CN103376659A - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

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Publication number
CN103376659A
CN103376659A CN2013101428498A CN201310142849A CN103376659A CN 103376659 A CN103376659 A CN 103376659A CN 2013101428498 A CN2013101428498 A CN 2013101428498A CN 201310142849 A CN201310142849 A CN 201310142849A CN 103376659 A CN103376659 A CN 103376659A
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methyl
photosensitive polymer
resin
coated film
polymer combination
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CN2013101428498A
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CN103376659B (en
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三浦洋之
宫芳子
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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
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • 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

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)

Abstract

The invention provides a photosensitive resin composition, which comprises (A) binder resin, (B) polymerized compound, (C) polymerization initiator and initiator adjuvant, and (D) solvent. The (A) weight-average molecular weight of binder resin is between 8000-10,0000, (C) the polymerization initiator and initiator adjuvant at least contain oxime compound, acyl group phosphine oxide compound and thioxathone compounds, (D) total solvent contains 70-99 mass percent of solvent whose solubility parameter is 8.0-9.1 (cal/cm3) 1/2, and 1-30 mass percent of solvent whose solubility parameter is 9.2-11.0 (cal/cm3) 1/2.

Description

Photosensitive polymer combination
Technical field
The present invention relates to photosensitive polymer combination.
Background technology
In JP2010-140042-A, putting down in writing a kind of photosensitive polymer combination, it contains resin, optical polymerism compound, colorant, N-benzoyloxy-1-(4-thiophenyl phenyl)-1-octanone-2-imines [trade name: IRGACURE (registered trademark) OXE-01], uses propylene glycol monoethyl ether acetate as solvent.
For photosensitive polymer combination in the past, not necessarily sufficient situation of the hardness of the pattern that made by described composition and viscosity has appearred.
The result that the inventor etc. study in order to address the above problem is, the composition of having found to contain certain solvent can prepare and has the hardness that can meet the demands and the pattern of viscosity.
Summary of the invention
That is, the invention provides following [1]～[11].
[1] a kind of photosensitive polymer combination; contain (A) resin glue, (B) polymerizable compound, (C) polymerization initiator and cause auxiliary agent and reach (D) solvent; wherein; (A) weight-average molecular weight of resin glue is 8; more than 000 100; below 000; (C) polymerization initiator and initiation auxiliary agent contain oxime compound, acylphosphine oxide based compound and thioxanthones based compound at least; for (D) solvent, the solubility parameter that contains 70 quality %～99 quality % in total solvent is 8.0～9.1 (cal/cm 3) 1/2Solvent, the solubility parameter that contains 1 quality %～30 quality % in total solvent is 9.2～11.0 (cal/cm 3) 1/2Solvent.
[2] according to the photosensitive polymer combination described in [1], wherein, (A) acid number of the solid state component of resin glue is more than 80 below 200.
[3] according to the photosensitive polymer combination described in [1] or [2], wherein, (A) ratio of resin glue and (B) polymerizable compound is take quality as benchmark and with (A) resin glue/when (B) polymerizable compound represents, is more than 50/50 below 80/20.
[4] according to the photosensitive polymer combination described in any one of [1]～[3], it also contains (E) colorant.
[5] according to the photosensitive polymer combination described in any one of [1]～[4], it also contains (F) levelling agent, and the amount of levelling agent is below 0.3 quality % more than the 0.001 quality %.
[6] a kind of patterned coated film, it is formed by the photosensitive polymer combination described in any one of [1]～[5].
[7] a kind of manufacture method of patterned coated film comprises the photosensitive polymer combination described in any one of [1]～[5] is coated on the supporting mass, desolventizing, and the operation of formation coated film,
And expose after sheltering described coated film, remove the operation of the unexposed portion of described coated film with developer solution.
[8] a kind of manufacture method of patterned coated film, it only comprises the photosensitive polymer combination described in any one of [1]～[5] is coated on the supporting mass, desolventizing forms the operation of coated film,
And expose after sheltering described coated film, remove the operation of the unexposed portion of described coated film with developer solution.
[9] a kind of manufacture method of patterned coated film comprises the photosensitive polymer combination described in any one of [1]～[5] is coated on the supporting mass, desolventizing, the operation of formation coated film,
Expose after sheltering described coated film, the operation of removing the unexposed portion of described coated film with developer solution,
And the operation of the coated film after preservation is removed unexposed portion with developer solution under the temperature below 200 ℃ more than 23 ℃.
[10] a kind of color filter comprises the patterned coated film described in [6].
[11] a kind of color filter comprises the patterned coated film that makes according to the manufacture method described in any one of [7]～[9].
According to the present invention, can provide to prepare the photosensitive polymer combination that pattern with the hardness that can meet the demands and viscosity is used.
Embodiment
Photosensitive polymer combination of the present invention contains (A) resin glue, (B) polymerizable compound, (C) polymerization initiator and initiation auxiliary agent, reaches (D) solvent.
Photosensitive polymer combination of the present invention contains (A) resin glue.(A) resin glue contain resin glue (A1) (below, the situation that is referred to as " resin (A1) " is arranged), described resin glue (A1) be make addition polymer (a) with the structural unit that derives from unsaturated carboxylic acid (below, the situation that is referred to as " (a) " is arranged) form with unsaturated compound (b) (below, the situation that is referred to as " (b) " is arranged) reaction with epoxy ethyl.
And regulation does not comprise the resin (resin glue) in the dispersible pigment dispersion of following (E) colorant in (A) resin glue.
As (a), can enumerate as: make unsaturated carboxylic acid (a1) (below, the situation that is referred to as " (a1) " is arranged) with have can carry out addition polymerization with (a1) and the monomer (a2) (below, the situation that is referred to as " (a2) " is arranged) that (b) carries out the unsaturated link of addition polymerization and must addition polymer.
As (a1), can specifically list acrylic acid, methacrylic acid, crotonic acid, adjacent vinyl benzoic acid, a vinyl benzoic acid, to unsaturated monocarboxylic acid 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, 1,2,3,6-tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid, the Isosorbide-5-Nitrae-unsaturated dicarboxylic classes such as cyclohexene dioctyl phthalate;
Methyl-5-norborene-2,3-dicarboxylic acid, 5-carboxyl dicyclo [2.2.1] hept-2-ene", 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-6-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-6-ethyl dicyclo [2.2.1] hept-2-ene" etc. contain the dicyclo unsaturated compound class of carboxyl;
Unsaturated list [(methyl) acryloxyalkyl] the ester class of the polybasic carboxylic acids more than 2 yuan such as mono succinate [2-(methyl) acryloxy ethyl] ester, phthalic acid list [2-(methyl) acryloxy ethyl] ester;
The unsaturated esters of acrylic acid that in a part, contains hydroxyl and carboxyl as alpha-hydroxymethyl acrylic acid etc.
Among them, consider from copolyreaction aspect and alkali dissolubility aspect, preferably use acrylic acid, methacrylic acid etc.
Herein, in this manual, " (methyl) acrylic acid " expression from the group that is consisted of by acrylic acid and methacrylic acid, select at least a kind." (methyl) acryloyl group " reaches marks such as " (methyl) acrylate " and also has the identical meaning.
As (a2), can enumerate such as (methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylates;
(methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methyl cyclohexyl, (methyl) acrylic acid three ring [5.2.1.0 2,6] last of the ten Heavenly stems-8-base ester (in the art,, is referred to as (methyl) acrylic acid dicyclo pentyl ester as popular name.), (methyl) acrylic acid cyclic alkyl ester class such as (methyl) acrylic acid dicyclo amoxy ethyl ester, (methyl) isobornyl acrylate;
(methyl) acrylic acid aryl or 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) acrylic acid 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-dihydroxymethyl dicyclo [2.2.1] hept-2-ene", 5,6-two (2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5,6-dimethoxy dicyclo [2.2.1] hept-2-ene", 5,6-diethoxy dicyclo [2.2.1] hept-2-ene", 5-hydroxy-5-methyl base dicyclo [2.2.1] hept-2-ene", 5-hydroxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-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-two (tert-butoxycarbonyl) dicyclo [2.2.1] hept-2-ene", the dicyclo unsaturated compound classes such as 5,6-two (cyclohexyloxy carbonyl) dicyclo [2.2.1] hept-2-ene";
The dicarbapentaborane imide derivative classes such as N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, N-succinimido-3-maleimide benzoic ether, N-succinimide ester-4-maleimide butyric ester, N-succinimide-6-maleimide capronate, N-succinimide-3-maleimide propionic ester, N-(9-acridinyl) maleimide;
Styrene, α-methyl styrene, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxy styrene, vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc.
