing agents,
Resin glue (A2) solution 24.7 parts (7.4 parts of resin glues (A2)) and
140 parts of propylene glycol methyl ether acetates (solvent E),
Use ball mill pigment is fully disperseed and obtain dispersible pigment dispersion;
By described dispersible pigment dispersion with
191 parts of resin glue (A2) solution (57.3 parts of resin glues (A2));
Polymerizable compound (B): dipentaerythritol acrylate (KAYARAD (registered trademark) DPHA; (Japanese chemical drug (strain) system)) 43 parts;
Polymerization initiator (C): N-benzoyloxy-1-(4-thiophenyl phenyl) octane-1-ketone-2-imines (IRGACURE (registered trademark) OXE-01; BASF Japan (strain) system) 5.4 parts;
Polymerization initiator (C): two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide (IRGACURE (registered trademark) 819; BASF Japan (strain) system) 8.6 parts;
Polymerization causes auxiliary agent (C): diethyl thioxanthone (KAYACURE (registered trademark) DETX-S; Japan's chemical drug (strain) system) 4.3 parts;
Extender pigment (D) dispersion liquid: PMA-ST; 36 parts of daily output chemistry (strain) systems;
Solvent (E): 530 parts of propylene glycol methyl ether acetates; And
Surfactant: polyether modified silicon oil (TORAY SILICONE SH8400; The beautiful DOW CORNING in east (strain) system) 0.5 part
Mix, make photosensitive polymer combination 4.
In whole solvents (E) in the photosensitive polymer combination making, propylene glycol methyl ether acetate (solvent (E1)) proportion is 95.1 quality %, and propylene glycol monomethyl ether (solvent (E2)) proportion is 4.9 quality %.In addition, resin glue (A2) is 60/40 with the quality ratio (resin glue (A2)/polymerizable compound (B)) of polymerizable compound (B).
Embodiment 5
[preparation of photosensitive polymer combination 5]
Mix
Colorant (F): C.I. pigment blue 15: 6 27 parts,
Colorant (F): 0.5 part of C.I. pigment Violet 23,
10 parts of acrylic acid series pigment dispersing agents,
Resin glue (A1) solution 24.7 parts (7.4 parts of resin glues (A1)) and
Solvent (E): 140 parts of propylene glycol methyl ether acetates,
Use ball mill to make pigment fully disperse to form dispersible pigment dispersion;
By described dispersible pigment dispersion with
245 parts of resin glue (A1) solution (73.5 parts of resin glues (A1));
Polymerizable compound (B): dipentaerythritol acrylate (KAYARAD (registered trademark) DPHA; (Japanese chemical drug (strain) system)) 27 parts;
Polymerization initiator (C): N-benzoyloxy-1-(4-thiophenyl phenyl) octane-1-ketone-2-imines (IRGACURE (registered trademark) OXE-01; BASF Japan (strain) system) 5.4 parts;
Polymerization initiator (C): two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide (IRGACURE (registered trademark) 819; BASF Japan (strain) system) 8.6 parts;
Polymerization causes auxiliary agent (C): diethyl thioxanthone (KAYACURE (registered trademark) DETX-S; Japan's chemical drug (strain) system) 4.3 parts;
Extender pigment (D) dispersion liquid: PMA-ST; 36 parts of daily output chemistry (strain) systems;
Solvent (E): 494 parts of propylene glycol methyl ether acetates; And
Surfactant: polyether modified silicon oil (TORAY SILICONE SH8400; The beautiful DOW CORNING in east (strain) system) 0.5 part
Mix, make photosensitive polymer combination 5.
In whole solvents (E) in the photosensitive polymer combination 5 making, propylene glycol methyl ether acetate (solvent (E1)) proportion is 93.8 quality %, and propylene glycol monomethyl ether (solvent (E2)) proportion is 6.2 quality %.In addition, resin glue (A1) is 75/25 with the quality ratio (resin glue (A1)/polymerizable compound (B)) of polymerizable compound (B).
