CN101727001A

CN101727001A - Photosensitive resin composition

Info

Publication number: CN101727001A
Application number: CN200910208141A
Authority: CN
Inventors: 井上胜治
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2008-10-30
Filing date: 2009-10-28
Publication date: 2010-06-09
Also published as: KR101715392B1; JP5994008B2; JP5850598B2; TWI608294B; JP2016029489A; JP2010134444A; KR20100048898A; TW201022842A

Abstract

The present invention provides a photosensitive resin composition which comprises the following components: adhesive resin (A), at least one compound selected from carboxylic acid anhydride and a compound with at least two carboxyls, photopolymerizable compound (C) and photopolymerization initiator (D). The adhesive resin (A) is obtained through polymerizing at least one monomer selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (A-a), and at least one monomer selected from one monomer (A-b) which can co-polymerize with the unsaturated carboxylic acid anhydride (A-a) and cyclic ether group with 2-4 carbon atoms.

Description

Photosensitive polymer combination

Technical field

The present invention relates to photosensitive polymer combination.

Background technology

Proposed between the color filter and array base palte that constitute display device such as liquid crystal indicator or touch-screen, to form the technical scheme of interval body (light interval body photospacer) by the photoetching process of usability photosensitive resin composition.According to this method, can be at the interval body of place formation arbitrarily.

As this photosensitive polymer combination, the known resin combination (patent documentation 1) that encircles adhesive resin, optical polymerism compound, Photoepolymerizationinitiater initiater and the solvent of the multipolymer of epoxy compound as unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides and aliphatics that contains more.

Patent documentation 1: TOHKEMY 2008-181087 communique

Summary of the invention

But when utilizing above-mentioned photosensitive polymer combination, the resolution of the pattern that obtains may not be abundant.

The objective of the invention is to, the photosensitive polymer combination that can form the pattern that shows sufficient resolution, high transmittance is provided.

The inventor finds, contain with unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides (A-a), can with the monomer (A-b) of this (A-a) copolymerization and/or to have carbon number be the adhesive resin (A) that the monomer (A-c) of 2～4 ring-type ether is polymerized, in the photosensitive polymer combination of optical polymerism compound (C) and Photoepolymerizationinitiater initiater (D), be selected from carboxylic acid anhydrides and have at least a kind of compound (B) in the compound of at least 2 carboxyls by use, the resolution of the pattern that obtains improves.

That is, the invention provides following [1]～[11].

[1]. photosensitive polymer combination, it contains adhesive resin (A), be selected from carboxylic acid anhydrides and have at least a kind of compound (B), optical polymerism compound (C) and Photoepolymerizationinitiater initiater (D) in the compound of at least 2 carboxyls,

Adhesive resin (A) will be for being selected from least a kind of monomer in unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides (A-a), can and having the adhesive resin that at least a kind of monomer polymerization in the monomer (A-c) that carbon number is 2～4 ring-type ether forms with the monomer (A-b) of this (A-a) copolymerization with being selected from.

[2] .[1] the middle photosensitive polymer combination of putting down in writing, wherein, adhesive resin (A) will be for being selected from least a kind of monomer in unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides (A-a), being the adhesive resin that the monomer (A-c) of 2～4 ring-type ether is polymerized with having carbon number.

[3] .[1] or [2] in photosensitive polymer combination of record, wherein, have carbon number and be the monomer of monomer (A-c) for having epoxy radicals of 2～4 ring-type ether.

[4] .[3] the middle photosensitive polymer combination of putting down in writing, wherein, the monomer with epoxy radicals is to have the monomer that aliphatics is encircled epoxy radicals more.

[5] .[4] the middle photosensitive polymer combination of putting down in writing, wherein, have aliphatics and encircle the monomer of epoxy radicals more for being selected from least a kind of compound in the compound shown in compound shown in the formula (I) and the formula (II).

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

X ₁And X ₂Represent independently that respectively it is 1～6 alkylidene that singly-bound maybe can contain heteroatomic carbon number.]

[6] .[1]～photosensitive polymer combination of any record in [5], wherein, at least a kind of monomer that is selected from unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides (A-a) is aliphatics unsaturated carboxylic acid, aliphatics unsaturated carboxylic acid anhydrides or aliphatics unsaturated carboxylic acid and aliphatics unsaturated carboxylic acid anhydrides.

[7] .[5] or [6] middle photosensitive polymer combination of putting down in writing, wherein, be selected from least a kind of compound in the compound shown in compound shown in the formula (I) and the formula (II) for being selected from least a kind of compound in the compound shown in compound shown in the formula (I ') and the formula (II ').

[formula (I ') and formula (II ') in, R ₁' and R ₂' represent independently that respectively hydrogen atom or carbon number are 1～4 alkyl.The hydrogen atom that contains in this alkyl can be replaced by hydroxyl.]

[8] .[1]～photosensitive polymer combination of any record in [7], wherein, be selected from carboxylic acid anhydrides and at least a kind of compound (B) of having in the compound of at least 2 carboxyls is a carboxylic acid anhydrides.

[9]. be used to form film or [1]～[8] of pattern in the application of photosensitive polymer combination of any record.

[10]. film or pattern, it is to use the photosensitive polymer combination of any record in [1]～[8] to form.

[11]. display device, it contains filming or pattern of putting down in writing in [10].

Embodiment

Below the present invention is carried out specific description.

Photosensitive polymer combination of the present invention contains adhesive resin (A), is selected from carboxylic acid anhydrides and has at least a kind of compound (B), optical polymerism compound (C) and Photoepolymerizationinitiater initiater (D) in the compound of at least 2 carboxyls,

Adhesive resin (A) for to major general's unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides (A-a), can with the monomer (A-b) of this (A-a) copolymerization and/or to have carbon number be the adhesive resin that the monomer (A-c) of 2～4 ring-type ether is polymerized.

As the adhesive resin that uses in the photosensitive polymer combination of the present invention (A), can enumerate adhesive resin (A1), adhesive resin (A2).Adhesive resin (A1) shows alkali dissolution, the reactivity that adhesive resin (A2) shows alkali dissolution and realizes by any one effect at least in the light and heat.