As (a2), be particularly preferably compound (a2-1) with at least a kind of skeleton from the group that is consisted of by tricyclodecane skeleton and tricyclo decene skeleton, selecting and ethene unsaturated link (below the situation that is referred to as " (a2-1) " is arranged).When (a2) being (a2-1), the film thickness that can suppress the pattern that caused by development reduces.
Herein, " tricyclodecane skeleton " in this instructions reaches " tricyclo decene skeleton " and refers to respectively following structure (it has respectively bonding position at an arbitrary position).
As (a2-1), can specifically 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 singly or two or more kinds in combination respectively.
As (b), can enumerate as: have structure that the chain type alkene epoxidation is formed and ethene unsaturated link monomer (b-1) (below the situation that is referred to as " (b-1) " is arranged), have the monomer (b-2) (below the situation that is referred to as " (b-2) " is arranged) of structure that the cycloolefin epoxidation is formed and ethene unsaturated link.As (b), consider to be preferably (b-1) from reactive viewpoint.
As (b-1), can specifically list (methyl) glycidyl acrylate, (methyl) acrylic acid Beta-methyl ethylene oxidic ester, (methyl) propenoic acid beta-ethyl ethylene oxidic ester, the glycidyl vinyl ether, adjacent vinyl benzyl glycidol ether, between the vinyl benzyl glycidol ether, to the vinyl benzyl glycidol ether, Alpha-Methyl-adjacent vinyl benzyl glycidol ether, an Alpha-Methyl-vinyl benzyl glycidol ether, Alpha-Methyl-to the vinyl benzyl glycidol ether, 2,3-two (glycidyl ether oxygen ylmethyl) styrene, 2,4-two (glycidyl ether oxygen ylmethyl) styrene, 2,5-two (glycidyl ether oxygen ylmethyl) styrene, 2,6-two (glycidyl ether oxygen ylmethyl) styrene, 2,3,4-three (glycidyl ether oxygen ylmethyl) styrene, 2,3,5-three (glycidyl ether oxygen ylmethyl) styrene, 2,3,6-three (glycidyl ether oxygen ylmethyl) styrene, 3,4,5-three (glycidyl ether oxygen ylmethyl) styrene, 2,4,6-three (glycidyl ether oxygen ylmethyl) styrene, compound described in the JPH07-248625-A etc.
As (b-2), can list vinyl cyclohexene monoxide, 1,2-epoxy-4-vinyl cyclohexane (for example, Celloxide (セ ロ キ サ イ De) 2000; Daicel chemical industry (strain) system), 3,4-epoxycyclohexyl methacrylate (for example, Cyclomer (サ イ Network ロ マ one) A400; Daicel chemical industry (strain) system), 3,4-epoxycyclohexyl methyl acrylate (for example, Cyclomer M100; Daicel chemical industry (strain) system), the represented compound of represented compound, the formula (II) of formula (I) etc.
Figure BDA00003090572900061
[in formula (I) and formula (II), R 1And R 2Represent independently of each other the alkyl of hydrogen atom or carbon number 1～4, the hydrogen atom that comprises 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 3The alkylidene of expression carbon number 1～6.
* represent the bonding end with O.]
Resin glue (A1) can be through the operation manufacturing of for example two-stage.At this moment, can reference example such as document " 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) described in method and the method described in the Japanese Patent Laid-Open 2001-89533 communique etc. make resin glue (A1).
In the manufacturing of resin glue (A1), at first,, make (a1) and addition polymer (a) (a2) as the phase one.But concrete example illustrates (a1) of ormal weight and (a2), polymerization initiator and solvent etc. drop in the 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 can use the arbitrary substance that usually is being used in the art.As polymerization initiator, can enumerate such as azo-compound (2,2 '-azoisobutyronitrile, 2,2 '-azo two (2,) or organic peroxide (benzoyl peroxide etc.) the 4-methyl pentane nitrile) etc., as solvent, get final product so long as dissolve the solvent of each monomer, can use solvent of mentioning in the back as the solvent of photosensitive composition etc.
In addition, the addition polymer that makes can use with the state of reacted solution, also can use with the state of concentrated or the solution that dilute, also can use the solid (powder) by method extractions such as precipitations again.
With respect to the total mole number of the entire infrastructure unit that consists of addition polymer, preferably derive from the ratio of (a1) and structural unit (a2) in following scope.
Derive from the structural unit of (a1); 5～50 % by mole (more preferably 10～45 % by mole)
Derive from the structural unit of (a2); 50～95 % by mole (more preferably 55～90 % by mole)
Then, as subordinate phase, make the part and (b) reaction of the carboxylic acid of deriving from the addition polymer that makes (a1).Because of reactive high, unreacted (b) is difficult for residual, pretends as (b) and is preferably (b-1).
Particularly, and then above-mentioned, be air with the nitrogen replacement of the atmosphere in the flask, in flask, drop into 5～80 % by mole (b) with respect to the molal quantity of (a1), with respect to (a1), (b) and (a2) total amount is the catalysts (such as three (dimethylamino methyl) phenol etc.) of 0.001～5 quality % and with respect to (a1), (b) and (a2) total amount is the polymerization inhibitor (such as p-dihydroxy-benzene etc.) of 0.001～5 quality %, usually, make it 60～130 ℃ of lower reactions 1～10 hour, can make resin (A1).And, with polymerizing condition in the same manner, can consider manufacturing equipment and the thermal value that caused by polymerization etc. suitably adjusted feeding method and temperature of reaction.
In addition, at this moment, with respect to the molal quantity of (a1), the molal quantity of preferred (b) is 10～75 % by mole, more preferably 15～70 % by mole.Molal quantity by making (b) in this scope, the tendency that has storage stability, solvent resistance and stable on heating balance to become good.
As the concrete example of resin glue (A1), the multipolymer that can enumerate (methyl) acrylic acid of sening as an envoy to/(methyl) acrylic acid dicyclo pentyl ester reacts the resin that forms with (methyl) glycidyl acrylate, make the multipolymer of (methyl) acrylic acid/(methyl) benzyl acrylate react the resin that forms with (methyl) glycidyl acrylate, make the multipolymer of (methyl) acrylic acid/(methyl) cyclohexyl acrylate react the resin that forms with (methyl) glycidyl acrylate, the resin that (methyl) acrylic acid/cinnamic multipolymer and the reaction of (methyl) glycidyl acrylate are formed, make the multipolymer of (methyl) acrylic acid/(methyl) methyl acrylate react the resin that forms with (methyl) glycidyl acrylate, make the multipolymer of (methyl) acrylic acid/N-N-cyclohexylmaleimide react the resin that forms with (methyl) glycidyl acrylate, make the multipolymer of crotonic acid/(methyl) acrylic acid dicyclo pentyl ester react the resin that forms with (methyl) glycidyl acrylate;
Make the multipolymer of crotonic acid/(methyl) benzyl acrylate react the resin that forms with (methyl) glycidyl acrylate, make the multipolymer of crotonic acid/(methyl) cyclohexyl acrylate react the resin that forms with (methyl) glycidyl acrylate, the resin that crotonic acid/cinnamic multipolymer and the reaction of (methyl) glycidyl acrylate are formed, make the multipolymer of crotonic acid/ethyl crotonate react the resin that forms with (methyl) glycidyl acrylate, make the multipolymer of crotonic acid/N-N-cyclohexylmaleimide react the resin that forms with (methyl) glycidyl acrylate;
Make the multipolymer of maleic acid/(methyl) acrylic acid dicyclo pentyl ester react the resin that forms with (methyl) glycidyl acrylate, make the multipolymer of maleic acid/(methyl) benzyl acrylate react the resin that forms with (methyl) glycidyl acrylate, make the multipolymer of maleic acid/(methyl) cyclohexyl acrylate react the resin that forms with (methyl) glycidyl acrylate, the resin that maleic acid/cinnamic multipolymer and the reaction of (methyl) glycidyl acrylate are formed, make the multipolymer of maleic acid/maleic acid methyl esters react the resin that forms with (methyl) glycidyl acrylate, make the multipolymer of maleic acid/N-N-cyclohexylmaleimide react the resin that forms with (methyl) glycidyl acrylate;
Make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester react the resin that forms with (methyl) glycidyl acrylate, make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) benzyl acrylate react the resin that forms with (methyl) glycidyl acrylate, make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) cyclohexyl acrylate react the resin that forms with (methyl) glycidyl acrylate, the resin that (methyl) acrylic acid/maleic anhydride/cinnamic multipolymer and the reaction of (methyl) glycidyl acrylate are formed, make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) methyl acrylate react the resin that forms with (methyl) glycidyl acrylate, make the multipolymer of (methyl) acrylic acid/maleic anhydride/N-N-cyclohexylmaleimide react the resin that forms with (methyl) glycidyl acrylate;
Make the multipolymer and 3 of (methyl) acrylic acid/(methyl) acrylic acid dicyclo pentyl ester, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make the multipolymer and 3 of (methyl) acrylic acid/(methyl) benzyl acrylate, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make the multipolymer and 3 of (methyl) acrylic acid/(methyl) cyclohexyl acrylate, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make (methyl) acrylic acid/cinnamic multipolymer and 3, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make the multipolymer and 3 of (methyl) acrylic acid/(methyl) methyl acrylate, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make the multipolymer of (methyl) acrylic acid/N-N-cyclohexylmaleimide and the resin that 3,4-epoxycyclohexyl methyl acrylate reactions forms;
Make the multipolymer and 3 of crotonic acid/(methyl) acrylic acid dicyclo pentyl ester, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make the multipolymer and 3 of crotonic acid/(methyl) benzyl acrylate, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make the multipolymer and 3 of crotonic acid/(methyl) cyclohexyl acrylate, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make crotonic acid/cinnamic multipolymer and 3, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make the multipolymer and 3 of crotonic acid/ethyl crotonate, the resin that 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 and 3 of maleic acid/(methyl) acrylic acid dicyclo pentyl ester, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make the multipolymer and 3 of maleic acid/(methyl) benzyl acrylate, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make the multipolymer and 3 of maleic acid/(methyl) cyclohexyl acrylate, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make maleic acid/cinnamic multipolymer and 3, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make the multipolymer and 3 of maleic acid/maleic acid methyl esters, the resin that 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 and 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make the multipolymer and 3 of (methyl) acrylic acid/maleic anhydride/(methyl) benzyl acrylate, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make the multipolymer and 3 of (methyl) acrylic acid/maleic anhydride/(methyl) cyclohexyl acrylate, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make (methyl) acrylic acid/maleic anhydride/cinnamic multipolymer and 3, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make the multipolymer and 3 of (methyl) acrylic acid/maleic anhydride/(methyl) methyl acrylate, the resin that 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 (A1), more preferably make addition polymer with (b) reaction and the resin that makes, wherein, described addition polymer is to make (a1), (a2-1) and (a2) copolymerization except (a2-1) and make.(A1) is above-mentioned formation by resin glue, and the pattern and the adaptation of substrate and the tendency of solvent resistance excellence that obtain are arranged.
