CN102375337A

CN102375337A - Photosensitive resin composition

Info

Publication number: CN102375337A
Application number: CN2011102272011A
Authority: CN
Inventors: 松浦龙一; 武部和男
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2010-08-10
Filing date: 2011-08-09
Publication date: 2012-03-14
Also published as: JP2012058728A; TW201214038A; KR20120023546A

Abstract

The present utility model provides a photosensitive resin composition for forming films and patterns with high visible light transmitivity. The photosensitive resin composition comprises resin (A), polymerized compound (B), polymerized initiator (C) and solvent (D). The polymerized initiator (C) comprises compound represented by the formula (1), wherein R1 represents naphthenic base with carbon number of 3 to 8, L1 represents alkane two base with carbon number of 1 to 5, L2 represents a single bond or CO, R2 represents methyl, phenyl or benzyl, and R3 represents thiophenyl phenyl with substitutent group or carbazolyl with substituent group.

Description

Photosensitive polymer combination

Technical field

The present invention relates to photosensitive polymer combination.

Background technology

In recent years in the display panels etc., in order to form optical interval spare (photo spacer), outer cover, the usability photosensitive resin composition.As such photosensitive polymer combination; For example comprise resin, polymerizable compound, polymerization initiator and solvent, known polymerization initiator is arranged is the photosensitive polymer combination (patent documentation 1) of N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] ethane-1-imines.

[prior art document]

[patent documentation]

[patent documentation 1] TOHKEMY 2008-181087 communique

Yet for the photosensitive polymer combination that proposed in the past, the viewpoint from the transmission of visible light of filming of obtaining, pattern may not necessarily satisfy sometimes fully.

Summary of the invention

The present invention provides following [1]～[6].

[1] a kind of photosensitive polymer combination, it comprises resin (A), polymerizable compound (B), polymerization initiator (C) and solvent (D), and polymerization initiator (C) is the polymerization initiator that contains the represented compound of formula (1),

In the formula (1), R ¹The naphthenic base of expression carbon number 3～8;

L ¹Alkane two bases of expression carbon number 1～5;

L ²The expression singly-bound or-CO-;

R ²Expression methyl, phenyl or benzyl;

R ³Expression can have substituent thiophenyl phenyl (Phenylsulfanyl phenyl), maybe can have substituent carbazyl].

[2] like above-mentioned [1] described photosensitive polymer combination, wherein, the L in the formula (1) ²Expression-CO-.

[3] like above-mentioned [1] or above-mentioned [2] described photosensitive polymer combination, wherein, the content of the compound that formula (1) is represented is 30～100 quality % with respect to the total amount of polymerization initiator (C).

[4] like each the described photosensitive polymer combination in above-mentioned [1]～[3], wherein, resin (A) is for comprising the resin from the structural unit of the monomer of cyclic ether structure with carbon number 2～4 and carbon-to-carbon unsaturated double-bond.

[5] a kind of filming, it is obtained by each the described photosensitive polymer combination in above-mentioned [1]～[4].

[6] a kind of pattern, it is obtained by each the described photosensitive polymer combination in above-mentioned [1]～[4].

[7] a kind of display device, its contain be selected from above-mentioned [5] described film with above-mentioned [6] described pattern at least a kind.

According to photosensitive polymer combination of the present invention, can form high the filming and pattern of transmission of visible light.

Embodiment

Below, the present invention is at length explained.

Photosensitive polymer combination of the present invention contains resin (A), polymerizable compound (B), contains the polymerization initiator (C) and the solvent (D) of the represented compound of formula (1).

[in the formula (1), R ¹The naphthenic base of expression carbon number 3～8.

L ¹Alkane two bases of expression carbon number 1～5.

L ²The expression singly-bound or-CO-.

R ²Expression methyl, phenyl or benzyl.

R ³Expression can have substituent thiophenyl phenyl, maybe can have substituent carbazyl.]

In addition, in this manual, as the illustrative compound of each composition, short of special instruction can be used alone or in combination.

Photosensitive polymer combination of the present invention contains resin (A).As resin (A), preferred bases soluble resin.So-called alkali soluble resin is meant the resin in the developer solution of stating after being dissolved in.

As the resin (A) that can in photosensitive polymer combination of the present invention, use, for example, can enumerate:

Resin (A-1): will be selected from least a kind (a) in unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides (below be sometimes referred to as " (a) ") and have the multipolymer that the cyclic ether structure of carbon number 2～4 and the monomer (b) of carbon-to-carbon unsaturated double-bond (below be sometimes referred to as " (b) ") are polymerized;

Resin (A-2): with (a) and (b) and can with (a) and (b) monomer of copolymerization (c) (the cyclic ether structure that wherein, does not comprise carbon number 2～4.) (below be sometimes referred to as " (c) ") multipolymer of being polymerized;

Resin (A-3): the multipolymer that makes (a) and (c) be polymerized;

Resin (A-4): make (b), with the resin that (a) obtains with (c) copolymer reaction;

Resin (A-5): make (a), with the resin that (b) obtains etc. with (c) copolymer reaction.As resin (A), preferred resin (A-1) and resin (A-2), more preferably resin (A-1).

As (a), can enumerate particularly: acrylic acid, methacrylic acid, crotonic acid, adjacent vinyl benzoic acid, a vinyl benzoic acid, unsaturated monocarboxylic classes such as vinyl benzoic acids;

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

Unsaturated list ((methyl) acryloxyalkyl) the ester class of the polybasic carboxylic acid more than mono succinate (2-(methyl) acryloxy ethyl), the phthalic acid list divalents such as (2-(methyl) acryloxy ethyls);

The unsaturated esters of acrylic acid that in a part, contains hydroxyl and carboxyl of α-(hydroxymethyl) acrylic acid and so on etc.

Wherein, preferably use acrylic acid, methacrylic acid, maleic anhydride etc. from the viewpoint of copolyreaction property and the viewpoint of alkali dissolution property.

At this, in this manual, so-called " (methyl) acrylic acid ", expression is selected from least a kind in acrylic acid and the methacrylic acid.Expression way such as " (methyl) acryloyl " and " (methyl) acrylic ester " also has the same meaning.

(b) for example be meant polymerizable compound with the cyclic ether structure (for example, at least a kind in oxirane ring, oxetanes ring and the tetrahydrofuran ring (dioxolanes)) that is selected from carbon number 2～4.(b) be preferably the cyclic ether structure with carbon number 2～4 and the monomer of carbon-to-carbon unsaturated double-bond, more preferably have the cyclic ether structure of carbon number 2～4 and the monomer of (methyl) acryloxy.

As (b), for example can enumerate monomer (b1) with Oxyranyle (below be sometimes referred to as " (b1) "), have Oxyranyle monomer (b2) (below be sometimes referred to as " (b2) "), have monomer (b3) (below be sometimes referred to as " (b3) ") of tetrahydrofuran base etc.

What is called has the monomer (b1) of Oxyranyle, is meant the polymerizable compound with Oxyranyle.As (b1); For example can enumerate: have the structure that the chain type alkene epoxidation is formed and the monomer (b1-1) (following " being sometimes referred to as (b1-1) ") of carbon-to-carbon unsaturated double-bond, have the monomer (b1-2) (below be sometimes referred to as " (b1-2) ") of structure that unsaturated lipid ring type hydrocarbon epoxidation is formed and carbon-to-carbon unsaturated double-bond.

As (b1), be preferably monomer with Oxyranyle and carbon-to-carbon unsaturated double-bond, more preferably have the monomer of Oxyranyle and (methyl) acryloxy, further preferably have (b1-2) of (methyl) acryloxy.

As (b1-1); Can enumerate particularly: glycidyl (methyl) acrylic ester, Beta-methyl glycidyl (methyl) acrylic ester, β-ethyl glycidyl (methyl) acrylic ester, glycidyl vinyl ether, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, vinyl benzyl glycidyl ether, Alpha-Methyl-O-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, 2,3 of 6-, 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 (b1-2), can enumerate VCH list oxide, 1,2-epoxy-4-vinyl cyclohexane (for example, " セロキサイト " 2000; Daicel chemical industry (strain) system), 3,4-epoxycyclohexyl methacrylate (for example, サイ Network ロマ one A400; Daicel chemical industry (strain) system), methacrylic acid 3,4-epoxycyclohexyl methyl ester (for example, サイ Network ロマ one M100; Daicel chemical industry (strain) system), the represented compound of represented compound, the formula (II) of formula (I) etc.

[in formula (I) and the formula (II), R ^aAnd R ^bRepresent hydrogen atom independently of each other, or the alkyl of carbon number 1～4, hydrogen atom contained in this alkyl can replace with hydroxyl.

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

R ^cAlkane two bases of expression carbon number 1～6.

* represent binding end with the O bonding.]

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

As using the substituted alkyl of hydroxyl, can enumerate hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyl-1-Methylethyl, 2-hydroxyl-1-Methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl etc.

As R ^aAnd R ^b, preferably can enumerate hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, more preferably can enumerate hydrogen atom, methyl.

As alkane two bases, can enumerate methylene, 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 can enumerate singly-bound, methylene, ethylidene, *-CH ₂-O-(* representes the binding end with the O bonding) base, *-CH ₂CH ₂-O-base, more preferably can enumerate singly-bound, *-CH ₂CH ₂-O-base.

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

As the represented compound of formula (II), can enumerate the represented compound of formula (II-1)～formula (II-15) etc.Preferably can enumerate formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), formula (II-11)～formula (II-15).

More preferably can enumerate formula (II-1), formula (II-7), formula (II-9), formula (II-15).

Compound that formula (I) is represented and the represented compound of formula (II) can be distinguished independent use.In addition, they can mix use by arbitrary proportion.During mixing, its mixture ratio is with molar ratio computing, and preferred formula (I): formula (II) is 5: 95～95: 5, and more preferably 10: 90～90: 10, especially preferred 20: 80～80: 20.

What is called has the monomer (b2) of Oxyranyle, is meant the polymerizable compound with Oxyranyle.As (b2), be preferably monomer with Oxyranyle and carbon-to-carbon unsaturated double-bond, more preferably have the monomer of Oxyranyle and (methyl) acryloxy.As (b2), for example can enumerate: 3-methyl-3-(methyl) acryloyl-oxy ylmethyl oxetanes, 3-ethyl-3-(methyl) acryloyl-oxy ylmethyl oxetanes, 3-methyl-3-(methyl) acryloxy ethyl oxetanes, 3-ethyl-3-(methyl) acryloxy ethyl oxetanes etc.