Embodiment 6
[preparation of photosensitive polymer combination 6]
Mix
Colorant (F): C.I. pigment blue 15: 6 27 parts,
Colorant (F): 0.5 part of C.I. pigment Violet 23,
10 parts of acrylic acid series pigment dispersing agents,
Resin glue (A1) solution 27.7 parts (8.3 parts of resin glues (A1)) and
Solvent (E): 140 parts of propylene glycol methyl ether acetates,
Use ball mill pigment is fully disperseed and obtain dispersible pigment dispersion;
By described dispersible pigment dispersion with
227 parts of resin glue (A1) solution (68.1 parts of resin glues (A1));
Polymerizable compound (B): dipentaerythritol acrylate (KAYARAD (registered trademark) DPHA; Japan's chemical drug (strain) system) 32 parts;
Polymerization initiator (C): N-benzoyloxy-1-(4-thiophenyl phenyl) octane-1-ketone-2-imines (IRGACURE (registered trademark) OXE-01; BASF Japan (strain) system) 5.8 parts;
Polymerization initiator (C): two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide (IRGACURE (registered trademark) 819; BASF Japan (strain) system) 9.4 parts;
Polymerization causes auxiliary agent (C): diethyl thioxanthone (KAYACURE (registered trademark) DETX-S; Japan's chemical drug (strain) system) 4.7 parts;
Extender pigment (D) dispersion liquid: PMA-ST; 36 parts of daily output chemistry (strain) systems;
Solvent (E): 190 parts of propylene glycol monomethyl ethers
Solvent (E): 317 parts of propylene glycol methyl ether acetates; And
Surfactant: polyether modified silicon oil (TORAY SILICONE SH8400; The beautiful DOW CORNING in east (strain) system) 0.5 part
Mix, make photosensitive polymer combination 6.
Propylene glycol methyl ether acetate in whole solvents in the photosensitive polymer combination 6 making (solvent (E1)) proportion is that 71.2 quality %, propylene glycol monomethyl ether (solvent (E2)) proportion are 28.9 quality %.In addition, resin glue (A1) is 70/30 with the quality ratio (resin glue (A1)/polymerizable compound (B)) of polymerizable compound (B).
Comparative example 1
(preparation of photosensitive polymer combination 7)
Make photosensitive polymer combination 7 according to TOHKEMY 2011-221310 communique embodiment 1.
Embodiment 7
(preparation of photosensitive polymer combination 8)
Mix
Colorant (F): C.I. pigment blue 15: 6 26 parts,
Colorant (F): represented 6.4 parts of the compounds of formula (F1),
9.0 parts of acrylic acid series pigment dispersing agents,
Resin glue (A4) solution 26.7 parts of (10 parts of resin glues (A4)), solvents (E): 31 parts of 4-hydroxy-4-methyl-2-pentanones and
Solvent (E): 282 parts of propylene glycol methyl ether acetates,
Use ball mill pigment is fully disperseed and obtain dispersible pigment dispersion;
By described dispersible pigment dispersion with
108 parts of resin glue (A3) solution (36.3 parts of resin glues (A3));
Polymerizable compound (B): dipentaerythritol acrylate (KAYARAD (registered trademark) DPHA; Japan's chemical drug (strain) system) 47 parts;
Polymerization initiator (C): N-benzoyloxy-1-(4-phenyl sulfydryl phenyl) octane-1-ketone-2-imines (IRGACURE (registered trademark) OXE-01; BASF Japan (strain) system) 9.3 parts;
Polymerization initiator (C): 2-methyl-2-morpholino-1-(4-methyl mercapto phenyl) propane-1-ketone (IRGACURE907; BASF Japan (strain) system) 1.9 parts;
Polymerization causes auxiliary agent (C): diethyl thioxanthone (KAYACURE (registered trademark) DETX-S; Japan's chemical drug (strain) system) 5.6 parts;
Extender pigment (D) dispersion liquid: PMA-ST; 37 parts of daily output chemistry (strain) systems;
Solvent (E): 168 parts of 4-hydroxy-4-methyl-2-pentanones
Solvent (E): 260 parts of propylene glycol methyl ether acetates; And
Surfactant: polyether modified silicon oil (TORAY SILICONE SH8400; The beautiful DOW CORNING in east (strain) system) 0.1 part
Mix, make photosensitive polymer combination 8.
