CN103676480A - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

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Publication number
CN103676480A
CN103676480A CN201310384385.1A CN201310384385A CN103676480A CN 103676480 A CN103676480 A CN 103676480A CN 201310384385 A CN201310384385 A CN 201310384385A CN 103676480 A CN103676480 A CN 103676480A
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methyl
acrylic acid
resin
multipolymer
obtains
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Inventor
三浦洋之
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • 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
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
    • G03F7/2016—Contact mask being integral part of the photosensitive element and subject to destructive removal during post-exposure processing
    • G03F7/202—Masking pattern being obtained by thermal means, e.g. laser ablation

Abstract

The invention provides a photosensitive resin composition comprising (A) adhesive resin, (B) polymerized compound shown by the formula (I), and (C) photopolymerization initiator. In the formula (I), R1, R2 and R3 represents hydrogen atom or methyl separately, X represents -R5-O-R6-, R5 represents a single bond or alkylene with the carbon number of 1-5, R6 represents alkylene with hydroxyl and the carbon number of 1-3, Y represents alkyl, hydrogen atom or hydroxyl, and R4 represents hydrogen atom or methy.

Description

Photosensitive polymer combination
Technical field
The present invention relates to photosensitive polymer combination.
Background technology
In JP2009-531727-A, record and comprise resin, glycerine 1, the photosensitive polymer combination of 3-bis-glycerine alkyd diacrylates and 2-dimethylamino-1-(4-morpholino phenyl)-2-benzyl butane-1-ketone (trade name: Irgacure (registered trademark) 369).
In photosensitive polymer combination in the past, there is the situation that development spot occurs in resulting patterned coating film.
Summary of the invention
The invention provides following (1)～(6).
(1) photosensitive polymer combination, it comprises the polymerizable compound shown in (A) adhesive resin, (B) following formula (I) and (C) Photoepolymerizationinitiater initiater.
< formula (I) >
Figure BDA0000374015210000011
(in formula (I), R 1, R 2and R 3represent respectively hydrogen atom or methyl, represent-R of X 5-O-R 6-, R 5the alkylidene that represents singly-bound or carbon number 1～5, R 6alkylidene, the Y that represents to have the carbon number 1～3 of hydroxyl represent alkyl, hydrogen atom, hydroxyl or
Figure BDA0000374015210000021
R 4represent hydrogen atom or methyl.
(2) according to the photosensitive polymer combination (1) described, wherein, (C) Photoepolymerizationinitiater initiater has the part-structure shown in following formula (II).
Figure BDA0000374015210000022
(in formula, * represents respectively associative key (bonding hand).)
(3) according to the photosensitive polymer combination (1) or (2) described, it also comprises colorant.
(4) according to the photosensitive polymer combination described in any one in (1)～(3), it also comprises naphthol green 58 or paratonere 242.
(5) patterned coating film, its photosensitive polymer combination described in any one in (1)～(4) forms.
(6) display device, it comprises (5) described patterned coating film.
According to the present invention, can provide the photosensitive polymer combination of giving the pattern that has reduced development spot.
Embodiment
Photosensitive polymer combination of the present invention comprises following (A), (B) and (C).
(A) adhesive resin (being sometimes referred to as below " resin (A) ")
(B) polymerizable compound shown in above-mentioned formula (I) (being sometimes referred to as below " polymerizable compound (B) ")
(C) Photoepolymerizationinitiater initiater (being sometimes referred to as below " Photoepolymerizationinitiater initiater (C) ")
Photosensitive polymer combination of the present invention comprises resin (A).Resin (A) is preferably and shows the deliquescent resin of alkali.Here, alkali dissolubility refers to the character being dissolved in as in the developer solution of the aqueous solution of alkali cpd.
As the deliquescent resin of aforesaid demonstration alkali, can list
Resin (A-1): make to be selected from least one (a) (being sometimes referred to as below " (a) ") in unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides and there is the multipolymer that the compound (b) (being sometimes referred to as below " (b) ") of the cyclic ether of carbon number 2～4 is polymerized;
Resin (A-2): allow to (a) and (b) monomer of copolymerization (c) (wherein, from (a) and (b) different.) (being sometimes referred to as below " (c) ") and (a) and the multipolymer (b) being polymerized;
Resin (A-3): make (a) and the multipolymer (c) being polymerized;
Resin (A-4): make (a) and the multipolymer that (c) is polymerized, then react with (b) and the resin that obtains;
Resin (A-5): multipolymer that (b) is polymerized with (c) is reacted again and the resin that obtains with (a); Deng.
As (a), particularly, can list acrylic acid, methacrylic acid, crotonic acid, adjacent vinyl benzoic acid, a vinyl benzoic acid, to unsaturated monocarboxylic classes such as vinyl benzoic acids;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2, the unsaturated dicarboxylic classes such as 3,6-tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid, Isosorbide-5-Nitrae-cyclohexene dicarboxylic acid;
Methyl-5-norborene-2,3-dicarboxylic acid, 5-carboxyl dicyclo [2.2.1] hept-2-ene", 5, the dicyclo unsaturated compound class that 6-dicarboxyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-6-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-6-ethyl dicyclo [2.2.1] hept-2-ene" etc. contain carboxyl;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrabydrophthalic anhydride, 1,2,3,6-tetrabydrophthalic anhydride, dimethyl tetrahydro phthalic anhydride, 5, the unsaturated dicarboxylic class acid anhydrides such as 6-dicarboxyl dicyclo [2.2.1] hept-2-ene" acid anhydrides (carbic anhydride);
Unsaturated list ((methyl) acryloxyalkyl) the ester class of 2 yuan of above polybasic carboxylic acids such as mono succinate (2-(methyl) acryloxy ethyl) ester, phthalic acid list (2-(methyl) acryloxy ethyl) ester;
As α-(methylol) acrylic acid, with containing unsaturated esters of acrylic acid of hydroxyl and carboxyl etc. in a part.
Wherein, from copolyreaction aspect and alkali dissolubility aspect, preferably use acrylic acid, methacrylic acid, maleic anhydride etc.
Here, in this instructions, " (methyl) acrylic acid " represents to be selected from least one in acrylic acid and methacrylic acid.The statement of " (methyl) acrylic ", " (methyl) acryloyl group " and " (methyl) acrylate " etc. also has same implication.
(b) refer to that the cyclic ether for example with carbon number 2～4 (for example, is selected from oxirane ring, oxetanes ring and tetrahydrofuran ring (tetrahydrofuran: polymerizable compound at least one oxolane)).(b) preferably there is the cyclic ether of carbon number 2～4 and the monomer of ethylenic unsaturated bond, more preferably there is the cyclic ether of carbon number 2～4 and the monomer of (methyl) acryloxy.
Have Oxyranyle monomer (b1) (being sometimes referred to as below " (b1) "), have oxetanyl monomer (b2) (being sometimes referred to as below " (b2) "), there is the monomer (b3) (being sometimes referred to as below " (b3) ") of tetrahydrofuran base etc.
The monomer (b1) with Oxyranyle refers to the polymerizable compound with Oxyranyle.As (b1), can list for example have make structure that chain type alkene epoxidation forms and ethylenic unsaturated bond monomer (b1-1) (being sometimes referred to as below " (b1-1) "), have and make structure that loop chain alkene epoxidation forms and the monomer (b1-2) (being sometimes referred to as below " (b1-2) ") of ethylenic unsaturated bond.
As (b1), preferably there is the monomer of Oxyranyle and ethylenic unsaturated bond, more preferably there is the monomer of Oxyranyle and (methyl) acryloxy, further preferably there is (b1-2) of (methyl) acryloxy.
As (b1-1), particularly, can list (methyl) acrylic acid glycidyl esters, (methyl) acrylic acid Beta-methyl glycidyl esters, (methyl) propenoic acid beta-ethyl glycidyl esters, glycidyl vinyl ether, adjacent vinyl benzyl glycidyl ether, between vinyl benzyl glycidyl ether, to vinyl benzyl glycidyl ether, Alpha-Methyl-adjacent vinyl benzyl glycidyl ether, an Alpha-Methyl-vinyl benzyl glycidyl ether, Alpha-Methyl-to vinyl benzyl glycidyl ether, two (glycidoxypropyl methyl) styrene of 2,3-, two (glycidoxypropyl methyl) styrene of 2,4-, two (glycidoxypropyl methyl) styrene of 2,5-, two (glycidoxypropyl methyl) styrene of 2,6-, 2,3,4-tri-(glycidoxypropyl methyl) styrene, 2,3,5-tri-(glycidoxypropyl methyl) styrene, 2,3,6-tri-(glycidoxypropyl methyl) styrene, 3,4,5-tri-(glycidoxypropyl methyl) styrene, 2,4,6-tri-(glycidoxypropyl methyl) styrene, the compound of recording in JPH07-248625-A etc.