As adhesive resin (A1), can enumerate at least a kind (A-a) being selected from unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides (below be sometimes referred to as " (A-a) ") with can be with the multipolymer of the monomer (A-b) (wherein except (A-a)) of (A-a) copolymerization (below be sometimes referred to as " (A-b) ") etc.

As (A-a), for example can enumerate, aliphatics unsaturated carboxylic acid and/or aliphatics unsaturated carboxylic acid anhydrides etc., specifically, for example can enumerate:

Unsaturated monocarboxylic classes such as acrylic acid, methacrylic acid, crotonic acid,

Unsaturated dicarboxylic classes such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid,

And the acid anhydrides of above-mentioned unsaturated dicarboxylic class,

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

Contain the unsaturated esters of acrylic acid of hydroxyl and carboxyl etc. in same a part of α-(methylol) acrylic acid etc.

Wherein, from the copolyreaction aspect, the alkali dissolution aspect considers, preferably uses acrylic acid, methacrylic acid or maleic anhydride etc.They are used alone or in combination.

As (A-b), can enumerate:

(methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate,

(methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methyl cyclohexane ester, (methyl) acrylic acid three ring [5.2.1.0 ^2.6] (methyl) acrylic acid cyclic alkyl ester classes such as decane-8-base ester (in this technical field,, being called (methyl) acrylic acid dicyclo pentyl ester as trivial name), (methyl) acrylic acid dicyclo amoxy ethyl ester, (methyl) isobornyl acrylate,

Cyclohexyl acrylate, acrylic acid 2-methyl cyclohexane ester, acrylic acid three ring [5.2.1.0 ^2.6] acrylic acid cyclic alkyl ester classes such as decane-8-base ester (in this technical field, as trivial name, being called acrylic acid dicyclo pentyl ester), acrylic acid dicyclo amoxy ethyl ester, isobornyl acrylate,

(methyl) acrylic acid aryl ester classes such as (methyl) phenyl acrylate, (methyl) acrylic acid benzene methyl,

Acrylic acid aryl ester classes such as phenyl acrylate, acrylic acid benzene methyl,

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

Hydroxyalkyl acrylate classes such as (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester,

Two ring [2.2.1] hept-2-ene"s, 5-methyl bicyclic [2.2.1] hept-2-ene", 5-ethyl two ring [2.2.1] hept-2-ene"s, 5-hydroxyl two ring [2.2.1] hept-2-ene"s, 5-carboxyl two ring [2.2.1] hept-2-ene"s, 5-methylol two ring [2.2.1] hept-2-ene"s, 5-(2 '-hydroxyethyl) two ring [2.2.1] hept-2-ene"s, 5-methoxyl two ring [2.2.1] hept-2-ene"s, 5-ethoxy two ring [2.2.1] hept-2-ene"s, 5,6-dihydroxy two ring [2.2.1] hept-2-ene"s, 5,6-dicarboxyl two ring [2.2.1] hept-2-ene"s, 5,6-two (methylol) two ring [2.2.1] hept-2-ene"s, 5,6-two (2 '-hydroxyethyl) two ring [2.2.1] hept-2-ene"s, 5,6-dimethoxy two ring [2.2.1] hept-2-ene"s, 5,6-diethoxy two ring [2.2.1] hept-2-ene"s, 5-hydroxy-5-methyl base two ring [2.2.1] hept-2-ene"s, 5-hydroxyl-5-ethyl two ring [2.2.1] hept-2-ene"s, 5-carboxyl-5-methyl bicyclic [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl two ring [2.2.1] hept-2-ene"s, 5-methylol-5-methyl bicyclic [2.2.1] hept-2-ene", 5-carboxyl-6-methyl bicyclic [2.2.1] hept-2-ene", 5-carboxyl-6-ethyl two ring [2.2.1] hept-2-ene"s, 5,6-dicarboxyl two ring [2.2.1] hept-2-ene" acid anhydrides (norbornene dicarboxylic acids acid anhydride (Ha ィミック Suan No water thing)), 5-tert-butoxycarbonyl two ring [2.2.1] hept-2-ene"s, 5-cyclohexyloxy carbonyl two ring [2.2.1] hept-2-ene"s, 5-phenyloxycarbonyl two ring [2.2.1] hept-2-ene"s, 5,6-two (tert-butoxycarbonyl) two ring [2.2.1] hept-2-ene"s, 5, two ring unsaturated compound classes such as 6-two (cyclohexyloxy carbonyl) two ring [2.2.1] hept-2-ene"s

Dicarbapentaborane imide derivative classes such as N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-succinimido-3-maleimide benzoic ether, N-succinimido-4-maleimide butyric ester, N-succinimido-6-maleimide capronate, N-succinimido-3-maleimide propionic ester, N-(9-acridinyl) maleimide

Styrene, α-Jia Jibenyixi, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxy styrene, vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc.

Wherein, consider, be preferably styrene, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, two ring [2.2.1] hept-2-ene"s etc. from copolyreaction and alkali dissolution aspect.

(A-a) and (A-b) be used alone or in combination.

In this instructions, (methyl) acrylate refers to acrylate and/or methacrylate.

In the multipolymer that with (A-a) and (A-b) copolymerization obtains, by the ratio of the constituent that imports separately, when the total molal quantity of the constituent that constitutes above-mentioned multipolymer is 100 moles of %, according to mole fraction preferably in following scope.

Formation unit by (A-a) importing: 2～40 moles of %

Formation unit by (A-b) importing: 60～98 moles of %

In addition, if the ratio of above-mentioned constituent in following scope then more preferably.

Formation unit by (A-a) importing: 5～35 moles of %

Formation unit by (A-b) importing: 65～95 moles of %

If above-mentioned component ratio is in above-mentioned scope, the trend that then has storage stability, development and solvent resistance to become good.

The citing document of putting down in writing in the method for record and the document during adhesive resin (A1) for example can list of references " experimental method of Polymer Synthesizing " (the big grand row work sale room in Tianjin (strain) chemistry is with the distribution on March 1st, 1972 of the 1st edition the 1st brush of people) prepares.