Addition polymer (a) is by (a1), when (a2-1) and (a2) except (a2-1) consists of, preferably derive from (a2-1) and (a2-1) in addition the ratio of structural unit of (a2) be 10: 90～60: 40, more preferably 10: 90～40: 60, more preferably 10: 90～30: 70.
As make (b) with make (a1) and (a2-1) and the addition polymer of (a2) copolymerization except (a2-1) reaction and resin, the multipolymer that can specifically enumerate (methyl) acrylic acid of sening as an envoy to/(methyl) acrylic acid dicyclo pentyl ester/(methyl) benzyl acrylate reacts the resin that forms with (methyl) glycidyl acrylate, make the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) cyclohexyl acrylate react the resin that forms with (methyl) glycidyl acrylate, the resin that (methyl) acrylic acid/(methyl) acrylic acid dicyclo pentyl ester/cinnamic multipolymer and the reaction of (methyl) glycidyl acrylate are formed, make the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) methyl acrylate react the resin that forms with (methyl) glycidyl acrylate, make the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid dicyclo pentyl ester/N-N-cyclohexylmaleimide react the resin that forms with (methyl) glycidyl acrylate;
Make the multipolymer of crotonic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) benzyl acrylate react the resin that forms with (methyl) glycidyl acrylate, make the multipolymer of crotonic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) cyclohexyl acrylate react the resin that forms with (methyl) glycidyl acrylate, the resin that crotonic acid/(methyl) acrylic acid dicyclo pentyl ester/cinnamic multipolymer and the reaction of (methyl) glycidyl acrylate are formed, make the multipolymer of crotonic acid/(methyl) acrylic acid dicyclo pentyl ester/ethyl crotonate react the resin that forms with (methyl) glycidyl acrylate, make the multipolymer of crotonic acid/(methyl) acrylic acid dicyclo pentyl ester/N-N-cyclohexylmaleimide react the resin that forms with (methyl) glycidyl acrylate;
Make the multipolymer of maleic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) benzyl acrylate react the resin that forms with (methyl) glycidyl acrylate, make the multipolymer of maleic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) cyclohexyl acrylate react the resin that forms with (methyl) glycidyl acrylate, the resin that maleic acid/(methyl) acrylic acid dicyclo pentyl ester/cinnamic multipolymer and the reaction of (methyl) glycidyl acrylate are formed, make the multipolymer of maleic acid/(methyl) acrylic acid dicyclo pentyl ester/maleic acid methyl esters react the resin that forms with (methyl) glycidyl acrylate, make the multipolymer of maleic acid/(methyl) acrylic acid dicyclo pentyl ester/N-N-cyclohexylmaleimide react the resin that forms with (methyl) glycidyl acrylate;
Make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester/(methyl) benzyl acrylate react the resin that forms with (methyl) glycidyl acrylate, make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester/(methyl) cyclohexyl acrylate react the resin that forms with (methyl) glycidyl acrylate, the resin that (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester/cinnamic multipolymer and the reaction of (methyl) glycidyl acrylate are formed, make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester/(methyl) methyl acrylate react the resin that forms with (methyl) glycidyl acrylate, make the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester/N-N-cyclohexylmaleimide react the resin that forms with (methyl) glycidyl acrylate;
Make the multipolymer and 3 of (methyl) acrylic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) benzyl acrylate, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make the multipolymer and 3 of (methyl) acrylic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) cyclohexyl acrylate, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make (methyl) acrylic acid/(methyl) acrylic acid dicyclo pentyl ester/cinnamic multipolymer and 3, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make the multipolymer and 3 of (methyl) acrylic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) methyl acrylate, the resin that 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 and 3 of crotonic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) benzyl acrylate, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make the multipolymer and 3 of crotonic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) cyclohexyl acrylate, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make crotonic acid/(methyl) acrylic acid dicyclo pentyl ester/cinnamic multipolymer and 3, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make the multipolymer and 3 of crotonic acid/(methyl) acrylic acid dicyclo pentyl ester/ethyl crotonate, the resin that 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 and 3 of maleic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) benzyl acrylate, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make the multipolymer and 3 of maleic acid/(methyl) acrylic acid dicyclo pentyl ester/(methyl) cyclohexyl acrylate, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make maleic acid/(methyl) acrylic acid dicyclo pentyl ester/cinnamic multipolymer and 3, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make the multipolymer and 3 of maleic acid/(methyl) acrylic acid dicyclo pentyl ester/maleic acid methyl esters, the resin that 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 and 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester/(methyl) benzyl acrylate, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make the multipolymer and 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester/(methyl) cyclohexyl acrylate, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester/cinnamic multipolymer and 3, the resin that 4-epoxycyclohexyl methyl acrylate reactions forms, make the multipolymer and 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo pentyl ester/(methyl) methyl acrylate, the resin that 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 (A1) can be used singly or two or more kinds in combination.
The weight-average molecular weight (Mw) of the polystyrene conversion of resin glue (A1) is 8,000～100,000, is preferably 10,000～50,000.If the weight-average molecular weight of resin (B1) in above-mentioned scope, then has coating and viscosity to become good tendency, be difficult for occuring film thickness during this external development and reduce, further, the good tendency of removability of non-pixel portion is arranged when developing.
The acid number of preferred binder resin (A1) is 50～200mg-KOH/g, more preferably 60～190mg-KOH/g, more preferably 80～180mg-KOH/g.Acid number be measure be used for and the amount (mg) of the potassium hydroxide that 1g resin glue (A1) is required and value, can obtain by carrying out titration with potassium hydroxide aqueous solution.
Although the resin glue (A) that comprises in the preferred photosensitive polymer combination of the present invention only comprises above-mentioned resin glue (A1), so long as do not damage the degree of effect of the present invention, just can contain other resins.As such resin, can enumerate such as epoxy resin, acryl resin, ammonia ester resin, vibrin, polyimide resin, polyolefin resin, linear phenol-aldehyde resin, polyamines resin etc.
When resin glue (A) contained resin except resin glue (A1), with respect to resin glue (A), the content of preferred binder resin (A1) was 1～80 quality %, more preferably 1～50 quality %.
Photosensitive polymer combination of the present invention contains (B) polymerizable compound.As long as (B) polymerizable compound is that the compound that the living radical that utilizes the effect of (C) polymerization initiator by light or heat to produce, acid etc. can initiated polymerizations just is not particularly limited.As (B) polymerizable compound, can list compound with polymerism carbon-to-carbon unsaturated bond etc., preferably use monofunctional monomer, bifunctional monomer, 3 officials can above polyfunctional monomer.