As (b1-2), can list vinyl cyclohexene list oxide, 1,2-epoxy-4-vinyl cyclohexane (for example, CELLOXIDE (registered trademark) 2000, (strain) Daicel system), 3,4-epoxycyclohexyl methacrylate is (for example, CYCLOMER (registered trademark) A400, (strain) Daicel system), 3,4-epoxycyclohexyl methyl acrylate (for example, CYCLOMER (registered trademark) M100; (strain) Daicel system), compound (being sometimes referred to as below " compound (IV) ") shown in the compound shown in formula (III) (being sometimes referred to as below " compound (III) "), formula (IV) etc.
Figure BDA0000374015210000051
[in formula (III) and formula (IV), R 7and R 8the alkyl that represents independently respectively hydrogen atom or carbon number 1～4, the contained hydrogen atom of this alkyl can be replaced by hydroxyl.
X 1and X 2represent independently respectively singly-bound ,-R 9, *-R 9-O-, *-R 9-S-or *-R 9-NH-.
R 9the alkane 2 basis that represents carbon number 1～6.
* represent the associative key with O.]
As the alkyl of carbon number 1～4, particularly, can list methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group etc.
Alkyl after being replaced by hydroxyl as hydrogen atom, can list methylol, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyl-1-Methylethyl, 2-hydroxyl-1-Methylethyl, 1-hydroxyl butyl, 2-hydroxyl butyl, 3-hydroxyl butyl, 4-hydroxyl butyl etc.
As R 7and R 8, preferably can list hydrogen atom, methyl, methylol, 1-hydroxyethyl and 2-hydroxyethyl, more preferably can list hydrogen atom and methyl.
As alkane 2 basis, can list methylene, ethylidene, propane-1,2-bis-bases, propane-1,3-bis-bases, butane-Isosorbide-5-Nitrae-bis-base, pentane-1,5-bis-bases, hexane-1,6-bis-bases etc.
As X 1and X 2, preferably can list singly-bound, methylene, ethylidene, *-CH 2-O-base and *-CH 2cH 2-O-base, more preferably can list singly-bound and *-CH 2cH 2-O-base.* represent the associative key with O.
As compound (III), can list the compound shown in formula (III-1)～formula (III-15) etc.Preferably can list the compound shown in any in formula (III-1), formula (III-3), formula (III-5), formula (III-7), formula (III-9) and formula (III-11)～formula (III-15).More preferably can list the compound shown in any in formula (III-1), formula (III-7), formula (III-9) and formula (III-15).
Figure BDA0000374015210000071
As compound (IV), can list the compound shown in formula (IV-1)～formula (IV-15) etc.Preferably can list the compound shown in any in formula (IV-1), formula (IV-3), formula (IV-5), formula (IV-7), formula (IV-9) and formula (IV-11)～formula (IV-15).More preferably can list the compound shown in any in formula (IV-1), formula (IV-7), formula (IV-9) and formula (IV-15).
Figure BDA0000374015210000081
Compound (III) and compound (IV) can be distinguished use separately.In addition, they can be with ratio mixing arbitrarily.In the situation of mixing, its mixture ratio is with molar ratio computing, preferred compound (III): compound (IV) is 5:95～95:5, more preferably 10:90～90:10, more preferably 20:80～80:20.
The monomer (b2) with oxetanyl refers to the polymerizable compound with oxetanyl.As (b2), preferably there is the monomer of oxetanyl and ethylenic unsaturated bond, more preferably there is the monomer of oxetanyl and (methyl) acryloxy.As (b2), can list such as 3-methyl-3-(methyl) acryloyl-oxy ylmethyl oxetanes, 3-ethyl-3-(methyl) acryloyl-oxy ylmethyl oxetanes, 3-methyl-3-(methyl) acryloxy Ethyloxetane, 3-ethyl-3-(methyl) acryloxy Ethyloxetane etc.
The monomer (b3) with tetrahydrofuran base refers to the polymerizable compound with tetrahydrofuran base.As (b3), preferably there is the monomer of tetrahydrofuran base and ethylenical unsaturated double bonds, more preferably there is the monomer of tetrahydrofuran base and (methyl) acryloxy.
As (b3), particularly, can list tetrahydrofurfuryl acrylate (for example, ViscoatV#150, Osaka organic chemistry industry (strain) system), tetrahydrofurfuryl methacrylate etc.
As (c), can list (methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butylacrylate, (methyl) acrylic acid sec-butyl ester, (methyl) acrylic acid tertiary butyl ester;
(methyl) acrylic acid cyclohexyl ester, (methyl) acrylic acid 2-methylcyclohexyl ester, three ring [5.2.1.0 2,6] decane-8-base (methyl) acrylate (in the art.As trivial name, be also referred to as (methyl) acrylic acid two cyclopentyl esters.), (methyl) acrylic acid cyclic alkyl ester class of two cyclopentyloxy ethyl (methyl) acrylate, (methyl) isobornyl acrylate etc.;
(methyl) acrylic acid aryl ester or the aralkyl ester class of (methyl) phenyl acrylate, (methyl) acrylic acid benzyl ester etc.;
The dicarboxylic diester of maleic acid diethyl ester, fumaric acid diethyl ester, itaconic acid diethyl ester etc.;
The hydroxyalkyl acrylate classes such as (methyl) HEA, (methyl) acrylic acid 2-hydroxypropyl ester;
Dicyclo [2.2.1] hept-2-ene", 5-methyl bicycle [2.2.1] hept-2-ene", 5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxyl dicyclo [2.2.1] hept-2-ene", 5-methylol dicyclo [2.2.1] hept-2-ene", 5-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5-methoxyl dicyclo [2.2.1] hept-2-ene", 5-ethoxy dicyclo [2.2.1] hept-2-ene", 5,6-dihydroxy dicyclo [2.2.1] hept-2-ene", 5,6-bis-(methylol) dicyclo [2.2.1] hept-2-ene", 5,6-bis-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5,6-dimethoxy dicyclo [2.2.1] hept-2-ene", 5,6-diethoxy dicyclo [2.2.1] hept-2-ene", 5-hydroxy-5-methyl base dicyclo [2.2.1] hept-2-ene", 5-hydroxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-methylol-5-methyl bicycle [2.2.1] hept-2-ene", 5-tertbutyloxycarbonyl dicyclo [2.2.1] hept-2-ene", 5-cyclohexyl oxygen carbonyl dicyclo [2.2.1] hept-2-ene", 5-phenyloxycarbonyl dicyclo [2.2.1] hept-2-ene", two (tert-butoxycarbonyl) dicyclo [2.2.1] hept-2-ene"s of 5,6-, the dicyclo unsaturated compound classes such as two (cyclohexyl oxygen base carbonyl) dicyclo [2.2.1] hept-2-ene"s of 5,6-,
The dicarbapentaborane imide derivative classes such as N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, N-succinimido-3-maleimide benzoic ether, N-succinimido-4-maleimide butyric ester, N-succinimido-6-maleimide capronate, N-succinimido-3-maleimide propionic ester, N-(9-acridinyl) maleimide;
Styrene, α-methyl styrene, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxy styrene, vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc.
Wherein, from copolyreaction and the deliquescent aspect of alkali, optimization styrene, N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide and dicyclo [2.2.1] hept-2-ene".
In resin (A-1), with respect to the total molal quantity that forms the structural unit of resin (A-1), the ratio that is derived from the structural unit of each monomer is preferably following scope.
Be derived from the structural unit of (a): 5～60 % by mole, more preferably 10～50 % by mole.
Be derived from the structural unit of (b): 40～95 % by mole, more preferably 50～90 % by mole.
The ratio of the structural unit of resin (A-1) is above-mentioned scope if, has storage stability, developability, solvent resistance, thermotolerance and physical strength to become good tendency.
As resin (A-1), preferably (b) is the resin of (b1), and more preferably (b) is the resin of (b1-2).
Resin (A-1) can reference example the citing document recorded of (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) recorded as the experimental method > > of document < < Polymer Synthesizing (the experiment method of Polymer Synthesizing) method and the document manufacture.
Particularly, can the following method of illustration: by (a) of ormal weight and (b), polymerization initiator and solvent etc. drop in reaction vessel, and by utilizing nitrogen replacement oxygen, the method that stirs, heats, is incubated under deoxidation.It should be noted that, polymerization initiator used herein and solvent etc. are not particularly limited, and can use any in material usually used in this field.As polymerization initiator; can list for example azo-compound (2; 2 '-azobis isobutyronitrile, 2; 2 '-azo two (2;) or organic peroxide (benzoyl peroxide etc.) 4-methyl pentane nitrile) etc.; as solvent, so long as the material that each monomer is dissolved, as the solvent of photosensitive composition, can use solvent described later etc.
It should be noted that, the multipolymer obtaining can directly be used reacted solution, also can use the solution after concentrated or dilution, the material that can also use methods such as using again precipitation to take out in solid (powder) mode.Especially when this polymerization, as solvent, use the solvent identical with solvent described later (E), can directly use reacted solution thus, and can simplify manufacturing process.
In resin (A-2), with respect to the total molal quantity that forms the entire infrastructure unit of resin (A-2), the ratio that is derived from the structural unit of each monomer is preferably following scope.