What is called has the monomer (b3) of tetrahydrofuran base, is meant the polymerizable compound with tetrahydrofuran base.As (b3), be preferably monomer with tetrahydrofuran base and carbon-to-carbon unsaturated double-bond, more preferably have the monomer of tetrahydrofuran base and (methyl) acryloxy.

As (b3), can enumerate tetrahydrofurfuryl acrylic ester (for example, ViscoatV#150, Osaka organic chemistry industry (strain) system), tetrahydrofurfuryl methacrylate etc. particularly.

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-methylcyclohexyl ester, three ring [5.2.1.0 ^2,6] (methyl) acrylic acid cyclic alkyl ester classes such as decane-8-base (methyl) acrylic ester (being called (methyl) acrylic acid two cyclopentyl esters in this technical field as trivial name, English: Dicyclopentanyl (meth) acrylate), two cyclopentyloxy ethyl (methyl) acrylic ester, bornyl (methyl) acrylic ester;

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

Dicarboxylic diesters such as maleic acid diethyl ester, fumaric acid diethyl ester, itaconic acid diethyl ester;

Hydroxyalkyl acrylate classes such as (methyl) acrylic acid 2-hydroxyethyl ester, (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-cyclohexyl oxygen base 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, 5 of 6-, dicyclo unsaturated compound classes such as two (cyclohexyl oxygen base carbonyl) dicyclo [2.2.1] hept-2-ene"s of 6-;

Diimide 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, 2; 3-dimethyl-1,3-butadiene etc.

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

In resin (A-1),, be preferably following scope from the ratio of the structural unit of each monomer total molal quantity with respect to the structural unit that constitutes resin (A-1).

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

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

When the ratio of the structural unit of resin (A-1) is in above-mentioned scope; The storage stability of photosensitive polymer combination, the development property when forming pattern by photosensitive polymer combination, and the solvent resistance of filming of obtaining and pattern, thermotolerance and physical strength tendency are for good.

As resin (A-1), preferred (b) is the resin of (b1), and more preferably (b) is the resin of (b1-2).

The citing document of putting down in writing in the method for record and the document during resin (A-1) for example can list of references " experimental method of Polymer Synthesizing " (the big grand row work sale room of Feng (strain) chemistry is with the distribution on March 1st, 1972 of the 1st edition the 1st brush of people) is made.

But illustration particularly, with ormal weight (a) and (b), polymerization initiator and solvent etc. drop in the reaction vessel, for example use the nitrogen replace oxygen, form deoxidation atmosphere, stir the method for on one side heating and insulation on one side.In addition, polymerization initiator used herein and solvent etc. do not have special the qualification, can use the normally used arbitrary substance in this field.For example, as polymerization initiator, can enumerate azo-compound (2; 2 '-azoisobutyronitrile, 2; 2 '-azo two (2, the 4-methyl pentane nitrile) etc.), organic peroxide (benzoyl peroxide etc.), as solvent; As long as can dissolve each monomer, state solvent (D) etc. after can using as the solvent of photosensitive polymer combination.

In addition, the multipolymer of gained can directly use reacted solution, also can use the solution that concentrates or diluted, the material that also can use methods such as utilization precipitates again to take out with solid (powder) form.Need to prove especially, during this polymerization through use with after state the same solvent of solvent (D) as solvent, can directly use reacted solution, can manufacturing process be simplified.

In resin (A-2),, preferably be in following scope from the ratio of the structural unit of each monomer total molal quantity with respect to the entire infrastructure unit that constitutes resin (A-2).

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

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

Structural unit from (c): 1～65 mole of % (more preferably 1～60 mole of %)

When the ratio of the structural unit of resin (A-2) is in above-mentioned scope, the storage stability of photosensitive polymer combination, the development property when forming pattern and filming of obtaining and solvent resistance, thermotolerance and the physical strength of pattern are tended to well by photosensitive polymer combination.

As resin (A-2), preferred (b) is the resin of (b1), and more preferably (b) is the resin of (b1-2).

Resin (A-2) is capable of using in the same method manufacturing of resin (A-1).

In resin (A-3),, preferably be in following scope from the ratio of the structural unit of each monomer total molal quantity with respect to the entire infrastructure unit that constitutes resin (A-3).

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

Structural unit from (c): 60～98 moles of % (more preferably 65～95 moles of %)

When the ratio of the structural unit of resin (A-3) is in above-mentioned scope, the storage stability of photosensitive polymer combination, the development property when forming pattern and filming of obtaining and solvent resistance, thermotolerance and the physical strength of pattern are tended to well by photosensitive polymer combination.

Resin (A-3) can be through the method manufacturing same with resin (A-1).

Resin (A-4) and resin (A-5) for example can pass through the two-stage operation and make.At this moment; Also can be with reference to the method for record in the above-mentioned document " experimental method of Polymer Synthesizing " (the big grand row work sale room of Feng (strain) chemistry is with the distribution on March 1st, 1972 of the 1st edition the 1st brush of people), the method for putting down in writing in the TOHKEMY 2001-89533 communique waits to be made.

For resin (A-4), at first,, likewise obtain (a) and multipolymer (c) with the manufacturing approach of above-mentioned resin (A-1) as the phase one.

At this moment, with above-mentioned same, the multipolymer of gained can directly use reacted solution, also can use the solution that concentrates or dilute, the material that also can use methods such as utilization precipitates again to take out with solid (powder) form.

From the ratio of (a) and structural unit (c) total molal quantity, preferably be in following scope with respect to the entire infrastructure unit that constitutes above-mentioned multipolymer.

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

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

Then, as subordinate phase, make from the part of the carboxylic acid of (a) of the multipolymer of gained and carboxylic acid anhydrides and (b) cyclic ether reaction.From the reactive height of cyclic ether, unreacted (b) is difficult to remaining viewpoint and sets out, as (b) preferred (b1), further preferred (b1-1).

Particularly; And then above-mentioned steps is replaced into air with atmosphere in the flask from nitrogen, with respect to the molal quantity of (a); (b) that in flask, adds 5～80 moles of %; With respect to (a), (b) add the carboxyl of 0.001～5 quality % and the catalysts of cyclic ether (for example three (dimethylaminomethyl) phenol etc.) with (c) total amount and with respect to (a), (b) and total amount (c) be the polymerization inhibitor (for example quinhydrones etc.) of 0.001～5 quality %; Make its reaction 1～10 hour at 60～130 ℃, can obtain resin (A-4).In addition, same with polymerizing condition, also can consider the thermal value of manufacturing equipment, polymerization generation etc., can be to charging process, the suitable adjustment of temperature of reaction.

In addition, at this moment, molal quantity (b) preferably is made as 10～75 moles of % with respect to the molal quantity of (a), more preferably 15～70 moles of %.Through the molal quantity of (b) is established to this scope, storage stability, solvent resistance and stable on heating balance are tended to well.

As the concrete example of resin (A-4), can enumerate:

The resin that the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters and glycidyl (methyl) acrylate reactions form; The resin that the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid benzyl ester and glycidyl (methyl) acrylate reactions form; The resin that multipolymer of (methyl) acrylic acid/(methyl) cyclohexyl acrylate and glycidyl (methyl) acrylate reactions form; The resin that (methyl) acrylic acid/cinnamic multipolymer and glycidyl (methyl) acrylate reactions form; The resin that multipolymer of (methyl) acrylic acid/(methyl) methyl acrylate and glycidyl (methyl) acrylate reactions form; The resin that the multipolymer of (methyl) acrylic acid/N-cyclohexyl maleimide and glycidyl (methyl) acrylate reactions form; The resin that multipolymer of (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) benzyl acrylate and glycidyl (methyl) acrylate reactions form; The resin that multipolymer of (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) cyclohexyl acrylate and glycidyl (methyl) acrylate reactions form; The resin that (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters/cinnamic multipolymer and glycidyl (methyl) acrylate reactions form; The resin that multipolymer of (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) methyl acrylate and glycidyl (methyl) acrylate reactions form; The resin that the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters/N-cyclohexyl maleimide and glycidyl (methyl) acrylate reactions form; The resin that the multipolymer of crotonic acid/(methyl) acrylic acid two cyclopentyl esters and glycidyl (methyl) acrylate reactions form;

The resin that multipolymer of crotonic acid/(methyl) benzyl acrylate and glycidyl (methyl) acrylate reactions form; The resin that multipolymer of crotonic acid/(methyl) cyclohexyl acrylate and glycidyl (methyl) acrylate reactions form; The resin that crotonic acid/cinnamic multipolymer and glycidyl (methyl) acrylate reactions form; The resin that the multipolymer of crotonic acid/ethyl crotonate and glycidyl (methyl) acrylate reactions forms; The resin that the multipolymer of crotonic acid/N-cyclohexyl maleimide and glycidyl (methyl) acrylate reactions form; The resin that multipolymer of crotonic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) benzyl acrylate and glycidyl (methyl) acrylate reactions form; The resin that multipolymer of crotonic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) cyclohexyl acrylate and glycidyl (methyl) acrylate reactions form; The resin that crotonic acid/(methyl) acrylic acid two cyclopentyl esters/cinnamic multipolymer and glycidyl (methyl) acrylate reactions form; The resin that the multipolymer of crotonic acid/(methyl) acrylic acid two cyclopentyl esters/ethyl crotonate and glycidyl (methyl) acrylate reactions form; The resin that the multipolymer of crotonic acid/(methyl) acrylic acid two cyclopentyl esters/N-cyclohexyl maleimide and glycidyl (methyl) acrylate reactions form;

The resin that the multipolymer of maleic acid/(methyl) acrylic acid two cyclopentyl esters and glycidyl (methyl) acrylate reactions form; The resin that multipolymer of maleic acid/(methyl) benzyl acrylate and glycidyl (methyl) acrylate reactions form; The resin that multipolymer of maleic acid/(methyl) cyclohexyl acrylate and glycidyl (methyl) acrylate reactions form; The resin that maleic acid/cinnamic multipolymer and glycidyl (methyl) acrylate reactions form; The resin that the multipolymer of maleic acid/maleic acid methyl esters and glycidyl (methyl) acrylate reactions form; The resin that the multipolymer of maleic acid/N-cyclohexyl maleimide and glycidyl (methyl) acrylate reactions form; The resin that multipolymer of maleic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) benzyl acrylate and glycidyl (methyl) acrylate reactions form; The resin that multipolymer of maleic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) cyclohexyl acrylate and glycidyl (methyl) acrylate reactions form; The resin that maleic acid/(methyl) acrylic acid two cyclopentyl esters/cinnamic multipolymer and glycidyl (methyl) acrylate reactions form; The resin that the multipolymer of maleic acid/(methyl) acrylic acid two cyclopentyl esters/maleic acid methyl esters and glycidyl (methyl) acrylate reactions form; The resin that the multipolymer of maleic acid/(methyl) acrylic acid two cyclopentyl esters/N-cyclohexyl maleimide and glycidyl (methyl) acrylate reactions form;

