CN102445844A

CN102445844A - Colored photosensitive resin composition

Info

Publication number: CN102445844A
Application number: CN201110292441XA
Authority: CN
Inventors: 宫芳子; 三浦洋之; 白川政和
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2010-10-05
Filing date: 2011-09-30
Publication date: 2012-05-09
Anticipated expiration: 2031-09-30
Also published as: KR20120035868A; JP5892760B2; TWI570509B; KR101777426B1; TW201232174A; JP2012098711A; CN102445844B

Abstract

The present invention provides a colored photosensitive resin composition which can obtain the pattern with excellent resolution. The colored photosensitive resin composition comprises the following components: (A) coloring agent; (B1) a copolymer of a structure unit which comprises at least one selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydride, and a structure unit of a monomer which is deviated from cyclic ether with 2-4 carbon atoms and olefinic unsaturated bonds (wherein, the side chain is not provided with olefinic unsaturated bonds); (B2) resin with olefinic unsaturated bonds at the side chain; (C) polymeric compound; (D) polymerization initiazing agent and (E) dissolvent.

Description

Photosensitive composition

Technical field

The present invention relates to be suitable for forming the photosensitive composition of the rendered image that constitutes the color filter that uses in liquid crystal display cells, the solid-state imager.

Background technology

The color filter that uses in the display device such as display panels, electroluminescence panel, plasma display can use photosensitive composition manufacturing.As this photosensitive composition; Known have a combinations thing; It contains pigment, resin, optical polymerism compound, Photoepolymerizationinitiater initiater and solvent, and resin is methacrylic acid and the multipolymer (patent documentation 1) with unsaturated compound of Oxyranyle.

Patent documentation 1: japanese kokai publication hei 2007-333847 communique.

Summary of the invention

When using above-mentioned photosensitive composition to form pattern, for the resolution of this pattern, may not be fully satisfactory.

The present invention provides following [1]～[8].

[1] photosensitive composition, it contains (A), (B1), (B2), (C), (D) and (E),

(A) colorant,

(B1) contain and come from least a structural unit that is selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides; With come from have carbon number be 2～4 cyclic ether and ethylenic unsaturated bond monomer structural unit multipolymer (wherein; Side chain does not have ethylenic unsaturated bond)

(B2) side chain has the resin of ethylenic unsaturated bond,

(C) polymerizable compound,

(D) polymerization initiator,

(E) solvent.

[2] photosensitive composition of above-mentioned [1] record, wherein, (B2) following for making (a) further reacts the resin that obtains with (b) with the multipolymer that (c) copolymerization obtains,

(a): be selected from least a of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides,

(b): have carbon number and be 2～4 the cyclic ether and the monomer of ethylenic unsaturated bond,

(c): have can with (a) and (b) monomer of the unsaturated link of copolymerization.

The photosensitive composition of [2-2] above-mentioned [1] record, wherein, (B2) following for making (a) further reacts the resin that obtains with (b) with the multipolymer that (c) copolymerization obtains,

(b): have the monomer of Oxyranyle and ethylenic unsaturated bond,

[3] photosensitive composition of above-mentioned [1] or [2] record, wherein, content (B1) with respect to (B1) and total amount (B2), is 10 quality %～95 quality %.

[4] pattern, its photosensitive composition by any record in above-mentioned [1]～[3] forms.

[5] color filter, it contains the pattern of above-mentioned [4] record.

[6] manufacturing method of color filter, it contains the step shown in following (1)～(4),

(1) be coated on the step that obtains coated film on the substrate through photosensitive composition with any record in above-mentioned [1]～[3],

(2) coated film is made public via mask, the step of coated film after obtaining thus making public,

(3) will make public the back coated film develop with alkaline developer, obtain the step of pattern thus,

(4) pattern is cured the step of the pattern that obtains thus solidifying.

[7] manufacturing method of color filter of above-mentioned [6] record, wherein, the step of step (4) under 25 ℃～120 ℃ temperature, curing.

[8] manufacturing method of color filter of above-mentioned [6] or [7] record, wherein, the substrate in the step (1) is a plastic base.

[invention effect]

According to photosensitive composition of the present invention, can obtain the good pattern of resolution.

Embodiment

Photosensitive composition of the present invention contains colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D) and solvent (E), and resin (B) is for containing

(B1) contain and come from least a structural unit that is selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides; With come from have carbon number be 2～4 cyclic ether and ethylenic unsaturated bond monomer structural unit multipolymer (wherein; Side chain does not have ethylenic unsaturated bond) (below be sometimes referred to as " resin (B1) ") and

(B2) side chain has the resin of the resin (below be sometimes referred to as " resin (B2) ") of ethylenic unsaturated bond.

Photosensitive composition of the present invention contains colorant (A).As colorant (A), can enumerate pigment and dyestuff, but consider from thermotolerance, photostability aspect, preferably contain pigment.

As pigment, can enumerate organic pigment and inorganic pigment, can enumerate the compound that in Colour Index (The Society of Dyers and Colourists publication), is categorized as pigment.

As organic pigment; Specifically; Can enumerate for example C.I. pigment yellow 1; C.I. pigment yellow 3; C.I. pigment Yellow 12; C.I. pigment yellow 13; C.I. pigment Yellow 14; C.I. pigment yellow 15; C.I. pigment yellow 16; C.I. pigment yellow 17; C.I. pigment yellow 20; C.I. pigment yellow 24; C.I. pigment yellow 31; C.I. pigment yellow 53; C.I. pigment yellow 83; C.I. pigment yellow 86; C.I. pigment yellow 93; C.I. pigment yellow 94; C.I. pigment yellow 109; C.I. pigment yellow 110; C.I. pigment yellow 117; C.I. pigment Yellow 12 5; C.I. pigment Yellow 12 8; C.I. pigment yellow 13 7; C.I. pigment yellow 13 8; C.I. pigment yellow 13 9; C.I. pigment yellow 147; C.I. pigment Yellow 14 8; C.I. pigment yellow 150; C.I. pigment yellow 153; C.I. pigment yellow 154; C.I. pigment yellow 166; C.I. pigment yellow 17 3; C.I. pigment yellow 194; C.I. pigment yellow 214 yellow uitramarines such as grade

C.I. orange pigments such as pigment orange 13, C.I. pigment orange 31, C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 40, C.I. pigment orange 42, C.I. pigment orange 43, C.I. pigment orange 51, C.I. pigment orange 55, C.I. pigment orange 59, C.I. pigment orange 61, C.I. pigment orange 64, C.I. pigment orange 65, C.I. pigment orange 71, C.I. pigment orange 73

C.I. Pigment Red 9; C.I. Pigment Red 97; C.I. paratonere 105; C.I. pigment red 122; C.I. pigment red 123; C.I. paratonere 144; C.I. pigment red 149; C.I. paratonere 166; C.I. paratonere 168; C.I. paratonere 176; C.I. paratonere 177; C.I. paratonere 180; C.I. paratonere 192; C.I. paratonere 209; C.I. pigment red 21 5; C.I. pigment red 21 6; C.I. paratonere 224; C.I. paratonere 242; C.I. paratonere 254; C.I. paratonere 255; C.I. paratonere 264; C.I. red pigment such as paratonere 265

C.I. pigment blue 15, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6, blue pigment such as C.I. pigment blue 60,

C.I. violet pigments such as pigment violet 1, C.I. pigment violet 19, C.I. pigment Violet 23, C.I. pigment violet 29, C.I. pigment violet 32, C.I. pigment violet 36, C.I. pigment violet 38,

C.I. viridine greens such as pigment Green 7, C.I. pigment green 36, C.I. naphthol green 58,

C.I. brown such as pigment brown 23, C.I. pigment brown 25 and

C.I. black pigment such as pigment black 1, C.I. pigment black 7.

Wherein, be preferably C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. paratonere 177, C.I. paratonere 242, C.I. paratonere 254, C.I. pigment purple 23, C.I. pigment blue 15: 3, C.I. pigment blue 15: 6 and C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 58.These pigment can separately or mix 2 kinds with on use.

Above-mentioned pigment; As required, can implement rosin and handle, use to import the surface treatment that pigment derivative that acidic-group or basic group are arranged, pigment dispersing agent etc. carry out; Grafting through macromolecular compound etc. carries out surface of pigments is handled; Micronize through sulfuric acid micronize method etc. is carried out is handled, or the carrying out washing treatment of utilizing organic solvent, water etc. to carry out that is used to remove impurity, ionic impurity utilize that ion exchange process etc. carries out remove processing etc.In addition, pigment optimization uniform particle diameter.Carry out dispersion treatment through containing pigment dispersing agent, can obtain the dispersible pigment dispersion of the state that pigment disperses equably in solution.

As above-mentioned pigment dispersing agent, can use commercially available surfactant.As surfactant, can enumerate the for example surfactant of type siloxane, fluorine class, ester class, cationic, anionic species, nonionic class, both sexes, polyesters, polyamines class and acrylic compounds.As above-mentioned surfactant; Except polyoxyethylene alkyl ether class, polyoxyethylene alkyl phenyl ether class, polyethylene glycol di class, sorbitan fatty acid esters class, fatty acid modified polyesters, tertiary amine modified polyurethane, polyethyleneimine: amine etc., can also enumerate KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system) with trade name name, Off ローレ Application (common prosperity society chemistry (strain) is made), ソ Le スパース (ゼネカ (strain) system), EFKA (CIBA society system), アジスパー (monosodium glutamate Off ァイ Application テ Network ノ (strain) system), Disperbyk (PVC ッ Network ケミー society system) etc.They can distinguish alone or in combination 2 kinds with on use.

When using pigment dispersing agent, its consumption is preferably below the 100 quality %, more preferably 5～50 quality % with respect to the weight of pigment.If the consumption of pigment dispersing agent then has the trend of the dispersible pigment dispersion that obtains the homogeneous disperse state in above-mentioned scope.

The content of colorant (A), the amount with respect to the solid formation of photosensitive composition divides is preferably 5～60 quality %, more preferably 5～45 quality %.If the content of colorant (A) then can obtain required beam split, color depth in above-mentioned scope.Wherein, and the solid formation branch in this instructions refers to the total amount of being removed the composition that obtains of desolvating by photosensitive composition.

Photosensitive composition of the present invention contains the resin (B) of resinous (B1).Resin (B1) is for containing the structural unit that comes from least a (below be sometimes referred to as " (a) ") that be selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides; Have the monomer that carbon number is 2～4 cyclic ether and ethylenic unsaturated bond with the coming from multipolymer (wherein, side chain does not have ethylenic unsaturated bond) of structural unit of (below be sometimes referred to as " (b) ").

Contain resin (B1) through photosensitive composition, the trend that exists the reliability such as thermotolerance, resistance to chemical reagents of the pattern of gained to become more good.

As resin (B1), for example can enumerate,

Resin (B1-1): with (a) and the multipolymer that (b) is polymerized and

Resin (B1-2): with (a) and (b) and have can with (a) and (b) multipolymer that is polymerized of the monomer of the unsaturated link of copolymerization (c) (below be sometimes referred to as " (c) ").As resin (B1), be preferably (B1-1).