Be derived from the structural unit of (a): 2～40 % by mole, more preferably 5～35 % by mole.
Be derived from the structural unit of (b): 2～95 % by mole, more preferably 5～80 % by mole.
Be derived from the structural unit of (c): 1～65 % by mole, more preferably 1～60 % by mole.
The ratio of the structural unit of resin (A-2) is above-mentioned scope if, has storage stability, developability, solvent resistance, thermotolerance and physical strength to become good tendency.
As resin (A-2), preferably (b) is the resin of (b1), and more preferably (b) is the resin of (b1-2).
Resin (A-2) can utilize the method same with resin (A-1) to manufacture.
In resin (A-3), with respect to the total molal quantity that forms the entire infrastructure unit of resin (A-3), be derived from the ratio of the structural unit of each monomer, be preferably following scope.
Be derived from the structural unit of (a): 2～40 % by mole, more preferably 5～35 % by mole.
Be derived from the structural unit of (c): 60～98 % by mole, more preferably 65～95 % by mole.
The structural unit ratio of resin (A-3) is above-mentioned scope if, has storage stability, developability and solvent resistance to become good tendency.
Resin (A-3) can utilize the method same with resin (A-1) to manufacture.
Resin (A-4) and resin (A-5) can be manufactured through the operation of for example two-stage.Now, can manufacture with reference to above-mentioned document < < Polymer Synthesizing experimental method > > (the experiment 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 the people) method of recording, the method that TOHKEMY 2001-89533 communique is recorded etc.
About resin (A-4), first, as the first stage, same with the manufacture method of above-mentioned resin (A-1), obtain (a) and multipolymer (c).
Now, with above-mentioned same, the multipolymer obtaining can be directly to use reacted solution, also can use the solution after concentrated or dilution, can also use the material taking out in solid (powder) mode by the method for precipitation again etc.
With respect to the total molal quantity of the entire infrastructure unit of aforesaid formation multipolymer, be derived from the ratio of (a) and structural unit (c), be preferably following scope.
(a) structural unit being derived from: 5～50 % by mole, more preferably 10～45 % by mole.
(c) structural unit being derived from: 50～95 % by mole, more preferably 55～90 % by mole.
Then,, as subordinate phase, the carboxylic acid of (a) that is derived from multipolymer and the part for carboxylic acid anhydrides that obtain are reacted with the cyclic ether of (b).The reactivity high, unreacted (b) of cyclic ether is difficult to residual, therefore as (b) preferred (b1), further preferred (b1-1).
Particularly, then above-mentioned, can from nitrogen replacement, be air by atmosphere in flask, molal quantity with respect to (a) is (b) of 5～80 % by mole, with respect to (a), (b) and total amount (c), is 0.001～5 carboxyl of quality % and the catalysts of cyclic ether (such as three (dimethylaminomethyl) phenol etc.) and with respect to (a), (b) and total amount (c), is 0.001～5 quality % polymerization inhibitor (such as quinhydrones etc.) is put into flask, at 60～130 ℃, make its reaction 1～10 hour, obtain resin (A-4).It should be noted that, same with polymerizing condition, consider thermal discharge due to manufacturing equipment and polymerization etc., can suitably adjust input method, temperature of reaction.
In addition, now, with respect to the molal quantity of (a), molal quantity (b) is preferably made as 10～75 % by mole, more preferably 15～70 % by mole.By making the molal quantity of (b), be this scope, have storage stability, solvent resistance and stable on heating balance to become good tendency.
Concrete example as resin (A-4), the multipolymer that can list (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid benzyl ester reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid cyclohexyl ester reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, (methyl) acrylic acid/cinnamic multipolymer reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of (methyl) acrylic acid/(methyl) methyl acrylate reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of (methyl) acrylic acid/N-N-cyclohexylmaleimide reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid benzyl ester reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid cyclohexyl ester reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters/cinnamic multipolymer reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) methyl acrylate reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters/N-N-cyclohexylmaleimide reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of crotonic acid/(methyl) acrylic acid two cyclopentyl esters reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains,
The multipolymer of crotonic acid/(methyl) acrylic acid benzyl ester reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of crotonic acid/(methyl) acrylic acid cyclohexyl ester reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, crotonic acid/cinnamic multipolymer reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of crotonic acid/ethyl crotonate reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of crotonic acid/N-N-cyclohexylmaleimide reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of crotonic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid benzyl ester reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of crotonic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid cyclohexyl ester reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, crotonic acid/(methyl) acrylic acid two cyclopentyl esters/cinnamic multipolymer reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of crotonic acid/(methyl) acrylic acid two cyclopentyl esters/ethyl crotonate reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of crotonic acid/(methyl) acrylic acid two cyclopentyl esters/N-N-cyclohexylmaleimide reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains,
The multipolymer of maleic acid/(methyl) acrylic acid two cyclopentyl esters reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of maleic acid/(methyl) acrylic acid benzyl ester reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of maleic acid/(methyl) acrylic acid cyclohexyl ester reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, maleic acid/cinnamic multipolymer reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of maleic acid/maleic acid methyl esters reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of maleic acid/N-N-cyclohexylmaleimide reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of maleic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid benzyl ester reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of maleic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid cyclohexyl ester reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, maleic acid/(methyl) acrylic acid two cyclopentyl esters/cinnamic multipolymer reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of maleic acid/(methyl) acrylic acid two cyclopentyl esters/maleic acid methyl esters reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of maleic acid/(methyl) acrylic acid two cyclopentyl esters/N-N-cyclohexylmaleimide reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains,
The multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid benzyl ester reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid cyclohexyl ester reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, (methyl) acrylic acid/maleic anhydride/cinnamic multipolymer reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) methyl acrylate reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of (methyl) acrylic acid/maleic anhydride/N-N-cyclohexylmaleimide reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid benzyl ester reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid cyclohexyl ester reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters/cinnamic multipolymer reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters/(methyl) methyl acrylate reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains, the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters/N-N-cyclohexylmaleimide reacts with (methyl) acrylic acid glycidyl esters and the resin that obtains,
The multipolymer and 3 of (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of (methyl) acrylic acid/(methyl) acrylic acid benzyl ester, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of (methyl) acrylic acid/(methyl) acrylic acid cyclohexyl ester, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, (methyl) acrylic acid/cinnamic multipolymer and 3, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of (methyl) acrylic acid/(methyl) methyl acrylate, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of (methyl) acrylic acid/N-N-cyclohexylmaleimide, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid benzyl ester, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid cyclohexyl ester, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters/cinnamic multipolymer and 3, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) methyl acrylate, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters/N-N-cyclohexylmaleimide, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains,
The multipolymer and 3 of crotonic acid/(methyl) acrylic acid two cyclopentyl esters, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of crotonic acid/(methyl) acrylic acid benzyl ester, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of crotonic acid/(methyl) acrylic acid cyclohexyl ester, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, crotonic acid/cinnamic multipolymer and 3, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer of crotonic acid/ethyl crotonate and 3, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of crotonic acid/N-N-cyclohexylmaleimide, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of crotonic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid benzyl ester, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of crotonic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid cyclohexyl ester, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, crotonic acid/(methyl) acrylic acid two cyclopentyl esters/cinnamic multipolymer and 3, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of crotonic acid/(methyl) acrylic acid two cyclopentyl esters/ethyl crotonate, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of crotonic acid/(methyl) acrylic acid two cyclopentyl esters/N-N-cyclohexylmaleimide, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains,
The multipolymer and 3 of maleic acid/(methyl) acrylic acid two cyclopentyl esters, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of maleic acid/(methyl) acrylic acid benzyl ester, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of maleic acid/(methyl) acrylic acid cyclohexyl ester, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, maleic acid/cinnamic multipolymer and 3, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of maleic acid/maleic acid methyl esters, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of maleic acid/N-N-cyclohexylmaleimide, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of maleic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid benzyl ester, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of maleic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid cyclohexyl ester, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, maleic acid/(methyl) acrylic acid two cyclopentyl esters/cinnamic multipolymer and 3, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of maleic acid/(methyl) acrylic acid two cyclopentyl esters/maleic acid methyl esters, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of maleic acid/(methyl) acrylic acid two cyclopentyl esters/N-N-cyclohexylmaleimide, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains,
The multipolymer and 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid benzyl ester, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid cyclohexyl ester, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, (methyl) acrylic acid/maleic anhydride/cinnamic multipolymer and 3, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of (methyl) acrylic acid/maleic anhydride/(methyl) methyl acrylate, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of (methyl) acrylic acid/maleic anhydride/N-N-cyclohexylmaleimide, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid benzyl ester, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid cyclohexyl ester, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters/cinnamic multipolymer and 3, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters/(methyl) methyl acrylate, 4-epoxycyclohexyl methyl acrylate reactions and the resin that obtains, the multipolymer and 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters/N-N-cyclohexylmaleimide, 4-epoxycyclohexyl methyl acrylate reactions and resin of obtaining etc.
About resin (A-5), as the first stage, same with the manufacture method of above-mentioned resin (A-1), obtain (b) and multipolymer (c).