The resin that the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters and glycidyl (methyl) acrylate reactions form; The resin that multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) benzyl acrylate and glycidyl (methyl) acrylate reactions form; The resin that multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) cyclohexyl acrylate and glycidyl (methyl) acrylate reactions form; The resin that (methyl) acrylic acid/maleic anhydride/cinnamic multipolymer and glycidyl (methyl) acrylate reactions form; The resin that multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) methyl acrylate and glycidyl (methyl) acrylate reactions form; The resin that the multipolymer of (methyl) acrylic acid/maleic anhydride/N-cyclohexyl maleimide and glycidyl (methyl) acrylate reactions form; The resin that multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters/(methyl) benzyl acrylate and glycidyl (methyl) acrylate reactions form; The resin that multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters/(methyl) cyclohexyl acrylate and glycidyl (methyl) acrylate reactions form; The resin that (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters/cinnamic multipolymer and glycidyl (methyl) acrylate reactions form; The resin that multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters/(methyl) methyl acrylate and glycidyl (methyl) acrylate reactions form; The resin that the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters/N-cyclohexyl maleimide and glycidyl (methyl) acrylate reactions form;

The multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) benzyl acrylate; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) cyclohexyl acrylate; Resin, (methyl) acrylic acid/cinnamic multipolymer and methacrylic acid 3 that the reaction of 4-epoxycyclohexyl methyl ester forms; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) methyl acrylate; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/N-cyclohexyl maleimide; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) benzyl acrylate; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) cyclohexyl acrylate; Resin, (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters/cinnamic multipolymer and methacrylic acid 3 that the reaction of 4-epoxycyclohexyl methyl ester forms; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) methyl acrylate; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid two cyclopentyl esters/N-cyclohexyl maleimide, the resin that the reaction of 4-epoxycyclohexyl methyl ester forms;

The multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) acrylic acid two cyclopentyl esters; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) benzyl acrylate; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) cyclohexyl acrylate; Resin, crotonic acid/cinnamic multipolymer and methacrylic acid 3 that the reaction of 4-epoxycyclohexyl methyl ester forms; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of crotonic acid/ethyl crotonate; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of crotonic acid/N-cyclohexyl maleimide; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) benzyl acrylate; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) cyclohexyl acrylate; Resin, crotonic acid/(methyl) acrylic acid two cyclopentyl esters/cinnamic multipolymer and methacrylic acid 3 that the reaction of 4-epoxycyclohexyl methyl ester forms; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) acrylic acid two cyclopentyl esters/ethyl crotonate; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) acrylic acid two cyclopentyl esters/N-cyclohexyl maleimide, the resin that the reaction of 4-epoxycyclohexyl methyl ester forms;

The multipolymer and the methacrylic acid 3 of maleic acid/(methyl) acrylic acid two cyclopentyl esters; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of maleic acid/(methyl) benzyl acrylate; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of maleic acid/(methyl) cyclohexyl acrylate; Resin, maleic acid/cinnamic multipolymer and methacrylic acid 3 that the reaction of 4-epoxycyclohexyl methyl ester forms; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of maleic acid/maleic acid methyl esters; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of maleic acid/N-cyclohexyl maleimide; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of maleic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) benzyl acrylate; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of maleic acid/(methyl) acrylic acid two cyclopentyl esters/(methyl) cyclohexyl acrylate; Resin, maleic acid/(methyl) acrylic acid two cyclopentyl esters/cinnamic multipolymer and methacrylic acid 3 that the reaction of 4-epoxycyclohexyl methyl ester forms; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of maleic acid/(methyl) acrylic acid two cyclopentyl esters/maleic acid methyl esters; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of maleic acid/(methyl) acrylic acid two cyclopentyl esters/N-cyclohexyl maleimide, the resin that the reaction of 4-epoxycyclohexyl methyl ester forms;

The multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/maleic anhydride/(methyl) benzyl acrylate; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/maleic anhydride/(methyl) cyclohexyl acrylate; Resin, (methyl) acrylic acid/maleic anhydride/cinnamic multipolymer and methacrylic acid 3 that the reaction of 4-epoxycyclohexyl methyl ester forms; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/maleic anhydride/(methyl) methyl acrylate; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/maleic anhydride/N-cyclohexyl maleimide; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters/(methyl) benzyl acrylate; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters/(methyl) cyclohexyl acrylate; Resin, (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters/cinnamic multipolymer and methacrylic acid 3 that the reaction of 4-epoxycyclohexyl methyl ester forms; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters/(methyl) methyl acrylate; The resin that the reaction of 4-epoxycyclohexyl methyl ester forms, the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid two cyclopentyl esters/N-cyclohexyl maleimide, the resin that the reaction of 4-epoxycyclohexyl methyl ester forms etc.

For resin (A-5),, likewise obtain (b) and multipolymer (c) with the manufacturing approach of above-mentioned resin (A-1) as the phase one.

At this moment, with above-mentioned same, the multipolymer of gained can directly use reacted solution, also can use the solution that concentrates or diluted, the material that also can use methods such as utilization precipitates again to take out with solid (powder) form.

From the ratio of (b) and structural unit (c) total molal quantity, preferably be in following scope with respect to the entire infrastructure unit that constitutes above-mentioned multipolymer.

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

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

And then, with the manufacturing approach of resin (A-4) likewise, make cyclic ether and carboxylic acid that (a) is had or carboxylic acid anhydrides reaction in (b) and the multipolymer (c) from (b), obtain therefrom.

With the use amount of (a) of above-mentioned copolymer reaction, be preferably 5～80 moles of % with respect to the molal quantity of (b).From the reactive height of cyclic ether, unreacted (b) is difficult to remaining viewpoint and sets out, as (b) preferred (b1), further preferred (b1-1).

The reaction of cyclic ether and carboxylic acid or carboxylic acid anhydrides and the hydroxyl that produces also can continue to react with carboxylic acid anhydrides.Through making the carboxylic acid anhydrides reaction, can adjust acid number.As carboxylic acid anhydrides, can enumerate maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4; 5; 6-tetrabydrophthalic anhydride, 1,2,3; 6-tetrabydrophthalic anhydride, dimethyl tetrahydro phthalic anhydride, 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene" acid anhydrides (humic acid anhydrides) etc.The use amount of carboxylic acid anhydrides is preferably 0.5～1 mole for 1 mole with respect to the use amount of (a).

As the concrete example of resin (A-5), can enumerate:

The multipolymer of (methyl) acrylic acid two cyclopentyl esters/glycidyl (methyl) acrylic ester reacts the resin that forms with (methyl) acrylic acid; The multipolymer of (methyl) benzyl acrylate/glycidyl (methyl) acrylic ester reacts the resin that forms with (methyl) acrylic acid; The multipolymer of (methyl) cyclohexyl acrylate/glycidyl (methyl) acrylic ester reacts the resin that forms with (methyl) acrylic acid; The multipolymer of styrene/glycidyl (methyl) acrylic ester reacts the resin that forms with (methyl) acrylic acid; The multipolymer of (methyl) methyl acrylate/glycidyl (methyl) acrylic ester reacts the resin that forms with (methyl) acrylic acid; The multipolymer of N-cyclohexyl maleimide/glycidyl (methyl) acrylic ester reacts the resin that forms with (methyl) acrylic acid; The multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) benzyl acrylate/glycidyl (methyl) acrylic ester reacts the resin that forms with (methyl) acrylic acid; The multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) cyclohexyl acrylate/glycidyl (methyl) acrylic ester reacts the resin that forms with (methyl) acrylic acid; The multipolymer of (methyl) acrylic acid two cyclopentyl esters/styrene/glycidyl (methyl) acrylic ester reacts the resin that forms with (methyl) acrylic acid; (multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) methyl acrylate/glycidyl (methyl) acrylic ester reacts the resin that forms with (methyl) acrylic acid; The multipolymer of (methyl) acrylic acid two cyclopentyl esters/N-cyclohexyl maleimide/glycidyl (methyl) acrylic ester reacts the resin that forms with (methyl) acrylic acid;

The resin that the multipolymer of (methyl) acrylic acid two cyclopentyl esters/glycidyl (methyl) acrylic ester and crotonic acid reaction form; The resin that the multipolymer of (methyl) benzyl acrylate/glycidyl (methyl) acrylic ester and crotonic acid reaction form; The resin that the multipolymer of (methyl) cyclohexyl acrylate/glycidyl (methyl) acrylic ester and crotonic acid reaction form; The resin that the multipolymer of styrene/glycidyl (methyl) acrylic ester and crotonic acid reaction form; The resin that the multipolymer of ethyl crotonate/glycidyl (methyl) acrylic ester and crotonic acid reaction form; The resin that the multipolymer of N-cyclohexyl maleimide/glycidyl (methyl) acrylic ester and crotonic acid reaction form; The resin that the multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) benzyl acrylate/glycidyl (methyl) acrylic ester and crotonic acid reaction form; The resin that the multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) cyclohexyl acrylate/glycidyl (methyl) acrylic ester and crotonic acid reaction form; The resin that the multipolymer of (methyl) acrylic acid two cyclopentyl esters/styrene/glycidyl (methyl) acrylic ester and crotonic acid reaction form; The resin that the multipolymer of (methyl) acrylic acid two cyclopentyl esters/ethyl crotonate/glycidyl (methyl) acrylic ester and crotonic acid reaction form; The resin that the multipolymer of (methyl) acrylic acid two cyclopentyl esters/N-cyclohexyl maleimide/glycidyl (methyl) acrylic ester and crotonic acid reaction form;