As the concrete example of single functionality monomer, can list acrylic acid nonyl phenyl carbitol ester, acrylic acid 2-hydroxyl-3-phenoxy group propyl ester, acrylic acid 2-ethylhexyl carbitol ester, acrylic acid 2-hydroxyl ethyl ester, NVP etc.
In addition, concrete example as bifunctional monomer, can list two (acryloxy ethyl) ethers, 3-methyl pentanediol two (methyl) acrylate of 1,6-hexanediol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, bisphenol-A etc.
Concrete example as the above polyfunctional monomer of 3 officials energy can list trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, the product of pentaerythrite three (methyl) acrylate and acid anhydrides, the product of dipentaerythritol five (methyl) acrylate and acid anhydrides, the V#1000 processed of Osaka organic chemistry society, V#802, STAR-501, chemistry (strain) UA-306H processed of common prosperity society, UA-306T, UA-306I, the urethane acrylates such as the first industrial New frontier processed R-1150 of pharmacy society etc.Wherein, preferably use bifunctional monomer, the above polyfunctional monomer of 3 officials energy.
In addition, also can add following polymerizable compound.
Figure BDA00003090572900131
Figure BDA00003090572900141
Figure BDA00003090572900161
Figure BDA00003090572900171
Figure BDA00003090572900181
Figure BDA00003090572900191
Figure BDA00003090572900201
Figure BDA00003090572900211
Figure BDA00003090572900221
Figure BDA00003090572900231
Figure BDA00003090572900241
Figure BDA00003090572900251
(B) polymerizable compound can separately or also be used more than two kinds and use.
With respect to the solid state component of photosensitive polymer combination, the content of preferred (B) polymerizable compound is 1～50 quality %, more preferably 5～30 quality %.In addition, (A) ratio of resin glue and (B) polymerizable compound is take quality as benchmark and with (A) resin glue/when (B) polymerizable compound represents, is preferably more than 50/50 and below 80/20.
If (A) resin glue and the ratio of (B) polymerizable compound are in above-mentioned scope, and be then suppressed because of viscosity, have make do not have the inhomogeneous color filter of color tendency so preferred.
Photosensitive polymer combination of the present invention contains (C) polymerization initiator and causes auxiliary agent.
As (C) polymerization initiator and initiation auxiliary agent, can list living radical initiating agent, sour initiating agent, polymerization accelerant, sensitizer etc.The living radical initiating agent produces living radical by the effect of light or heat.(C) polymerization initiator and initiation auxiliary agent contain oxime compound, acylphosphine oxide based compound and thioxanthones based compound.
As above-mentioned oxime compound, can list the compound with the represented part-structure of formula (C-1).In the following formula, * represents bonding position.
As such oxime compound; can enumerate such as N-benzoyloxy-1-(4-thiophenyl phenyl) butane-1-ketone-2-imines; N-benzoyloxy-1-(4-thiophenyl phenyl) octane-1-ketone-2-imines; N-benzoyloxy-1-(4-thiophenyl phenyl)-3-cyclopentyl propane-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; N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-3-cyclopentyl propane-1-imines; N-benzoyloxy-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-3-cyclopentyl propane-1-ketone-compound or IRGACURE (registered trademark) OXE01 such as 2-imines; OXE02 (more than, BASF AG's system); the commercially available products such as N-1919 (Chinese mugwort Dicon A/S system) etc.Preferred IRGACURE (registered trademark) OXE01 (BASF AG's system) wherein.
As above-mentioned acylphosphine oxide based compound, can list TMDPO, two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide etc.Can use the commercially available products such as Lucirin (registered trademark) TPO (BASF AG's system), IRGACURE (registered trademark) 819 (BASF AG's system).
As above-mentioned thioxanthones based compound, can enumerate such as ITX, ITX, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones etc.Wherein be preferably 2,4-diethyl thioxanthone.
In addition, so long as do not damage the degree of effect of the present invention, just can further and with the polymerization initiator that is usually using in this area or polymerization cause auxiliary agent, cause auxiliary agent as described polymerization initiator or polymerization, can enumerate such as acetophenone based compound, bisglyoxaline based compound, triazine based compound, benzoin based compound, benzophenone based compound, anthracene based compound, amine compound, thiazoline based compound, alkoxy anthracene based compound, carboxylic acid based compound etc.
As above-mentioned acetophenone based compound, can list diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, the benzil dimethyl ketal, 2-hydroxyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-2-methyl isophthalic acid-acetone, 1-hydroxy-cyclohexyl phenyl ketone, 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholinyl propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butane-1-ketone, 2-(2-methyl-benzyl)-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone, 2-(3-methyl-benzyl)-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone, 2-(4-methyl-benzyl)-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone, 2-(2-Ethylbenzyl)-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone, 2-(2-propyl group benzyl)-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone, 2-(2-butyl benzyl)-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone, 2-(2, the 3-dimethyl benzyl)-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone, 2-(2,4-dimethyl benzyl)-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone, 2-(2-chlorobenzyl)-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone, 2-(2-bromobenzyl)-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone, 2-(3-chlorobenzyl)-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone, 2-(4-chlorobenzyl)-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone, 2-(3-bromobenzyl)-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone, 2-(4-bromobenzyl)-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone, 2-(2-methoxy-benzyl)-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone, 2-(3-methoxy-benzyl)-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone, 2-(4-methoxy-benzyl)-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone, 2-(2-methyl-4-methoxy-benzyl)-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone, 2-(2-methyl-4-bromobenzyl)-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone, 2-(2-bromo-4-methoxy-benzyl)-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone, 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] oligomer etc. of propane-1-ketone.
As above-mentioned bisglyoxaline based compound, can list 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,3-dichlorophenyls)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline is (for example, with reference to JPH06-75372-A, JPH06-75373-A etc.), 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxaline, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (dialkoxy phenyl) bisglyoxaline, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxaline is (for example, with reference to JPS48-38403-B, JPS62-174204-A 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 JPH07-10913-A etc.) etc., can preferably list 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline.
As above-mentioned triazine based compound, can list 2, two (the trichloromethyl)-6-(4-methoxyphenyl) of 4--1,3,5-triazines, 2, two (the trichloromethyl)-6-(4-methoxyl naphthyl)-1 of 4-, 3,5-triazine, two (the trichloromethyl)-6-piperonyls-1 of 2,4-, 3, the 5-triazine, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1,3 of 2,4-, the 5-triazine, 2, two (trichloromethyl)-6-[2-(5-methylfuran-2-yl) vinyl of 4-]-1,3,5-triazines, 2, two (trichloromethyl)-6-[2-(furans-2-yl) vinyl of 4-]-1,3,5-triazine, two (trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl of 2,4-]-1,3, the 5-triazine, two (trichloromethyl)-6-[2-(3, the 4-Dimethoxyphenyl) vinyl of 2,4-]-1,3,5-triazine etc.
As above-mentioned benzoin based compound, can enumerate such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether etc.
As above-mentioned benzophenone based compound; can enumerate such as benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl thioether, 3; 3 '; 4; 4 '-four (t-butyl peroxy carbonyl) benzophenone, 2; 4,6-tri-methyl benzophenone etc.
As above-mentioned anthracene based compound, can enumerate such as 9,10-dimethoxy anthracene, EDMO, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene etc.
As above-mentioned amine compound, can enumerate such as triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl esters, EDMAB, 4-dimethylaminobenzoic acid isopentyl ester, benzoic acid-2-dimethylamino ethyl ester, 4-dimethylaminobenzoic acid-2-Octyl Nitrite, N, the N-dimethyl-p-toluidine, 4,4 '-two (dimethylamino) benzophenone (common name Michler's keton), 4,4 '-two (lignocaine) benzophenone, 4,4 '-two (ethylmethylamino) benzophenone etc., wherein be preferably 4,4 '-two (lignocaine) benzophenone.
As the thiazoline based compound, can list the represented compound of formula (III-1)～formula (III-3) etc.
Figure BDA00003090572900291
As above-mentioned alkoxy anthracene based compound, can enumerate such as 9,10-dimethoxy anthracene, EDMO, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene 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.
In addition, as polymerization initiator, commercially available trade name " EAB-F " (hodogaya chemical industry (strain) system) etc. can be shown for example also.
In addition, (C) among the polymerization initiator, the polymerization initiator as having the group that can cause the chain transfer can use the polymerization initiator of putting down in writing in JP2002-544205-A.
Polymerization initiator with the group that can cause above-mentioned chain transfer also can be used as the constituent (A3) of above-mentioned multipolymer.Then, the multipolymer that makes also can be used as (A) resin glue.