Now, with above-mentioned same, the multipolymer obtaining can directly be used reacted solution, also can use the solution after concentrated or dilution, the material that can also use methods such as using again precipitation to take out with solid (powder) form.
Be derived from the ratio of (b) and structural unit (c), the total molal quantity with respect to forming the entire infrastructure unit of aforesaid multipolymer, is preferably following scope.
Be derived from the structural unit of (b): 5～95 % by mole, more preferably 10～90 % by mole.
Be derived from the structural unit of (c): 5～95 % by mole, more preferably 10～90 % by mole.
And then same with the manufacture method of resin (A-4), the carboxylic acid having with (a) by the cyclic ether that is derived from (b) making in the multipolymer of (b) and (c) or carboxylic acid anhydrides react and obtain.Utilize the hydroxyl that cyclic ether is produced with reacting of carboxylic acid or carboxylic acid anhydrides further to react with carboxylic acid anhydrides.
The use amount of (a) of aforesaid and copolymer reaction, is preferably 5～80 % by mole with respect to the molal quantity of (b).The reactivity high, unreacted (b) of cyclic ether is difficult to residual, therefore as (b) preferred (b1), further preferred (b1-1).
Concrete example as resin (A-5), the multipolymer that can list (methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and the resin that obtains, the multipolymer of (methyl) acrylic acid benzyl ester/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and the resin that obtains, the multipolymer of (methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and the resin that obtains, the multipolymer of styrene/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and the resin that obtains, the multipolymer of (methyl) methyl acrylate/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and the resin that obtains, the multipolymer of N-N-cyclohexylmaleimide/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and the resin that obtains, the multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid benzyl ester/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and the resin that obtains, the multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and the resin that obtains, the multipolymer of (methyl) acrylic acid two cyclopentyl esters/styrene/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and the resin that obtains, the multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) methyl acrylate/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and the resin that obtains, the multipolymer of (methyl) acrylic acid two cyclopentyl esters/N-N-cyclohexylmaleimide/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and the resin that obtains,
The multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid glycidyl esters reacts with crotonic acid and the resin that obtains, the multipolymer of (methyl) acrylic acid benzyl ester/(methyl) acrylic acid glycidyl esters reacts with crotonic acid and the resin that obtains, the multipolymer of (methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid glycidyl esters reacts with crotonic acid and the resin that obtains, the multipolymer of styrene/(methyl) acrylic acid glycidyl esters reacts with crotonic acid and the resin that obtains, the multipolymer of ethyl crotonate/(methyl) acrylic acid glycidyl esters reacts with crotonic acid and the resin that obtains, the multipolymer of N-N-cyclohexylmaleimide/(methyl) acrylic acid glycidyl esters reacts with crotonic acid and the resin that obtains, the multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid benzyl ester/(methyl) acrylic acid glycidyl esters reacts with crotonic acid and the resin that obtains, the multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid glycidyl esters reacts with crotonic acid and the resin that obtains, the multipolymer of (methyl) acrylic acid two cyclopentyl esters/styrene/(methyl) acrylic acid glycidyl esters reacts with crotonic acid and the resin that obtains, the multipolymer of (methyl) acrylic acid two cyclopentyl esters/ethyl crotonate/(methyl) acrylic acid glycidyl esters reacts with crotonic acid and the resin that obtains, the multipolymer of (methyl) acrylic acid two cyclopentyl esters/N-N-cyclohexylmaleimide/(methyl) acrylic acid glycidyl esters reacts with crotonic acid and the resin that obtains,
The multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid glycidyl esters reacts with maleic acid and the resin that obtains, the multipolymer of (methyl) acrylic acid benzyl ester/(methyl) acrylic acid glycidyl esters reacts with maleic acid and the resin that obtains, the multipolymer of (methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid glycidyl esters reacts with maleic acid and the resin that obtains, the multipolymer of styrene/(methyl) acrylic acid glycidyl esters reacts with maleic acid and the resin that obtains, the multipolymer of maleic acid methyl esters/(methyl) acrylic acid glycidyl esters reacts with maleic acid and the resin that obtains, the multipolymer of N-N-cyclohexylmaleimide/(methyl) acrylic acid glycidyl esters reacts with maleic acid and the resin that obtains, the multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid benzyl ester/(methyl) acrylic acid glycidyl esters reacts with maleic acid and the resin that obtains, the multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid glycidyl esters reacts with maleic acid and the resin that obtains, the multipolymer of (methyl) acrylic acid two cyclopentyl esters/styrene/(methyl) acrylic acid glycidyl esters reacts with maleic acid and the resin that obtains, the multipolymer of (methyl) acrylic acid two cyclopentyl esters/maleic acid methyl esters/(methyl) acrylic acid glycidyl esters reacts with maleic acid and the resin that obtains, the multipolymer of (methyl) acrylic acid two cyclopentyl esters/N-N-cyclohexylmaleimide/(methyl) acrylic acid glycidyl esters reacts with maleic acid and the resin that obtains,
The multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains, the multipolymer of (methyl) acrylic acid benzyl ester/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains, the multipolymer of (methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains, the multipolymer of styrene/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains, the multipolymer of (methyl) methyl acrylate/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains, the multipolymer of N-N-cyclohexylmaleimide/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains, the multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid benzyl ester/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains, the multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains, the multipolymer of (methyl) acrylic acid two cyclopentyl esters/styrene/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains, the multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) methyl acrylate/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains, the multipolymer of (methyl) acrylic acid two cyclopentyl esters/N-N-cyclohexylmaleimide/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains,
(methyl) acrylic acid two cyclopentyl ester/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with (methyl) acrylic acid and the resin that obtains, (methyl) acrylic acid benzyl ester/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with (methyl) acrylic acid and the resin that obtains, (methyl) acrylic acid cyclohexyl ester/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with (methyl) acrylic acid and the resin that obtains, styrene/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with (methyl) acrylic acid and the resin that obtains, (methyl) methyl acrylate/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with (methyl) acrylic acid and the resin that obtains, N-N-cyclohexylmaleimide/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with (methyl) acrylic acid and the resin that obtains, (methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid benzyl ester/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with (methyl) acrylic acid and the resin that obtains, (methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid cyclohexyl ester/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with (methyl) acrylic acid and the resin that obtains, (methyl) acrylic acid two cyclopentyl esters/styrene/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with (methyl) acrylic acid and the resin that obtains, (methyl) acrylic acid two cyclopentyl esters/(methyl) methyl acrylate/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with (methyl) acrylic acid and the resin that obtains, (methyl) acrylic acid two cyclopentyl esters/N-N-cyclohexylmaleimide/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with (methyl) acrylic acid and the resin that obtains,
(methyl) acrylic acid two cyclopentyl ester/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with crotonic acid and the resin that obtains, (methyl) acrylic acid benzyl ester/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with crotonic acid and the resin that obtains, (methyl) acrylic acid cyclohexyl ester/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with crotonic acid and the resin that obtains, styrene/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with crotonic acid and the resin that obtains, ethyl crotonate/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with crotonic acid and the resin that obtains, N-N-cyclohexylmaleimide/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with crotonic acid and the resin that obtains, (methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid benzyl ester/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with crotonic acid and the resin that obtains, (methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid cyclohexyl ester/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with crotonic acid and the resin that obtains, (methyl) acrylic acid two cyclopentyl esters/styrene/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with crotonic acid and the resin that obtains, (methyl) acrylic acid two cyclopentyl esters/ethyl crotonate/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with crotonic acid and the resin that obtains, (methyl) acrylic acid two cyclopentyl esters/N-N-cyclohexylmaleimide/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with crotonic acid and the resin that obtains,
(methyl) acrylic acid two cyclopentyl ester/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with maleic acid and the resin that obtains, (methyl) acrylic acid benzyl ester/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with maleic acid and the resin that obtains, (methyl) acrylic acid cyclohexyl ester/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with maleic acid and the resin that obtains, styrene/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with maleic acid and the resin that obtains, maleic acid methyl esters/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with maleic acid and the resin that obtains, N-N-cyclohexylmaleimide/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with maleic acid and the resin that obtains, (methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid benzyl ester/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with maleic acid and the resin that obtains, (methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid cyclohexyl ester/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with maleic acid and the resin that obtains, (methyl) acrylic acid two cyclopentyl esters/styrene/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with maleic acid and the resin that obtains, (methyl) acrylic acid two cyclopentyl esters/maleic acid methyl esters/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with maleic acid and the resin that obtains, (methyl) acrylic acid two cyclopentyl esters/N-N-cyclohexylmaleimide/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with maleic acid and the resin that obtains,
(methyl) acrylic acid two cyclopentyl ester/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains, (methyl) acrylic acid benzyl ester/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains, (methyl) acrylic acid cyclohexyl ester/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains, styrene/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains, (methyl) methyl acrylate/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains, N-N-cyclohexylmaleimide/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains, (methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid benzyl ester/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains, (methyl) acrylic acid two cyclopentyl esters/(methyl) acrylic acid cyclohexyl ester/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains, (methyl) acrylic acid two cyclopentyl esters/styrene/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains, (methyl) acrylic acid two cyclopentyl esters/(methyl) methyl acrylate/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains, (methyl) acrylic acid two cyclopentyl esters/N-N-cyclohexylmaleimide/3, the multipolymer of 4-epoxycyclohexyl methyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and resin of obtaining etc.