Specifically, unit (A-a) and ormal weight (A-b), polymerization initiator and the solvent that constitutes multipolymer joined in the reaction vessel, use the nitrogen replace oxygen, under the non-existent condition of oxygen, stir, heat, be incubated thus, thereby obtain polymkeric substance.And, for the multipolymer that obtains, can directly use reacted solution, also can use to concentrate or the solution of dilution, can also use the material that obtains with solid (powder) form by methods such as precipitations again.

The polystyrene conversion weight-average molecular weight of adhesive resin (A1) is preferably 3000～100000, and more preferably 5000～50000.If the weight-average molecular weight of resin (A1) with alkali dissolution is in above-mentioned scope, the trend that then exists coating to become good, be difficult for during this external development producing membrane damage (film Minus り), and then exist in the trend that the detachment (order け) of non-pixel portion when developing becomes good, so preferred.

The molecular weight distribution of adhesive resin (A1) [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] is preferably 1.1～6.0, and more preferably 1.2～4.0.If molecular weight distribution is then preferred owing to the trend that has the development excellence in above-mentioned scope.

The content that can be used for the adhesive resin (A1) of photosensitive polymer combination of the present invention with respect to the solid constituent in the photosensitive polymer combination, according to massfraction, is preferably 5～90 quality %, more preferably 10～70 quality %.If the content of adhesive resin (A1) is in above-mentioned scope, then the dissolubility in developer solution is abundant, on the substrate of non-pixel portion, be difficult for producing the development residue, in addition, the membrane damage that when developing, is difficult for the pixel portion of generation exposure portion, so the trend that exists the detachment of non-exposed portion to become good is preferred.

As showing alkali dissolution and, can enumerating (A2-1)～(A2-3) by reactive adhesive resin (A2) that at least a effect in the light and heat realizes.

Adhesive resin (A2-1) is (A-a), (A-b) and the multipolymer with monomer (A-c) that carbon number is 2～4 ring-type ether (below be sometimes referred to as " (A-c) ").

Adhesive resin (A2-2) in (A-a) and (A-b) the multipolymer is a multipolymer that 2～4 cyclic ether radical reaction obtain from the part of the carboxyl of (A-a) and carbon number from (A-c) for making.

Adhesive resin (A2-3) is (A-a) and multipolymer (A-c).

(A-c) for example refer to have and be selected from the polymerizable compound that carbon number is at least a kind of group in 2～4 the ring-type ether (for example, epoxy radicals, oxa-cyclobutyl and tetrahydrofuran base).(A-c) be preferably and have that to be selected from carbon number be at least a kind of group in 2～4 the ring-type ether and the compound with unsaturated link.More preferably have to be selected from and have at least a kind of group in the group that carbon number is 2～4 cyclic ether structure and have acryloyl group or the compound of methacryl.

As (A-c), for example can enumerate, have epoxy radicals monomer, have the oxa-cyclobutyl monomer, have the monomer of tetrahydrofuran base etc.

Above-mentioned monomer with epoxy radicals for example refers to has the polymerizable compound that is selected from least a kind of group in aliphatic epoxy base and the alicyclic ring epoxy radicals.This monomer with epoxy radicals is preferably has the compound that is selected from least a kind of group in aliphatic epoxy base and the alicyclic ring epoxy radicals and has unsaturated link.

As the compound that has the aliphatic epoxy base in the above-mentioned monomer with epoxy radicals, specifically, can enumerate the compound shown in the following formula of putting down in writing in (methyl) glycidyl acrylate, (methyl) acrylic acid Beta-methyl ethylene oxidic ester, (methyl) propenoic acid beta-ethyl ethylene oxidic ester, glycidyl vinyl ether, the Japanese kokai publication hei 7-248625 communique etc.

(in the formula, R ¹¹～R ¹³Be respectively that hydrogen atom or carbon number are 1～10 alkyl independently, m is 1～5 integer).

As the compound shown in the following formula, for example can enumerate, adjacent vinyl benzyl glycidyl ether, between the vinyl benzyl glycidyl ether, to the vinyl benzyl glycidyl ether, Alpha-Methyl-adjacent vinyl benzyl glycidyl ether, an Alpha-Methyl-vinyl benzyl glycidyl ether, Alpha-Methyl-to the vinyl benzyl glycidyl ether, 2,3-diglycidyl oxygen ylmethyl styrene, 2,4-diglycidyl oxygen ylmethyl styrene, 2,5-diglycidyl oxygen ylmethyl styrene, 2,6-diglycidyl oxygen ylmethyl styrene, 2,3,4-triglycidyl group oxygen ylmethyl styrene, 2,3,5-triglycidyl group oxygen ylmethyl styrene, 2,3,6-triglycidyl group oxygen ylmethyl styrene, 3,4,5-triglycidyl group oxygen ylmethyl styrene, 2,4,6-triglycidyl group oxygen ylmethyl styrene etc.

Have a monomer that has the alicyclic ring epoxy radicals in the monomer of epoxy radicals as above-mentioned, for example can enumerate, have aliphatics monocycle epoxy radicals monomer, have aliphatics and encircle monomer of epoxy radicals etc. more.

Above-mentioned monomer with aliphatics monocycle epoxy radicals refers to the polymerizable compound that has epoxy radicals on the ring of aliphatics monocyclic compound.This monomer with aliphatics monocycle epoxy radicals is preferably the compound that has epoxy radicals and have unsaturated link on the ring of aliphatics monocyclic compound, and the ring and the epoxide ring that more preferably have the ester ring type hydrocarbon of monocycle condense the structure that forms and have acryloyl group or the compound of methacryl.

As this aliphatics monocyclic compound, for example can enumerate, cyclopentane, cyclohexane, cycloheptane, cyclooctane etc., wherein, preferred carbon number is 5～7 compound.

Has the monomer of aliphatics monocycle epoxy radicals as this, specifically, can enumerate an oxyethylene group cyclohexene 1, the 2-epoxy-the 4-vinyl cyclohexane (for example, セロキサィ De 2000, ダィセ Le chemical industry (strain) system), acrylic acid 3,4-epoxycyclohexyl methyl ester (for example, サィ Network ロマ one A400, ダィセ Le chemical industry (strain) system), methacrylic acid 3,4-epoxycyclohexyl methyl ester (for example, サィ Network ロマ one M100, ダィセ Le chemical industry (strain) system) etc.