Cause auxiliary agent as (C), can enumerate such as: amine compound described above, thiazoline based compound, alkoxy anthracene based compound, carboxylic acid based compound, commercially available trade name " EAB-F " etc.
With regard to the content of (C) polymerization initiator and initiation auxiliary agent, with respect to the solid state component of photosensitive polymer combination, oxime compound, acylphosphine oxide based compound, thioxanthones based compound are preferably respectively 1～20 quality %.In addition, reach (B) total amount of polymerizable compound with respect to (A) resin glue, take quality percentage as benchmark, the content of preferred (C) polymerization initiator and initiation auxiliary agent is 0.1～40 quality %, more preferably 1～30 quality %.
If (C) total amount of polymerization initiator and initiation auxiliary agent is in above-mentioned scope, the photosensitive polymer combination high sensitivity that becomes then must be inclined to so preferred because the flatness on the surface of intensity that the pixel section that uses the color filter that above-mentioned photosensitive polymer combination forms is arranged and above-mentioned pixel becomes good.
Preferred photosensitive polymer combination of the present invention also contains (E) colorant.(E) colorant as such can list pigment and dyestuff, but aspect thermotolerance, photostability, preferably contains pigment.
As pigment, can list organic pigment and inorganic pigment, can list the compound that in Colour Index (The Society of Dyers and Colourists publication), is sorted in the pigment.
As organic pigment, can specifically enumerate 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, the yellow uitramarines such as 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. pigment brown 23, the browns such as 25;
C.I. pigment black 1, the black pigments such as 7 etc.
Wherein, more preferably C.I. pigment yellow 13 8,139,150; C.I. paratonere 177,242,254; C.I. pigment purple 23; C.I. pigment blue 15: 3,15: 6 and C.I. pigment Green 7,36,58.These pigment can separately or mix more than 2 kinds and use.
As required, the micronize that the grafting of can implement surface treatment that rosin processes, uses the pigment derivative of having introduced acidic-group or basic group or pigment dispersing agent etc. to carry out to above-mentioned pigment, surface of pigments being carried out by macromolecular compound etc. processes, undertaken by sulfuric acid micronize method etc. is processed or is removed processing etc. by what remove that carrying out washing treatment that organic solvent that impurity uses or water etc. carry out, ion exchange process etc. by ionic impurity carry out.In addition, the particle diameter of preferred pigments is even.Then carry out dispersion treatment by containing pigment dispersing agent, can make the dispersible pigment dispersion that pigment is dispersed in the state in the solution.
As above-mentioned pigment dispersing agent, can use commercially available surfactant, can enumerate such 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 the polyoxyethylene alkyl ether class, the polyoxyethylene alkyl phenyl ether class, the polyethylene glycol di class, the sorbitan aliphatic ester class, fatty acid modified polyesters, the tertiary amine modified polyurethane, beyond the polyethyleneimine: amine etc., can list commodity KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system) by name, Flowlen (Off ロ one レ Application) (common prosperity society chemistry (strain) system), Solsperse (Jie Likang (strain) system), EFKA (EFKA) (BASF AG's system), Ajisper (ア ジ ス パ one) (registered trademark) (aginomoto fine chemistry (strain) system), Disperbyk (Bi Ke chemistry society system) etc.They can be used singly or two or more kinds in combination respectively.
When using pigment dispersing agent, with respect to pigment, preferably its consumption is below the 100 quality %, more preferably 5～50 quality %.If the consumption of pigment dispersing agent in above-mentioned scope, then has the tendency of the dispersible pigment dispersion that makes homogeneously dispersed state.
With respect to the solid state component of photosensitive polymer combination, the content of preferred (E) colorant is 5～60 quality %, more preferably 5～45 quality %.If (E) content of colorant is in above-mentioned scope, then can obtain desirable spectrum and color density.
It is 8.0～9.1 (cal/cm that (D) solvent of photosensitive polymer combination of the present invention contains solubility parameter 3) 1/2Solvent and solubility parameter be 9.2～11.0 (cal/cm 3) 1/2Solvent.
Be 8.0～9.1 (cal/cm as solubility parameter 3) 1/2Solvent, can list the glycol monomethyl isobutyl ether, diethylene glycol single 2-ethyl hexyl ether, the single positive propyl ether of dipropylene glycol, the dipropylene glycol mono-n-butyl ether, tripropylene glycol list positive propyl ether, the tripropylene glycol mono-n-butyl ether, glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, the diethylene glycol di-n-butyl ether, TRIGLYME, diethylene glycol ethyl-methyl ether, diethylene glycol mono-n-butyl ether acetic acid esters, propylene glycol methyl ether acetate, the dipropylene glycol monomethyl ether acetic acid esters, ethyl-3-ethoxy-c acid esters, n-propyl acetate, n propyl propionate, n-butyl propionate, the propionic acid n-pentyl ester, methyl isobutyl ketone, cyclohexane, toluene, ethyl acetate, butyl acetate, tetrahydrofuran, phenixin, 2-HEPTANONE etc.Wherein consider preferred propylene glycol methyl ether acetate from deliquescent viewpoint.
Be 9.2～11.0 (cal/cm as solubility parameter 3) 1/2Solvent, can list ethylene glycol ether, the glycol monomethyl isopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol ether, ethyleneglycol monophenylether, ethylene glycol monobenzyl ether, the glycol monomethyl allyl ether, diethylene glycol monomethyl ether, the diethylene glycol mono-n-butyl ether, the diethylene glycol monohexyl ether, diethylene glycol single 2-ethyl hexyl ether, diethylene glycol list benzyl oxide, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, the triethylene glycol mono-n-butyl ether, poly glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol list positive propyl ether, the propylene glycol mono-n-butyl ether, propylene glycol list uncle butyl ether, the propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, Tripropylene glycol monomethyl Ether, the ethylene glycol mono-n-butyl ether acetic acid esters, propylene glycol diacetate, methyl-3-methoxy propyl acid esters, methyl lactate, butyl lactate, cyclohexanone, diacetone alcohol, the 1-propyl alcohol, n-butyl alcohol, MEK, dioxane, methylene chloride, chloroform, dimethyl sulfoxide (DMSO), acetone, dimethyl carbonate, 1,1,2,2-tetrachloroethane etc.Wherein consider preferred propylene glycol monomethyl ether from deliquescent viewpoint.
With regard to the content of solvent, with respect to the whole solvents in the photosensitive polymer combination, preferred dissolution degree parameter is 8.0～9.1 (cal/cm 3) 1/2Solvent be 70 quality %～99 quality %, solubility parameter is 9.2～11.0 (cal/cm 3) 1/2Solvent be 1 quality %～30 quality %, more preferably solubility parameter is 8.0～9.1 (cal/cm 3) 1/2Solvent be 70 quality %～97 quality %, solubility parameter is 9.2～11.0 (cal/cm 3) 1/2Solvent be 3 quality %～30 quality %.If the flatness when the quality % ratio of solvent in above-mentioned scope, then has dissolubility, coating becomes good must the tendency.
And solubility parameter is obtained by following formula.
Solubility parameter=(△ E/V) 1/2
△ E: cohesive energy (enthalpy of vaporization), V: molar volume
With regard to (D) solvent, when being used for (A) resin glue synthetic and during the preparation photosensitive polymer combination, the solubility parameter that can contain 70 quality %～99 quality % is 8.0～9.1 (cal/cm 3) 1/2Solvent and the solubility parameter of 1 quality %～30 quality % be 9.2～11.0 (cal/cm 3) 1/2Solvent.
With respect to photosensitive polymer combination, the content of preferred (D) solvent is 60～95 quality %, more preferably 70～90 quality %.In other words, the solid state component of preferred photosensitive polymer combination is 5～40 quality %, more preferably 10～30 quality %.If (D) content of solvent is in above-mentioned scope, the flatness when coating is then arranged becomes good tendency.
Photosensitive polymer combination of the present invention can contain (F) surfactant.As surfactant, can enumerate as: silicone-based surfactant, fluorine be surfactant, have the silicone-based surfactant of fluorine atom etc.By containing surfactant, the flatness when coating is arranged becomes good must the tendency.
As the silicone-based surfactant, can list the surfactant with siloxane bond.Can specifically list TORAY SILICONE DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DC11PA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA, polyether modified silicone oil SH8400 (trade name: 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 figure new high-tech material Japan contract commercial firm system) etc.
Be surfactant as fluorine, can list the surfactant with fluorocarbon chain.Can specifically list Fluorinert (Off ロ リ Na one ト) (registered trademark) FC430, Fluorinert FC431 (Sumitomo 3M (strain) system), Megafac (メ ガ Off ア Star Network) (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac R30 (large Japanese ink chemistry (strain) system), Eftop (エ Off ト Star プ) (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (the Mitsubishi Materials electronics changes into (strain) system), Surflon (サ one Off ロ Application) (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass (strain) system), E5844 (Daikin Industries (strain) system) etc.