As (a), specifically, can enumerate 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 phthalandione, 4-vinyl phthalic acid, 3,4,5; 6-tetrahydrophthalic acid, 1; 2,3,6-tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid, 1; Unsaturated dicarboxylic classes such as 4-cyclohexene dicarboxylic acid

Methyl-5-ENB-2; 3-dicarboxylic acid, 5-carboxyl dicyclo [2.2.1] hept-2-ene", 5; 6-dicarboxyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-6-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-6-ethyl dicyclo [2.2.1] hept-2-ene" etc. contain the dicyclo unsaturated compound class of carboxyl

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5; 6-tetrahydrophthalic anhydride, 1; 2,3,6-tetrahydrophthalic anhydride, dimethyl tetrahydro phthalic anhydride, dicyclo [2.2.1] hept-2-ene"-5; 6-dicarboxylic anhydride unsaturated dicarboxylic acid anhydride classes such as (carbic anhydrides)

Unsaturated list [(methyl) acryloxyalkyl] the ester class of the polybasic carboxylic acids more than 2 yuan such as mono succinate [2-(methyl) acryloxy ethyl] ester, phthalic acid list [2-(methyl) acryloxy ethyl] ester,

α-(hydroxymethyl) acrylic acid etc. contains the unsaturated esters of acrylic acid of hydroxyl and carboxyl etc. in a part.

Wherein, acrylic acid, methacrylic acid, maleic anhydride etc. are considered preferred the use from the viewpoint of copolyreaction property, the viewpoint of alkali dissolution property.

Wherein, in this instructions, " (methyl) acrylic acid " expression is selected from least a kind in acrylic acid and the methacrylic acid.The statement of " (methyl) acryloyl group " and " (methyl) acrylic ester " etc. has same meaning.

As (b), can enumerate the monomer (b-1) that for example has Oxyranyle and ethylenic unsaturated bond (below be sometimes referred to as " (b-1) "), have the monomer (b-2) (below be sometimes referred to as " (b-2) ") of oxa-cyclobutyl and ethylenic unsaturated bond and have the monomer (b-3) (below be sometimes referred to as " (b-3) ") of tetrahydrofuran base and ethylenic unsaturated bond.

As (b-1), can enumerate the monomer (b-11) that for example has structure that the chain type alkene epoxidation is formed and ethylenic unsaturated bond (below be sometimes referred to as " (b-11) ") and have structure that the cycloolefin epoxidation is formed and the monomer (b-12) of ethylenic unsaturated bond (below be sometimes referred to as " (b-12) ").

As (b-1), be preferably monomer with Oxyranyle and (methyl) acryloxy, further be preferably (b-12) with (methyl) acryloxy.

As (b-11), specifically, can enumerate (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, a 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, 2; Two (the glycidyl oxygen ylmethyl) styrene, 2 of 3-; Two (the glycidyl oxygen ylmethyl) styrene, 2 of 4-, two (the glycidyl oxygen ylmethyl) styrene, 2 of 5-, two (the glycidyl oxygen ylmethyl) styrene, 2 of 6-; 3; 4-three (glycidyl oxygen ylmethyl) styrene, 2,3,5-three (glycidyl oxygen ylmethyl) styrene, 2; 3; 6-three (glycidyl oxygen ylmethyl) styrene, 3,4,5-three (glycidyl oxygen ylmethyl) styrene, 2; 4, the compound of putting down in writing in 6-three (glycidyl oxygen ylmethyl) styrene, the japanese kokai publication hei 7-248625 communique etc.

As (b-12); Can enumerate VCH list oxide, 1; (for example セロキサイ De 2000 for 2-epoxy-4-vinyl cyclohexane; ダイセ Le chemical industry (strain) system), acrylic acid 3,4-epoxycyclohexyl methyl ester (for example サイ Network ロマー A400, ダイセ Le chemical industry (strain) system), methacrylic acid 3; Compound shown in 4-epoxycyclohexyl methyl ester (for example サイ Network ロマー M100, ダイセ Le chemical industry (strain) system), the formula (I), the compound shown in the formula (II) etc.

[in formula (I) and the formula (II), R ¹And R ²Represent that independently of each other hydrogen atom or carbon number are 1～4 alkyl, the hydrogen atom that contains in this alkyl can be replaced by hydroxyl.

X ¹And X ²Represent independently of each other singly-bound ,-R ³-, *-R ³-O-, *-R ³-S-, *-R ³-NH-.

R ³The expression carbon number is 1～6 alkane two bases.

* represent bonding key with O.]

As carbon number is 1～4 alkyl, specifically, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group etc.

As hydroxy alkyl, can enumerate hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyl-1-Methylethyl, 2-hydroxyl-1-Methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl etc.

As R ¹And R ², preferably enumerate hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, more preferably enumerate hydrogen atom, methyl.

As alkane two bases, can enumerate methylene, 1,2-ethylidene, propane-1,2-two bases, propane-1,3-two bases, butane-1,4-two bases, pentane-1,5-two bases, hexane-1,6-two bases etc.

As X ¹And X ², preferably enumerate singly-bound, methylene, 1,2-ethylidene, *-CH ₂-O-(* representes the bonding key with O) base, *-CH ₂CH ₂-O-base is more preferably enumerated singly-bound, *-CH ₂CH ₂-O-base.

As the compound shown in the formula (I), can enumerate the compound shown in formula (I-1)～formula (I-15) etc.Preferably enumerate formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), formula (I-11)～formula (I-15).More preferably enumerate formula (I-1), formula (I-7), formula (I-9), formula (I-15).

As the compound shown in the formula (II), can enumerate the compound shown in formula (II-1)～formula (II-15) etc.Preferably enumerate formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), formula (II-11)～formula (II-15).More preferably enumerate formula (II-1), formula (II-7), formula (II-9), formula (II-15).

Compound shown in compound shown in the formula (I) and the formula (II) can be distinguished independent use.In addition, they also can mix with arbitrary ratio.During mixing, its mixture ratio, according to mol ratio, preferred formula (I): formula (II) is 5:95～95:5, more preferably 10:90～90:10 is preferably 20:80～80:20 especially.

As (b-2), be preferably monomer with oxa-cyclobutyl and (methyl) acryloxy.As (b-2), can enumerate for example 3-methyl-3-(methyl) acryloyl-oxy ylmethyl oxetanes, 3-ethyl-3-(methyl) acryloyl-oxy ylmethyl oxetanes, 3-methyl-3-(methyl) acryloxy ethyl oxetanes and 3-ethyl-3-(methyl) acryloxy ethyl oxetanes.

As (b-3), more preferably has the monomer of tetrahydrofuran base and (methyl) acryloxy.As (b-3), specifically, can enumerate acrylic acid tetrahydro furfuryl ester (for example PVC スコート V#150, Osaka organic chemistry industry (strain) system), methacrylic acid tetrahydro furfuryl ester etc.

As (c), for example can enumerate (methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate,

(methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methyl cyclohexane ester, (methyl) acrylic acid three ring [5.2.1.0 ^2,6] (methyl) acrylic acid cyclic alkyl ester classes such as decane-8-base ester (in this technical field,, being called (methyl) acrylic acid dicyclo amyl group ester as trivial name), the two cyclopentyloxy ethyl esters of (methyl) acrylic acid, (methyl) isobornyl acrylate,

(methyl) acrylic acid aryl ester or aralkyl ester classes such as (methyl) phenyl acrylate, (methyl) benzyl acrylate,

Dicarboxylic diesters such as diethyl maleate, DEF, diethyl itaconate,

Hydroxyalkyl acrylate classes such as (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl 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-hydroxymethyl dicyclo [2.2.1] hept-2-ene"; 5-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene"; 5-methoxyl dicyclo [2.2.1] hept-2-ene"; 5-ethoxy dicyclo [2.2.1] hept-2-ene"; 5; 6-dihydroxy dicyclo [2.2.1] hept-2-ene"; 5; 6-two (hydroxymethyl) dicyclo [2.2.1] hept-2-ene"; 5; 6-two (2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene"; 5; 6-dimethoxy dicyclo [2.2.1] hept-2-ene"; 5; 6-diethoxy dicyclo [2.2.1] hept-2-ene"; 5-hydroxy-5-methyl base dicyclo [2.2.1] hept-2-ene"; 5-hydroxyl-5-ethyl dicyclo [2.2.1] hept-2-ene"; 5-hydroxymethyl-5-methyl bicycle [2.2.1] hept-2-ene"; 5-tert-butoxycarbonyl dicyclo [2.2.1] hept-2-ene"; 5-cyclohexyloxy carbonyl dicyclo [2.2.1] hept-2-ene"; 5-phenyloxycarbonyl dicyclo [2.2.1] hept-2-ene"; 5; Two (tert-butoxycarbonyl) dicyclo [2.2.1] hept-2-ene"s of 6-; 5; Dicyclo unsaturated compound classes such as two (cyclohexyloxy carbonyl) dicyclo [2.2.1] hept-2-ene"s of 6-

Dicarbapentaborane imide derivative classes such as N-phenylmaleimide, N-cyclohexyl maleimide, 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, AMS, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxy styrene, vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylic amide, Methacrylamide, vinyl acetate, 1; 3-butadiene, isoprene and 2; 3-dimethyl-1,3-butadiene etc.

Wherein, styrene, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, dicyclo [2.2.1] hept-2-ene" etc. are considered preferred from the viewpoint of copolyreaction property and alkali dissolution property.

In the resin (B1-1), as the ratio of the structural unit that comes from each monomer, with respect to the total mole number of the structural unit that constitutes resin (B1-1), preferably in following scope.

Come from the structural unit of (a): 5～60 moles of % (10～50 moles of % more preferably)

Come from the structural unit of (b): 40～95 moles of % (50～90 moles of % more preferably)

If the ratio of the structural unit of resin (B1-1) is in above-mentioned scope, the trend that then exists storage stability, development property, solvent resistance, thermotolerance and physical strength to become good.

As resin (B1-1), preferably (b) is the resin of (b-1), is more preferably (b-1) resin for (b-12).

The citing document of putting down in writing in the method for record and the document during resin (B1-1) for example can list of references " the high son that divides closes into the experiment method " (the big grand row work sale room in Tianjin (strain) chemistry is with the 1st edition the 1st printing distribution on March 1st, 1972 of people) prepares.

Specifically, can enumerate (a) and ormal weight (b), polymerization initiator and solvent etc. are joined in the reaction vessel, utilize the nitrogen replace oxygen, carry out deoxidation thus, and the method that stirs, heats, is incubated.And, use therein polymerization initiator and solvent etc. are not limited especially, can use normally used polymerization initiator arbitrarily and solvent in this field.As polymerization initiator; For example can enumerate azo-compound (2,2 '-azobis isobutyronitrile, 2,2 '-azo two (2;) and organic peroxide (benzoyl peroxide etc.) the 4-methyl pentane nitrile) etc.; As solvent, so long as the solvent of each monomer of solubilized gets final product the solvent that the solvent of photosensitive composition is stated after can using etc.