Above-mentioned have aliphatics and encircle the monomer of epoxy radicals more and refer to the polymerizable compound that has epoxy radicals on the ring of aliphatics polycyclic compund.This has aliphatics and encircles the monomer of epoxy radicals more and be preferably the compound that has epoxy radicals and have unsaturated link on the ring of aliphatics polycyclic compund, and the ring and the epoxide ring that more preferably have the ester ring type hydrocarbon of many rings condense the structure that forms and have acryloyl group or the compound of methacryl.

As this aliphatics polycyclic compund, for example can enumerate, dicyclo pentane, tristane, norbornane, different norbornane, double-octane, bicyclic nonane, dicyclo undecane, three ring undecanes, dicyclo dodecane, three cyclododecanes etc., wherein, preferred carbon number is 8～12 compound.

Has a monomer that aliphatics is encircled epoxy radicals more as above-mentioned, can enumerate for example acrylic acid 3,4-epoxy norborneol ester, methacrylic acid 3, are selected from least a kind of compound in the compound shown in compound shown in the formula (I) and the formula (II) etc. at 4-epoxy norborneol ester.

In formula (I) and the formula (II), R ₁And R ₂Represent independently that respectively hydrogen atom or the carbon number that can be replaced by hydroxyl are 1～4 alkyl.

X ₁And X ₂Represent independently that respectively it is 1～6 alkylidene that singly-bound maybe can contain heteroatomic carbon number.

As R ₁And R ₂, specifically, can enumerate hydrogen atom, alkyl such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group,

The alkyl of hydroxyls such as methylol, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxyl n-pro-pyl, 2-hydroxyl n-pro-pyl, 3-hydroxyl n-pro-pyl, 1-hydroxyl isopropyl, 2-hydroxyl isopropyl, 1-hydroxyl normal-butyl, 2-hydroxyl normal-butyl, 3-hydroxyl normal-butyl, 4-hydroxyl normal-butyl.Wherein, preferably enumerate hydrogen atom, methyl, methylol, 1-hydroxyethyl, 2-hydroxyethyl, more preferably enumerate hydrogen atom, methyl.

As X ₁And X ₂, specifically, can enumerate singly-bound, alkylidenes such as methylene, ethylidene, propylidene,

Oxygen methylene, oxygen base ethylidene, oxygen base propylidene, sulfenyl methylene, sulfenyl ethylidene, sulfenyl propylidene, aminomethylene, amino ethylidene, amino propylidene etc. contain heteroatomic alkylidene etc.Wherein, preferably enumerate singly-bound, methylene, ethylidene, oxygen methylene, oxygen base ethylidene, more preferably enumerate singly-bound, oxygen base ethylidene.

As at least a kind of compound that is selected from the compound shown in compound shown in the formula (I) and the formula (II), be preferably at least a kind of compound that is selected from the compound shown in the compound shown in the following formula (I ') and the formula (II ').

Formula (I ') and formula (II ') in, R ₁' and R ₂' definition respectively with above-mentioned R ₁And R ₂Identical.

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

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

At least a kind of compound that is selected from the compound shown in compound shown in the formula (I) and the formula (II) can be distinguished use separately, also can be with ratio mixing arbitrarily.During mixing, its mixture ratio is preferably formula (I) according to mol ratio: formula (II) is 5: 95～95: 5, more preferably 10: 90～90: 10, and more preferably 20: 80～80: 20.

Above-mentioned monomer with oxa-cyclobutyl for example refers to has the polymerizable compound that is selected from least a kind of group in aliphatics oxa-cyclobutyl and the alicyclic ring oxa-cyclobutyl.This monomer with oxa-cyclobutyl is preferably has the compound that is selected from least a kind of group in aliphatics oxa-cyclobutyl and the alicyclic ring oxa-cyclobutyl and has unsaturated link.

Has the monomer of oxa-cyclobutyl as this, specifically, can enumerate 3-methyl-3-methacryloxy methyl oxetanes, 3-methyl-3-acryloyl-oxy ylmethyl oxetanes, 3-ethyl-3-methacryloxy methyl oxetanes, 3-ethyl-3-acryloyl-oxy ylmethyl oxetanes, 3-methyl-3-methacryloxyethyl oxetanes, 3-methyl-3-acryloxy ethyl oxetanes, 3-ethyl-3-methacryloxyethyl oxetanes or 3-ethyl-3-acryloxy ethyl oxetanes etc.

They are used alone or in combination.

Above-mentioned monomer with tetrahydrofuran base for example refers to has the polymerizable compound that is selected from least a kind of group in aliphatics tetrahydrofuran base and the alicyclic ring tetrahydrofuran base.This monomer with tetrahydrofuran base is preferably has the compound that is selected from least a kind of group in aliphatics tetrahydrofuran base and the alicyclic ring tetrahydrofuran base and has unsaturated link.

Have the monomer of tetrahydrofuran base as this, specifically, can enumerate acrylic acid tetrahydro furfuryl ester (for example, PVC スコ one ト V#150, Osaka organic chemistry industry (strain) system), methacrylic acid tetrahydro furfuryl ester etc.

They are used alone or in combination.

In adhesive resin (A2-1), by the ratio of the constituent that imports separately, with respect to the total molal quantity of the constituent that constitutes adhesive resin (A2-1), according to mole fraction preferably in following scope.

Formation unit by (A-a) importing: 2～40 moles of %

Formation unit by (A-b) importing: 1～65 mole of %

Formation unit by (A-c) importing: 2～95 moles of %

Formation unit by (A-a) importing: 5～35 moles of %

Formation unit by (A-b) importing: 1～60 mole of %

Formation unit by (A-c) importing: 5～80 moles of %

If above-mentioned component ratio is in above-mentioned scope, then storage stability, development, solvent resistance, thermotolerance and physical strength have the trend that becomes good.

The citing document of putting down in writing in the method for record and the document during adhesive resin (A2-1) for example can list of references " experimental method of Polymer Synthesizing " (the big grand row work sale room in Tianjin (strain) chemistry is with the distribution on March 1st, 1972 of the 1st edition the 1st brush of people) prepares.