Silicone-based surfactant as having fluorine atom can list the surfactant with siloxane bond and fluorocarbon chain.Can specifically 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 be 0.001 quality % above, below the 0.3 quality %, more preferably 0.002 quality % above, below the 0.2 quality %, be particularly preferably 0.01 quality % above, below the 0.1 quality %.By containing the surfactant of this scope, can make the flatness of filming 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 as required can be in the presence of (E) colorant, (D) solvent and other compositions, and reaching (C) by mixing (A) resin glue, (B) polymerizable compound, polymerization initiator prepares with the initiation auxiliary agent.
In addition, when mixing the pigment of conduct (E) colorant, for example preferably in the following order modulation.
At first, in advance with pigment and (D) solvent, use ball mill etc. to make Pigments until the mean grain size of pigment fades to the following degree of 0.2 μ m.At this moment, as required, can the hybrid pigment spreading agent, (A) resin glue part or all.Can in the dispersible pigment dispersion that obtains, add remaining (A) resin glue, (B) polymerizable compound or (C) polymerization initiator etc., other compositions that use as required, the solvent of further adding as required can make photosensitive polymer combination to the concentration of regulation.
As the coating process of photosensitive polymer combination of the present invention to substrate, can enumerate such as: extrusion coated method, directly intaglio plate rubbing method, oppositely 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 (situation that is referred to as mould coating machine, showering curtain type coating machine, sol evenning machine (Spinless coater) is also arranged), inkjet printing to be coated with.Wherein, preferably use slit coater, spin coater, roll coater etc. to be coated with.
As the drying means of coating the film on the substrate, can enumerate such as methods such as: heat drying, natural drying, aeration-drying, drying under reduced pressure, the several different methods combination can be carried out.
As baking temperature, be preferably 10～120 ℃, more preferably 25～100 ℃.In addition, as heat time heating 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 20～25 ℃ the temperature range.
The thickness of dried coated film is not particularly limited, and can suitably adjust according to the material that uses, purposes etc., and for example, 0.1～20 μ m is preferably 1～6 μ m.
Across the photomask that is used to form target pattern, dried coated film is exposed.This moment, the pattern form on photomask was not particularly limited, and can use the pattern form that meets the target purposes.
As the light source that is used for exposure, preferably send the light source of light of the wavelength of 250～450nm.For example, can block light less than 350nm with the wave filter that blocks this wavelength coverage, use that the bandpass filter of these wavelength coverages of intercepting optionally intercepts near the 436nm, near near the light the 408nm, the 365nm.As light source, can specifically list mercury lamp, light emitting diode, metal halide lamp, Halogen lamp LED etc.
Because shining equably parallel rays to plane of exposure integral body, making mask and base material in correct aligned in position, so preferably use the devices such as mask aligning machine, stepper.
After the exposure, by making the established part of the coated film that contacts with developer solution, for example, make the unexposed portion dissolving, develop, can obtain pattern.As developer solution, although also can with an organic solvent dissolve or swelling because developer solution is difficult for making the exposed portion of coated film, can obtain the reason of the pattern of good shape, 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 when 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 and Tetramethylammonium hydroxide.
Preferred 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 aliphatic ester, polyoxyethylene sorbitan aliphatic 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.
The concentration of the surfactant in the aqueous solution of preferred alkali compounds is 0.01～10 quality %, and more preferably 0.05～8 quality % is particularly preferably 0.1～5 quality %.
In the present invention, also can be omitted in the operation that then the rear intensification of developing keeps.Then can add the operation that then intensification keeps if be necessary in addition.
The temperature of the operation then keep as heating up in the present invention usually more than 23 ℃, below 200 ℃, is preferably more than 25 ℃, below 180 ℃, more preferably more than 25 ℃, below 160 ℃, and more preferably more than 25 ℃, below 120 ℃.Time as heating up and then keeping is generally 1～300 minute, is preferably 1～180 minute, more preferably 1～60 minute.
If can omit the operation that then intensification keeps, then reduce the man-hour of operation, can reduce manufacturing cost.In addition, if can omit the operation that then intensification keeps, then film substrate can be used, flexible display can be made.
Photosensitive composite of the present invention can make the good pattern such as color density, brightness, contrast, sensitivity, resolution, thermotolerance and the color filter that comprises described pattern.In addition, can be in possessing these color filters or the pattern display device as the part of its component parts, for example, in the machine that relates to the rendered images such as known liquid crystal indicator, organic El device, solid state image sensor, Electronic Paper, be used with known form.
Embodiment
Synthesizing of＜resin glue solution A 1 〉
Get propylene glycol methyl ether acetate 67 weight portions, propylene glycol monomethyl ether 33 weight portions in the flask that possesses stirring apparatus, tap funnel, condenser, thermometer, gas introduction tube, the limit is replaced as the nitrogen limit and stirs, and is warming up to 120 ℃.Then, in the monomer mixture that is consisted of by methacrylic acid three ring ester 11 weight portions in the last of the ten Heavenly stems, benzyl methacrylate 31 weight portions, methacrylic acid 23 weight portions, add Perbutyl O (the peroxidating 2 ethyl hexanoic acid tert-butyl ester, Japanese grease (strain) system) 1 weight portion with respect to monomer mixture 100 weight portions.It is splashed into the flask with 2 hours from tap funnel, further, made multipolymer in 2 hours 120 ℃ of lower stirrings.Then, air will be replaced in the flask, in the solution of above-mentioned multipolymer, drop into glycidyl methacrylate 10 weight portions, triphenylphosphine 0.46 weight portion and methylnaphthohydroquinone 0.08 weight portion, 120 ℃ of lower sustained responses until the solid state component acid number finishes reaction when becoming 150KOHmg/g, add propylene glycol methyl ether acetate 75 weight portions, propylene glycol monomethyl ether 5 weight portions, make thus resin glue (Mw:30000) solution A 1 of the alkali-developable of non-volatile content 30%.
Synthesizing of＜resin glue solution A 2 〉
Get propylene glycol methyl ether acetate 67 weight portions, propylene glycol monomethyl ether 33 weight portions in the flask that possesses stirring apparatus, tap funnel, condenser, thermometer, gas introduction tube, the limit is replaced into the nitrogen limit and stirs, and is warming up to 120 ℃.Then, in the monomer mixture that is consisted of by methacrylic acid three ring ester 10 weight portions in the last of the ten Heavenly stems, benzyl methacrylate 34 weight portions, methacrylic acid 20 weight portions, add Perbutyl O (the peroxidating 2 ethyl hexanoic acid tert-butyl ester, Japanese grease (strain) system) 1 weight portion with respect to monomer mixture 100 weight portions.It is splashed into the flask with 2 hours from tap funnel, further, made multipolymer in 2 hours 120 ℃ of lower stirrings.Then, air will be replaced in the flask, in the solution of above-mentioned multipolymer, drop into glycidyl methacrylate 10 weight portions, triphenylphosphine 0.44 weight portion and methylnaphthohydroquinone 0.08 weight portion, 120 ℃ of lower sustained responses until the solid state component acid number finishes reaction when becoming 130KOHmg/g, add propylene glycol methyl ether acetate 74 weight, propylene glycol monomethyl ether 5 weight portions, make thus resin glue (Mw:30000) solution A 2 of the alkali-developable of non-volatile content 30%.
＜resin glue solution A 3 synthetic〉Resin A described in the JP2010-140042-A
Possessing stirrer, thermometer, reflux condensing tube, add propylene glycol methyl ether acetate 182g in the flask of tap funnel and nitrogen ingress pipe, after atmosphere in the flask is nitrogen from air displacement, after being warming up to 100 ℃, by benzyl methacrylate 70.5g (0.40 mole), methacrylic acid 43.0g (0.5 mole), add azoisobutyronitrile 3.6g in the potpourri that the monomethacrylates of tricyclodecane skeleton (Hitachi changes into (strain) FA-513M processed) 22.0g (0.10 mole) and propylene glycol methyl ether acetate 136g consist of, make solution, described solution is splashed into the flask with 2 hours from tap funnel, further stirred 5 hours 100 ℃ of lower continuing.Then, be air with atmosphere in the flask from nitrogen replacement, in flask, drop into glycidyl methacrylate 35.5g[0.25 mole, (with respect to 50 % by mole of the carboxyl of the methacrylic acid that is used for this reaction)], three (dimethylamino) methylphenol 0.9g and quinhydrones 0.145g, continue to carry out reaction in 6 hours under 110 ℃, making the solid state component acid number is the resin glue solution A 3 (Mw:13000) of 79mgKOH/g.