And resulting multipolymer can directly use reacted solution, also can use to concentrate or the solution of dilution, can also use the multipolymer that takes out with solid (powder) mode through methods such as depositions again.Particularly during this polymerization, as solvent, through use with after the identical solvent of solvent (E) stated, can directly use reacted solution, thereby can simplify preparation process.

In the resin (B1-2), as the ratio of the structural unit that comes from each monomer, with respect to the total mole number of the entire infrastructure unit that constitutes resin (B1-2), preferably in following scope.

Come from the structural unit of (a): 2～40 moles of % (5～35 moles of % more preferably)

Come from the structural unit of (b): 2～95 moles of % (5～80 moles of % more preferably)

Come from the structural unit of (c): 1～65 mole of % (1～60 mole of % more preferably)

If the ratio of the structural unit of resin (B1-2) is in above-mentioned scope, the trend that then exists storage stability, development property, solvent resistance, thermotolerance and physical strength to become good.

As resin (B1-2), preferably (b) is the resin of (b-1), is more preferably (b) resin for (b-12).

Resin (B1-2) can be through the method preparation identical with resin (B1-1).

The weight-average molecular weight (Mw) of the polystyrene conversion of resin (B1) is preferably 3000～100000, and more preferably 5000～50000.If the weight-average molecular weight of resin (B1) is in above-mentioned scope, the trend that then exists coating to become good in addition, is difficult to produce film and reduces during development, and then the trend that exists when developing the deciduous of non-pixel portion to become good.

The molecular weight distribution of resin (B1) [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] is preferably 1.5～6.0, and more preferably 1.8～4.0.If, then there is the excellent trend of development property in above-mentioned scope in the molecular weight distribution of resin (B1).

The acid number of resin (B1) is 20～150mg-KOH/g, is preferably 30～135mg-KOH/g, more preferably 40～125mg-KOH/g.Wherein, acid number is as being used for resin (B1) 1g and the value that the amount (mg) of essential potassium hydroxide is measured can be carried out titration through the use potassium hydroxide aqueous solution and tried to achieve.

The content of resin (B1), the total amount with respect to resin (B1) and resin (B2) is preferably 10～95 quality %, and more preferably 10～85 quality % are preferably 10～80 quality % especially.If the content of resin (B1) is in above-mentioned scope, then development property, adaptation, solvent resistance, mechanical property have the trend that becomes good.

The resin that contains in the photosensitive composition of the present invention (B) further contains resin (B2).Resin (B2) is for having the resin of ethylenic unsaturated bond at side chain; Can enumerate the resin (B2-1) that multipolymer that (a) and (c) copolymerization are obtained further obtains with (b) reaction, the resin (B2-2) that the multipolymer that (b) and (c) copolymerization are obtained further obtains with (a) reaction etc.Wherein, as resin (B2), be preferably resin (B2-1).

As the (a) and (b) that constitute resin (B2) with (c); Can enumerate and the identical material of above-mentioned resin (B1); As (c), be preferably compound (c1) with at least a kind of skeleton being selected from tricyclodecane skeleton and tricyclo decene skeleton and ethylenic unsaturated bond (below be sometimes referred to as " (c1) ") especially.(c) be under the situation of (c1), can suppress because the film of the pattern that development is caused reduces.

Wherein, " tricyclodecane skeleton " in this instructions and " tricyclo decene skeleton " refer to following structure (separately carbon atom have the bonding key) arbitrarily respectively.

As (c1), specifically, can enumerate (methyl) acrylic acid dicyclo amyl group ester, (methyl) acrylic acid double cyclopentenyl ester, the two cyclopentyloxy ethyl esters of (methyl) acrylic acid, (methyl) acrylic acid double cyclopentenyl oxygen base ethyl ester.They can be distinguished separately or make up more than 2 kinds and use.

Resin (B2-1) and resin (B2-2) for example can pass through two stage step and prepare.At this moment, can wait with reference to the method for putting down in writing in the method for record in the above-mentioned document " high divide son close into the experiment method " (the big grand row work sale room in Tianjin (strain) chemistry is with the 1st edition the 1st printing distribution on March 1st, 1972 of people), the TOHKEMY 2001-89533 communique and prepare.

For resin (B2-1),, likewise obtain (a) and (c) multipolymer with the preparation method of above-mentioned resin (B1-1) at first as the phase one.

At this moment, with likewise above-mentioned, the multipolymer of gained can directly use reacted solution, also can use to concentrate or the solution of dilution, can also use the multipolymer that obtains with solid (powder) mode through methods such as depositions again.

As the ratio that comes from (a) and structural unit (c), with respect to the total mole number of the entire infrastructure unit that constitutes above-mentioned multipolymer, preferably in following scope.

Come from the structural unit of (a): 5～50 moles of % (10～45 moles of % more preferably)

Come from the structural unit of (c): 50～95 moles of % (55～90 moles of % more preferably)

Then, as subordinate phase, make the part and (b) cyclic ether reaction of carboxylic acid and carboxylic acid anhydrides of (a) of the multipolymer that comes from gained.The reactivity of cyclic ether is high, is difficult to (b) of remained unreacted, therefore,, is preferably (b-1) as (b), further is preferably (b-11).

Specifically; After above-mentioned; Atmosphere in the flask is replaced into air by nitrogen; In flask, add with respect to the molal quantity of (a) be 5～80 moles of % (b), be the carboxyl of 0.001～5 quality % and the catalysts of cyclic ether (for example three (dimethylaminomethyl) phenol), be the polymerization inhibitor (for example quinhydrones) of 0.001～5 quality % with respect to (a) and (b) and total amount (c) with respect to (a) and (b) and total amount (c); Reacted 1～10 hour down at 60～130 ℃, can obtain resin (B2-1).And, with polymerizing condition likewise, consider thermal discharge that preparation equipment, polymerization cause etc., can suitably adjust adding method, temperature of reaction.

In addition, at this moment, molal quantity (b) with respect to the molal quantity of (a), is preferably 10～75 moles of %, more preferably 15～70 moles of %.Molal quantity through making (b) is in this scope, and storage stability, solvent resistance and stable on heating balance have the trend that becomes good.

Concrete example as resin (B2-1); Can enumerate the resin that the multipolymer that makes (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/(methyl) benzyl acrylate obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/(methyl) acrylic acid cyclohexyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that (methyl) acrylic acid/cinnamic multipolymer is obtained with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/(methyl) methyl acrylate obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/N-cyclohexyl maleimide obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes crotonic acid/(methyl) acrylic acid dicyclo amyl group ester obtains with the reaction of (methyl) acrylic acid glycidyl esters

The resin that the multipolymer that makes crotonic acid/(methyl) acrylic acid benzyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes crotonic acid/(methyl) acrylic acid cyclohexyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that crotonic acid/cinnamic multipolymer is obtained with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes crotonic acid/ethyl crotonate obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes crotonic acid/N-cyclohexyl maleimide obtains with the reaction of (methyl) acrylic acid glycidyl esters

The resin that the multipolymer that makes maleic acid/(methyl) acrylic acid dicyclo amyl group ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes maleic acid/(methyl) acrylic acid benzyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes maleic acid/(methyl) acrylic acid cyclohexyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that maleic acid/cinnamic multipolymer is obtained with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes maleic acid/maleic acid methyl esters obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes maleic acid/N-cyclohexyl maleimide obtains with the reaction of (methyl) acrylic acid glycidyl esters

The resin that the multipolymer that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid benzyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid cyclohexyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that (methyl) acrylic acid/maleic anhydride/cinnamic multipolymer is obtained with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/maleic anhydride/(methyl) methyl acrylate obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/maleic anhydride/N-cyclohexyl maleimide obtains with the reaction of (methyl) acrylic acid glycidyl esters

Make the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid benzyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid cyclohexyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make (methyl) acrylic acid/cinnamic multipolymer and methacrylic acid 3; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) methyl acrylate; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/N-cyclohexyl maleimide; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains

Make the multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) acrylic acid dicyclo amyl group ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, multipolymer and the methacrylic acid 3 that makes crotonic acid/(methyl) acrylic acid benzyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, multipolymer and the methacrylic acid 3 that makes crotonic acid/(methyl) acrylic acid cyclohexyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, make crotonic acid/cinnamic multipolymer and methacrylic acid 3; 4-epoxycyclohexyl methyl ester is reacted and the resin that obtains, the multipolymer that makes crotonic acid/ethyl crotonate and methacrylic acid 3; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, multipolymer and the methacrylic acid 3 that makes crotonic acid/N-cyclohexyl maleimide, 4-epoxycyclohexyl methyl ester react and the resin that obtains

Make the multipolymer and the methacrylic acid 3 of maleic acid/(methyl) acrylic acid dicyclo amyl group ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, multipolymer and the methacrylic acid 3 that makes maleic acid/(methyl) acrylic acid benzyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, multipolymer and the methacrylic acid 3 that makes maleic acid/(methyl) acrylic acid cyclohexyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, make maleic acid/cinnamic multipolymer and methacrylic acid 3; 4-epoxycyclohexyl methyl ester is reacted and the resin that obtains, the multipolymer that makes maleic acid/maleic acid methyl esters and methacrylic acid 3; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, multipolymer and the methacrylic acid 3 that makes maleic acid/N-cyclohexyl maleimide, 4-epoxycyclohexyl methyl ester react and the resin that obtains

Make the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, multipolymer and the methacrylic acid 3 that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid benzyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, multipolymer and the methacrylic acid 3 that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid cyclohexyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, make (methyl) acrylic acid/maleic anhydride/cinnamic multipolymer and methacrylic acid 3; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, multipolymer and the methacrylic acid 3 that makes (methyl) acrylic acid/maleic anhydride/(methyl) methyl acrylate; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, multipolymer and the methacrylic acid 3 that makes (methyl) acrylic acid/maleic anhydride/N-cyclohexyl maleimide, 4-epoxycyclohexyl methyl ester react and the resin that obtains etc.

Further, as resin (B2-1), be more preferably and make (a), (c1) and (c1) resin that obtains with (b) reaction of the multipolymer that obtains of in addition (c) copolymerization.Through making resin (B2-1) be above-mentioned formation, there is adaptation and the excellent trend of solvent resistance with substrate in the pattern of gained.

(a) comprise (a), (c1) with (c) multipolymer and (c1) during in addition (c), come from (c1) and (c1) in addition the ratio of structural unit of (c) be preferably 10:90～60:40, more preferably 10:90～40:60 further is preferably 10:90～30:70.