Specifically, the ormal weight, polymerization initiator and the solvent that import the unit (A-a), (A-b) and the compound (A-c) that constitute multipolymer are joined in the reaction vessel, use the nitrogen replace oxygen, thus under the non-existent condition of oxygen, stir, heat, be incubated, thereby obtain polymkeric substance.And the multipolymer that obtains can directly use reacted solution, also can use to concentrate or the solution of dilution, can also use the material that obtains with solid (powder) form by methods such as precipitations again.

The preparation adhesive resin is when (A2-2), at first make (A-a) and (A-b) copolymerization prepare multipolymer.By the ratio of the constituent that imports separately, with respect to the total molal quantity of the constituent that constitutes above-mentioned multipolymer, according to mole fraction preferably in following scope.

Formation unit by (A-a) importing: 5～50 moles of %

Formation unit by (A-b) importing: 50～95 moles of %

Formation unit by (A-a) importing: 10～45 moles of %

Formation unit by (A-b) importing: 55～90 moles of %

Then in order to make it have the reactivity that realizes by light, hot effect, make from (A-a) and (A-b) carboxylic acid of (A-a) of the multipolymer that obtains of copolymerization and the part of carboxylic acid anhydrides, with epoxy radicals, oxa-cyclobutyl or tetrahydrofuran radical reaction from (A-c).

(A-c) molal quantity is 5～80 moles of % with respect to the molal quantity of (A-a), is preferably 10～75 moles of %, more preferably 15～70 moles of %.

If component ratio is in above-mentioned scope, then the combination property of storage stability, development, solvent resistance, thermotolerance, physical strength and sensitivity has the trend that becomes good.

Adhesive resin (A2-2) can prepare through two stage step.The method of for example can list of references " experimental method of Polymer Synthesizing " putting down in writing in the method, TOHKEMY 2001-89533 communique of record in (the big grand row work sale room in Tianjin (strain) chemistry is with the distribution on March 1st, 1972 of the 1st edition the 1st brush of people) prepares.

Specifically, at first the step of phase one is described.To derive and constitute that the unit (A-a) of the multipolymer (being adhesive resin) that obtains of copolymerization and ormal weight, polymerization initiator and the solvent of compound (A-b) join in the reaction vessel with (A-a) with (A-b), use the nitrogen replace oxygen, thus under the non-existent condition of oxygen, stir, heat, be incubated, thereby obtain adhesive resin.And the resin that obtains can directly use reacted solution, also can use and concentrate or the solution of dilution, can also use the material that obtains with solid (powder) form by methods such as precipitations again.The polystyrene conversion weight-average molecular weight of above-mentioned resin is preferably 3000～100000, and more preferably 5000～50000.If the weight-average molecular weight of resin is in above-mentioned scope, the trend that then exists coating to become good is difficult for producing membrane damage during this external developments, and then exists in the good trend of detachment of non-pixel portion when developing, so preferably.

The molecular weight distribution of above-mentioned resin [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] is preferably 1.1～6.0, and more preferably 1.2～4.0.If molecular weight distribution is in above-mentioned scope, then owing to the trend that has coating or development excellence, so preferred.

Then, the step to subordinate phase describes.Then, atmosphere gas in the flask is replaced into air by nitrogen, to be the constituent (A-c) of 5～80 moles of % with respect to the molal quantity of constituent (A-a), with respect to the total amount of monomer (A-a)～(A-c) according to quality criteria be 0.001～5% as carboxyl and epoxy radicals, for example three (dimethylamino) methylphenol of the catalysts of oxa-cyclobutyl or tetrahydrofuran base, and be that 0.001～5% for example quinhydrones as polymerization inhibitor joins in the flask according to quality criteria with respect to the total amount of monomer (A-a)～(A-c), 60～130 ℃ of following sustained responses 1～10 hour, can make above-mentioned resin and constituent (A-c) reaction thus.And, with polymerizing condition similarly, can consider that thermal discharge that preparation equipment, polymerization produce waits suitably to adjust adding method or temperature of reaction.

In adhesive resin (A2-3), by the ratio of the constituent that imports separately, with respect to the total molal quantity of the constituent that constitutes adhesive resin (A2-3), according to mole fraction, preferably in following scope.

Formation unit by (A-a) importing: 5～95 moles of %

Formation unit by (A-c) importing: 5～95 moles of %

Formation unit by (A-a) importing: 10～90 moles of %

Formation unit by (A-c) importing: 10～90 moles of %

The citing document of putting down in writing in the method for record and the document during adhesive resin (A2-3) for example can list of references " experimental method of Polymer Synthesizing " (the big grand row work sale room in Tianjin (strain) chemistry is with the distribution on March 1st, 1972 of the 1st edition the 1st brush of people) prepares.

Specifically, join in the reaction vessel deriving the unit (A-a) of formation multipolymer and ormal weight, polymerization initiator and the solvent of compound (A-c), use the nitrogen replace oxygen, thus under the non-existent condition of oxygen, stir, heat, be incubated, thereby obtain polymkeric substance.And the multipolymer that obtains can directly use reacted solution, also can use to concentrate or the solution of dilution, can also use the material that obtains with solid (powder) form by methods such as precipitations again.

Be selected from carboxylic acid anhydrides and have at least a kind of compound (B) in the compound of at least 2 carboxyls as what contain in the photosensitive polymer combination of the present invention, for example can enumerate polybasic acid anhydride, polybasic carboxylic acid etc.

As above-mentioned polybasic acid anhydride, for example can enumerate,

Aliphatic dicarboxylic acid acid anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic acid acid anhydride, maleic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, norbornene dicarboxylic acids, norbornene dicarboxylic acids acid anhydride

1,2,3, aliphatics polybasic carboxylic acid dianhydrides such as 4-butane tetracarboxylic acid dianhydride, cyclopentane tetracarboxylic dianhydride,

Aromatic polycarboxylic acid acid anhydrides such as phthalate anhydride, pyromellitic acid acid anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride,

Ethylene glycol bisthioglycolate trimellitate, glycerine three trimellitates etc. contain the acid anhydrides of ester bond etc.

Wherein,, resolution high aspect high from the transparency considered, is preferably phthalic anhydride, trimellitic anhydride.