Propylene glycol methyl ether acetate (solvent (the E1)) proportion of the whole solvents (E) in the photosensitive polymer combination 8 obtaining is 75.7 quality %, and 4-hydroxy-4-methyl-2-pentanone (solvent (E2)) proportion is 24.3 quality %.In addition, resin glue (A3) is 11/39/50 with resin glue (A4) with the quality ratio (resin glue (A3)/resin glue (A4)/polymerizable compound (B)) of polymerizable compound (B).
Embodiment 8
(preparation of photosensitive polymer combination 9)
Mix
Colorant (F): C.I. pigment blue 15: 6 26 parts,
Colorant (F): represented 6.4 parts of the compounds of formula (F1),
9.0 parts of acrylic acid series pigment dispersing agents,
Resin glue (A4) solution 26.7 parts of (10 parts of resin glues (A4)), solvents (E): 31 parts of 4-hydroxy-4-methyl-2-pentanones and
Solvent (E): 282 parts of propylene glycol methyl ether acetates,
Use ball mill pigment is fully disperseed and obtain dispersible pigment dispersion;
By described dispersible pigment dispersion with
97 parts of resin glue (A4) solution (36.4 parts of resin glues (A4));
Polymerizable compound (B): dipentaerythritol acrylate (KAYARAD (registered trademark) DPHA; Japan's chemical drug (strain) system) 47 parts;
Polymerization initiator (C): N-benzoyloxy-1-(4-phenyl sulfydryl phenyl) octane-1-ketone-2-imines (IRGACURE (registered trademark) OXE-01; BASF Japan (strain) system) 9.3 parts;
Polymerization initiator (C): 2-methyl-2-morpholino-1-(4-methyl mercapto phenyl) propane-1-ketone (IRGACURE907; BASF Japan (strain) system) 1.9 parts;
Polymerization causes auxiliary agent (C): diethyl thioxanthone (KAYACURE (registered trademark) DETX-S; Japan's chemical drug (strain) system) 5.6 parts;
Extender pigment (D) dispersion liquid: PMA-ST; 37 parts of daily output chemistry (strain) systems;
Solvent (E): 168 parts of 4-hydroxy-4-methyl-2-pentanones;
Solvent (E): 272 parts of propylene glycol methyl ether acetates; And
Surfactant: polyether modified silicon oil (TORAY SILICONE SH8400; The beautiful DOW CORNING in east (strain) system) 0.1 part
Mix, make photosensitive polymer combination 9.
Propylene glycol methyl ether acetate (solvent (the E1)) proportion of the whole solvents (E) in the photosensitive polymer combination 9 obtaining is 75.7 quality %, and 4-hydroxy-4-methyl-2-pentanone (solvent (E2)) proportion is 24.3 quality %.In addition, resin glue (A4) is 50/50 with the quality ratio (resin glue (A4)/polymerizable compound (B)) of polymerizable compound (B).