As making (a); (c1) and (c1) resin that obtains with (b) reaction of the multipolymer that obtains of in addition (c) copolymerization; Specifically; Can enumerate the resin that the multipolymer that makes (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester/cinnamic multipolymer is obtained with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) methyl acrylate obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide obtains with the reaction of (methyl) acrylic acid glycidyl esters

The resin that the multipolymer that makes crotonic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes crotonic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that crotonic acid/(methyl) acrylic acid dicyclo amyl group ester/cinnamic multipolymer is obtained with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes crotonic acid/(methyl) acrylic acid dicyclo amyl group ester/ethyl crotonate obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes crotonic acid/(methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide obtains with the reaction of (methyl) acrylic acid glycidyl esters

The resin that the multipolymer that makes maleic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes maleic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that maleic acid/(methyl) acrylic acid dicyclo amyl group ester/cinnamic multipolymer is obtained with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes maleic acid/(methyl) acrylic acid dicyclo amyl group ester/maleic acid methyl esters obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes maleic acid/(methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide obtains with the reaction of (methyl) acrylic acid glycidyl esters

The resin that the multipolymer that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester/cinnamic multipolymer is obtained with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester/(methyl) methyl acrylate obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide obtains with the reaction of (methyl) acrylic acid glycidyl esters

Make the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester/cinnamic multipolymer and methacrylic acid 3; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) methyl acrylate; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains

Make the multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make crotonic acid/(methyl) acrylic acid dicyclo amyl group ester/cinnamic multipolymer and methacrylic acid 3; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) acrylic acid dicyclo amyl group ester/ethyl crotonate; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains

Make the multipolymer and the methacrylic acid 3 of maleic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of maleic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make maleic acid/(methyl) acrylic acid dicyclo amyl group ester/cinnamic multipolymer and methacrylic acid 3; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of maleic acid/(methyl) acrylic acid dicyclo amyl group ester/maleic acid methyl esters; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of maleic acid/(methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains

Make the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, multipolymer and the methacrylic acid 3 that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, make (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester/cinnamic multipolymer and methacrylic acid 3; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, multipolymer and the methacrylic acid 3 that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester/(methyl) methyl acrylate; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, multipolymer and the methacrylic acid 3 that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide, 4-epoxycyclohexyl methyl ester react and the resin that obtains etc.

For resin (B2-2),, likewise obtain (b) and (c) multipolymer with the preparation method of above-mentioned resin (B1-1) as the phase one.

At this moment, with likewise above-mentioned, the multipolymer of gained can directly use reacted solution, also can use the solution that concentrates or dilute, the multipolymer that can also use methods such as using again deposition to obtain with solid (powder) mode.

As the ratio that comes from (b) and structural unit (c), with respect to the total mole number of the entire infrastructure unit that constitutes above-mentioned multipolymer, preferably in following scope.

Come from the structural unit of (b): 5～95 moles of % (10～90 moles of % more preferably)

Come from the structural unit of (c): 5～95 moles of % (10～90 moles of % more preferably)

Further, with the preparation method of resin (B2-1) likewise, can obtain through the cyclic ether that comes from (b) in (b) and the multipolymer (c) is reacted with carboxylic acid that (a) has or carboxylic acid anhydrides.The hydroxyl that reaction through cyclic ether and carboxylic acid or carboxylic acid anhydrides is produced further reacts with carboxylic acid anhydrides.

Consumption with (a) of above-mentioned copolymer reaction with respect to the molal quantity of (b), is preferably 5～80 moles of %.The reactivity of cyclic ether is high, is difficult for (b) of remained unreacted, therefore,, is preferably (b-1) as (b), further is preferably (b-11).

Concrete example as resin (B2-2); Can enumerate the resin that the multipolymer that makes (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid glycidyl esters obtains with the reaction of (methyl) acrylic acid; The resin that the multipolymer that makes (methyl) acrylic acid benzyl ester/(methyl) acrylic acid glycidyl esters obtains with the reaction of (methyl) acrylic acid; The resin that the multipolymer that makes (methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid glycidyl esters obtains with the reaction of (methyl) acrylic acid; The resin that the multipolymer that makes styrene/(methyl) acrylic acid glycidyl esters obtains with the reaction of (methyl) acrylic acid; The resin that the multipolymer that makes (methyl) methyl acrylate/(methyl) acrylic acid glycidyl esters obtains with the reaction of (methyl) acrylic acid; The resin that the multipolymer that makes N-cyclohexyl maleimide/(methyl) acrylic acid glycidyl esters obtains with the reaction of (methyl) acrylic acid; The resin that the multipolymer that makes (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester/(methyl) acrylic acid glycidyl esters obtains with the reaction of (methyl) acrylic acid; The resin that the multipolymer that makes (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid glycidyl esters obtains with the reaction of (methyl) acrylic acid; The resin that the multipolymer that makes (methyl) acrylic acid dicyclo amyl group ester/styrene/(methyl) acrylic acid glycidyl esters obtains with the reaction of (methyl) acrylic acid; The resin that the multipolymer that makes (methyl) acrylic acid dicyclo amyl group ester/(methyl) methyl acrylate/(methyl) acrylic acid glycidyl esters obtains with the reaction of (methyl) acrylic acid; The resin that the multipolymer that makes (methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide/(methyl) acrylic acid glycidyl esters obtains with the reaction of (methyl) acrylic acid

The resin that makes multipolymer and the crotonic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the crotonic acid reaction of (methyl) acrylic acid benzyl ester/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the crotonic acid reaction of (methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the crotonic acid reaction of styrene/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the crotonic acid reaction of ethyl crotonate/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the crotonic acid reaction of N-cyclohexyl maleimide/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the crotonic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the crotonic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the crotonic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/styrene/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the crotonic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/ethyl crotonate/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the crotonic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide/(methyl) acrylic acid glycidyl esters and obtain

The resin that makes multipolymer and the maleic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the maleic acid reaction of (methyl) acrylic acid benzyl ester/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the maleic acid reaction of (methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the maleic acid reaction of styrene/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the maleic acid reaction of maleic acid methyl esters/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the maleic acid reaction of N-cyclohexyl maleimide/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the maleic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the maleic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the maleic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/styrene/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the maleic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/maleic acid methyl esters/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the maleic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide/(methyl) acrylic acid glycidyl esters and obtain

The multipolymer that makes (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains; The multipolymer that makes (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 that makes (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 that makes styrene/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains; The multipolymer that makes (methyl) methyl acrylate/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains; The multipolymer that makes N-cyclohexyl maleimide/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains; The multipolymer that makes (methyl) acrylic acid dicyclo amyl group ester/(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 that makes (methyl) acrylic acid dicyclo amyl group ester/(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 that makes (methyl) acrylic acid dicyclo amyl group ester/styrene/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains; The multipolymer that makes (methyl) acrylic acid dicyclo amyl group ester/(methyl) methyl acrylate/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains; The multipolymer that makes (methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains

Make (methyl) acrylic acid dicyclo amyl group ester/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester obtains with the reaction of (methyl) acrylic acid; Make (methyl) acrylic acid benzyl ester/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester obtains with the reaction of (methyl) acrylic acid; Make (methyl) acrylic acid cyclohexyl ester/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester obtains with the reaction of (methyl) acrylic acid; Make styrene/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester obtains with the reaction of (methyl) acrylic acid; Make (methyl) methyl acrylate/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester obtains with the reaction of (methyl) acrylic acid; Make N-cyclohexyl maleimide/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester obtains with the reaction of (methyl) acrylic acid; Make (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester obtains with the reaction of (methyl) acrylic acid; Make (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester obtains with the reaction of (methyl) acrylic acid; Make (methyl) acrylic acid dicyclo amyl group ester/styrene/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester obtains with the reaction of (methyl) acrylic acid; Make (methyl) acrylic acid dicyclo amyl group ester/(methyl) methyl acrylate/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester obtains with the reaction of (methyl) acrylic acid; Make (methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester obtains with the reaction of (methyl) acrylic acid

Make (methyl) acrylic acid dicyclo amyl group ester/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid and the resin that obtains; Make (methyl) acrylic acid benzyl ester/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid and the resin that obtains; Make (methyl) acrylic acid cyclohexyl ester/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid and the resin that obtains; Make styrene/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid and the resin that obtains; Make ethyl crotonate/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid and the resin that obtains; Make N-cyclohexyl maleimide/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid and the resin that obtains; Make (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid and the resin that obtains; Make (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid and the resin that obtains; Make (methyl) acrylic acid dicyclo amyl group ester/styrene/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid and the resin that obtains; Make (methyl) acrylic acid dicyclo amyl group ester/ethyl crotonate/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid and the resin that obtains; Make (methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid and the resin that obtains

Make (methyl) acrylic acid dicyclo amyl group ester/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid and the resin that obtains; Make (methyl) acrylic acid benzyl ester/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid and the resin that obtains; Make (methyl) acrylic acid cyclohexyl ester/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid and the resin that obtains; Make styrene/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid and the resin that obtains; Make maleic acid methyl esters/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid and the resin that obtains; Make N-cyclohexyl maleimide/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid and the resin that obtains; Make (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid and the resin that obtains; Make (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid and the resin that obtains; Make (methyl) acrylic acid dicyclo amyl group ester/styrene/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid and the resin that obtains; Make (methyl) acrylic acid dicyclo amyl group ester/maleic acid methyl esters/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid and the resin that obtains; Make (methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid and the resin that obtains

Make (methyl) acrylic acid dicyclo amyl group ester/methacrylic acid 3; The multipolymer of 4-epoxycyclohexyl methyl ester and (methyl) acrylic acid react with maleic anhydride and the resin that obtains, make (methyl) acrylic acid benzyl ester/methacrylic acid 3; The multipolymer of 4-epoxycyclohexyl methyl ester and (methyl) acrylic acid react with maleic anhydride and the resin that obtains, make (methyl) acrylic acid cyclohexyl ester/methacrylic acid 3; The multipolymer of 4-epoxycyclohexyl methyl ester and (methyl) acrylic acid react with maleic anhydride and the resin that obtains, make styrene/methacrylic acid 3; The multipolymer of 4-epoxycyclohexyl methyl ester and (methyl) acrylic acid react with maleic anhydride and the resin that obtains, make (methyl) methyl acrylate/methacrylic acid 3; The multipolymer of 4-epoxycyclohexyl methyl ester and (methyl) acrylic acid react with maleic anhydride and the resin that obtains, make N-cyclohexyl maleimide/methacrylic acid 3; The multipolymer of 4-epoxycyclohexyl methyl ester and (methyl) acrylic acid react with maleic anhydride and the resin that obtains, make (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester/methacrylic acid 3; The multipolymer of 4-epoxycyclohexyl methyl ester and (methyl) acrylic acid react with maleic anhydride and the resin that obtains, make (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester/methacrylic acid 3; The multipolymer of 4-epoxycyclohexyl methyl ester and (methyl) acrylic acid react with maleic anhydride and the resin that obtains, make (methyl) acrylic acid dicyclo amyl group ester/styrene/methacrylic acid 3; The multipolymer of 4-epoxycyclohexyl methyl ester and (methyl) acrylic acid react with maleic anhydride and the resin that obtains, make (methyl) acrylic acid dicyclo amyl group ester/(methyl) methyl acrylate/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester and (methyl) acrylic acid obtain with the maleic anhydride reaction, make (methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide/methacrylic acid 3, the multipolymer of 4-epoxycyclohexyl methyl ester reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains etc.