Synthesizing of＜resin glue solution A 4 〉
Possessing stirrer, thermometer, reflux condensing tube, add 591 parts of propylene glycol methyl ether acetates in the flask of tap funnel and nitrogen ingress pipe, after atmosphere in the flask is nitrogen from air displacement, after being warming up to 110 ℃, by 17.6 parts of benzyl methacrylates, add 3.6 parts of azoisobutyronitriles in the monomer mixture of 22.0 parts of the monomethacrylates of 113.7 parts of glycidyl methacrylate and tricyclodecane skeleton (Hitachi changes into (strain) FA-513M processed) and 153 parts of formations of propylene glycol methyl ether acetate, make solution, described solution is splashed into the flask with 2 hours from tap funnel, further stirred 2 hours 100 ℃ of lower continuing.Then, be air with atmosphere in the flask from nitrogen replacement, in flask, drop into 0.145 one of 68.9 parts of methacrylic acids, three (dimethylamino) methylphenol 0.9g and quinhydrones, under 110 ℃, continue to carry out reaction in 6 hours, until the solid state component acid number finishes reaction when becoming 1mgKOH/g.
Then add 53.3 parts of tetrabydrophthalic anhydrides, 0.8 part of triethylamine, under 120 ℃, make its reaction make the resin glue solution A 4 (Mw:7900) of solid state component 37.9%, acid number 68.6mgKOH/g (solid state component conversion) in 3.5 hours.
Synthesizing of＜resin glue solution A 5 〉
In the flask of the 1L that possesses reflux condenser, tap funnel and stirrer, pass into an amount of nitrogen and make nitrogen atmosphere, drop into propylene glycol methyl ether acetate 100 weight portions, be heated to while stirring 85 ℃.Then, in this flask, with methacrylic acid 19 weight portions, 3,4-epoxy three ring [5.2.1.0 2.6] decyl acrylate (compound that formula (I-1) is represented and the represented compound of formula (II-1)) 171 weight portions are dissolved in propylene glycol methyl ether acetate 40 weight portions, make solution, splash into described solution with about 5 hours of dropping liquid pump time spent.On the other hand, with polymerization initiator 2,2 '-azo two (2,4-methyl pentane nitrile) 26 weight portions are dissolved in propylene glycol methyl ether acetate 120 weight portions, make solution, described solution is splashed in the flask with about 5 hours of other dropping liquid pump time spent.After polymerization initiator dropwises, under uniform temp, kept about 3 hours, be cooled to afterwards room temperature, make the resin glue solution A 5 (Mw:8000) of solid state component 43.5 % by weight, acid number 52mgKOH/g (solid state component conversion).
Figure BDA00003090572900381
Adopt the GPC method, under following condition, carry out the mensuration of the weight-average molecular weight (Mw) of the resin glue solution that made by synthesis example.
Device: K2479 ((strain) Shimadzu Seisakusho Ltd. system)
Post: the Shim-pack GPC-80M of Shimadzu Seisakusho Ltd.
Column temperature: 40 ℃
Solvent: THF (tetrahydrofuran)
Flow velocity: 1.0mL/min
Detecting device: RI
Embodiment 1
[preparation of photosensitive polymer combination 1]
Mix
Figure BDA00003090572900391
Use ball mill to make pigment fully disperse to form dispersible pigment dispersion;
With described dispersible pigment dispersion with
Figure BDA00003090572900392
Mix, make photosensitive polymer combination 1.
In the solvent of the photosensitive polymer combination that makes, propylene glycol methyl ether acetate is that 92.7 quality %, propylene glycol monomethyl ether are 7.3 quality % in total solvent.In addition, convert by solid state component, resin glue (A1) is 70/30 with the ratio of polymerizable compound (B).
Embodiment 2
[preparation of photosensitive polymer combination 2]
Mix
Figure BDA00003090572900393
Figure BDA00003090572900401
, use ball mill to make pigment fully disperse to form dispersible pigment dispersion;
With described dispersible pigment dispersion with
Figure BDA00003090572900402
Mix, make photosensitive polymer combination 2.
In the solvent of the photosensitive polymer combination that makes, propylene glycol methyl ether acetate is that 96.4 quality %, propylene glycol monomethyl ether are 3.6 quality % in total solvent.In addition, convert by solid state component, resin glue (A1) is 60/40 with the ratio of polymerizable compound (B).
Embodiment 3
[preparation of photosensitive polymer combination 3]
Figure BDA00003090572900403
, use ball mill to make pigment fully disperse to form dispersible pigment dispersion;
With described dispersible pigment dispersion with
Figure BDA00003090572900411
, make photosensitive polymer combination 3.
In the solvent of the photosensitive polymer combination that makes, propylene glycol methyl ether acetate is that 93.7 quality %, propylene glycol monomethyl ether are 6.3 quality % in total solvent.In addition, convert by solid state component, resin glue (A1) is 70/30 with the ratio of polymerizable compound (B).
Embodiment 4
[preparation of photosensitive polymer combination 4]
Mix
Figure BDA00003090572900412
, use ball mill to make pigment fully disperse to form dispersible pigment dispersion;
With described dispersible pigment dispersion with
Figure BDA00003090572900413
Figure BDA00003090572900421
Mix, make photosensitive polymer combination 4.
In the solvent of the photosensitive polymer combination that makes, propylene glycol methyl ether acetate is that 94.7 quality %, propylene glycol monomethyl ether are 5.3 quality % in total solvent.In addition, convert by solid state component, resin glue (A2) is 60/40 with the ratio of polymerizable compound (B).
Embodiment 5
[preparation of photosensitive polymer combination 5]
Mix
, use ball mill to make pigment fully disperse to form dispersible pigment dispersion;
With described dispersible pigment dispersion with
Figure BDA00003090572900423
Figure BDA00003090572900431
Mix, make photosensitive polymer combination 5.
In the solvent of the photosensitive polymer combination that makes, propylene glycol methyl ether acetate is that 93.2 quality %, propylene glycol monomethyl ether are 6.8 quality % in total solvent.In addition, convert by solid state component, resin glue (A1) is 75/25 with the ratio of polymerizable compound (B).
Embodiment 6
[preparation of photosensitive polymer combination 6]
Mix
, use ball mill to make pigment fully disperse to form dispersible pigment dispersion;
With described dispersible pigment dispersion with
Figure BDA00003090572900441
Mix, make photosensitive polymer combination 6.
In the solvent of the photosensitive polymer combination that makes, propylene glycol methyl ether acetate is that 70.7 quality %, propylene glycol monomethyl ether are 29.3 quality % in total solvent.In addition, convert by solid state component, resin glue (A2) is 70/30 with the ratio of polymerizable compound (B).
Embodiment 7
[preparation of photosensitive polymer combination 7]
Mix
, use ball mill to make pigment fully disperse to form dispersible pigment dispersion;
With described dispersible pigment dispersion with
Mix, make photosensitive polymer combination 7.
In the solvent of the photosensitive polymer combination that makes, propylene glycol methyl ether acetate is 70.7 quality % in total solvent, and propylene glycol monomethyl ether is 29.3 quality %.In addition, convert by solid state component, resin glue (A2) is 70/30 with the ratio of polymerizable compound (B).
Comparative example 8
[preparation of photosensitive polymer combination 8]
Mix
Figure BDA00003090572900452
, use ball mill to make pigment fully disperse to form dispersible pigment dispersion;
With described dispersible pigment dispersion with
Figure BDA00003090572900461
Mix, make photosensitive polymer combination 8.
In the solvent of the photosensitive polymer combination that makes, propylene glycol methyl ether acetate is 100 quality % in total solvent.In addition, convert by solid state component, resin glue (A3) is 46/57 with the ratio of polymerizable compound (B).
Comparative example 9
[preparation of photosensitive polymer combination 9]
Mix
Figure BDA00003090572900462
, use ball mill to make pigment fully disperse to form dispersible pigment dispersion;
Make dispersible pigment dispersion with
Figure BDA00003090572900463
Mix, make photosensitive polymer combination 9.
In the solvent of the photosensitive polymer combination that makes, propylene glycol methyl ether acetate is that 93.0 quality %, propylene glycol monomethyl ether are 7.0 quality % in total solvent.In addition, convert by solid state component, resin glue (A1) is 70/30 with the ratio of polymerizable compound (B).
Comparative example 10
[preparation of photosensitive polymer combination 10]
Mix
Figure BDA00003090572900471
, use ball mill to make pigment fully disperse to form dispersible pigment dispersion;
With dispersible pigment dispersion with
Figure BDA00003090572900472
Mix, make photosensitive polymer combination 10.
In the solvent of the photosensitive polymer combination that makes, propylene glycol methyl ether acetate is 100 quality % in total solvent.In addition, convert by solid state component, resin glue (A1) is 70/30 with the ratio of polymerizable compound (B).