The resin that the multipolymer of (methyl) acrylic acid two cyclopentyl esters/glycidyl (methyl) acrylic ester and maleic acid reaction form; The resin that the multipolymer of (methyl) benzyl acrylate/glycidyl (methyl) acrylic ester and maleic acid reaction form; The resin that the multipolymer of (methyl) cyclohexyl acrylate/glycidyl (methyl) acrylic ester and maleic acid reaction form; The resin that the multipolymer of styrene/glycidyl (methyl) acrylic ester and maleic acid reaction form; The resin that the multipolymer of maleic acid methyl esters/glycidyl (methyl) acrylic ester and maleic acid reaction form; The resin that the multipolymer of N-cyclohexyl maleimide/glycidyl (methyl) acrylic ester and maleic acid reaction form; The resin that the multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) benzyl acrylate/glycidyl (methyl) acrylic ester and maleic acid reaction form; The resin that the multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) cyclohexyl acrylate/glycidyl (methyl) acrylic ester and maleic acid reaction form; The resin that the multipolymer of (methyl) acrylic acid two cyclopentyl esters/styrene/glycidyl (methyl) acrylic ester and maleic acid reaction form; The resin that the multipolymer of (methyl) acrylic acid two cyclopentyl esters/maleic acid methyl esters/glycidyl (methyl) acrylic ester and maleic acid reaction form; The resin that the multipolymer of (methyl) acrylic acid two cyclopentyl esters/N-cyclohexyl maleimide/glycidyl (methyl) acrylic ester and maleic acid reaction form;

The multipolymer of (methyl) acrylic acid two cyclopentyl esters/glycidyl (methyl) acrylic ester reacts the resin that forms with (methyl) acrylic acid and maleic anhydride; The multipolymer of (methyl) benzyl acrylate/glycidyl (methyl) acrylic ester reacts the resin that forms with (methyl) acrylic acid and maleic anhydride; The multipolymer of (methyl) cyclohexyl acrylate/glycidyl (methyl) acrylic ester reacts the resin that forms with (methyl) acrylic acid and maleic anhydride; The multipolymer of styrene/glycidyl (methyl) acrylic ester reacts the resin that forms with (methyl) acrylic acid and maleic anhydride; The multipolymer of (methyl) methyl acrylate/glycidyl (methyl) acrylic ester reacts the resin that forms with (methyl) acrylic acid and maleic anhydride; (multipolymer of N-cyclohexyl maleimide/glycidyl (methyl) acrylic ester reacts the resin that forms with (methyl) acrylic acid and maleic anhydride; The multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) benzyl acrylate/glycidyl (methyl) acrylic ester reacts the resin that forms with (methyl) acrylic acid and maleic anhydride; The multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) cyclohexyl acrylate/glycidyl (methyl) acrylic ester reacts the resin that forms with (methyl) acrylic acid and maleic anhydride; The multipolymer of (methyl) acrylic acid two cyclopentyl esters/styrene/glycidyl (methyl) acrylic ester reacts the resin that forms with (methyl) acrylic acid and maleic anhydride; The multipolymer of (methyl) acrylic acid two cyclopentyl esters/(methyl) methyl acrylate/glycidyl (methyl) acrylic ester reacts the resin that forms with (methyl) acrylic acid and maleic anhydride; The multipolymer of (methyl) acrylic acid two cyclopentyl esters/N-cyclohexyl maleimide/glycidyl (methyl) acrylic ester reacts the resin that forms with (methyl) acrylic acid and maleic anhydride;

(methyl) acrylic acid two cyclopentyl esters/methacrylic acid 3; The multipolymer of 4-epoxycyclohexyl methyl ester reacts resin, (methyl) benzyl acrylate/methacrylic acid 3 that forms with (methyl) acrylic acid; The multipolymer of 4-epoxycyclohexyl methyl ester reacts resin, (methyl) cyclohexyl acrylate/methacrylic acid 3 that forms with (methyl) acrylic acid; The multipolymer of 4-epoxycyclohexyl methyl ester reacts resin, the styrene/methacrylic acid 3 that forms with (methyl) acrylic acid; The multipolymer of 4-epoxycyclohexyl methyl ester reacts resin, (methyl) methyl acrylate/methacrylic acid 3 that forms with (methyl) acrylic acid; The multipolymer of 4-epoxycyclohexyl methyl ester reacts resin, the N-cyclohexyl maleimide/methacrylic acid 3 that forms with (methyl) acrylic acid; The multipolymer of 4-epoxycyclohexyl methyl ester reacts resin, (methyl) acrylic acid two cyclopentyl esters/(methyl) benzyl acrylate/methacrylic acid 3 that form with (methyl) acrylic acid; The multipolymer of 4-epoxycyclohexyl methyl ester reacts resin, (methyl) acrylic acid two cyclopentyl esters/(methyl) cyclohexyl acrylate/methacrylic acid 3 that form with (methyl) acrylic acid; The multipolymer of 4-epoxycyclohexyl methyl ester reacts resin, (methyl) acrylic acid two cyclopentyl esters/styrene/methacrylic acid 3 that form with (methyl) acrylic acid; The multipolymer of 4-epoxycyclohexyl methyl ester reacts resin, (methyl) acrylic acid two cyclopentyl esters/(methyl) methyl acrylate/methacrylic acid 3 that form with (methyl) acrylic acid; The multipolymer of 4-epoxycyclohexyl methyl ester reacts resin, (methyl) acrylic acid two cyclopentyl esters/N-cyclohexyl maleimide/methacrylic acid 3 that form with (methyl) acrylic acid, and the multipolymer of 4-epoxycyclohexyl methyl ester reacts the resin that forms with (methyl) acrylic acid;

(methyl) acrylic acid two cyclopentyl esters/methacrylic acid 3; Resin, (methyl) benzyl acrylate/methacrylic acid 3 that the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid reaction form; Resin, (methyl) cyclohexyl acrylate/methacrylic acid 3 that the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid reaction form; Resin, styrene/methacrylic acid 3 that the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid reaction form; Resin, ethyl crotonate/methacrylic acid 3 that the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid reaction form; Resin, N-cyclohexyl maleimide/methacrylic acid 3 that the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid reaction form; Resin, (methyl) acrylic acid two cyclopentyl esters/(methyl) benzyl acrylate/methacrylic acid 3 that the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid reaction form; Resin, (methyl) acrylic acid two cyclopentyl esters/(methyl) cyclohexyl acrylate/methacrylic acid 3 that the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid reaction form; Resin, (methyl) acrylic acid two cyclopentyl esters/styrene/methacrylic acid 3 that the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid reaction form; Resin, (methyl) acrylic acid two cyclopentyl esters/ethyl crotonate/methacrylic acid 3 that the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid reaction form; Resin, (methyl) acrylic acid two cyclopentyl esters/N-cyclohexyl maleimide/methacrylic acid 3 that the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid reaction form, the resin that the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid reaction form;

(methyl) acrylic acid two cyclopentyl esters/methacrylic acid 3; Resin, (methyl) benzyl acrylate/methacrylic acid 3 that the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid reaction form; Resin, (methyl) cyclohexyl acrylate/methacrylic acid 3 that the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid reaction form; Resin, styrene/methacrylic acid 3 that the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid reaction form; Resin, maleic acid methyl esters/methacrylic acid 3 that the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid reaction form; Resin, N-cyclohexyl maleimide/methacrylic acid 3 that the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid reaction form; Resin, (methyl) acrylic acid two cyclopentyl esters/(methyl) benzyl acrylate/methacrylic acid 3 that the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid reaction form; Resin, (methyl) acrylic acid two cyclopentyl esters/(methyl) cyclohexyl acrylate/methacrylic acid 3 that the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid reaction form; Resin, (methyl) acrylic acid two cyclopentyl esters/styrene/methacrylic acid 3 that the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid reaction form; Resin, (methyl) acrylic acid two cyclopentyl esters/maleic acid methyl esters/methacrylic acid 3 that the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid reaction form; Resin, (methyl) acrylic acid two cyclopentyl esters/N-cyclohexyl maleimide/methacrylic acid 3 that the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid reaction form, the resin that the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid reaction form;

(methyl) acrylic acid two cyclopentyl esters/methacrylic acid 3; The multipolymer of 4-epoxycyclohexyl methyl ester reacts resin, (methyl) benzyl acrylate/methacrylic acid 3 that forms with (methyl) acrylic acid and maleic anhydride; The multipolymer of 4-epoxycyclohexyl methyl ester reacts resin, (methyl) cyclohexyl acrylate/methacrylic acid 3 that forms with (methyl) acrylic acid and maleic anhydride; The multipolymer of 4-epoxycyclohexyl methyl ester reacts resin, the styrene/methacrylic acid 3 that forms with (methyl) acrylic acid and maleic anhydride; The multipolymer of 4-epoxycyclohexyl methyl ester reacts resin, (methyl) methyl acrylate/methacrylic acid 3 that forms with (methyl) acrylic acid and maleic anhydride; The multipolymer of 4-epoxycyclohexyl methyl ester reacts resin, the N-cyclohexyl maleimide/methacrylic acid 3 that forms with (methyl) acrylic acid and maleic anhydride; The multipolymer of 4-epoxycyclohexyl methyl ester reacts resin, (methyl) acrylic acid two cyclopentyl esters/(methyl) benzyl acrylate/methacrylic acid 3 that form with (methyl) acrylic acid and maleic anhydride; The multipolymer of 4-epoxycyclohexyl methyl ester reacts resin, (methyl) acrylic acid two cyclopentyl esters/(methyl) cyclohexyl acrylate/methacrylic acid 3 that form with (methyl) acrylic acid and maleic anhydride; The multipolymer of 4-epoxycyclohexyl methyl ester reacts resin, (methyl) acrylic acid two cyclopentyl esters/styrene/methacrylic acid 3 that form with (methyl) acrylic acid and maleic anhydride; The multipolymer of 4-epoxycyclohexyl methyl ester reacts resin, (methyl) acrylic acid two cyclopentyl esters/(methyl) methyl acrylate/methacrylic acid 3 that form with (methyl) acrylic acid and maleic anhydride; The multipolymer of 4-epoxycyclohexyl methyl ester reacts resin, (methyl) acrylic acid two cyclopentyl esters/N-cyclohexyl maleimide/methacrylic acid 3 that form with (methyl) acrylic acid and maleic anhydride, the resin that the multipolymer of 4-epoxycyclohexyl methyl ester and (methyl) acrylic acid and maleic anhydride reaction form etc.

The weight-average molecular weight of the polystyrene conversion of resin (A) is preferably 3000～100000, and more preferably 5000～50000.When the weight-average molecular weight of resin (A) is in above-mentioned scope; The coating of photosensitive polymer combination tends to well; In addition; The uncured pixel portion of filming that is caused by development when forming pattern is difficult to take place the film loss, and then when developing, the deciduous of uncured non-pixel portion of filming (i.e. dissolubility in developer solution) is tended to well.

The molecular weight distribution of resin (A) [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] is preferably 1.1～6.0, and more preferably 1.2～4.0.When molecular weight distribution was in above-mentioned scope, the development sexual orientation was in well.