Comparative example 2
(preparation of photosensitive polymer combination 10)
Mix
Colorant (F): C.I. pigment blue 15: 6 26 parts,
Colorant (F): represented 6.4 parts of the compounds of formula (F1),
4.3 parts of acrylic acid series pigment dispersing agents,
Resin glue (A4) solution 32 parts of (12 parts of resin glues (A4)), solvents (E): 29 parts of 4-hydroxy-4-methyl-2-pentanones and
Solvent (E): 243 parts of propylene glycol methyl ether acetates,
Use ball mill pigment is fully disperseed and obtain dispersible pigment dispersion;
By described dispersible pigment dispersion with
121 parts of resin glue (A4) solution (45.4 parts of resin glues (A4));
Polymerizable compound (B): dipentaerythritol acrylate (KAYARAD (registered trademark) DPHA; Japan's chemical drug (strain) system) 52 parts;
Polymerization initiator (C): N-benzoyloxy-1-(4-phenyl sulfydryl phenyl) octane-1-ketone-2-imines (IRGACURE (registered trademark) OXE-01; BASF Japan (strain) system) 11 parts;
Polymerization initiator (C): 2-methyl-2-morpholino-1-(4-methyl mercapto phenyl) propane-1-ketone (IRGACURE907; BASF Japan (strain) system) 2.1 parts;
Polymerization causes auxiliary agent (C): diethyl thioxanthone (KAYACURE (registered trademark) DETX-S; Japan's chemical drug (strain) system) 6.3 parts;
Solvent (E): 168 parts of 4-hydroxy-4-methyl-2-pentanones;
Solvent (E): 320 parts of propylene glycol methyl ether acetates; And
Surfactant: polyether modified silicon oil (TORAY SILICONE SH8400; The beautiful DOW CORNING in east (strain) system) 0.1 part
Mix, make photosensitive polymer combination 10.
Propylene glycol methyl ether acetate (solvent (the E1)) proportion of the whole solvents (E) in the photosensitive polymer combination 10 obtaining is 75.8 quality %, and 4-hydroxy-4-methyl-2-pentanone (solvent (E2)) proportion is 24.2 quality %.In addition, resin glue (A4) is 50/50 with the quality ratio (resin glue (A4)/polymerizable compound (B)) of polymerizable compound (B).
The making > of < pattern
On 2 inches of square glass substrates, after spin-coating method photosensitive resin coating composition, within 3 minutes, form desciccator diaphragm at 100 DEG C of preliminary dryings.Place cooling after, across the quartz glass photomask processed so that the mode that is spaced apart 100 μ m of desciccator diaphragm configures therewith, use exposure machine (TME-150RSK; Open up Pu Kang (strain) system), under air atmosphere, with 50mJ/cm 2exposure (taking 365nm as benchmark) desciccator diaphragm forming on aforesaid substrate is carried out to irradiation.As photomask, use the photomask that has formed 50 μ m live widths and distance between centers of tracks pattern.After irradiation, the exposed film obtaining containing in the water system developer solution that nonionic is surfactant 0.12% and sodium carbonate 2% 24 DEG C of 60 seconds of immersion development, after washing, in baking oven, is dried after carrying out 30 minutes at 230 DEG C, obtain pattern.
< exploring degree is evaluated >
Observe the pattern making with laser microscope (Axio Imager MAT Carl Zeiss Inc. system), using the minimum dimension of telling as exploring degree.Exploring degree is higher, more can be used for the manufacture of high-accuracy color filter.
The uneven > that evaluates of < development
Observe the pattern making with laser microscope (Axio Imager MAT Carl Zeiss Inc. system), to on pattern, there is no water stain zero (could not observe the inequality of developing) that be evaluated as, will have water stain being evaluated as × (can observe the inequality of developing).Can observe and develop in uneven situation, during for the manufacture of color filter, produce color inhomogeneous.
< solvent resistance is evaluated >
The 1ml propylene glycol methyl ether acetate that drips on the pattern forming on aforesaid substrate, left standstill after 30 seconds, used spin coater to make it rotate for 10 seconds with revolution 1000rpm, got rid of the propylene glycol methyl ether acetate on pattern.
By before contacting with propylene glycol methyl ether acetate with contact after the following formula of film thickness value substitution measured, calculate thickness conservation rate.The higher curability of thickness conservation rate is better, during for the manufacture of color filter, can prevent colour mixture, and development inequality is improved.