In addition, as this carboxylic acid anhydrides, can use the commercially available colourless epoxy curing agent that contains acid anhydrides suitably.Specifically, can enumerate ァデカ Ha one De Na one EH-700 (trade name (following identical), rising sun electrochemical industry (strain) system), リカシッ De one HH, リカシッ De one MH-700 (new Japanese physics and chemistry (strain) system), ェピキニァ 126, ェピキニァ YH-306, ェピキニァ DX-126 (oiling シニ Le ェ Port キシ (strain) system) etc.

As above-mentioned polybasic carboxylic acid, for example can enumerate, aliphatics polybasic carboxylic acids such as succinic acid, glutaric acid, hexane diacid, BTCA, maleic acid, itaconic acid,

Hexahydrophthalic acid, 1,2-cyclohexane-carboxylic acid, 1,2, alicyclic polybasic carboxylic acids such as 4-cyclohexane tricarboxylic acids, cyclopentane tetrabasic carboxylic acid,

Phthalic acid, m-phthalic acid, terephthalic acid (TPA), trimellitic acid, pyromellitic acid, 1,4,5, aromatic polycarboxylic acids such as 8-naphthalene tetracarboxylic acid, benzophenone tetrabasic carboxylic acid etc.

Wherein,, resolution high aspect high from the transparency considered, is preferably phthalic acid, trimellitic acid.

These polybasic acid anhydrides and polybasic carboxylic acid can use separately or with two or more and use.

The content of the compound in the photosensitive polymer combination of the present invention (B), with respect to the total amount of adhesive resin (A) and optical polymerism compound (C) according to massfraction, be preferably 0.1～20 quality %, 1～15 quality % more preferably, 2～10 quality % more preferably, further 2～8 quality % more preferably.The content of compound (B) is during less than 0.1 quality %, and resolution might reduce.On the other hand, when the content of compound (B) surpassed 20 quality %, residual film ratio might reduce.

As the optical polymerism compound (C) that contains in the photosensitive polymer combination of the present invention, can enumerate the above polyfunctional monomer of monofunctional monomer, bifunctional monomer or other 3 official energy etc.

As the object lesson of monofunctional monomer, can enumerate nonyl phenyl carbitol (methyl) acrylate, 2-hydroxyl-3-phenoxy propyl (methyl) acrylate, 2-ethylhexyl carbitol (methyl) acrylate, 2-hydroxyethyl (methyl) acrylate, lauryl (methyl) acrylate, stearyl (methyl) acrylate, 2-(2-ethoxy ethoxy) ethyl (methyl) acrylate, tetrahydrofurfuryl (methyl) acrylate, caprolactone (methyl) acrylate, ethoxylated nonylphenol (methyl) acrylate, propoxylation nonyl phenol (methyl) acrylate or N-vinyl pyrrolidone etc.

In addition, object lesson as bifunctional monomer, can enumerate 1,3-butylene glycol two (methyl) acrylate, 1,3-butylene glycol (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, polyethyleneglycol diacrylate, two (acryloxy ethyl) ether of bisphenol-A, ethoxylation bisphenol-A two (methyl) acrylate, ethoxylated neopentylglycol two (methyl) acrylate, ethoxylation neopentyl glycol two (methyl) acrylate or 3-methyl pentanediol two (methyl) acrylate etc.

As the object lesson of the above polyfunctional monomer of other 3 officials energy, can enumerate trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylate, ethoxylated trimethylolpropane three (methyl) acrylate, propoxylation trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, tripentaerythritol four (methyl) acrylate, tripentaerythritol five (methyl) acrylate, tripentaerythritol six (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, tripentaerythritol eight (methyl) acrylate, the reactant of pentaerythrite three (methyl) acrylate and acid anhydrides, the reactant of dipentaerythritol five (methyl) acrylate and acid anhydrides, tripentaerythritol seven (methyl) acrylate and acid anhydrides caprolactone modification trimethylolpropane tris (methyl) acrylate, caprolactone modification pentaerythrite three (methyl) acrylate, caprolactone modification three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylate, caprolactone modification pentaerythrite four (methyl) acrylate, caprolactone modification dipentaerythritol five (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate, caprolactone modification tripentaerythritol four (methyl) acrylate, caprolactone modification tripentaerythritol five (methyl) acrylate, caprolactone modification tripentaerythritol six (methyl) acrylate, caprolactone modification tripentaerythritol seven (methyl) acrylate, caprolactone modification tripentaerythritol eight (methyl) acrylate, the reactant of caprolactone modification pentaerythrite three (methyl) acrylate and acid anhydrides, the reactant of caprolactone modification dipentaerythritol five (methyl) acrylate and acid anhydrides, or caprolactone modification tripentaerythritol seven (methyl) acrylate and acid anhydrides etc.

And in this instructions, caprolactone modification refers between the position and (methyl) acryloxy from alcohol of (methyl) acrylate compounds, imports the open loop body or the ring-opening polymerization polymer of caprolactone.

Especially preferably use the above polyfunctional monomer of 2 officials energy.These optical polymerism compounds (C) can use separately or with two or more and use.

The content of optical polymerism compound (C) is preferably 1～70 quality % with respect to the total amount of adhesive resin (A) and optical polymerism compound (C) according to massfraction, more preferably 5～60 quality %.If in above-mentioned scope, then there is sensitivity in the content of optical polymerism compound (C), film and trend that intensity, flatness, reliability and the physical strength of pattern becomes good, so preferred.

As the Photoepolymerizationinitiater initiater that contains in the photosensitive polymer combination of the present invention (D); be the compound of effect initiated polymerization by light or heat; be preferably bisglyoxaline (PVC ィミダゾ one Le) compounds, acetophenone compounds, compound in triazine class, acylphosphine oxide compounds or oxime compound, the bisglyoxaline compounds is preferred especially because sensitivity is excellent.

As above-mentioned united imidazole, can enumerate 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2, the 3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline 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-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2-chlorphenyls)-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 Japanese Patent Publication 48-38403 communique, Japanese kokai publication sho 62-174204 communique etc.), 4,4 ', the imidazolium compoundss that replaced by alkoxy carbonyl group of phenyl of 5,5 '-position (for example with reference to Japanese kokai publication hei 7-10913 communique etc.) etc. preferably 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, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline.