The acid number of resin (A) is 20～150mg-KOH/g, is preferably 40～135mg-KOH/g, more preferably 50～135mg-KOH/g.Here acid number is meant the value of measuring with the amount (mg) of the required potassium hydroxide of 1g resin (A) as being used for, and can use potassium hydroxide aqueous solution to carry out titration and try to achieve.

The content of resin (A) is preferably 5～95 quality % with respect to the total amount of resin (A) and polymerizable compound (B), and more preferably 20～80 quality % are preferably 40～60 quality % especially.When the content of resin (A) was in above-mentioned scope, development property, adherence, solvent resistance, mechanical property were tended to well.

Photosensitive polymer combination of the present invention contains polymerizable compound (B).

Polymerizable compound (B) is to utilize the living radical that is produced by polymerization initiator (C) that polymeric compounds can take place, and for example can enumerate the compound of the carbon-to-carbon unsaturated double-bond with polymerism etc., preferred (methyl) acrylate compounds.

As the polymerizable compound (B) of carbon-to-carbon unsaturated double-bond with 1 polymerism, can enumerate as above-mentioned (a) and (b) and the compound of (c) enumerating, wherein, preferred (methyl) esters of acrylic acid.

Polymerizable compound (B) as carbon-to-carbon unsaturated double-bond with 2 polymerisms; Can enumerate 1; 3-butanediol two (methyl) acrylic ester, 1; 3-butanediol (methyl) acrylic ester, 1; Two (acrylyl oxy-ethyl) ethers of 6-hexane diol two (methyl) acrylic ester, ethylene glycol bisthioglycolate (methyl) acrylic ester, diglycol 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-methylpentane glycol two (methyl) acrylic ester etc.

As the polymerizable compound (B) of carbon-to-carbon unsaturated double-bond, can enumerate the reactant etc. of reactant, caprolactone modification dipentaerythritol five (methyl) acrylic ester He the reactant of acid anhydrides, caprolactone modification tripentaerythritol seven (methyl) acrylic ester and acid anhydrides of reactant, tripentaerythritol seven (methyl) acrylic ester and acid anhydrides 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, dipentaerythritol five (methyl) acrylic ester and the acid anhydrides of 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 with 3 above polymerisms.Wherein, preferred 3 officials can above monomer, more preferably dipentaerythritol six (methyl) acrylic ester.

The content of polymerizable compound (B) is preferably 5～95 quality % with respect to the total amount of resin (A) and polymerizable compound (B), more preferably 20～80 quality %.When the content of polymerizable compound (B) was in above-mentioned scope, intensity, flatness, reliability, the physical strength of the pattern after sensitivity, the curing were tended to well.

Photosensitive polymer combination of the present invention contains polymerization initiator (C), and polymerization initiator (C) contains the represented compound of formula (1) (below be sometimes referred to as " compound (1) ").So-called polymerization initiator is meant the compound through the effect initiated polymerization of light or heat.

[in the formula (1), R ¹The naphthenic base of expression carbon number 3～8.

L ¹Alkane two bases of expression carbon number 1～5.

L ²The expression singly-bound or-CO-.

R ²Expression methyl, phenyl or benzyl.

As the naphthenic base of carbon number 3～8, can enumerate cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, norborny etc.Wherein, preferred cyclopentyl.

As alkane two bases of carbon number 1～5, can enumerate methylene, ethylidene, propylidene, butylidene, pentylidene etc.Wherein, preferred methylene and ethylidene.

As L ², be preferably-CO-.L ²During for-CO-, obtain film, the transmission of visible light of pattern has high trend.

As compound (1), preferred formula (the 1-1)～represented compound of formula (1-3).During for these compounds, obtain film, the transmission of visible light of pattern has the trend of raising.

For photosensitive polymer combination of the present invention, as polymerization initiator (C), can contain the polymerization initiator different with compound (1) (below be sometimes referred to as " polymerization initiator (C0) ".)。As polymerization initiator (C0),, can use known polymerization initiator so long as pass through the just not special qualification of compound of the effect initiated polymerization of light or heat.

As polymerization initiator (C0), for example can enumerate united imidazole, acetophenone compound, triaizine compounds, acylphosphine oxide compound, oxime compound.In addition, can use the light put down in writing in the TOHKEMY 2008-181087 communique and/or hot cationic polymerization initiators (for example, by kation and the material that constitutes from lewis acidic negative ion).Wherein, be preferably selected from least a kind in united imidazole, acetophenone compound and the oxime compound, preferred especially united imidazole.Preferred polymeric initiating agent (C0) uses above-mentioned compound, through using with compound (1) is common, the trend that becomes high sensitivity is arranged.

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

As above-mentioned acetophenone compound; Can enumerate diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzyl dimethyl ketal, 2-hydroxyl-1-(4-(2-hydroxyl-oxethyl) phenyl)-2-methylpropane-1-ketone, 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propiono)-benzyl]-phenyl }-2-methyl-propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-(4-first sulfydryl phenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 2-(2-methyl-benzyl)-2-dimethylamino-1-(4-morpholino phenyl) butanone, 2-(3-methyl-benzyl)-2-dimethylamino-1-(4-morpholino phenyl) butanone, 2-(4-methyl-benzyl)-2-dimethylamino-1-(4-morpholino phenyl) butanone, 2-(2-Ethylbenzyl)-2-dimethylamino-1-(4-morpholino phenyl) butanone, 2-(2-propyl group benzyl)-2-dimethylamino-1-(4-morpholino phenyl) butanone, 2-(2-butyl benzyl)-2-dimethylamino-1-(4-morpholino phenyl) butanone, 2-(2; The 3-dimethyl benzyl)-oligomer of 2-dimethylamino-1-(4-morpholino phenyl) butanone, 2-(2, the 4-dimethyl benzyl)-2-dimethylamino-1-(4-morpholino phenyl) butanone, 2-(2-benzyl chloride base)-2-dimethylamino-1-(4-morpholino phenyl) butanone, 2-(2-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl) butanone, 2-(3-benzyl chloride base)-2-dimethylamino-1-(4-morpholino phenyl) butanone, 2-(4-benzyl chloride base)-2-dimethylamino-1-(4-morpholino phenyl) butanone, 2-(3-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl) butanone, 2-(4-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl) butanone, 2-(2-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl) butanone, 2-(3-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl) butanone, 2-(4-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl) butanone, 2-(2-methyl-4-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl) butanone, 2-(2-methyl-4-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl) butanone, 2-(2-bromo-4-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl) butanone, 2-hydroxy-2-methyl-1-(4-(1-methyl ethylene) phenyl) propane-1-ketone etc.

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 compound, can enumerate 2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc.

As above-mentioned oxime compound; Can enumerate N-benzoyl Oxy-1-(4-thiophenyl phenyl) butane-1-ketone-2-imines, N-ethoxy carbonyl Oxy-1-phenyl-propane-1-ketone-2-imines, N-benzoyl Oxy-1-(4-thiophenyl 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.Can use IrgacureOXE-01, OXE-02 (more than, vapour crust Japanese firm system), N-1919 commercially available article such as (ADEKA corporate systems).

As polymerization initiator (C0), can also be able to 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 (t-butylperoxy 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, benzil, phenyl glyoxalic acid methylester, two cyclopentadiene titanium compounds etc.These preferably with after the polymerization stated cause auxiliary agent (C1) combination and use.

In addition,, also can use the Japan spy to show to be put down in writing in the 2002-544205 communique, have the polymerization initiator of the group that can cause chain transfer as polymerization initiator (C0).

As above-mentioned polymerization initiator, for example, can enumerate the compound of following formula (a)～(f) with the group that can cause chain transfer.

Above-mentioned polymerization initiator with the group that can cause chain transfer also can be used as the composition (c) that constitutes resin (A) and uses.

In the photosensitive polymer combination of the present invention, can use polymerization to cause auxiliary agent (C1) jointly with above-mentioned polymerization initiator (C).

Cause auxiliary agent (C1) as polymerization, for example can enumerate the represented compound of formula (III).

[in the formula (III), W ¹Shown dotted line represent can by halogen atom the aromatic rings of substituted carbon number 6～12.

Y ¹Expression-O-or-S-.

R ⁴1 valency saturated hydrocarbyl of expression carbon number 1～6.

R ⁵Expression can be by the saturated hydrocarbyl of the substituted carbon number 1～12 of halogen atom or can be by the aryl of the substituted carbon number 6～12 of halogen atom.]

As halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms etc.

As the aromatic rings of carbon number 6～12, can enumerate phenyl ring, naphthalene nucleus etc.

As can be by the aromatic rings of the substituted carbon number 6～12 of halogen atom; For example, can enumerate phenyl ring, methyl phenyl ring, dimethyl phenyl ring, ethyl phenyl ring, propyl group phenyl ring, butyl phenyl ring, amyl group phenyl ring, hexyl phenyl ring, cyclohexyl phenyl ring, chlorobenzene ring, dichloro phenyl ring, bromobenzene ring, dibromo phenyl ring, phenyl phenyl ring, chlorphenyl phenyl ring, bromophenyl phenyl ring, naphthalene nucleus, chloronaphthalene ring, bromonaphthalene ring etc.

Saturated hydrocarbyl as carbon number 1～6; For example can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, 1-methyl-propyl, 2-methyl-propyl, the tert-butyl group, n-pentyl, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 1; 1-dimethyl propyl, 1; 2-dimethyl propyl, 2,2-dimethyl propyl, n-hexyl, cyclohexyl etc.

As can be by the saturated hydrocarbyl of the substituted carbon number 1～12 of halogen atom; For example except the saturated hydrocarbyl of above-mentioned carbon number 1～6, can enumerate heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, 1-chlorobutyl, 2-chlorobutyl, 3-chlorobutyl etc.

As can being enumerated phenyl, chlorphenyl, dichlorophenyl, bromophenyl, dibromo phenyl, chloro-bromobenzene base, xenyl, chlorodiphenyl, DCBP base, bromophenyl, dibromo phenyl, naphthyl, chloronaphthyl, methylnaphthyl, dichloro naphthyl, bromonaphthalene base, dibromo naphthyl etc. by the aryl of the substituted carbon number 6～12 of halogen atom.