Comparative example 11
[preparation of photosensitive polymer combination 11]
Mix
Figure BDA00003090572900481
, use ball mill to make pigment fully disperse to form dispersible pigment dispersion;
With dispersible pigment dispersion with
Mix, make photosensitive polymer combination 11.
In the solvent of the photosensitive polymer combination that makes, propylene glycol methyl ether acetate is 100 quality % in total solvent.In addition, convert by solid state component, resin glue (A1) is 70/30 with the ratio of polymerizable compound (B).
Comparative example 12
[preparation of photosensitive polymer combination 12]
Mix
Figure BDA00003090572900491
, use ball mill to make pigment fully disperse to form dispersible pigment dispersion;
With dispersible pigment dispersion with
Mix, make photosensitive polymer combination 12.
In the solvent of the photosensitive polymer combination that makes, propylene glycol methyl ether acetate is that 65.0 quality %, propylene glycol monomethyl ether are 35.0 quality % in total solvent.In addition, convert by solid state component, resin glue (A1) is 70/30 with the ratio of polymerizable compound (B).
The making of＜patterned coating film 〉
Applying PET film on 2 inches square glass plates (east beautiful Lumirror processed (Le ミ ラ one) 75-T60) is made substrate.In the PET of substrate film side by spin-coating method coating by the above-mentioned photosensitive polymer combination that makes, on electric hot plate 80 ℃ of lower preliminary dryings 2 minutes.After placing cooling, use exposure machine (TME-150RSK; Open up Pu Kang (strain) system), under air atmosphere, with 150mJ/cm 2Exposure (take 365nm as benchmark) the whole real estate of the substrate that is coated with this solidification compound is carried out irradiation.And, use the photomask of the live width be formed with 10～100 μ m and distance between centers of tracks pattern as photomask.Behind irradiation, dipping develops for 50 seconds in the water system developer solution that nonionic is surfactant 0.12% and potassium hydroxide 0.04% under 23 ℃ described photomask being contained, and by washing with purified water, makes patterned coating film.With elcometer (DEKTAK3; Japan's vacuum technique (strain) system) measure the thickness of the patterned coating film make, the result is 2 μ m.
＜evaluation resolution 〉
Observe the patterned coating film make with laser microscope (Axio Imager MAT Ka Er Zeiss society system), with the minimum dimension told as resolution.Resolution is higher, more can be used for the manufacturing of high-accuracy color filter.
＜evaluation is developed uneven 〉
Observe the patterned coating film that makes with laser microscope (Axio Imager MAT Ka Er Zeiss society system), to not have water stain filming to be evaluated as zero (not observing the inequality of developing) at pattern, will have water stain filming to be evaluated as * (observing the inequality of developing).Observe in the uneven situation of developing, when being used for the manufacturing of color filter, it is uneven to produce color and luster.
＜evaluation solvent resistance 〉
The pattern that forms at the aforesaid substrate 1ml propylene glycol methyl ether acetate that drips, left standstill for 30 seconds after, use spin coater to make it rotate for 10 seconds with revolution 1000rpm, get rid of the propylene glycol methyl ether acetate on the pattern.
Will with before propylene glycol methyl ether acetate contacts with contact after the following formula of film thickness value substitution measured, calculate the thickness conservation rate.The higher then curing property of thickness conservation rate is better, when being used for the manufacturing of color filter, can prevent colour mixture, and the development inequality is improved.
(thickness conservation rate) (%)=(thickness after the contact)/(contact before thickness)
The making of＜full edition film (filming of whole exposure) 〉
Applying PET film on 2 inches square glass plates (the beautiful Lumirror75-T60 processed in east) is made substrate.In the PET of substrate film side by spin-coating method coating by the above-mentioned photosensitive polymer combination that makes, on electric hot plate, 80 ℃ of lower preliminary dryings 2 minutes.After placing cooling, use exposure machine (TME-150RSK; Open up Pu Kang (strain) system), under air atmosphere, with 150mJ/cm 2Exposure (take 365nm as benchmark) the whole real estate of the substrate that is coated with this solidification compound is carried out irradiation.And, do not use photomask, whole face is exposed.With elcometer (DEKTAK3; Japan's vacuum technique (strain) system) measure the thickness that the solid make is filmed, the result is 2 μ m.
＜gridiron pattern cutting test 〉
Film for the solid that makes, carry out the belt stripping test (gridiron pattern cutting test) based on JIS K5600-5-6, estimate the adaptation of itself and PET film.The result is presented in the table 1,2.
＜pencil hardness 〉
The solid that makes is filmed, use pencil scratch hardness instrument (Co., Ltd.'s smart mechanism in peace field is done made) to carry out the mensuration based on the pencil hardness of JIS-K5400.And load is set to 1,000g.
＜viscosity evaluation 〉
Use film-making machine (helping very much AP75 processed of machine material Co., Ltd.) to be coated with by the above-mentioned photosensitive polymer combination that makes at the square PET film of 5cm (the beautiful Lumirror75-T60 processed in east), on electric hot plate, 80 ℃ of lower preliminary dryings 2 minutes.After placing cooling, after the face that is coated with this solidification compound is fitted the square PET film of uncoated 5cm (the beautiful Lumirror75-T60 processed in east), peel off the square PET film of uncoated 5cm (the beautiful Lumirror75-T60 processed in east).The PET film that was coated with is not produced inequality, and the PET film that does not form transfer printing on uncoated PET film is evaluated as zero (not observing viscosity), to produce inequality at the PET film that was coated with, and be evaluated as * (observing viscosity) at the PET film of uncoated PET film formation transfer printing.When observing viscosity, when being used for the manufacturing of color filter, it is uneven to produce color and luster.
[table 1]
Figure BDA00003090572900521
[table 2]
Figure BDA00003090572900522
According to the present invention, can provide to prepare the photosensitive polymer combination that pattern with the hardness that can meet the demands and viscosity is used.
The photosensitive polymer combination of the application of the invention can improve the development inequality and the high pattern of resolution.Useful as using color filter for the demonstration of liquid crystal indicator or organic EL display, display device of electronic paper etc. by the pattern that the present invention obtains.

Claims (11)

1. photosensitive polymer combination contains (A) resin glue, (B) polymerizable compound, (C) polymerization initiator and causes auxiliary agent and (D) solvent,
Wherein, (A) weight-average molecular weight of resin glue is 8000～100000, and (C) polymerization initiator and initiation auxiliary agent contain oxime compound, acylphosphine oxide based compound and thioxanthones based compound at least,
With regard to (D) solvent, the solubility parameter that contains 70 quality %～99 quality % in total solvent is 8.0～9.1 (cal/cm 3) 1/2Solvent, and the solubility parameter that contains 1 quality %～30 quality % in total solvent is 9.2～11.0 (cal/cm 3) 1/2Solvent.
2. photosensitive polymer combination according to claim 1, wherein, (A) acid number of the solid state component of resin glue is 80～200.
3. photosensitive polymer combination according to claim 1 and 2, wherein, (A) resin glue and (B) ratio of polymerizable compound, take quality as benchmark and with (A) resin glue/when (B) polymerizable compound represents, be more than 50/50 and below 80/20.
4. the described photosensitive polymer combination of any one according to claim 1～3, it also contains (E) colorant.
5. the described photosensitive polymer combination of any one according to claim 1～4, it also contains (F) levelling agent, and the amount of levelling agent is at 0.001 quality %～0.3 quality %.
6. patterned coated film, it is formed by the described photosensitive polymer combination of any one in the claim 1～5.
7. the manufacture method of a patterned coated film comprises the described photosensitive polymer combination of any one in the claim 1～5 is coated on the supporting mass, desolventizing, and the operation of formation coated film, and
Expose after sheltering described coated film, remove the operation of the unexposed portion of described coated film with developer solution.
8. the manufacture method of a patterned coated film, it only comprises following operation:
The described photosensitive polymer combination of any one in the claim 1～5 is coated on the supporting mass, desolventizing, the operation of formation coated film, and
Expose after sheltering described coated film, remove the operation of the unexposed portion of described coated film with developer solution.
9. the manufacture method of a patterned coated film comprises the described photosensitive polymer combination of any one in the claim 1～5 is coated on the supporting mass, desolventizing, and the operation of formation coated film,
Expose after sheltering described coated film, the operation of removing the unexposed portion of described coated film with developer solution, and
The operation of the coated film after maintenance is removed unexposed portion with developer solution under 23 ℃～200 ℃ the temperature.
10. a color filter comprises patterned coated film claimed in claim 6.
11. a color filter comprises the patterned coated film that the described manufacture method of any one of utilizing in the claim 7～9 makes.
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