The weight-average molecular weight of the polystyrene conversion of resin (A) is preferably 3,000～100, and 000, more preferably 5,000～50,000.The weight-average molecular weight of resin (A) in aforesaid scope, has coating to become good tendency if, and when being difficult to produce film while developing in addition and reducing and develop, the property pulled out of non-exposure portion becomes good tendency.
The molecular weight distribution of resin (A) [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] is preferably 1.1～6.0, and more preferably 1.2～4.0.Molecular weight distribution in aforesaid scope, has the tendency of developability excellence if.
The acid number of resin (A) is preferably 20～180mg-KOH/g, more preferably 50～170mg-KOH/g, be particularly preferably 70～160mg-KOH/g.Herein acid number be with in and the value measured of the mode of the amount (mg) of the needed potassium hydroxide of resin (A) 1g, can obtain by using potassium hydroxide aqueous solution carry out titration.
The content of the resin in photosensitive polymer combination of the present invention (A), with respect to the solid constituent of photosensitive polymer combination, preferably 10～90 quality %, more preferably 20～80 quality %.Here, the solid constituent in this instructions refers to the total amount except the composition desolventizing from photosensitive polymer combination.
In addition, with respect to the total amount of resin (A) and polymerizable compound described later, the content of resin (A) is preferably 10～90 quality %, more preferably 20～80 quality %.If the content of resin (A) is aforesaid scope, there is the solvent resistance of the pattern after developability, adaptation, sclerosis to become good tendency, therefore preferably.
Photosensitive polymer combination of the present invention comprises the polymerizable compound (B) shown in formula (I).
The R stipulating in X as formula (1) 5in the alkylidene of carbon number 1～5, can list methylene, ethylidene, trimethylene, tetramethylene, pentamethylene, propylidene, ethyl ethylidene, 1,2-dimethyl ethylidene, 1,1-dimethyl ethylidene, 2,2-dimethyl ethylidene etc.
As the alkylidene with the carbon number 1～3 of hydroxyl, can list-C (OH) H-,-C (OH) HCH 2-,-CH 2c (OH) H-,-C (OH) HC (OH) H-,-C (OH) HCH 2cH 2-,-CH 2c (OH) HCH 2-,-CH 2cH 2c (OH) H-,-C (OH) HC (OH) HCH 2-,-C (OH) HCH 2c (OH) H-,-CH 2c (OH) HC (OH) H-,-CH 2c (OH) 2cH 2-and-C (OH) HC (OH) HC (OH) H-etc.
As the alkyl in the Y of formula (1), can list methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, octyl group, dodecyl etc.
R in formula (1) 1, R 2and R 3be preferably hydrogen atom.
R 5be preferably singly-bound.R 6be preferably the alkylidene of the carbon number 2～3 with hydroxyl, more preferably there is the alkylidene of the carbon number 3 of hydroxyl.
Y is preferably hydrogen atom, hydroxyl, more preferably hydrogen atom.
The concrete example of polymerizable compound (B) is listed below.
Figure BDA0000374015210000241
Figure BDA0000374015210000251
Figure BDA0000374015210000261
Wherein, preferred following compound.
Figure BDA0000374015210000271
These polymerizable compounds (B) can be used commercially available product, also can be synthetic by corresponding raw material.
The photosensitive polymer combination that comprises these polymerizable compounds (B) by use can form pattern thus at low temperature, and can obtaining developing, spot reduces and the pattern of adaptation and thickness conservation rate excellence.
Photosensitive polymer combination of the present invention can also comprise the polymerizable compound (being sometimes also recited as below " polymerizable compound (B2) ") beyond the polymerizable compound shown in formula (I).As described polymerizable compound (B2), can list the polyfunctional monomer that monofunctional monomer, 2 functional monomers, 3 officials can be above.
As the concrete example of monofunctional monomer, can list nonyl phenyl carbitol acrylate, 2-hydroxyl-3-phenoxy propyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxy ethyl methacrylate, NVP etc.
Concrete example as 2 functional monomers, can list two (acryloxy ethyl) ethers, 3-methylpentane glycol two (methyl) acrylate of 1,6-hexane diol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, bisphenol-A etc.
The concrete example of polyfunctional monomer that can be above as 3 officials, can list the reactant etc. of reactant, dipentaerythritol five (methyl) acrylate and the acid anhydrides of trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, pentaerythrite three (methyl) acrylate and acid anhydrides.Wherein, preferably use the polyfunctional monomer that 3 officials can be above.These polymerizable compounds can be used separately and also can be used together more than two kinds.
With respect to the solid constituent of photosensitive polymer combination, the total content of above-mentioned polymerizable compound (B) and polymerizable compound (B2) is preferably 5～50 quality %, more preferably 10～45 quality %.Aforesaid scope if, figuratum intensity, solvent resistance, mechanical property become good tendency.
The contained Photoepolymerizationinitiater initiater (C) of photosensitive polymer combination of the present invention preferably has the part-structure shown in aforesaid formula (II).By using described Photoepolymerizationinitiater initiater, photosensitive polymer combination becomes high sensitivity, use in addition the film resolution of its formation and solvent resistance excellent, and pattern becomes good.And then, by and with photopolymerization, cause auxiliary agent (C-1), the photosensitive polymer combination obtaining thus further becomes high sensitivity, the throughput rate while using it to form colored filter improves, therefore preferably.
Concrete example as Photoepolymerizationinitiater initiater (C); can list N-benzoyl Oxy-1-(4-phenyl sulfenyl (ス Le Off ア ニ Le) phenyl) butane-1-ketone-2-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-card azoles-3-yl] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-{2-methyl-4-(3; 3-dimethyl-2,4-dioxa cyclopentyl-methyl oxygen base) benzoyl }-9H-carbazole-3-yl] ethane-1-imines etc.Also can use the commercially available product of Irgacure (registered trademark) OXE-01, OXE-02 (more than, BASF JAPAN company system), N-1919 (ADEKA society system) etc.Wherein, preferably use N-benzoyl Oxy-1-(4-phenyl sulfenyl phenyl) octane-1-ketone-2-imines (following formula).
Figure BDA0000374015210000281
In addition; so long as do not damage the degree of effect of the present invention; can also and with normally used Photoepolymerizationinitiater initiater in this field etc., for example can list the Photoepolymerizationinitiater initiaters such as di-imidazolium compounds, alkyl phenones compound, triaizine compounds, acylphosphine oxide compound.
More specifically, can list the compound of the following stated, can use separately respectively these, or combine two or more use.
As aforesaid di-imidazolium compounds, can list 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl di-imidazoles, 2,2 '-bis-(2,3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl di-imidazoles is (such as with reference to JPH06-75372-A, JPH06-75373-A etc.), 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl di-imidazoles, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetra-(alkoxyl phenyl) di-imidazoles, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetra-(dialkoxy phenyl) di-imidazoles, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetra-(tri-alkoxy phenyl) di-imidazoles is (such as with reference to JPS48-38403-B, JPS62-174204-A etc.), the imidazolium compounds that replaced by carbonyl alkoxy of phenyl of 4,4 ', 5,5 '-position is (for example,, with reference to JPH07-10913-A etc.) etc.Preferably can list 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl di-imidazoles, 2,2 '-bis-(2,3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl di-imidazoles, 2,2 '-bis-(2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl di-imidazoles.
As aforesaid alkyl phenones compound, can list diethoxy acetophenone, 2-methyl-2-morpholino-1-(4-methyl sulfenyl phenyl) propane-1-ketone, 2-dimethylamino-1-(4-morpholino phenyl)-2-benzyl butane-1-ketone, 2-dimethylamino-1-(4-morpholino phenyl)-2-(4-aminomethyl phenyl methyl) butane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzil dimethyl ketal, 2-hydroxy-2-methyl-1-(4-(2-hydroxyl-oxethyl) phenyl) propane-1-ketone, 1-hydroxycyclohexylphenylketone, the oligomer of 2-hydroxy-2-methyl-1-(4-isopropenyl phenyl) propane-1-ketone etc., preferably can list 2-methyl-2-morpholino-1-(4-methyl sulfenyl phenyl) propane-1-ketone, 2-dimethylamino-1-(4-morpholino phenyl)-2-benzyl butane-1-ketone etc.Can also use the commercially available product of Irgacure (registered trademark) 369,907 (more than, BASF JAPAN company system) etc.