As the represented compound of formula (III), can enumerate particularly:

2-[2-oxo-2-(2-phenyl) ethylidene]-3-methyl naphtho-[2; 1-d] thiazoline, 2-[2-oxo-2-(2-phenyl) ethylidene]-3-methyl naphtho-[1; 2-d] thiazoline, 2-[2-oxo-2-(2-phenyl) ethylidene]-3-methyl naphtho-[2; 3-d] thiazoline, 2-[2-oxo-2-(2-naphthyl) ethylidene]-3-methylbenzothiazole quinoline, 2-[2-oxo-2-(1-naphthyl) ethylidene]-3-methylbenzothiazole quinoline, 2-[2-oxo-2-(2-naphthyl) ethylidene]-3-methyl-5-phenyl benzothiazole quinoline, 2-[2-oxo-2-(1-naphthyl) ethylidene]-3-methyl-5-phenyl benzothiazole quinoline, 2-[2-oxo-2-(2-naphthyl) ethylidene]-3-methyl-5-fluoro benzo thiazoline, 2-[2-oxo-2-(1-naphthyl) ethylidene]-3-methyl-5-fluoro benzo thiazoline, 2-[2-oxo-2-(2-naphthyl) ethylidene]-3-methyl-5-chloro for benzothiazole quinoline, 2-[2-oxo-2-(1-naphthyl) ethylidene]-3-methyl-5-chloro for benzothiazole quinoline, 2-[2-oxo-2-(2-naphthyl) ethylidene]-3-methyl-5-bromo benzo thiazoline, 2-[2-oxo-2-(1-naphthyl) ethylidene]-3-methyl-5-bromo benzo thiazoline, 2-[2-oxo-2-(4-phenyl) ethylidene]-3-methylbenzothiazole quinoline, 2-[2-oxo-2-(4-phenyl) ethylidene]-3-methyl-5-phenyl benzothiazole quinoline, 2-[2-oxo-2-(2-naphthyl) ethylidene]-3-methyl naphtho-[2; 1-d] thiazoline, 2-[2-oxo-2-(2-naphthyl) ethylidene]-3-methyl naphtho-[1; 2-d] thiazoline, 2-[2-oxo-2-(4-phenyl) ethylidene]-3-methyl naphtho-[2; 1-d] thiazoline, 2-[2-oxo-2-(4-phenyl) ethylidene]-3-methyl naphtho-[1; 2-d] thiazoline, 2-[2-oxo-2-(4-fluoro phenyl) ethylidene]-3-methyl naphtho-[2; 1-d] thiazoline, 2-[2-oxo-2-(4-fluoro phenyl) ethylidene]-3-methyl naphtho-[1; 2-d] thiazoline, 2-[2-oxo-2-(2-phenyl) ethylidene]-3-methyl naphtho-[2; 1-d] oxazoline, 2-[2-oxo-2-(2-phenyl) ethylidene]-3-methyl naphtho-[1; 2-d] oxazoline, 2-[2-oxo-2-(2-phenyl) ethylidene]-3-methyl naphtho-[2; 3-d] oxazoline, 2-[2-oxo-2-(2-naphthyl) ethylidene]-3-first base benzoxazole quinoline, 2-[2-oxo-2-(1-naphthyl) ethylidene]-3-first base benzoxazole quinoline, 2-[2-oxo-2-(2-naphthyl) ethylidene]-3-methyl-5-benzene base benzoxazole quinoline, 2-[2-oxo-2-(1-naphthyl) ethylidene]-3-methyl-5-benzene base benzoxazole quinoline, 2-[2-oxo-2-(2-naphthyl) ethylidene]-3-methyl-5-fluoro benzo oxazoline, 2-[2-oxo-2-(1-naphthyl) ethylidene]-3-methyl-5-fluoro benzo oxazoline, 2-[2-oxo-2-(2-naphthyl) ethylidene]-3-methyl-5-chloro be for benzoxazole quinoline, 2-[2-oxo-2-(1-naphthyl) ethylidene]-3-methyl-5-chloro benzoxazole quinoline, 2-[2-oxo-2-(2-naphthyl) ethylidene]-3-methyl-5-bromoxynil oxazoline quinoline, 2-[2-oxo-2-(1-naphthyl) ethylidene]-3-methyl-5-bromoxynil oxazoline quinoline, 2-[2-oxo-2-(4-phenyl) ethylidene]-3-first base benzoxazole quinoline, 2-[2-oxo-2-(4-phenyl) ethylidene]-3-methyl-5-benzene base benzoxazole quinoline, 2-[2-oxo-2-(1-naphthyl) ethylidene]-3-methyl naphtho-[2; 1-d] oxazoline, 2-[2-oxo-2-(1-naphthyl) ethylidene]-3-methyl naphtho-[1; 2-d] oxazoline, 2-[2-oxo-2-(4-phenyl) ethylidene]-3-methyl naphtho-[2; 1-d] oxazoline, 2-[2-oxo-2-(4-phenyl) ethylidene]-3-methyl naphtho-[1; 2-d] oxazoline, 2-[2-oxo-2-(4-fluoro phenyl) ethylidene]-3-methyl naphtho-[2; 1-d] oxazoline, 2-[2-oxo-2-(4-fluoro phenyl) ethylidene]-3-methyl naphtho-[1,2-d] oxazoline etc.

In addition, cause auxiliary agent (C1), can use formula (IV) or the represented compound of formula (V) as polymerization.

[in formula (IV) and the formula (V), ring W ², the ring W ³With ring W ⁴Expression can be by the heterocycle of the aromatic rings of the substituted carbon number 6～12 of halogen atom or carbon number 2～10 independently of each other.Y ²～Y ⁵Independently of each other expression-O-or-S-.R ⁶～R ⁹The saturated hydrocarbyl of 1 valency of expression carbon number 1～12 or the aryl of carbon number 6～12, contained hydrogen atom in this saturated hydrocarbyl and this aryl can be replaced by the alkoxy of halogen atom, hydroxyl or carbon number 1～6.]

As aromatic rings, can enumerate with formula (III) in the same aromatic rings of material enumerated, contained hydrogen atom in this aromatic rings can at random be replaced by the above-mentioned halogen atom of enumerating.

As can being enumerated pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, pyranoid ring etc. by the substituted heterocycle of halogen atom.

Hydroxyl as 1 valency replaces saturated hydrocarbyl, can enumerate hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl etc.

As the hydroxyl substituted aryl, can enumerate hydroxy phenyl, hydroxyl naphthyl etc.

Alkoxy as 1 valency replaces saturated hydrocarbyl, can enumerate methoxy, methoxy ethyl, methoxy-propyl, methoxyl butyl, butoxymethyl, ethoxyethyl group, ethoxycarbonyl propyl, propoxyl group butyl etc.

As the alkoxy substituted aryl, can enumerate methoxyphenyl, ethoxy naphthyl etc.

As formula (IV) and the represented compound of formula (V), can enumerate particularly:

Dialkoxy naphthalene classes such as dimethoxy-naphthalene, diethoxy naphthalene, dipropoxy naphthalene, diisopropoxy naphthalene, dibutoxy naphthalene;

9; 10-dimethoxy anthracene, 2-ethyl-9; 10-dimethoxy anthracene, 9; 10-diethoxy anthracene, 2-ethyl-9, dialkoxy anthracene classes such as 10-diethoxy anthracene, dipropoxy anthracene, diisopropoxy anthracene, dibutoxy anthracene, diamyl oxygen base anthracene, dihexyl oxygen base anthracene, methoxy ethoxy anthracene, methoxy propoxy anthracene, methoxyl isopropoxy anthracene, methoxyl butoxy anthracene, ethoxy propoxyl group anthracene, ethoxy isopropoxy anthracene, ethoxy butoxy anthracene, propoxyl group isopropoxy anthracene, propoxyl group butoxy anthracene, isopropoxy butoxy anthracene;

Dialkoxy aphthacene classes such as dimethoxy aphthacene, diethoxy aphthacene, dipropoxy aphthacene, diisopropoxy aphthacene, dibutoxy aphthacene etc.

In addition, cause auxiliary agent (C1), also can use the thioxanthones compound as polymerization.As the thioxanthones compound, for example can enumerate 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones etc.

And then, cause auxiliary agent (C1) as polymerization, can enumerate amines and carboxylic acid compound etc.

As amines; Can enumerate fatty amine compound, 4-dimethylaminobenzoic acid methyl esters, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, benzoic acid 2-dimethylamino ethyl ester, N such as triethanolamine, methyldiethanolamine, triisopropanolamine; N-dimethyl-p-toluidine, 4, (the common name of 4 '-two (dimethylamino) benzophenone; Michler ' s ketone), the aromatic amines compound of 4,4 '-two (diethylamino) benzophenone and so on.

As carboxylic acid compound, can enumerate the assorted acetate class of aromatic series such as thiophenyl acetate, methylbenzene ethyl thioglycollic acid, ethylbenzene ethyl thioglycollic acid, ethyl methyl benzene ethyl thioglycollic acid, dimethyl benzene ethyl thioglycollic acid, methoxybenzene ethyl thioglycollic acid, dimethoxy benzene ethyl thioglycollic acid, chlorobenzene ethyl thioglycollic acid, dichloro-benzenes ethyl thioglycollic acid, N-phenylglycine, phenoxyacetic acid, naphthalene TGA, N-naphthyl glycocoll, naphthoxy acetic acid.

The content of compound (1) is preferably 30～100 quality % with respect to the total amount of polymerization initiator (C), more preferably 50～100 quality %.When the content of compound (1) is in above-mentioned scope, can obtain pattern with high sensitivity.

The content of polymerization initiator (C) is preferably 0.5～30 mass parts with respect to content 100 mass parts of resin (A) and polymerizable compound (B), more preferably 1～20 mass parts, further preferred 1～10 mass parts.When the content of polymerization initiator (C) is in above-mentioned scope, can obtain pattern with high sensitivity, and the transmission of visible light of the pattern that obtains there is high trend.

Polymerization causes content 100 mass parts of the content of auxiliary agent (C1) with respect to resin (A) and polymerizable compound (B), is preferably 0～10 mass parts, more preferably 0～7 mass parts.When the amount that polymerization causes auxiliary agent (C1) is in above-mentioned scope, can obtain pattern with high sensitivity, the shape of the pattern that obtains is good.

Photosensitive polymer combination of the present invention contains solvent (D).

As spendable solvent among the present invention; For example can (molecule contains-COO-from ester solvent; Do not contain-solvent of O-), (molecule contains-O-ether solvents; Do not contain-solvent of COO-), select to use in ether-ether solvent (molecule contains-COO-and-O-solvent), ketone solvent (molecule contains-CO-, does not contain-solvent of COO-), alcoholic solvent, aromatic hydrocarbon solvents, amide solvent, the dimethyl sulfoxide (DMSO) etc.

As ester solvent, can enumerate methyl lactate, ethyl lactate, butyl lactate, 2-hydroxyl isobutyl alkanoic acid methyl esters, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, adnoral acetate, gamma-butyrolacton etc.