The weight-average molecular weight (Mw) of the polystyrene conversion of resin (B2) is preferably 3000～100000, and more preferably 5000～50000.If the weight-average molecular weight of resin (B2) is in above-mentioned scope, the trend that then exists coating to become good in addition, is difficult to produce film and reduces during development, and then the trend that exists when developing the deciduous of non-pixel portion to become good.

The molecular weight distribution of resin (B2) [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] is preferably 1.5～6.0, and more preferably 1.8～4.0.If, then there is the excellent trend of development property in above-mentioned scope in the molecular weight distribution of resin (B2).

The acid number of resin (B2) is 20～150mg-KOH/g, is preferably 50～135mg-KOH/g, more preferably 65～135mg-KOH/g.Acid number is as being used for resin (B2) 1g and the value that the amount (mg) of essential potassium hydroxide is measured can be carried out titration through the use potassium hydroxide aqueous solution and tried to achieve.

The content of resin (B2), the total amount with respect to resin (B1) and resin (B2) is preferably 5～90 quality %, and more preferably 15～90 quality % are preferably 20～90 quality % especially.If the content of resin (B2) is in above-mentioned scope, then development property, adaptation, solvent resistance, mechanical property have the trend that becomes good.

Photosensitive composition of the present invention can contain the resin (BX) different with resin (B2) with resin (B1) as resin (B).As resin (BX), for example can enumerate (a) and multipolymer (c).The content of resin (BX) with respect to the gross mass of resin (B), is preferably 0～50 quality %, more preferably 0～30 quality %.

The gross mass of the resin that contains in the photosensitive composition of the present invention (B), the amount with respect to the solid formation of photosensitive composition divides is preferably 20～70 quality %, more preferably 25～50 quality %.

In addition, the total amount of resin (B), the total amount with respect to resin (B) and polymerizable compound (C) is preferably 20～80 quality %, more preferably 40～60 quality %.

Photosensitive composition of the present invention contains polymerizable compound (C).

Polymerizable compound (C) is to carry out polymeric compounds through the living radical that produced by polymerization initiator (D) and acid etc., can enumerate the compound that for example has ethylenic unsaturated bond, preferably enumerates (methyl) acrylate compounds.

As the polymerizable compound with 1 ethylenic unsaturated bond (C), can enumerate and be identical compound with the compound (c) enumerated as above-mentioned (a) and (b), wherein, be preferably (methyl) esters of acrylic acid.

As the polymerizable compound with 2 ethylenic unsaturated bonds (C); Can enumerate 1; 3-butylene glycol two (methyl) acrylic ester, 1; 3-butylene glycol (methyl) acrylic ester, 1, two (acryloxy ethyl) ethers of 6-hexanediol two (methyl) acrylic ester, ethylene glycol bisthioglycolate (methyl) acrylic ester, diethylene glycol two (methyl) acrylic ester, neopentyl glycol two (methyl) acrylic ester, triethylene glycol two (methyl) acrylic ester, TEG two (methyl) acrylic ester, polyethyleneglycol diacrylate, bisphenol-A, ethoxylation bisphenol-A two (methyl) acrylic ester, ethoxylated neopentylglycol two (methyl) acrylic ester, ethoxylation neopentyl glycol two (methyl) acrylic ester, 3-methyl pentanediol two (methyl) acrylic ester etc.

As the polymerizable compound with 3 above ethylenic unsaturated bonds (C), the reactant, caprolactone modification dipentaerythritol five (methyl) acrylic ester of reactant, caprolactone modification trimethylolpropane tris (methyl) acrylic ester, caprolactone modification pentaerythrite three (methyl) acrylic ester, caprolactone modification three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylic ester, caprolactone modification pentaerythrite four (methyl) acrylic ester, caprolactone modification dipentaerythritol five (methyl) acrylic ester, caprolactone modification dipentaerythritol six (methyl) acrylic ester, caprolactone modification tripentaerythritol four (methyl) acrylic ester, caprolactone modification tripentaerythritol five (methyl) acrylic ester, caprolactone modification tripentaerythritol six (methyl) acrylic ester, caprolactone modification tripentaerythritol seven (methyl) acrylic ester, caprolactone modification tripentaerythritol eight (methyl) acrylic ester, caprolactone modification pentaerythrite three (methyl) acrylic ester and acid anhydrides of reactant, tripentaerythritol seven (methyl) acrylic ester and acid anhydrides of reactant, dipentaerythritol five (methyl) acrylic ester and acid anhydrides that can enumerate trimethylolpropane tris (methyl) acrylic ester, pentaerythrite three (methyl) acrylic ester, three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylic ester, ethoxylated trimethylolpropane three (methyl) acrylic ester, propoxylation trimethylolpropane tris (methyl) acrylic ester, pentaerythrite four (methyl) acrylic ester, dipentaerythritol five (methyl) acrylic ester, dipentaerythritol six (methyl) acrylic ester, tripentaerythritol four (methyl) acrylic ester, tripentaerythritol five (methyl) acrylic ester, tripentaerythritol six (methyl) acrylic ester, tripentaerythritol seven (methyl) acrylic ester, tripentaerythritol eight (methyl) acrylic ester, pentaerythrite three (methyl) acrylic ester and acid anhydrides is Yu the reactant of the reactant of acid anhydrides, caprolactone modification tripentaerythritol seven (methyl) acrylic ester and acid anhydrides etc.Wherein, being preferably 3 officials can above monomer, more preferably dipentaerythritol six (methyl) acrylic ester.

The content of polymerizable compound (C), the amount with respect to the solid formation of photosensitive composition divides is preferably 5～50 quality %, more preferably 10～45 quality %.In addition, the total amount with respect to resin (B) and polymerizable compound (C) is preferably 20～80 quality %, more preferably 40～60 quality %.If the content of polymerizable compound (C), then exists intensity or the flatness of sensitivity, pattern, the trend that reliability becomes good in above-mentioned scope.

Photosensitive composition of the present invention contains polymerization initiator (D).

As polymerism initiating agent (D), so long as produce living radical and acid etc. through the effect of light, the polymeric compounds of initiated polymerization property compound (C) gets final product, and not special the qualification can be used known polymerization initiator.

As polymerization initiator (D), be preferably united imidazole, benzene alkyl ketone compound, triaizine compounds, acylphosphine oxide compound, oxime compound.In addition, can use the light cationic polymerization initiators of putting down in writing in the TOHKEMY 2008-181087 communique (for example by kation and the material that comes from lewis acidic negative ion formation).Wherein, consider, be preferably oxime compound from the sensitivity viewpoint.

As above-mentioned united imidazole, can enumerate 2,2 '-two (2-chlorphenyl)-4,4 ', 5; 5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2, the 3-dichlorophenyl)-4,4 '; 5,5 '-tetraphenyl bisglyoxaline (for example with reference to japanese kokai publication hei 6-75372 communique and japanese kokai publication hei 6-75373 communique), 2,2 '-two (2-chlorphenyl)-4,4 '; 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2-chlorphenyl)-4,4 '; 5,5 '-four (alkoxyl phenyl) bisglyoxaline, 2,2 '-two (2-chlorphenyl)-4,4 '; 5,5 '-four (dialkoxy phenyl) bisglyoxaline, 2,2 '-two (2-chlorphenyl)-4,4 '; 5,5 '-four (tri-alkoxy phenyl) bisglyoxaline (for example with reference to special public clear 48-38403 communique of Japan and japanese kokai publication sho 62-174204 communique), 4,4 ' 5,5 '-phenyl by the substituted imidazolium compounds of alkoxy carbonyl group (for example with reference to japanese kokai publication hei 7-10913 communique) etc.Preferably enumerate 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2, the 3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline.

As above-mentioned benzene alkyl ketone compound; The oligomer of diethoxy acetophenone, 2-methyl-2-morpholino-1-(4-methyl sulfane base 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, benzyldimethylketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl] propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenyl phenyl) propane-1-ketone etc. be can enumerate, 2-methyl-2-morpholino-1-(4-methyl sulfane base phenyl) propane-1-ketone, 2-dimethylamino-1-(4-morpholino phenyl)-2-benzyl butane-1-ketone etc. preferably enumerated.Also can use commercially available article such as イ Le ガキュア 369, イ Le ガキュア 907 (above BASF ジャパ Application society system).

As above-mentioned triaizine compounds, can enumerate 2, two (the trichloromethyl)-6-(4-methoxyphenyl) of 4--1,3,5-triazines, 2; Two (the trichloromethyl)-6-(4-methoxyl naphthyl) of 4--1,3,5-triazines, 2, two (the trichloromethyl)-6-piperonyls-1,3 of 4-; 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene) of 4--1,3,5-triazines, 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]-1,3 of 4-; 5-triazine, 2, two (the trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl] of 4--1,3,5-triazines, 2; Two (the trichloromethyl)-6-[2-(3, the 4-Dimethoxyphenyl) vinyl] of 4--1,3,5-triazines etc.

As above-mentioned acylphosphine oxide initiating agent, can enumerate 2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc.Also can use イ Le ガキュア 819 commercially available article such as (チバジャパ Application society systems).

As above-mentioned oxime compound; Can enumerate N-benzoyloxy-1-(4-phenyl sulfane base phenyl) butane-1-ketone-2-imines, N-benzoyloxy-1-(4-phenyl sulfane base phenyl) octane-1-ketone-2-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-[2-methyl-4-(3; 3-dimethyl-2,4-dioxa cyclopentyl-methyl oxygen base) benzoyl]-9H-carbazole-3-yl] ethane-1-imines etc.Also can use イ Le ガキュア OXE-01, OXE-02 (above BASF ジャパ Application society system), N-1919 commercially available article such as (ADEKA society systems).

And then, as polymerization initiator (D), can enumerate benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether, benzoin isobutyl ether; Benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 3,3 ', 4; 4 '-four (tert-butyl peroxide carbonyl) benzophenone, 2; 4, benzophenone cpds such as 6-tri-methyl benzophenone, 9; Naphtoquinone compounds such as 10-phenanthrenequione, 2-EAQ, camphorquinone, 10-butyl-2-chloro-acridine ketone, dibenzoyl, phenylglyoxylic acid methyl esters, two cyclopentadiene titanium compounds etc.They preferably with after the polymerization stated cause auxiliary agent (D1) (particularly amine) combination and use.

Further, can contain polymerization and cause auxiliary agent (D1).Polymerization causes auxiliary agent (D1) can be used with polymerization initiator (D) combination, and it is compound or the sensitizer that is used by the polymerization of the polymerizable compound of polymerization initiator initiated polymerization in order to promote.

Cause auxiliary agent (D1) as polymerization, can enumerate amines, thiazolinium compounds, alkoxy anthracene compound, thioxanthones compound, carboxylic acid compound etc.

As amines; Can enumerate triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl esters, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, benzoic acid 2-dimethylamino ethyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, N; N-dimethyl-p-toluidine, 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, 4; 4 '-two (ethylmethylamino) benzophenone etc.; Wherein, be preferably 4,4 '-two (diethylamino) benzophenone.Also can use the commercially available article of EAB-F (hodogaya chemical industry (strain) system) etc.

As thiazolinium compounds, can enumerate the compound shown in formula (III-1)～formula (III-3) etc.