As aforesaid triaizine compounds, can list 2, two (the trichloromethyl)-6-(4-methoxyphenyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl naphthyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-of 4-piperonyl-1, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(2-(5-methylfuran-2-yl) vinyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(2-(furans-2-yl) vinyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(2-(4-diethylamino-2-aminomethyl phenyl) vinyl)-1 of 4-, 3, 5-triazine, 2, (2-(3 for two (the trichloromethyl)-6-of 4-, 4-Dimethoxyphenyl) vinyl)-1, 3, 5-triazine etc.
As aforesaid acylphosphine oxide initiating agent, can list 2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc.Can use the commercially available product of Irgacure (registered trademark) 819 (BASF JAPAN company system) etc.
And then, as polymerization initiator, can list the benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether, benzoin isobutyl ether; Benzophenone, o-benzoyl base benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 3,3 ', 4,4 '-tetra-(t-butyl peroxy carbonyl) benzophenone, 2, the benzophenone cpds such as 4,6-tri-methyl benzophenone; The naphtoquinone compounds such as 9,10-phenanthrenequione, 2-EAQ, camphorquinone; 1O-butyl-2-chloro-acridine ketone, benzil, phenyl glyoxalic acid methylester, two cyclopentadiene titanium compounds etc.
Preferably these are used in combination with polymerization described later initiation auxiliary agent (C-1) (especially amine).
Polymerization causes auxiliary agent (C-1) and is used in combination with polymerization initiator, the polymerization of the polymerizable compound obtaining in order to promote to utilize polymerization initiator initiated polymerization and the compound or the sensitizer that use.
As polymerization, cause auxiliary agent (C-1), can list amines, thiazolinium compounds, alkoxy anthracene compound, thioxanthones compound, carboxylic acid compound etc.
As amines, can list triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylamino benzoic acid methyl ester, 4-dimethylamino ethyl benzoate, 4-dimethylamino benzoic acid isopentyl ester, benzoic acid 2-dimethylamino ethyl ester, 4-dimethylamino benzoic acid 2-Octyl Nitrite, N, N-dimethyl-p-toluidine, 4, 4 '-bis-(dimethylamino) benzophenone (common name Michler's keton), 4, 4 '-bis-(diethylamino) benzophenone, 4, 4 '-bis-(ethylmethylamino) benzophenone etc., wherein, preferably 4, 4 '-bis-(diethylamino) benzophenone.Can use the commercially available products such as EAB-F (hodogaya chemical industry (strain) system).
As thiazolinium compounds, can list the compound shown in formula (V-1)～formula (V-3) etc.
Figure BDA0000374015210000311
As alkoxy anthracene compound, can list 9,10-dimethoxy anthracene, EDMO, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene, 9,10-dibutoxy anthracene, 2-ethyl-9,10-dibutoxy anthracene etc.
As thioxanthones compound, can list ITX, ITX, 2,4-diethyl thioxanthone, 2,4-bis-clopenthixal ketones, the chloro-4-propoxyl group of 1-thioxanthones etc.
As carboxylic acid compound, can list phenyl ethyl thioglycollic acid, aminomethyl phenyl ethyl thioglycollic acid, ethylphenyl ethyl thioglycollic acid, Methylethyl phenyl ethyl thioglycollic acid, 3,5-dimethylphenyl ethyl thioglycollic acid, methoxyphenyl ethyl thioglycollic acid, Dimethoxyphenyl ethyl thioglycollic acid, chlorphenyl ethyl thioglycollic acid, dichlorophenyl ethyl thioglycollic acid, N-phenylglycine, phenoxyacetic acid, naphthyl ethyl thioglycollic acid, N-naphthyl glycocoll, naphthoxy acetic acid etc.
Total amount 100 mass parts with respect to resin (A) and polymerizable compound (total of polymerizable compound (B) and polymerizable compound (B2)), the content of Photoepolymerizationinitiater initiater (C) is preferably 0.1～80 mass parts, more preferably 1～60 mass parts.
In addition, with respect to the solid constituent of photosensitive polymer combination, the content of Photoepolymerizationinitiater initiater (C) is preferably 0.1～45 quality %, more preferably 1～40 quality %.
If the total amount of Photoepolymerizationinitiater initiater is this scope, have and can form pattern with high sensitivity, and the resistance to chemical reagents of pattern, physical strength, surface smoothness becomes good tendency.
Use polymerization to cause in the situation of auxiliary agent (C-1), its use amount, with respect to total amount 100 mass parts of resin (A) and Photoepolymerizationinitiater initiater (C), is preferably 0.01～50 mass parts, more preferably 0.1～40 mass parts.In addition, with respect to 1 mole of Photoepolymerizationinitiater initiater, be preferably 0.01～10 mole, more preferably 0.01～5 mole.If it is this scope that polymerization causes the amount of auxiliary agent (C-1), has and can form with high sensitivity the tendency of the throughput rate raising of pattern and pattern.
Photosensitive polymer combination of the present invention preferably also comprises colorant (D).As described colorant (D), can list pigment and dyestuff, from thermotolerance, sunproof viewpoint, consider, preferably comprise pigment.
As pigment, can list organic pigment and inorganic pigment, can list the compound that is classified as pigment in color index (The Society of Dyers and Colourists publication).
As organic pigment, particularly, can list such as yellow uitramarines such as C.I. pigment yellows 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,137,138,139,147,148,150,153,154,166,173,194,214;
C.I. pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65,71, the orange pigments such as 73;
C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,209,215,216,224,242,254,255,264, the red pigments such as 265;
C.I. pigment blue 15,15:3,15:4,15:6, the blue pigments such as 60; C.I. pigment violet 1,19,23,29,32,36, the violet pigments such as 38;
C.I. pigment Green 7,36, the viridine greens such as 58;
C.I. the brown pigments such as bistre 23,25;
C.I. black pigment such as pigment black 1,7 etc.
Wherein, preferred C.I. pigment yellow 13 8,139,150, C.I. paratonere 177,242,254, C.I. pigment Violet 23, C.I. pigment blue 15: 3,15:6 and C.I. pigment Green 7,36,58, more preferably naphthol green 58 or paratonere 242.These pigment can be used separately or mix two or more use.
Aforementioned pigment as required, can also implement that rosin processes, used the surface treatment, the grafting to surface of pigments based on macromolecular compound etc. that have imported the pigment derivative of acidic-group or basic group or pigment dispersing agent etc. to process, the micronize based on sulfuric acid micronize method etc. is processed or for remove impurity the carrying out washing treatment based on organic solvent or water etc., based on ionic impurity from son, hand over Change method etc. remove processing etc.In addition, to be preferably particle diameter even for pigment.By making it contain pigment dispersing agent, carry out dispersion treatment, can access thus the dispersible pigment dispersion of pigment homodisperse state in solution.
As aforementioned pigment dispersing agent, can use commercially available surfactant, for example, the surfactants such as silicone-based, fluorine system, ester system, kation system, negative ion system, nonionic system, both sexes, polyester system, polyamine system, acrylic acid series etc.As aforementioned surfactants, can list polyethylene oxide alkyl ethers class, polyoxyethylene alkyl phenyl ethers, polyethylene glycol di class, sorbitan fatty acid ester class, fatty acid modified polyesters, tertiary amine modified polyurethane, polyethylene imine based class etc., in addition, also can exemplify out commodity KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system), Floren by name (common prosperity society chemistry (strain) system), Solsperse (Zeneca (strain) system), EFKA (BASF society system), Ajisper (aginomoto Fine Techno (strain) system), Disperbyk (Byk Chemie society system) etc.These can be used alone or in combination of two or more kinds respectively.
Use in the situation of pigment dispersing agent, its use amount, with respect to pigment, is preferably below 100 quality %, more preferably 5～50 quality %.If the use amount of pigment dispersing agent is aforesaid scope, there is the tendency of the dispersible pigment dispersion that obtains homogeneously dispersed state.
As colorant (D), be not particularly limited, can use known dyestuff, can list such as oil-soluble dyes, acid dyes etc.
These dyestuffs can be according to the solubleness in solvent or the fast light fadedness during pattern while using the photosensitive composition comprise this dyestuff to form colored filter, spectrophotometric spectra and suitably select.
With respect to the solid constituent of photosensitive polymer combination, the content of colorant (D) is preferably 5～60 quality %, more preferably 5～45 quality %.If the content of colorant (D) is aforesaid scope, the light splitting that can obtain wanting or colour saturation.
Photosensitive polymer combination of the present invention preferably comprises solvent (E).Solvent (E) is not particularly limited.Can use at the normally used solvent in this field.Choice for use for example, ketone solvent (solvent of comprise-CO-) beyond ether solvents (solvent of comprise-O-) that, can be beyond ester solvent (solvent of comprise-COO-), ester solvent, ether-ether solvent (comprise-COO-and-solvent of O-), ester solvent, alcoholic solvent, aromatic hydrocarbon solvents, amide solvent, dimethyl sulfoxide etc.These solvents can be used separately, also can combine two or more use.
As ester solvent, can list methyl lactate, ethyl lactate, butyl lactate, 2-hydroxyl isobutyl alkanoic acid methyl esters, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, adnoral acetate, gamma-butyrolacton etc.