As above-mentioned acetophenone compounds; can enumerate diethoxy acetophenone; 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; benzoin dimethylether (ベ Application ジ Le ジメチ Le ケタ one Le); 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; the 1-hydroxycyclohexylphenylketone; 2-methyl isophthalic acid-(4-methyl sulfenyl phenyl)-2-morpholino base propane-1-ketone; 2-benzyl-2-dimethylamino-1-(4-morpholino base phenyl) butane-1-ketone; 2-(2-methyl-benzyl)-2-dimethylamino-1-(4-morpholino base phenyl) butanone; 2-(3-methyl-benzyl)-2-dimethylamino-1-(4-morpholino base phenyl) butanone; 2-(4-methyl-benzyl)-2-dimethylamino-1-(4-morpholino base phenyl) butanone; 2-(2-Ethylbenzyl)-2-dimethylamino-1-(4-morpholino base phenyl) butanone; 2-(2-propyl group benzyl)-2-dimethylamino-1-(4-morpholino base phenyl) butanone; 2-(2-butyl benzyl)-2-dimethylamino-1-(4-morpholino base phenyl) butanone; 2-(2; the 3-dimethyl benzyl)-2-dimethylamino-1-(4-morpholino base phenyl) butanone; 2-(2, the 4-dimethyl benzyl)-2-dimethylamino-1-(4-morpholino base phenyl) butanone; 2-(2-benzyl chloride base)-2-dimethylamino-1-(4-morpholino base phenyl) butanone; 2-(2-bromobenzyl)-2-dimethylamino-1-(4-morpholino base phenyl) butanone; 2-(3-benzyl chloride base)-2-dimethylamino-1-(4-morpholino base phenyl) butanone; 2-(4-benzyl chloride base)-2-dimethylamino-1-(4-morpholino base phenyl) butanone; 2-(3-bromobenzyl)-2-dimethylamino-1-(4-morpholino base phenyl) butanone; 2-(4-bromobenzyl)-2-dimethylamino-1-(4-morpholino base phenyl) butanone; 2-(2-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino base phenyl) butanone; 2-(3-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino base phenyl) butanone; 2-(4-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino base phenyl) butanone; 2-(2-methyl-4-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino base phenyl) butanone; 2-(2-methyl-4-bromobenzyl)-2-dimethylamino-1-(4-morpholino base phenyl) butanone; 2-(2-bromo-4-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino base phenyl) butanone; 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] oligomer etc. of propane-1-ketone.

As above-mentioned compound in triazine class, can enumerate 2,4-two (trichloromethyl)-6-(4-methoxyphenyl)-1,3, the 5-triazine, 2,4-two (trichloromethyl)-6-(4-methoxyl naphthyl)-1,3, the 5-triazine, 2,4-two (trichloromethyl)-6-piperonyl-1,3, the 5-triazine, 2,4-two (trichloromethyl)-6-(4-methoxyl-styrene)-1,3, the 5-triazine, 2,4-two (trichloromethyl)-6-[2-(5-methylfuran-2-yl) vinyl]-1,3,5-triazines, 2,4-two (trichloromethyl)-6-[2-(furans-2-yl) vinyl]-1,3, the 5-triazine, 2,4-two (trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-1,3, the 5-triazine, 2,4-two (trichloromethyl)-6-[2-(3, the 4-Dimethoxyphenyl) vinyl]-1,3,5-triazine etc.

As above-mentioned acylphosphine oxide class initiating agent, can enumerate 2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc.

As above-mentioned oxime compound, can enumerate the compound shown in the compound shown in O-ethoxy carbonyl-α-oxygen base imino group-1-phenyl-propane-1-ketone, the formula (IV), the formula (V) etc.

If the degree of not damaging effect of the present invention then can be further and with Photoepolymerizationinitiater initiater etc.,, can enumerate for example benzoin compounds, benzophenone compound or thioxanthones compounds etc. as this Photoepolymerizationinitiater initiater.

More particularly, can enumerate following compound, they can be used singly or in combination of two or more respectively.

As above-mentioned benzoin compounds, for example can enumerate benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether or benzoin isobutyl ether etc.

As above-mentioned benzophenone compound; for example can enumerate; benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 3; 3 '; 4; 4 '-four (t-butyl peroxy carbonyl) benzophenone or 2,4,6-tri-methyl benzophenone etc.

As above-mentioned thioxanthones compounds, for example can enumerate 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones or 1-chloro-4-propoxyl group thioxanthones etc.

In addition, can enumerate 10-butyl-2-chloro-acridine ketone, 2-EAQ, dibenzoyl, 9,10-phenanthrenequione, camphorquinone, phenyl glyoxalic acid methylester or two cyclopentadiene titanium compounds etc. are as Photoepolymerizationinitiater initiater.

In addition, as Photoepolymerizationinitiater initiater, can use the Photoepolymerizationinitiater initiater of putting down in writing in the Japanese Unexamined Patent Application Publication 2002-544205 communique with the group that can cause chain transfer.

As above-mentioned Photoepolymerizationinitiater initiater, can enumerate for example Photoepolymerizationinitiater initiater of following formula (5)～following formula (10) with the group that can cause chain transfer.

In addition, can make and use up and/or hot cationic polymerization initiators.

Light and/or hot cationic polymerization initiators can use by kation and the polymerization initiator that constitutes from lewis acidic negative ion.