As the alkoxy anthracene compound, can enumerate 9,10-dimethoxy anthracene, 2-ethyl-9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene, 9,10-dibutoxy anthracene, 2-ethyl-9,10-dibutoxy anthracene etc.

As the thioxanthones compound, can enumerate 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones etc.

As carboxylic acid compound, can enumerate phenyl sulfane guanidine-acetic acid, aminomethyl phenyl sulfane guanidine-acetic acid, ethylphenyl sulfane guanidine-acetic acid, Methylethyl phenyl sulfane guanidine-acetic acid, 3,5-dimethylphenyl sulfane guanidine-acetic acid, methoxyphenyl sulfane guanidine-acetic acid, Dimethoxyphenyl sulfane guanidine-acetic acid, chlorphenyl sulfane guanidine-acetic acid, dichlorophenyl sulfane guanidine-acetic acid, N-phenylglycine, phenoxyacetic acid, naphthyl thioacetic acid, N-naphthyl glycocoll, naphthoxy acetic acid etc.

The content of polymerization initiator (D), total amount 100 mass parts with respect to resin (B) and polymerizable compound (C) are preferably 0.1～40 mass parts, more preferably 1～30 mass parts.If the content of polymerization initiator (D) in this scope, then can form pattern with high sensitivity, the trend that exists resistance to chemical reagents, physical strength, the surface smoothing property of pattern to become good.

When using polymerization to cause auxiliary agent (D1), its consumption, total amount 100 mass parts with respect to resin (B) and polymerizable compound (C) are preferably 0.01～50 mass parts, more preferably 0.1～40 mass parts.In addition, with respect to 1 mole of polymerization initiator (D), be preferably 0.01～10 mole, more preferably 0.01～5 mole.If polymerization causes the amount of auxiliary agent (D1) in this scope, then can form pattern with further high sensitivity, there is the trend of the productivity raising of pattern.

In addition, photosensitive composition of the present invention can further contain multi-functional thiol's compound (T).This multi-functional thiol's compound (T) is for having the compound of 2 above sulfane bases in the molecule.Wherein, if use the compound have more than 2 with the sulfane base of aliphatic alkyl adjacency, then can form pattern, so preferred with high sensitivity.

As multi-functional thiol's compound (T); Can enumerate ethanthiol, the last of the ten Heavenly stems two mercaptan, 1; Two (the methyl sulfane base) benzene of 4-, butylene glycol two (3-sulfane base propionic ester), butylene glycol two (3-sulfane yl acetate), ethylene glycol bis (3-sulfane yl acetate), trimethylolpropane tris (3-sulfane yl acetate), butylene glycol two (3-sulfane base propionic ester), trimethylolpropane tris (3-sulfane base propionic ester), trimethylolpropane tris (3-sulfane yl acetate), pentaerythrite four (3-sulfane base propionic ester), pentaerythrite four (3-sulfane yl acetate), trihydroxyethyl three (3-sulfane base propionic ester), pentaerythrite four (3-sulfane base butyric ester), 1, two (3-sulfane base butoxy) butane of 4-etc.

The content of multi-functional thiol's compound (T) with respect to polymerization initiator (D) 100 mass parts, is preferably 0.5～20 mass parts, more preferably 1～15 mass parts.If the content of multi-functional thiol's compound (T) is in this scope, then sensitivity improves the trend that exists development property to become good in addition.

Solvent (E) is not limited especially, can use normally used solvent in this field.For example can from ester solvent (molecule contains-COO-, do not contain-O-solvent), ether solvents (molecule contains-O-, do not contain-COO-solvent), ether-ether solvent (molecule contains-COO-and-O-solvent), ketone solvent (molecule contains-CO-, do not contain-COO-solvent), alcoholic solvent, aromatic hydrocarbon solvents, amide solvent and dimethyl sulfoxide (DMSO) beyond the ester solvent beyond the ester solvent, select to use.These solvents can separately or make up more than 2 kinds and use.

As ester solvent, can enumerate methyl lactate, ethyl lactate, butyl lactate, 2-hydroxy-methyl isobutyl acid, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, 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 enumerate glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl 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-1-butanols, 3-methoxyl-3-methyl butanol, tetrahydrofuran, oxinane, 1,4-two

alkane, 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, methylbenzene methyl ether etc.

As the ether-ether solvent, can enumerate methoxy menthyl acetate, methoxyacetic acid ethyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 2-methoxypropionic acid methyl esters, 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, monoethylene 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 enumerate 4-hydroxy-4-methyl-2 pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2 pentanone, cyclopentanone, cyclohexanone, isophorone etc.

As alcoholic solvent, can enumerate methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, monoethylene glycol, propylene glycol, glycerine etc.

As aromatic hydrocarbon solvents, can enumerate benzene,toluene,xylene, mesitylene etc.

As amide solvent, can enumerate N, dinethylformamide, DMAC N,N, N-Methyl pyrrolidone etc.

In the above-mentioned solvent, consider that from the viewpoint of coating, drying property preferably the boiling point under the 1atm is 120 ℃～180 ℃ a organic solvent.Wherein, be preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether etc.

The content of solvent (E) with respect to the photosensitive composition total amount, is preferably 60～95 quality %, more preferably 70～90 quality %.In other words, the solid formation branch of photosensitive composition is preferably 5～40 quality %, more preferably 10～30 quality %.If the content of solvent (E) is in above-mentioned scope, the flatness when then being coated with has the trend that becomes good.

Photosensitive composition of the present invention preferably contains surfactant (F).As surfactant, for example can enumerate siloxane type surfactants, fluorine class surfactant and have the siloxane type surfactants of fluorine atom.Through containing surfactant, the flatness during coating has the trend that becomes good.

As siloxane type surfactants, can enumerate surfactant with siloxane bond.Specifically; Can enumerate トーレシリコー Application DC3PA 、トーレシリコー Application SH7PA 、トーレシリコー Application DC11PA 、トーレシリコー Application SH21PA 、トーレシリコー Application SH28PA 、トーレシリコー Application SH29PA 、トーレシリコー Application SH30PA, polyether modified silicon oil SH8400 (trade name: eastern レダウコーニ Application グ (strain) system); KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (モメ Application ティ Block パフォーマ Application スマテリア Le ズジャパ Application contract commercial firm system) etc.

As fluorine class surfactant, can enumerate surfactant with fluorocarbon chain.Specifically; Can enumerate Off ロリナート (registered trademark) FC430, Off ロリナート FC431 (Sumitomo スリーエ system (strain) system); メガ Off ァッ Network (registered trademark) F142D, メガ Off ァッ Network F171, メガ Off ァッ Network F172, メガ Off ァッ Network F173, メガ Off ァッ Network F177, メガ Off ァッ Network F183, メガ Off ァッ Network R30 (DIC (strain) system); エ Off トップ (registered trademark) EF301, エ Off トップ EF303, エ Off トップ EF351, エ Off トップ EF352 (the マテリア of Mitsubishi Le electronics changes into (strain) system), サー Off ロ Application (registered trademark) S381, サー Off ロ Application S382, サー Off ロ Application SC101, サー Off ロ Application SC105 (Asahi Glass (strain) system), E5844 ((strain) ダイキ Application Off ァイ Application ケミカ Le institute system) etc.

As siloxane type surfactants, can enumerate surfactant with siloxane bond and fluorocarbon chain with fluorine atom.Specifically, can enumerate メガ Off ァッ Network (registered trademark) R08, メガ Off ァッ Network BL20, メガ Off ァッ Network F475, メガ Off ァッ Network F477, メガ Off ァッ Network F443 (DIC (strain) system) etc.Be preferably メガ Off ァッ Network (registered trademark) F475.

Surfactant (F) with respect to photosensitive composition total amount of the present invention, is 0.001 quality %～0.2 quality %, is preferably 0.002 quality %～0.1 quality %, more preferably 0.01 quality %～0.05 quality %.Content through making surfactant can make the flatness of filming good in this scope.

Photosensitive composition of the present invention can contain filling agent, other various adjuvants such as macromolecular compound, driving fit promoter, anti-oxidant, ultraviolet light absorber, light stabilizer, chain-transferring agent as required.

Photosensitive composition of the present invention for example can be prepared as follows.

At first, the pigment of colorant (A) is mixed with solvent (E), the mean grain size of using ball mill etc. to be dispersed to pigment be below the 0.2 μ m about.Can cooperate a part of or whole of pigment dispersing agent, resin (B) this moment as required.In the dispersible pigment dispersion of gained; Add remaining resin (B), polymerizable compound (C) and polymerization initiator (D), other composition and then the solvent that appends as required of use as required with the concentration of regulation, can obtain the photosensitive composition of purpose.

Photosensitive composition of the present invention for example passes through the step shown in following (1)～(4), is processed as color filter.

(1) through photosensitive composition of the present invention is coated on the step that obtains coated film on the substrate,

(4) pattern is cured the step of the pattern that obtains thus solidifying.

As obtaining method of patterning, can enumerate photoetching process, ink-jet method, print process etc.Wherein, be preferably photoetching process.Photoetching process is that above-mentioned photosensitive composition is coated on the substrate and carries out drying, via photomask exposure, develops, and obtains method of patterning thus.

As aforesaid substrate, can enumerate for example glass, metal and plastics, can be for tabular, also can be for membranaceous.

As plastics; For example polyolefin such as tygon, polypropylene, norbornene polymer be can enumerate, polyvinyl alcohol (PVA), polyethylene terephthalate, PEN, (methyl) acrylic ester, cellulose esters, polycarbonate, polysulfones, polyethersulfone, polyetherketone, polyphenylene sulfide and polyphenylene oxide gathered.Wherein, (methyl) acrylic acid refers at least a kind that is selected from acrylic acid and methacrylic acid.On these substrates, can form color filter, various insulation or structures such as conducting film, driving circuit.

According to photosensitive composition of the present invention, can be formed on the more following pattern that solidifies of low temperature.Therefore, when on plastic base, forming pattern, particularly useful.

As coating process for substrate, for example can enumerate, extrusion coated method, direct photogravure rubbing method, reversal photogravure rubbing method, lid are coated with method and metal mold rubbing method.In addition, can use dip coater, roll coater, rod to be coated with apparatus for coating such as machine, spin coater, slit & spin coater, slit coater (being sometimes referred to as metal mold coating machine, curtain flow coater, non-rotary coating machine), ink-jet is coated with.Wherein, preferably using slit coater, spin coater, roll coater to wait is coated with.

As the drying means that is coated on the film on the substrate, can enumerate the for example method of heat drying, air dry, aeration-drying and drying under reduced pressure.Can make up several different methods carries out.

As baking temperature, be preferably 10～120 ℃, more preferably 25～100 ℃.In addition, as heat time heating time, be preferably 10 seconds～60 minutes, more preferably 30 seconds～30 minutes.

Drying under reduced pressure preferably under the pressure of 50～150Pa, 20～25 ℃ temperature range carries out.

Thickness to dried coated film does not limit especially, can wait suitably adjustment according to employed material, purposes, is generally 0.1～20 μ m, is preferably 1～6 μ m.