As ether solvents; Can enumerate glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl propyl ether, ethylene glycol monobutyl ether, diglycol monotertiary methyl ether, carbiphene, diglycol monotertiary 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-diox, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diglycol methyl ethyl ether, diglycol dipropyl ether, diglycol 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, 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, diethylene glycol monoethyl ether acetate, diglycol monotertiary 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, trimethylbenzene etc.

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

These solvents can use separately also and can the above combination of 2 kinds use.

In the above-mentioned solvent, from the viewpoint of coating, drying property, the boiling point among the preferred 1atm is the organic solvent below 180 ℃ more than 120 ℃.Wherein, preferred propylene glycol monomethyl ether, propylene glycol monomethyl ether, diglycol methyl ethyl ether, 3-ethoxy-propionic acid ethyl, 3-methoxyl butylacetic acid ester, 3-methoxyl-1-butanols etc.

The content of the solvent in the photosensitive polymer combination (D) is with respect to photosensitive polymer combination, preferred 60～95 quality %, more preferably 70～90 quality %.In other words, preferred 5～40 quality % of the solid constituent of photosensitive polymer combination, more preferably 10～30 quality %.Here, the solid constituent ester is removed the amount of solvent (D) from photosensitive polymer combination.When the content of solvent (D) was in above-mentioned scope, the flatness of the film that the photosensitive resin coating composition forms had higher trend.

In addition, photosensitive polymer combination of the present invention can also contain multi-functional thiol's compound (T).So-called multi-functional thiol's compound (T) is meant sulfydryl (compound SH) that has in the molecule more than 2.Especially, when use contained the compound that is bonded to more than 2 from the sulfydryl of the carbon atom of aliphatic alkyl, the sensitivity of photosensitive polymer combination of the present invention had the trend of raising.

As multi-functional thiol's compound (T); Can enumerate hexane two mercaptan, decane two mercaptan, 1 particularly; Two (methyl mercapto) benzene of 4-, butanediol two (3-mercaptopropionic acid ester), butanediol two (3-mercaptoacetate), ethylene glycol bis (3-mercaptoacetate), trimethylolpropane tris (3-mercaptoacetate), butanediol two (3-mercaptopropionic acid ester), trimethylolpropane tris (3-mercaptopropionic acid ester), trimethylolpropane tris (3-mercaptoacetate), pentaerythrite four (3-mercaptopropionic acid ester), pentaerythrite four (3-mercaptoacetate), trihydroxy ethyl three (3-mercaptopropionic acid ester), pentaerythrite four (3-sulfydryl butyric ester), 1, two (3-sulfydryl butyl oxygen base) butane of 4-etc.

The content of multi-functional thiol's compound (T) is preferably 0.1～10 mass parts with respect to polymerization initiator (C) 100 mass parts, more preferably 0.5～7 mass parts.When the content of multi-functional thiol's compound (T) was in above-mentioned scope, the sensitivity of photosensitive polymer combination improved, and the development sexual orientation when forming pattern in addition is in well, thereby preferred.

Photosensitive polymer combination of the present invention preferably contains surfactant (E).As surfactant, for example, can to enumerate silicone-based surfactant, fluorine be surfactant, have the silicone-based surfactant of fluorine atom etc.

As the silicone-based surfactant, can enumerate surfactant with siloxane bond.

Can enumerate TORAY Silicone DC3PA particularly; TORAY SiliconeSH7PA; TORAY SiliconeDC11PA; TORAY SiliconeSH21PA; TORAY SiliconeSH28PA; TORAY SiliconeSH29PA; TORAY SiliconeSH30PA; Polyether modified silicone oil SH8400 (trade name: eastern beautiful DOW CORNING (strain) system); KP321; KP322; KP323; KP324; KP326; KP340; KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system); TSF400; TSF401; TSF410; TSF4300; TSF4440; TSF4445; TSF-4446; TSF4452; TSF4460 (Momentive new high-tech material Japan contract commercial firm system) etc.

As fluorine is surfactant, can enumerate the surfactant with fluorocarbon chain.

Can enumerate Fluorinent (registered trademark) FC430, FluorinentFC431 (Sumitomo 3M (strain) system), MegaFac (registered trademark) F142D, MegaFac F171, MegaFacF172, MegaFac F173, MegaFac F177, MegaFac F183, MegaFac R30 (DIC (strain) system), F-top (エ Off ト Star プ, registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 (the Mitsubishi Materials electronics changes into (strain) system), SURFLON (サ one Off ロ Application, registered trademark) S381, SURFLON S382, SURFLON SC101, SURFLONSC105 (Asahi Glass (strain) system), E5844 ((strain) big aurin refinement institute system) etc. particularly.

As silicone-based surfactant, can enumerate surfactant with siloxane bond and fluorocarbon chain with fluorine atom.Can enumerate MegaFac (registered trademark) R08, MegaFac BL20, MegaFac F475, MegaFac F477, MegaFac F443 (DIC (strain) system) etc. particularly.Preferred MegaFac (registered trademark) F475.

The content of surfactant (E) is more than the 0.001 quality % below the 0.2 quality % with respect to photosensitive polymer combination, below the above 0.1 quality % of preferred 0.002 quality %, more preferably below the above 0.05 quality % of 0.01 quality %.Through containing surfactant, can make the flatness of filming good in above-mentioned scope.

In the photosensitive polymer combination of the present invention, can contain various adjuvants such as filling agent, other macromolecular compounds, driving fit promoter, anti-oxidant, ultraviolet light absorber, light stabilizer, chain-transferring agent as required.

Photosensitive polymer combination of the present invention does not contain colorants such as pigment and dyestuff in fact.That is, in photosensitive polymer combination of the present invention, colorant for example is preferably less than 1 quality % with respect to the content of composition in its entirety, is more preferably less than 0.5 quality %.

Average transmittance when photosensitive polymer combination of the present invention is filled in the transmissivity that the use spectrophotometer records in the quartz colorimetric utensil that optical path length is 1cm under the condition of measuring wavelength 400～700nm is preferably more than 70%, more preferably more than 80%.

Photosensitive polymer combination of the present invention is being processed when filming, and the average transmittance of filming is preferably more than 90%, more preferably reaches more than 95%.This average transmittance is to be the mean value of filming of 3 μ m when using spectrophotometer under the condition of measuring wavelength 400～700nm, to measure for the thickness after be heating and curing (for example, 100～250 ℃, 5 minutes～3 hours).Thus, can be provided at transparent good the filming of visible region.

Known is in the past filmed by what the resin combination that does not contain colorant was made, and near the transmissivity mensuration wavelength 400nm is low, is colored as yellow, dark brown more.Yet, photosensitive polymer combination of the present invention in the visible region universe (400～700nm), can provide to show the filming of high-transmission rate, pattern.

Photosensitive polymer combination of the present invention for example passes through the substrate at glass, metal, plastics etc., has formed to be coated with on optical filter, various insulation or the aforesaid substrates such as conducting film, driving circuit, can form and film.Film and be preferably filming of dry and curing.After coating on the substrate, be patterned as required shape, can form pattern.

At first, photosensitive polymer combination of the present invention is coated on the substrate.

Coating can use various apparatus for coating such as spin coater, slit & spin coater, slit coater, ink-jet, roll coater, roll coater to carry out as stated.

Then, preferably carry out drying or prebake conditions, remove volatile ingredient such as desolvate, make its drying.Thus, can obtain level and smooth uncured filming.

At this moment the thickness of filming does not have special qualification, can be according to suitable adjustment such as material therefor, purposes, for example, but about illustration 1～6 μ m.

And then, the uncured of gained filmed across the photomask that is used to form target pattern irradiates light, the ultraviolet ray that for example produces etc. by mercury lamp, light emitting diode.The shape of the photomask of this moment does not have special qualification, and shape, size can be selected according to the purposes of pattern.

In recent years in the exposure machine; Can use the wave filter of chopping certain wavelength domain off to chop the light of not enough 350nm off; The BPF. that some wavelength domains is taken out in use optionally takes out near the 436nm, near near the light the 408nm, the 365nm, and plane of exposure integral body is shone parallel rays equably.At this moment, for mask and base material are correctly located, also can use devices such as mask alignment device, ledex.

Filming after the exposure contacted with developer solution, make established part, for example non-exposure portion (being non-pixel portion) dissolving, develop, obtain the target pattern shape thus.

Developing method can be that liquid floats kind arbitrarily such as method (Japanese: liquid is contained the り method), infusion process, spraying process.And then base material can be to angle tilt arbitrarily during development.

The WS of the preferred alkali compounds of developer solution that uses in the development.

Alkali compounds can be any of inorganic and organic alkali compounds.

As the concrete example of inorganic alkali compounds, can enumerate 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 etc.

As organic basic compound; For example, can enumerate TMAH, 2-hydroxyethyl trimethylammonium hydroxide, monomethyl amine, dimethyl amine, Trimethylamine, single ethylamine, diethylamide, triethylamine, single isopropylamine, diisopropylamine, monoethanolamine etc.

Concentration in the WS of these inorganic and organic alkali compounds is preferably 0.01～10 quality %, more preferably 0.03～5 quality %.

Above-mentioned developer solution can contain surfactant.

Surfactant can be that non-ionization series surfactant, negative ion are that surfactant or kation are any of surfactant.

As nonionic is surfactant; For example, can enumerate polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other polyoxyethylene derivs, 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 etc.

As negative ion is surfactant; For example; Can enumerate the higher alcohol sulfate salt of lauryl alcohol sodium sulfovinate, oleyl alcohol sodium sulfovinate and so on; The alkylsurfuric acid salt of lauryl sodium sulfate, ammonium lauryl sulfate and so on, the alkyl aryl sulfonate class of neopelex, dodecyl sodium naphthalene sulfonate and so on etc.

As kation is surfactant, for example, can enumerate amine salt or quaternary ammonium salt of stearmide hydrochloride, dodecyl trimethyl ammonium chlorination and so on etc.

Surfactant concentrations in the alkaline developer is preferably the scope of 0.01～10 quality %, more preferably 0.05～8 quality %, more preferably 0.1～5 quality %.

After the development,, can obtain pattern through washing.Further as required, can carry out the back baking.Back baking for example preferably 150～240 ℃ temperature range, carried out under the condition in 10～180 minutes.

When making public uncured filming, do not use to form figuratum photomask, whole face is carried out rayed and/or omits development, can not had filming of pattern.