(thickness conservation rate) (%)=(thickness after contact)/(thickness before contact)
The making > of the development film of whole exposure of <
The PET film (the beautiful Lumirror75-T60 processed in east) of fitting on 2 inches of square glass plates is made substrate.In the PET of substrate film side by spin-coating method photosensitive resin coating composition, on electric hot plate, 80 DEG C of preliminary dryings 2 minutes.Place cooling after, use exposure machine (TME-150RSK; Open up Pu Kang (strain) system), under air atmosphere, with 150mJ/cm 2exposure (taking 365nm as benchmark) the whole face of the desciccator diaphragm forming on aforesaid substrate is carried out to irradiation.After irradiation, containing in the water system developer solution that nonionic is surfactant 0.12% and potassium hydroxide 0.04%, develop for 50 seconds at 23 DEG C of dippings, clean with pure water, make thus the development film of whole exposure.With determining film thickness device (DEKTAK3; (strain) Japanese vacuum technique system) measure the thickness of the development film of whole exposure making, result is 2 μ m.
< gridiron pattern cutting test >
About the development film of whole the exposure making, carry out the belt stripping test (gridiron pattern cutting test) based on JIS K5600-5-6, evaluate the adaptation of itself and PET film.Result is presented in table 1.
< pencil hardness >
About the development film of whole the exposure making, use pencil scratch hardness test machine (Co., Ltd.'s peace field essence mechanism is done made) to carry out the mensuration of the pencil hardness based on JIS-K5400.It should be noted that, load is set to 1,000g.
< viscosity is evaluated >
Use film-making machine (helping very much machine material (strain) AP75 processed) to go up photosensitive resin coating composition at the square PET film of 5cm (east beautiful Lumirror 75-T60 processed), on electric hot plate, 80 DEG C of preliminary dryings 2 minutes.Place cooling after, on the desciccator diaphragm forming on the square PET film of above-mentioned 5cm, press after the square PET film of other 5cm (east beautiful (Co., Ltd.) Lumirror 75-T60 processed), peel off the PET film that this is pressed.Desciccator diaphragm is not produced to inequality, and on the PET film peeling off, do not form zero (could not observe viscosity) that be evaluated as of transfer printing, desciccator diaphragm is produced to inequality, and on the PET film peeling off, form being evaluated as × (can observe viscosity) of transfer printing.When viscosity can be observed, during for the manufacture of color filter, produce color inhomogeneous.
Table 1
According to the present invention, can provide to manufacture to there is the low-viscosity desciccator diaphragm that can meet, and manufacture the photosensitive polymer combination of the pattern with hardness that can be satisfied.
The photosensitive polymer combination of the application of the invention, can make the uneven high pattern of exploring degree being improved that develops.Utilize pattern that the present invention makes as color filter such as the demonstration for liquid crystal indicator, organic EL display, display device of electronic paper etc. and useful.

Claims (10)

1. a photosensitive polymer combination, it contains resin glue A, polymerizable compound B, polymerization initiator C, extender pigment D and solvent E, wherein,
It is 8.0～9.1 (cal/cm that described solvent E contains 70～99 quality % solubility parameters with respect to described solvent E 3) 1/2solvent E1, and to contain 1～30 quality % solubility parameter with respect to described solvent E be 9.2～11.0 (cal/cm 3) 1/2solvent E2.
2. photosensitive polymer combination according to claim 1, wherein,
Described polymerization initiator C is oxime compound.
3. photosensitive polymer combination according to claim 1 and 2, wherein,
The acid number of described resin glue A is 50～180mg-KOH/g.
4. according to the photosensitive polymer combination described in any one of claim 1～3, wherein,
With respect to total amount 100 mass parts of described resin glue A and described polymerizable compound B, the content of described resin glue A is 30～80 mass parts.
5. according to the photosensitive polymer combination described in any one of claim 1～4, wherein,
Described extender pigment D is monox.
6. according to the photosensitive polymer combination described in any one of claim 1～5, wherein,
Also contain colorant.
7. photosensitive polymer combination according to claim 6, wherein,
Described colorant is the colorant that contains pigment.
8. according to the photosensitive polymer combination described in claim 6 or 7, wherein,
Described colorant is the colorant that contains dyestuff.
9. a pattern, it is to be formed by the photosensitive polymer combination described in any one of claim 1～8.
10. a display device, it contains pattern claimed in claim 9.
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