For dried coated film, make public via the photomask that is used to form the purpose pattern.Pattern form on the photomask of this moment is not limited especially, can use the pattern form that adapts with the purpose purposes.

Light source as using in the exposure preferably produces the light source that wavelength is the light of 250～450nm.For example can use to stop wavelength to stop the light of this wavelength region may, or use the BPF. that obtains near near near the light that 436nm is, 408nm is, 365nm is optionally to obtain the light of these wavelength region may less than the light filter of the light of 350nm.Specifically, can enumerate mercury lamp, light emitting diode, metal halide lamp and halogen lamp.

In order to shine parallel rays equably, or carry out the correct location matches of mask and base material, preferably use devices such as mask aligner, ledex during exposure whole plane of exposure.

After the exposure, coated film is contacted with developer solution,, develop, can obtain pattern thus for example unexposed portion dissolving of established part.As developer solution, can with an organic solvent, can obtain the pattern of good shape still for the exposure portion that makes coated film is difficult to produce dissolving, swelling by developer solution, preferably use the WS of alkali compounds.

Developing method can be any means in slurry method, infusion process, the spray-on process etc.Further, substrate can be with angle tilt arbitrarily during development.

Preferably wash after the development.

As above-mentioned alkali compounds; Can enumerate 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, soda mint, saleratus, sodium borate, potassium borate, ammonia, and organic basic compound such as TMAH, 2-hydroxyethyl trimethylammonium hydroxide, monomethyl amine, dimethyl amine, Trimethylamine, single ethylamine, diethylamide, triethylamine, single isopropylamine, diisopropylamine, monoethanolamine.As above-mentioned alkali compounds, be preferably potassium hydroxide, soda mint and TMAH.

The concentration of these alkali compounds in the WS is preferably 0.01～10 quality %, more preferably 0.03～5 quality %.

The WS of above-mentioned alkali compounds can contain surfactant.

As surfactant; Can enumerate polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other nonionic class surfactant such as polyoxyethylene deriv, ethylene oxide/propylene oxide segmented copolymer, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid ester, fatty acid glyceride, polyoxyethylene fatty acid ester, polyoxyethylene alkyl amine

Anionic species surfactants such as dodecanol sodium sulfovinate, oleyl alcohol sodium sulfovinate, lauryl sodium sulfate, ammonium lauryl sulfate, neopelex, dodecyl sodium naphthalene sulfonate, and cationic surfactant such as stearic amine hydrochloride, DTAC.

Surfactant concentrations in the WS of alkali compounds is preferably 0.01～10 quality %, and more preferably 0.05～8 quality % is preferably 0.1～5 quality % especially.

Pattern to obtaining as stated further cures, the pattern that can obtain solidifying thus.As stoving temperature, be 25 ℃～230 ℃, be preferably 25 ℃～200 ℃, more preferably 25 ℃～160 ℃, further be preferably 25 ℃～120 ℃.As the time of curing, be 1～300 minute, be preferably 1～180 minute, more preferably 1～60 minute.

By photosensitive composition of the present invention, suitably repetition can be made color filter thus by the pattern manufacturing that said method carries out.The color filter of gained can be used to have the display device of this color filter as the part of component parts with known method, in the instrument that for example liquid crystal indicator, organic El device, solid camera head, Electronic Paper etc. are relevant with rendered image.

[embodiment]

Below through embodiment the present invention is explained more specifically." % " in the example and " part " only otherwise specify are quality % and mass parts.

Synthetic example 1

An amount of person who lives in exile's nitrogen forms the nitrogen atmosphere in the flask with reflux condenser, tap funnel and stirring machine, adds 100 parts of propylene glycol monomethyl ether, is heated to 85 ℃ in the time of stirring.Then, use to drip pump, in this flask, drip, 4-epoxy three ring [5.2.1.0 19 parts of methacrylic acids, acrylic acid 3 with about 5 hours ^2.6] 171 parts of decyl ester (compound shown in compound shown in the formula (I-1) and the formula (II-1) is mixed with mol ratio 50:50) are dissolved in the solution that forms in 40 parts of the propylene glycol monomethyl ether.On the other hand, use other dropping pump in flask, to drip polymerization initiator 2 with about 5 hours, two (2, the 4-methyl pentane nitrile) 26 parts of 2 '-azo are dissolved in the solution that forms in 120 parts of the propylene glycol monomethyl ether.After the dropping of polymerization initiator finishes, under identical temperature, kept about 3 hours, be cooled to room temperature then, obtain that solid formation is divided into 43.5%, acid number is the 53mgKOH/g resin solution Ba of (solid formation divided conversion).The weight-average molecular weight Mw of resulting resin B a is 8000, and molecular weight distribution (Mw/Mn) is 1.98.

Synthetic example 2

In flask with stirring machine, thermometer, reflux condensing tube, tap funnel and nitrogen ingress pipe; Import propylene glycol monomethyl ether 123g; After making the interior atmosphere of flask by the spoiled nitrogen of air; After being warming up to 100 ℃; By tap funnel with in flask, dripping the solution that interpolation azobis isobutyronitrile 3.6g forms in the potpourri of the monomethacrylates that comprises benzyl methacrylate 72.6g (0.41 mole), methacrylic acid 42.0g (0.49 mole), tricyclodecane skeleton (Hitachi changes into (strain) system FA-513M) 23.0g (0.10 mole) and propylene glycol monomethyl ether 137g in 2 hours, further 100 ℃ of following continuous stirring 5 hours.Make the interior atmosphere of flask become air then by nitrogen; In flask, add methyl propenoic acid glycidyl base ester 21.3g [0.15 mole, (carboxyl with respect to the methacrylic acid of use in this reaction is 31 moles of %)], three (dimethylaminomethyl) phenol 0.9g and quinhydrones 0.145g; 110 ℃ of successive reactions 6 hours, obtain that solid formation is divided into 38.3%, acid number is the resin solution Bb of 120.1mgKOH/g (converting Gu form to divide).The weight-average molecular weight of the polystyrene conversion of measuring through GPC is 10500, and molecular weight distribution (Mw/Mn) is 2.1.

Synthetic example 3

In flask with stirring machine, thermometer, reflux condensing tube, tap funnel and nitrogen ingress pipe; Import propylene glycol monomethyl ether 125.1g; After making the interior atmosphere of flask become nitrogen by air; After being warming up to 100 ℃; By tap funnel with in flask, dripping the solution that interpolation azobis isobutyronitrile 3.6g forms in the potpourri of the monomethacrylates that comprises benzyl methacrylate 96.0g (0.55 mole), methacrylic acid 30.6g (0.36 mole), tricyclodecane skeleton (Hitachi changes into (strain) system FA-513M) 22.0g (0.10 mole) and propylene glycol monomethyl ether 149g in 2 hours, further 100 ℃ of continuous stirring 5 hours.Then make the interior atmosphere of flask become air by nitrogen; In flask, add methyl propenoic acid glycidyl base ester 21.3g [0.15 mole, (carboxyl with respect to the methacrylic acid of use in this reaction is 42 moles of %)], three (dimethylaminomethyl) phenol 0.9g and quinhydrones 0.145g; 110 ℃ of successive reactions 6 hours, obtain that solid formation is divided into 37.8%, acid number is the resin solution Bc of 67.7mgKOH/g (converting Gu form to divide).The weight-average molecular weight of the polystyrene conversion of measuring through GPC is 9400, and molecular weight distribution (Mw/Mn) is 2.0.

Synthetic example 4

In flask, flowed into nitrogen, form the nitrogen atmosphere, add 100 parts of 3-methoxyl-200 parts in 1-butanols and acetate 3-methoxyl butyl esters, be heated to 70 ℃ in the time of stirring with 0.02L/ minute with reflux condenser, tap funnel and stirring machine.Then, with 54 parts of methacrylic acids, acrylic acid 3,4-epoxy three ring [5.2.1.0 ^2.6] 180 parts of decyl ester (compound shown in compound shown in the formula (I-1) and the formula (II-1) is mixed with mol ratio 50:50) and 67 parts of N-cyclohexyl maleimides be dissolved in 140 parts of the 3-methoxyls-1-butanols; Preparation solution use to drip pump and this solution is used to be added drop-wise to insulation in 4 hours be in 70 ℃ the flask.On the other hand, use other dropping pump in flask, to drip polymerization initiator 2 with 4 hours, two (2, the 4-methyl pentane nitrile) 20 parts of 2 '-azo are dissolved in the solution that forms in 240 parts of the acetate 3-methoxyl butyl esters.After the dropping of the solution of polymerization initiator finishes, kept 4 hours, be cooled to room temperature then, obtain that solid formation is divided into 32.6%, the solution acid number is the solution of the resin solution Bd of 34.3mg-KOH/g at 70 ℃.The weight-average molecular weight Mw of the resin B d of gained is 9000, and molecular weight distribution (Mw/Mn) is 1.9.

Synthetic example 5

In flask, import 250 parts of propylene glycol monomethyl ether with stirring machine, thermometer, reflux condensing tube, tap funnel and gas introduction tube.Then, the using gases ingress pipe imports to nitrogen in the flask, and atmosphere in the flask is replaced into nitrogen.Then; After solution in the flask is warming up to 100 ℃; Use tap funnel with 2 hours in flask dropping comprise the potpourri of 150 parts of 152.6 parts of benzyl methacrylates, 41.7 parts of methacrylic acids, 1.5 parts of azobis isobutyronitriles and propylene glycol monomethyl ether; After being added dropwise to complete, further 100 ℃ of continuous stirring 2.5 hours, obtaining weight-average molecular weight Mw was 2.3 * 10 ⁴, solid form be divided into 34%, the solution acid number is the resin solution Be of 47mg-KOH/g.

The weight-average molecular weight (Mw) of the resin that obtains in the synthetic example and the mensuration of number-average molecular weight (Mn) are used the GPC method, under following condition, carry out.

Device: K2479 ((strain) Shimadzu Seisakusho Ltd. system)

Pillar: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ℃

Solvent: THF (tetrahydrofuran)

Flow velocity, 1.0mL/min

Detecting device: RI

With the ratio (Mw/Mn) of the weight-average molecular weight of the above-mentioned polystyrene conversion that obtains and number-average molecular weight as molecular weight distribution.

Embodiment 1

[preparation of photosensitive composition 1]

With pigment: 177 49 parts of C.I. paratoneres

16 parts of polyesters pigment dispersing agents

29 parts of resin solution Be

280 parts of propylene glycol monomethyl ether

Mix, use ball mill that pigment is fully disperseed and form dispersible pigment dispersion A,

With pigment: 254 5.9 parts of C.I. paratoneres

2.2 parts of acrylic compounds pigment dispersing agents

4.9 parts of resin solution Be

29 parts of propylene glycol monomethyl ether

Mix, use ball mill that pigment is fully disperseed and form dispersible pigment dispersion B,

With above-mentioned dispersible pigment dispersion A, above-mentioned dispersible pigment dispersion B,

Resin (B1): 126 parts of resin solution Ba,

Resin (B2): 72 parts of resin solution Bb,

Polymerizable compound: 63 parts of dipentaerythritol acrylates (KAYARAD DPHA, Japanese chemical drug (strain) system),

Polymerization initiator: 9.4 parts of N-benzoyloxy-1-(4-phenyl sulfane base phenyl) octanes-1-ketone-2-imines (イ Le ガキュア OXE-01, BASF ジャパ Application society system),

Solvent: 313 parts of propylene glycol monomethyl ether and

Surfactant: polyether modified silicon oil 1-amino-2-naphthol-4-sulfonic acid トーレシリコー Application SH8400, eastern レダウコーニ Application グ (strain) system) 0.02 part

Mix, obtain photosensitive composition 1.