As ether solvents, can list ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol list propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol single-butyl ether, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list propyl ether, propylene glycol single-butyl ether, 3-methoxyl-n-butyl alcohol, 3-methoxyl-3-methyl butanol, tetrahydrofuran, oxinane, 1, 4-diox, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ethers, methyl phenyl ethers anisole, phenetol, methylanisole etc.
As ether-ether solvent, can list methoxy menthyl acetate, methoxyacetic acid ethyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 2-methoxy methyl propionate, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, 2-ethoxyl ethyl propionate, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester, 3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butylacetic acid ester, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, propylene glycol list propyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, TC acetic acid esters, diethylene glycol single-butyl ether acetic acid esters etc.
As ketone solvent, can list 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-HEPTANONE, 3-heptanone, 4-heptanone, 4-methyl-2 pentanone, cyclopentanone, cyclohexanone, isophorone etc.
As alcoholic solvent, can list methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerine etc.
As aromatic hydrocarbon solvents, can list benzene,toluene,xylene, trimethylbenzene etc.
As amide solvent, can list DMF, N, N-dimethyl acetyl amide, 1-METHYLPYRROLIDONE etc.
In above-mentioned solvent, from the viewpoint of coating, drying property, preferably the boiling point under 1atm is 120 ℃ of above and 180 ℃ of following organic solvents, wherein, and more preferably propylene glycol monomethyl ether and propylene glycol monomethyl ether.
With respect to photosensitive polymer combination, the content of solvent (E) is preferably 60～95 quality %, more preferably 70～90 quality %.In other words, the solid constituent of photosensitive polymer combination is preferably 5～40 quality %, more preferably 10～30 quality %.If the content of solvent (E) is aforesaid scope, the flatness while having coating becomes good tendency.
Photosensitive polymer combination of the present invention can also contain surfactant.As surfactant, for example, can to list silicone-based surfactant, fluorine be surfactant, have the silicone-based surfactant of fluorine atom etc.By containing surfactant, the flatness while having coating becomes good tendency.
As silicon, be surfactant, can list the surfactant with siloxane bond.
Particularly, can list Toraysilicone DC3PA, Toraysilicone SH7PA, Toraysilicone DC11PA, Toraysilicone SH21PA, Toraysilicone SH28PA, Toraysilicone SH29PA, Toraysilicone SH30PA, polyether modified silicon oil SH8400 (trade name: Dow Corning Toray Co., Ltd. make), 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 (Momentive Performance Materials Janpan Japan contract commercial firm system) etc.
As fluorine, be surfactant, can list the surfactant with fluorocarbon chain.
Particularly, can list Florado (registered trademark) FC430, Florado FC431 (Sumitomo 3M (strain) system), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac R30 (DIC (strain) system), FTOP (registered trademark) EF301, FTOP EF303, FTOP EF351, FTOP EF352 (Mitsubishi's material electronics changes into (strain) system), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass (strain) system), E5844 ((strain) DAIKIN FINE CHEMICAL institute system) etc.
As the silicon with fluorine atom, be surfactant, can list the surfactant with siloxane bond and fluorocarbon chain.Particularly, can list Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, Megafac F443 (DIC (strain) system) etc.Preferably can list Megafac (registered trademark) F475.
With respect to photosensitive polymer combination, surfactant is preferably below the above 0.2 quality % of 0.001 quality %, more preferably below the above 0.1 quality % of 0.002 quality %, more preferably below the above 0.05 quality % of 0.01 quality %.By containing surfactant in this scope, can make thus the flatness of filming good.
Photosensitive polymer combination of the present invention can be according to containing the various adjuvants such as filling agent, other macromolecular compound, closely sealed promoter, antioxidant, ultraviolet light absorber, light stabilizer, chain-transferring agent.
Photosensitive polymer combination of the present invention under the existence of colorant (D), solvent (E) or other composition, obtains by hybrid resin (A), polymerizable compound (B) and Photoepolymerizationinitiater initiater (C) as required.
In addition, in the situation that mix the pigment as colorant (D), preference is as standby according to following sequential system.
First, pigment is mixed with solvent (E) in advance, use ball mill that it is disperseed, until the mean grain size of pigment is left and right below 0.2 μ m.Now, can coordinate as required part or all of pigment dispersing agent, resin (A).Can add remainder, polymerizable compound (B) and the Photoepolymerizationinitiater initiater (C) etc. of resin (A), other compositions of use as required, the solvent further appending as required to concentration according to the rules in the dispersible pigment dispersion obtaining, and obtain photosensitive polymer combination.
As photosensitive polymer combination of the present invention to the coating process of substrate, for example, can list 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 coater, roll coater, excellent painting machine, spin coater, slit and spin coater, slit coater (be sometimes coated with machine, curtain also referred to as mould and be coated with machine, coating machine without spin), ink-jet to be coated with.Wherein, preferably use slit coater, spin coater, roll coater etc. to be coated with.
As the drying means of the film forming in base plate coating, can list such as methods such as heat drying, natural drying, aeration-drying, drying under reduced pressure.Also can combine a plurality of methods carries out.
As baking temperature, be preferably 10～120 ℃, more preferably 25～100 ℃.In addition as the heat time, be preferably 10 second～60 minute, 30 second～30 minute more preferably.
Drying under reduced pressure is preferably under the pressure of 50～150Pa, carry out in the temperature range of 20～25 ℃.
The thickness of dried coated film is not particularly limited, can suitably adjust according to used material, purposes etc., and for example, be 0.1～20 μ m, be preferably 1～6 μ m.
Dried coated film is exposed across the photomask that is used to form the pattern of object.Pattern form on photomask is now not particularly limited, and adopts and is suitable for the pattern form as the purposes of object.
As the light source for exposing, preferably send the light source of light of the wavelength of 250～450nm.For example, can use the wave filter of the following wavelength domain of cut-off to end the light of not enough 350nm, or use that the bandpass filter of taking out following wavelength domain is selected to take out near 436nm, near near light 408nm, 365nm.As light source, particularly, can list mercury lamp, light emitting diode, metal halide lamp, Halogen lamp LED etc.
Owing to can or mask being overlapped with the correct position of base material to the whole uniform irradiation parallel rays of plane of exposure, therefore preferably use the exposure device of mask aligner and stepper etc.
After exposure, coated film contact with developer solution and make established part for example unexposed portion dissolves, also development, can obtain pattern.As developer solution, can be with an organic solvent, but because the exposure portion of coated film is because developer solution is not soluble or swelling, can obtain the pattern of good shape, therefore preferably use alkali compounds aqueous solution.
Developing method can be any in paddling process (paddle method), infusion process, gunite etc.And then can when developing, make substrate tilt for angle arbitrarily.
After preferably developing, wash.
As aforementioned 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, dimethyl amine, Trimethylamine, MEA, diethylamide, triethylamine, single isopropylamine, diisopropylamine, monoethanolamine, wherein, preferred potassium hydroxide, sodium bicarbonate and Tetramethylammonium hydroxide.
These inorganic and organic basic compound concentration in aqueous solution are preferably 0.01～10 quality %, more preferably 0.03～5 quality %.
The aqueous solution of aforementioned alkali compounds can contain surfactant.
As surfactant, can list polyethylene oxide alkyl ethers, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other the nonionic such as polyethylene oxide derivatives, ethylene oxide/propylene oxide segmented copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene D-sorbite fatty acid ester, fatty acid glyceride, polyoxyethylene fatty acid esters, 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 kation of stearic ammonium salt hydrochlorate, lauryl trimethyl ammonium chloride etc. is surfactant etc.
The concentration of surfactant in the aqueous solution of alkali compounds be preferably 0.01～10 quality %, more preferably 0.05～8 quality %, be particularly preferably 0.1～5 quality %.
The pattern obtaining as mentioned above by further baking, the pattern after can being solidified.As baking temperature, be generally 25 ℃ above 230 ℃ following, be preferably 25 ℃ above 200 ℃ following, more preferably 25 ℃ above 160 ℃ following, more preferably 25 ℃ above below 120 ℃.As baking time, be generally 1～300 minute, be preferably 1～180 minute, more preferably 1～60 minute.
Obtaining thus pattern is being useful as for example light spacing body (Off ォ ト ス ペ mono-サ), the protective finish of patternable, the colored filter for liquid crystal indicator.In addition, photosensitive polymer combination of the present invention can be applicable to being used in and is used to form filming or pattern etc. as the pixel of liquid crystal indicator or imageing sensor, can be used in possess these film or pattern as colored filter, the array base palte of a part for its component parts, and then be used in display device, such as liquid crystal indicator, organic El device, solid camera head etc. that possesses these colored filters and/or array base palte etc.
Embodiment
By the following examples photosensitive composition of the present invention is illustrated in greater detail.
" % and " " part " in example is quality % and mass parts unless otherwise specified.
Trade name and structural formula thereof for the polymerizable compound (B) of each embodiment are as described below.