Thus; The pattern that obtains by photosensitive polymer combination of the present invention; For example as the outer cover of the optical interval spare of a part that constitutes filter sheet base plate and/or array base palte, patternable, interlayer dielectric, liquid crystal aligning control with projection, lenticule, to be used for the parts that coating that thickness adjusts etc., touch pad use be useful; What obtain as stated does not have filming of pattern, is useful as one one the outer cover that constitutes filter sheet base plate and/or array base palte.Above-mentioned filter sheet base plate and array base palte are applicable to liquid crystal indicator, organic EL display, Electronic Paper etc.

[embodiment]

Below, illustrate in greater detail the present invention through embodiment." % " in the example and " part " are represented quality % and mass parts like no specified otherwise.

(synthetic example 1)

In the flask that possesses reflux cooler, tap funnel and stirring machine, feed the nitrogen that 0.02L/ divides, form blanket of nitrogen, add 3-methoxyl-1-butanols 200 mass parts and 3-methoxyl butylacetic acid ester 105 mass parts, be heated to 70 ℃ while stir.Then, with methacrylic acid 60 mass parts, 3,4-epoxy three ring [5.2.1.0 ^2.6] (mol ratio of the compound that compound that formula (I-1) is represented and formula (II-1) are represented is 50: 50 a potpourri to the decyl acrylic ester.) 240 mass parts are dissolved in 3-methoxyl butylacetic acid ester 140 mass parts, preparation solution with 4 hours tap funnel times spent, splashes into insulation with this lysate in 70 ℃ flask.On the other hand, with polymerization initiator 2, two (2, the 4-methyl pentane nitrile) 30 mass parts of 2 '-azo are dissolved in 3-methoxyl butylacetic acid ester 225 mass parts processes solution, uses drip in flask 4 hours other tap funnel times spent this solution.After the dropping of the solution of polymerization initiator finishes, kept 4 hours down, be cooled to room temperature subsequently, obtain multipolymer (Resin A solution a) of solid constituent 32.6 quality %, acid number 110mg-KOH/g (solid constituent conversion) at 70 ℃.The weight-average molecular weight Mw of the Resin A a of gained is 13400, and molecular weight distribution (Mw/Mn) is 2.50.

(synthetic example 2)

In the flask that possesses reflux cooler, tap funnel and stirring machine, feed the nitrogen that 0.02L/ divides, form blanket of nitrogen, add 3-methoxyl-1-butanols 200 mass parts and 3-methoxyl butylacetic acid ester 105 mass parts, be heated to 70 ℃ while stir.Then, with methacrylic acid 55 mass parts, 3,4-epoxy three ring [5.2.1.0 ^2.6] (compound that formula (I-1) is represented and the represented compound of formula (II-1) mix with mol ratio the decyl acrylic ester at 50: 50.) 175 mass parts and N-cyclohexyl maleimide 70 mass parts are dissolved in 3-methoxyl butylacetic acid ester 140 mass parts, preparation solution, this lysate use 4 hours dropping liquid pump times spent to drip in the flask of 70 ℃ of insulations.On the other hand, with polymerization initiator 2, two (2, the 4-methyl pentane nitrile) 30 mass parts of 2 '-azo are dissolved in 3-methoxyl butylacetic acid ester 225 mass parts and process solution, and this solution was added dropwise in the flask with 5 hours other dropping liquid pump times spent.After the dropping of the solution of polymerization initiator finishes; 70 ℃ kept 4 hours down; Be cooled to room temperature subsequently, obtain the solution of the multipolymer (Resin A b) of viscosity (23 ℃) 114mPas, solid constituent 32.6 quality %, acid number 34.3mg-KOH/g (acid number that solid constituent converts is 105.2mg-KOH/g).The weight-average molecular weight Mw of the Resin A b of gained is 13600, and molecular weight distribution (Mw/Mn) is 2.54.In addition, the viscosity of copolymer solution utilizes Brookfield viscometer to measure.

The mensuration of the weight-average molecular weight of the Resin A a of gained and Resin A b (Mw) and number-average molecular weight (Mn) is used the GPC method, and the condition below utilizing is carried out.

Device; K2479 ((strain) island Feng makes made)

Chromatographic column; SHIMADZU Shim-pack GPC-80M

Chromatogram 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 polystyrene conversion of above-mentioned gained and number-average molecular weight as molecular weight distribution.

(embodiment 1～4 and comparative example 1)

< preparation of photosensitive polymer combination >

The composition of table 1 is mixed respectively, obtain photosensitive polymer combination.

[table 1]

Each composition is following in the table 1.

Resin (A); The Resin A a of gained in the synthetic example 1.Umber in the table 1 is represented the mass parts that solid constituent converts.

Polymerizable compound (B); Dipentaerythritol acrylate (KAYARAD DPHA; Japan's chemical drug (strain) system)

Compound (1); 1-1; Compound (the TR-PBG-304 that formula (1-1) is represented; The powerful electronics new material in Changzhou (having) system)

Compound (1); 1-2; Compound (the TR-PBG-305 that formula (1-3) is represented; The powerful electronics new material in Changzhou (having) system)

Compound (1); 1-3; Compound (the TR-PBG-309 that formula (1-2) is represented; The powerful electronics new material in Changzhou (having) system)

Polymerization initiator (C0); N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] ethane-1-imines (IRGACURE OXE 02; BASF Japanese firm system)

Solvent (D); (Da); 3-methoxyl-1-butanols

Solvent (D); (Db); Propylene glycol monomethyl ether

Solvent (D); (Dc); The 3-ethoxyl ethyl propionate

Solvent (D); (Dd); 3-methoxyl butylacetic acid ester

Solvent (D) is that " solid constituent amount (%) " of table 1 mixes the mass ratio in the value representation solvent (D) of the solvent composition (Da)～(Dd) in the solvent (D) according to the solid constituent amount of photosensitive polymer combination.

< average transmittance of composition >

For the photosensitive polymer combination of gained, use UV, visible light near infrared spectrometer (V-650 respectively; Japan's beam split (strain) system) (quartz colorimetric utensil, optical path length; 1cm) the average transmittance (%) among mensuration 400～700nm.The result is shown in table 2.

< formation of filming >

Glass substrate (Eagle XG with 2 inches sides; Corning Incorporated's system) cleans successively with neutral lotion, water and alcohol, carry out drying.On this glass substrate, the thickness after the baking later on of the photosensitive polymer combination of above-mentioned gained is reached the mode spin coating of 3.0 μ m, then, in purifying stove, carry out 3 minutes prebake conditions with 90 ℃.Subsequently, carrying out heating in 20 fens at 230 ℃ is filmed.

< transmissivity of filming >

For filming of gained, use micro-spectral light measurer (OSP-SP200; The OLYMPUS corporate system), transmissivity (%) among the mensuration 400nm and the average transmittance (%) under 400～700nm condition.Transmissivity under the 400nm condition is high more, representes the painted few more of yellow.In addition, if the transmissivity of filming is high, then the transmissivity of the pattern of following formation is also high.The result is shown in table 2.

< formation of pattern >

Glass substrate (Eagle XG with 2 inches sides; Corning Incorporated's system) cleans with neutral lotion, water and alcohol successively, carry out drying.Mode on this glass substrate the thickness after the photosensitive polymer combination baking later on being reached 3.0 μ m is carried out spin coating, on heating plate, carries out 2 minutes prebake conditions with 80 ℃, makes its drying.After the cooling, the interval between substrate that has been coated with this photosensitive polymer combination and the quartz glass system photomask is made as 200 μ m, uses exposure machine (TME-150RSK; トプコ Application (strain) system, light source; Ultrahigh pressure mercury lamp), under the air atmosphere, irradiation exposure 60mJ/cm ²The light of (365nm benchmark).In addition, the light to the irradiation of photosensitive polymer combination of this moment is to make the radiating light that is sent by ultrahigh pressure mercury lamp through optical filter (UV-33; Morning sun beam split (strain) system) light that gets.In addition, as photomask, use pattern (having 1 limit is the foursquare transmittance section of 13 μ m, these foursquare 100 μ m that are spaced apart) (being the transmittance section) to be formed at the photomask on the same plane.

After the rayed; At 25 ℃ above-mentioned filming contained in the water system developer solution that nonionic is surfactant 0.12% and potassium hydroxide 0.04% dipping 60 seconds and shaken and develop, after the washing, in baking oven; Carry out baking after 15 minutes with 235 ℃, form pattern.Pattern is not peeled off and residual situation is made as zero.The result is shown in table 2.

[table 2]

Since by photosensitive polymer combination gained of the present invention film or pattern shown in above-mentioned result; Therefore through utilizing by filming of forming of photosensitive polymer combination of the present invention and/or pattern carries out the display device manufacturing, can improve the display characteristic of this display device.

(embodiment 5～8)

< preparation of photosensitive polymer combination >

The composition of table 3 is mixed respectively, obtain photosensitive polymer combination.In addition, each composition in the table 3 is the composition same with table 1.

[table 3]

< formation of pattern >

Carry out the operation same for the photosensitive polymer combination of embodiment 5～8, obtain high the filming and pattern of transmissivity under the 400nm with embodiment 1.

[utilizing on the industry possibility]

Transmission of visible light by filming of obtaining of photosensitive polymer combination of the present invention, pattern is high.

Claims

1. photosensitive polymer combination, it contains Resin A, polymerizable compound B, polymerization initiator C and solvent D, and wherein, polymerization initiator C is the polymerization initiator that contains the represented compound of formula (1),

In the formula (1), R ¹The naphthenic base of expression carbon number 3～8;

L ¹Alkane two bases of expression carbon number 1～5;

L ²The expression singly-bound or-CO-;

R ²Expression methyl, phenyl or benzyl;

R ³Expression can have substituent thiophenyl phenyl, maybe can have substituent carbazyl.

2. photosensitive polymer combination as claimed in claim 1, wherein,

L in the formula (1) ²Expression-CO-.

3. according to claim 1 or claim 2 photosensitive polymer combination, wherein,

The content of the compound that said formula (1) is represented is 30～100 quality % with respect to the total amount of polymerization initiator C.

4. like each the described photosensitive polymer combination in the claim 1～3,

Said Resin A is the resin that contains from the structural unit of following monomer, and said monomer has the cyclic ether structure and the carbon-to-carbon unsaturated double-bond of carbon number 2～4.

5. film for one kind, it is to be obtained by each the described photosensitive polymer combination in the claim 1～4.

6. pattern, it is to be obtained by each the described photosensitive polymer combination in the claim 1～4.

7. display device, its contain be selected from claim 5 described film with the described pattern of claim 6 at least a kind.