Embodiment 2

[preparation of photosensitive composition 2]

With pigment: 9 18 parts of C.I. pigment yellow 13s

7.2 parts of polyesters pigment dispersing agents

13 parts of resin solution Be

116 parts of propylene glycol monomethyl ether

With pigment: 177 72 parts of C.I. paratoneres

20 parts of polyesters pigment dispersing agents

61 parts of resin solution Be

310 parts of propylene glycol monomethyl ether

Resin (B1): 90 parts of resin solution Ba,

Resin (B2): 78 parts of resin solution Bc,

Polymerizable compound: 40 parts of dipentaerythritol acrylates (KAYARAD DPHA, Japanese chemical drug (strain) system),

Polymerization initiator: 8.1 parts of N-benzoyloxy-1-(4-phenyl sulfane base phenyl) octanes-1-ketone-2-imines (イ Le ガキュア OXE-01, BASF ジャパ Application society system),

Solvent: 165 parts of propylene glycol monomethyl ether and

Mix, obtain photosensitive composition 2.

Embodiment 3

[preparation of photosensitive composition 3]

To with pigment: 254 51 parts of C.I. paratoneres

15 parts of polyesters pigment dispersing agents

287 parts of propylene glycol monomethyl ether

Mix, and use in the dispersible pigment dispersion that ball mill fully disperses pigment to form, then mix

Resin (B1): 184 parts of resin solution Ba

Resin (B2): 50 parts of resin solution Bb

Polymerizable compound: 64 parts of dipentaerythritol acrylates (KAYARAD DPHA, Japanese chemical drug (strain) system)

Polymerization initiator: 13 parts of N-benzoyloxy-1-(4-phenyl sulfane base phenyl) octanes-1-ketone-2-imines (イ Le ガキュア OXE-01, BASF ジャパ Application society system)

Solvent: 336 parts of propylene glycol monomethyl ether

Surfactant: polyether modified silicon oil 1-amino-2-naphthol-4-sulfonic acid トーレシリコー Application SH8400; East レダウコーニ Application グ (strain) system) 0.02 part

Obtain photosensitive composition 3.

Embodiment 4

[preparation of photosensitive composition 4]

With pigment: 14 parts of C.I. pigment green 36s

2.7 parts of polyesters pigment dispersing agents

4.0 parts of resin solution Be

56 parts of propylene glycol monomethyl ether

With pigment: 8 12 parts of C.I. pigment yellow 13s

2.5 parts of polyesters pigment dispersing agents

1.9 parts of resin solution Be

66 parts of propylene glycol monomethyl ether

With above-mentioned dispersible pigment dispersion A, above-mentioned dispersible pigment dispersion B, resin (B1): 142 parts of resin solution Ba,

Resin (B2): 41 parts of resin solution Bc,

Polymerizable compound: 80 parts of dipentaerythritol acrylates (KAYARAD DPHA, Japanese chemical drug (strain) system),

Polymerization initiator: 9.6 parts of N-benzoyloxy-1-(4-phenyl sulfane base phenyl) octanes-1-ketone-2-imines (イ Le ガキュア OXE-01, BASF ジャパ Application society system),

Solvent: 570 parts of propylene glycol monomethyl ether and

Mix, obtain photosensitive composition 4.

Embodiment 5

[preparation of photosensitive composition 5]

With pigment: 58 53 parts of C.I. naphthol greens

11 parts of acrylic compounds pigment dispersing agents

62 parts of resin solution Be

251 parts of propylene glycol monomethyl ether

With pigment: 8 30 parts of C.I. pigment yellow 13s

4.4 parts of polyesters pigment dispersing agents

31 parts of resin solution Be

136 parts of propylene glycol monomethyl ether

Resin (B1): 18 parts of resin solution Ba,

Resin (B2): 147 parts of resin solution Bb,

Polymerizable compound: 64 parts of dipentaerythritol acrylates (KAYARAD DPHA, Japanese chemical drug (strain) system),

Polymerization initiator: 13 parts of N-benzoyloxy-1-(4-phenyl sulfane base phenyl) octanes-1-ketone-2-imines (イ Le ガキュア OXE-01, BASF ジャパ Application society system),

Solvent: 181 parts of propylene glycol monomethyl ether and

Mix, obtain photosensitive composition 5.

Embodiment 6

[preparation of photosensitive composition 6]

To with pigment: 177 28 parts of C.I. paratoneres

Pigment: 254 86 parts of C.I. paratoneres

10 parts of polyesters pigment dispersing agents

27 parts of resin solution Be

403 parts of propylene glycol monomethyl ether

Resin (B1): 87 parts of resin solution Bd

Resin (B2): 99 parts of resin solution Bb

Polymerizable compound: 33 parts of dipentaerythritol acrylates (Japanese chemical drug (strain) system)

Polymerization initiator: 13 parts in 2-methyl-2-morpholino-1-(4-methyl sulfane base phenyl) propane-1-ketone (イ Le ガキュア 907, BASF ジャパ Application society system)

Polymerization causes auxiliary agent: 7.6 parts of 4,4 '-two (diethylamino) benzophenone (EAB-F, hodogaya chemical industry (strain) system)

Solvent: 294 parts of propylene glycol monomethyl ether,

Obtain photosensitive composition 6.

Comparative example 1

[preparation of photosensitive composition 7]

To with pigment: 177 28 parts of C.I. paratoneres

Pigment: 254 86 parts of C.I. paratoneres

10 parts of polyesters pigment dispersing agents

27 parts of resin solution Be

404 parts of propylene glycol monomethyl ether

Resin: 169 parts of resin solution Bd

Polymerizable compound: 32 parts of dipentaerythritol acrylates (Japanese chemical drug (strain) system)

Polymerization initiator: 12 parts in 2-methyl-2-morpholino-1-(4-methyl sulfane base phenyl) propane-1-ketone (イ Le ガキュア 907, BASF ジャパ Application society system)

Polymerization causes auxiliary agent: 7.4 parts of 4,4 '-two (diethylamino) benzophenone (EAB-F, hodogaya chemical industry (strain) system)

Solvent: 92 parts of propylene glycol monomethyl ether

67 parts of 3-methoxyls-1-butanols

67 parts of acetate 3-methoxyl butyl esters,

Obtain photosensitive composition 7.

< making of pattern >

Applying PET film on 2 inches square glass plates (eastern レ system Le ミラー 75-T60) is made substrate.In the PET of substrate film side, through spin-coating method coating photosensitive composition, on heating plate in 60 ℃ of preliminary dryings 2 minutes.Put cold after, make the 150 μ m that are spaced apart of this substrate that is coated with photosensitive composition and quartz glass system photomask, use exposure machine (TME-150RSK, トプコ Application (strain) system), under atmospheric atmosphere, with 150mJ/cm ²Exposure (365nm benchmark) carry out rayed.And, as photomask, use to have formed the line of 10～100 μ m and the photomask of space pattern.After the rayed, in the water system developer solution that contains nonionic class surfactant 0.12% and potassium hydroxide 0.04%, developed in 40 seconds, wash, form pattern with pure water at 23 ℃ of dippings.Use determining film thickness device (DEKTAK3, Japanese vacuum technique (strain) system) to measure the thickness of gained pattern, the result is 2 μ m.

Pattern to above-mentioned same formation further heats 5 minutes (back baking), the pattern that obtains solidifying at 50 ℃.In addition, the pattern with above-mentioned same formation is further heated 5 minutes (back baking), the pattern that obtains solidifying at 100 ℃.With the thickness of the pattern of the above-mentioned curing of likewise measuring gained, the result is 2 μ m.

< solvent resistance evaluation >

Drip propylene glycol monomethyl ether 1ml to the pattern that on aforesaid substrate, forms, after static 30 seconds, use spin coater under the condition of rotating speed 1000rpm, to rotate 10 seconds, get rid of the propylene glycol monomethyl ether on the pattern.

By the film thickness value of measuring before and after contacting with propylene glycol monomethyl ether, through computes thickness conservation rate.The thickness conservation rate is high more, and then curable is good more, when making color filter, can prevent colour mixture.The result is as shown in table 1.

(thickness conservation rate) (%)=(thickness after the contact)/(contact before thickness)

< evaluation of resolution >

To the pattern that obtains, observe through laser microscope (Axio Imager MAT カー Le Star ァイス society system), with the minimum dimension of differentiating as resolution.Resolution is high more, can make high meticulous color filter.The result is as shown in table 1.

[table 1]

Can confirm to use the excellent in resolution of the pattern that the photosensitive composition of embodiment forms.In addition, even when the high temperature that surpasses 200 ℃ carries out baking step, can confirm that also solvent resistance is excellent.Hence one can see that, even use low heat resistant substrate, also can obtain high meticulous and high-quality color filter.

The industry utilizability

According to photosensitive composition of the present invention, can obtain high pattern of resolution and high-quality color filter.

Claims

1. photosensitive composition, it contains:

(A) colorant,

(B1) contain come from least a structural unit that is selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides and come from have carbon number be 2～4 cyclic ether and ethylenic unsaturated bond monomer structural unit multipolymer (wherein; Side chain does not have ethylenic unsaturated bond)

(B2) side chain has the resin of ethylenic unsaturated bond,

(C) polymerizable compound,

(D) polymerization initiator and

(E) solvent.

2. the described photosensitive composition of claim 1 wherein, (B2) is the resin that multipolymer that following (a) and (c) copolymerization are obtained further obtains with (b) reaction,

(a) be selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides at least a,

(b) be that to have carbon number be 2～4 the cyclic ether and the monomer of ethylenic unsaturated bond,

(c) be have can with (a) and (b) monomer of the unsaturated link of copolymerization.

3. claim 1 or 2 described photosensitive compositions, wherein, content (B1) is 10 quality %～95 quality % with respect to (B1) and total amount (B2).

4. pattern, it is formed by the described photosensitive composition of claim 1.

5. color filter, it contains the described pattern of claim 4.

6. manufacturing method of color filter, it contains the step shown in following (1)～(4),

(1) through any described photosensitive composition in the claim 1～3 is coated on the step that obtains coated film on the substrate,

(3) develop with alkaline developer through the back coated film of will making public, obtain the step of pattern,

(4) through pattern is cured, the step of the pattern that obtains solidifying.

7. the described manufacturing method of color filter of claim 6, wherein, step (4) is the step of curing 25 ℃～120 ℃ temperature.

8. claim 6 or 7 described manufacturing method of color filter, wherein, the substrate in the step (1) is a plastic base.