DENACOL ACRYLATE DA-314:Nagasechemtex society system
Figure BDA0000374015210000391
Synthesis example 1
There is stirrer, thermometer, reflux condensing tube, in the flask of tap funnel and nitrogen ingress pipe, import propylene glycol monomethyl ether 182g, by atmosphere in flask from air is changed to nitrogen, be warmed up to after 100 ℃, to by methacrylic acid benzyl ester 70.5g (0.40 mole), methacrylic acid 43.0g (0.5 mole), in the potpourri that the monomethacrylates of tricyclodecane skeleton (Hitachi changes into (strain) FA-513M processed) 22.0g (0.10 mole) and propylene glycol monomethyl ether 136g form, add azobis isobutyronitrile 3.6g, and with 2 hours, will obtain thus solution and be added drop-wise in flask by tap funnel, and then continue to stir 5 hours at 100 ℃.Then, atmosphere in flask is changed to air from nitrogen, by 35.5g[0.25 mole of methyl propenoic acid glycidyl base ester, (carboxyl of the methacrylic acid using with respect to this reaction is 50 % by mole)], three (dimethylamino) methylphenol 0.9g and quinhydrones 0.145g put in flask, at 110 ℃, continue reaction 6 hours, obtaining solid constituent acid number is the resin solution A-1 (solid constituent: 35.1%) of 79mgKOH/g.Utilizing the weight-average molecular weight of the polystyrene conversion of GPC mensuration is 13,000, and molecular weight distribution (Mw/Mn) is 2.1.
Synthesis example 2
To having, in the flask of 1L of reflux condensing tube, tap funnel and stirrer, suitably flow into nitrogen and become nitrogen atmosphere, add propylene glycol monomethyl ether 100 weight portions, be heated to while stirring 85 ℃.Then, use dropping liquid pump, the solution obtaining to methacrylic acid 19 weight portions, epoxidation dicyclopentadienyl acrylate (trade name " E-DCPA ", Co., Ltd.'s Daicel system) 171 weight portions being dissolved in to propylene glycol monomethyl ether 40 weight portions with dropping in 5 hours in this flask.On the other hand, use other dropping pump, with approximately 5 hours, by polymerization initiator 2,2, ' two (2,4-methyl pentane nitrile) 26 weight portions of azo were dissolved in propylene glycol monomethyl ether 120 weight portions and the solution that obtains is added drop-wise in flask.Polymerization initiator remains on this temperature approximately 3 hours after dripping and finishing, and cool to room temperature then obtains the resin solution A-2 of solid constituent 43.5 % by weight.The weight-average molecular weight Mw of the multipolymer generating is 8000, and dispersion degree is 1.98.
About the weight-average molecular weight (Mw) of resin and the mensuration of number-average molecular weight (Mn) that obtain in synthesis example, use GPC method to carry out according to following condition.
Device: K2479 ((strain) Shimadzu Seisakusho Ltd. system)
Post: SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ℃
Solvent: THF (tetrahydrofuran)
Flow velocity: 1.0mL/min
Detecting device: RI
With the weight-average molecular weight of polystyrene conversion obtained above and the ratio (Mw/Mn) of number-average molecular weight as molecular weight distribution.
Embodiment 1
(preparation of photosensitive polymer combination 1)
Mix following compositions, obtain photosensitive polymer combination 1.
Figure BDA0000374015210000411
Embodiment 2
(preparation of photosensitive polymer combination 2)
Mix following compositions, obtain photosensitive polymer combination 2.
Figure BDA0000374015210000421
Embodiment 3
(preparation of photosensitive polymer combination 3)
Mix following compositions, obtain photosensitive polymer combination 3.
Figure BDA0000374015210000422
And 145 parts of mixing of propylene glycol monomethyl ether, and the dispersible pigment dispersion that the use abundant dispersed color of ball mill is obtained,
Figure BDA0000374015210000431
Embodiment 4
(preparation of photosensitive polymer combination 4)
Mix following compositions, obtain photosensitive polymer combination 4.
Figure BDA0000374015210000432
Embodiment 5
(preparation of photosensitive polymer combination 5)
Mix following compositions, obtain photosensitive polymer combination 5.
Embodiment 6
(preparation of photosensitive polymer combination 6)
Mix following compositions, obtain photosensitive polymer combination 6.
Figure BDA0000374015210000442
Figure BDA0000374015210000451
Embodiment 7
(preparation of photosensitive polymer combination 7)
Mix following compositions, obtain photosensitive polymer combination 7.
Figure BDA0000374015210000452
Embodiment 8
(preparation of photosensitive polymer combination 8)
Mix following compositions, obtain photosensitive polymer combination 8.
Comparative example 1
(preparation of photosensitive polymer combination 1R)
Mix following compositions, obtain photosensitive polymer combination 9.
Figure BDA0000374015210000471
The making > of < pattern
The PET film (east beautiful Lumirror75-T60 processed) of fitting on 2 inches of square glass plates, making substrate.Utilize spin-coating method at the PET of substrate film side photosensitive resin coating composition, in arrival, press under 66Pa and carry out drying under reduced pressure, then, on heating plate, at 60 ℃, carry out preliminary drying 2 minutes.Place cooling after, will be coated with the substrate of this photosensitive polymer combination and the interval of quartz glass photomask processed is made as 150 μ m, use exposure machine (TME-150RSK, Topcon (strain) system) under atmospheric atmosphere, with 150mJ/cm 2exposure (365nm benchmark) carry out irradiation.In addition, the mask that use is formed with 10～100 lines of μ m and the pattern at interval is as photomask.Carry out after irradiation, in containing the water system developer solution that nonionic is surfactant 0.12% and potassium hydroxide 0.04%, 23 ℃ of 40 seconds of dipping, develop, with pure water washing, obtain thus pattern.And then carry out the pattern after heating in 5 minutes (drying afterwards) is solidified by the temperature shown in table 1.Use determining film thickness device (DEKTAK3; Japan's vacuum technique (strain) system) thickness of the pattern to the pattern obtaining or after solidifying is measured, and result is 2 μ m.
< solvent resistance is evaluated >
Be formed at pattern on aforesaid base plate or solidify after pattern on drip propylene glycol monomethyl ether 1ml, after static 30 seconds, use spin coater to rotate for 10 seconds with rotating speed 1000rpm, get rid of the propylene glycol monomethyl ether on pattern.
By the film thickness value of measuring, according to following formula, calculate thickness conservation rate before and after contacting with propylene glycol monomethyl ether.The higher curability of thickness conservation rate is better, while making colored filter, can prevent colour mixture.The results are shown in table 1.
(thickness conservation rate) (%)=(thickness after contact)/(thickness before contact)
< resolution is evaluated >
With the observable pattern of laser microscope (Axio Imager MAT CarlZeiss company system), using the minimum dimension of telling as resolution.Resolution is higher, more can make the colored filter of fine.The results are shown in table 1.
< development spot is evaluated >
With the observable pattern of laser microscope (Axio Imager MAT CarlZeiss company system), not have the situation of washmarking to be evaluated as zero (not seeing development spot) on pattern, to have the situation of washmarking to be evaluated as * (seeing development spot).See in the situation of development spot, during for the manufacture of colored filter, produce color spot.
< cross-cut test >
For filming of obtaining, carry out the band disbonded test (cross-cut test) based on JIS K5600-5-6, evaluated the adaptation with PET film.The results are shown in table 1 and 2.
[table 1]
[table 2]
According to the present invention, can provide the photosensitive polymer combination of giving the pattern that development spot is reduced.The adaptation of resulting pattern and thickness conservation rate are also excellent.
In addition, according to the present invention, can be provided in the photosensitive polymer combination that can form pattern at lower temperature.
The pattern obtaining thus can be preferably used as the colored filter using in the display device such as display panels, electroluminescence panel, Plasmia indicating panel, Electronic Paper.

Claims (6)

1. a photosensitive polymer combination, it comprises the polymerizable compound shown in (A) adhesive resin, (B) following formula (I) and (C) Photoepolymerizationinitiater initiater,
< formula (I) >
Figure FDA0000374015200000011
In formula (I), R 1, R 2and R 3represent hydrogen atom or methyl, represent-R of X 5-O-R 6-, R 5the alkylidene that represents singly-bound or carbon number 1～5, R 6represent to have the alkylidene of the carbon number 1～3 of hydroxyl, Y represent alkyl, hydrogen atom, hydroxyl or
Figure FDA0000374015200000012
R 4represent hydrogen atom or methyl.
2. photosensitive polymer combination according to claim 1, wherein,
(C) Photoepolymerizationinitiater initiater has the part-structure shown in following formula (II),
Figure FDA0000374015200000013
In formula, * represents respectively associative key.
3. photosensitive polymer combination according to claim 1 and 2, it also comprises colorant.
4. according to the photosensitive polymer combination described in any one in claim 1～3, it also comprises naphthol green 58 or paratonere 242.
5. a patterned coating film, it is formed by the photosensitive polymer combination described in any one in claim 1～4.
6. a display device, it comprises patterned coating film claimed in claim 5.
CN201310384385.1A 2012-09-03 2013-08-29 Photosensitive resin composition Pending CN103676480A (en)

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