As above-mentioned cationic object lesson, can enumerate diphenyl iodine, two (p-methylphenyl) iodine, two (to tert-butyl-phenyl) iodine, two (to octyl phenyl) iodine, two (to the octadecyl phenyl) iodine, two (to octyloxyphenyl) iodine, two (to octadecane oxygen base phenyl) iodine, phenyl (to octadecane oxygen base phenyl) iodine, (p-methylphenyl) (p-isopropyl phenyl) iodine, triphenylsulfonium, three (p-methylphenyl) sulfonium, three (p-isopropyl phenyl) sulfonium, three (2, the 6-3,5-dimethylphenyl) sulfonium, three (to tert-butyl-phenyl) sulfonium, three (to cyano-phenyl) sulfonium, three (rubigan) sulfonium, dimethyl (methoxyl) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxyl group) sulfonium, dimethyl (butoxy) sulfonium, dimethyl (octyloxy) sulfonium, dimethyl (octadecane oxygen base) sulfonium, dimethyl (isopropoxy) sulfonium, dimethyl (tert-butoxy) sulfonium, dimethyl (cyclopentyloxy) sulfonium, dimethyl (cyclohexyloxy) sulfonium, dimethyl (fluorine methoxyl) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromine propoxyl group) sulfonium, dimethyl (4-cyano group butoxy) sulfonium, dimethyl (8-nitro octyloxy) sulfonium, dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium, dimethyl (2-hydroxyl isopropoxy) sulfonium or dimethyl (three (trichloromethyl) methyl) sulfonium etc.

As preferred cation, can enumerate two (p-methylphenyl) iodine, (p-methylphenyl) (p-isopropyl phenyl) iodine, two (to tert-butyl-phenyl) iodine, triphenylsulfonium or three (to tert-butyl-phenyl) sulfonium etc.

From lewis acidic anionic object lesson, can enumerate hexafluorophosphate, hexafluoro arsenate, hexafluoro antimonate or four (pentafluorophenyl group) borate etc. as above-mentioned.From lewis acidic negative ion, can enumerate hexafluoro antimonate or four (pentafluorophenyl group) borate as preferably.

Above-mentioned kation and can combination in any from lewis acidic negative ion.

Object lesson as cationic polymerization initiators, can enumerate hexafluorophosphoric acid diphenyl iodine, hexafluorophosphoric acid two (p-methylphenyl) iodine, hexafluorophosphoric acid two (to tert-butyl-phenyl) iodine, hexafluorophosphoric acid two (to octyl phenyl) iodine, hexafluorophosphoric acid two (to the octadecyl phenyl) iodine, hexafluorophosphoric acid two (to octyloxyphenyl) iodine, hexafluorophosphoric acid two (to octadecane oxygen base phenyl) iodine, hexafluorophosphoric acid phenyl (to octadecane oxygen base phenyl) iodine, hexafluorophosphoric acid (p-methylphenyl) (p-isopropyl phenyl) iodine, hexafluorophosphoric acid methyl naphthalene iodide, hexafluorophosphoric acid ethyl naphthalene iodide, the hexafluorophosphoric acid triphenylsulfonium, hexafluorophosphoric acid three (p-methylphenyl) sulfonium, hexafluorophosphoric acid three (p-isopropyl phenyl) sulfonium, hexafluorophosphoric acid three (2, the 6-3,5-dimethylphenyl) sulfonium, hexafluorophosphoric acid three (to tert-butyl-phenyl) sulfonium, hexafluorophosphoric acid three (to cyano-phenyl) sulfonium, hexafluorophosphoric acid three (rubigan) sulfonium, hexafluorophosphoric acid dimethyl naphthyl sulfonium, hexafluorophosphoric acid diethyl naphthyl sulfonium, hexafluorophosphoric acid dimethyl (methoxyl) sulfonium, hexafluorophosphoric acid dimethyl (ethoxy) sulfonium, hexafluorophosphoric acid dimethyl (propoxyl group) sulfonium, hexafluorophosphoric acid dimethyl (butoxy) sulfonium, hexafluorophosphoric acid dimethyl (octyloxy) sulfonium, hexafluorophosphoric acid dimethyl (octadecane oxygen base) sulfonium, hexafluorophosphoric acid dimethyl (isopropoxy) sulfonium, hexafluorophosphoric acid dimethyl (tert-butoxy) sulfonium, hexafluorophosphoric acid dimethyl (cyclopentyloxy) sulfonium, hexafluorophosphoric acid dimethyl (cyclohexyloxy) sulfonium, hexafluorophosphoric acid dimethyl (fluorine methoxyl) sulfonium, hexafluorophosphoric acid dimethyl (2-chloroethoxy) sulfonium, hexafluorophosphoric acid dimethyl (3-bromine propoxyl group) sulfonium, hexafluorophosphoric acid dimethyl (4-cyano group butoxy) sulfonium, hexafluorophosphoric acid dimethyl (8-nitro octyloxy) sulfonium, hexafluorophosphoric acid dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium, hexafluorophosphoric acid dimethyl (2-hydroxyl isopropoxy) sulfonium, hexafluorophosphoric acid dimethyl (three (trichloromethyl) methyl) sulfonium

Hexafluoroarsenate diphenyl iodine, hexafluoroarsenate two (p-methylphenyl) iodine, hexafluoroarsenate two (to tert-butyl-phenyl) iodine, hexafluoroarsenate two (to octyl phenyl) iodine, hexafluoroarsenate two (to the octadecyl phenyl) iodine, hexafluoroarsenate two (to octyloxyphenyl) iodine, hexafluoroarsenate two (to octadecane oxygen base phenyl) iodine, hexafluoroarsenate phenyl (to octadecane oxygen base phenyl) iodine, hexafluoroarsenate (p-methylphenyl) (p-isopropyl phenyl) iodine, hexafluoroarsenate methyl naphthalene iodide, hexafluoroarsenate ethyl naphthalene iodide, the hexafluoroarsenate triphenylsulfonium, hexafluoroarsenate three (p-methylphenyl) sulfonium, hexafluoroarsenate three (p-isopropyl phenyl) sulfonium, hexafluoroarsenate three (2, the 6-3,5-dimethylphenyl) sulfonium, hexafluoroarsenate three (to tert-butyl-phenyl) sulfonium, hexafluoroarsenate three (to cyano-phenyl) sulfonium, hexafluoroarsenate three (rubigan) sulfonium, hexafluoroarsenate dimethyl naphthyl sulfonium, hexafluoroarsenate diethyl naphthyl sulfonium, hexafluoroarsenate dimethyl (methoxyl) sulfonium, hexafluoroarsenate dimethyl (ethoxy) sulfonium, hexafluoroarsenate dimethyl (propoxyl group) sulfonium, hexafluoroarsenate dimethyl (butoxy) sulfonium, hexafluoroarsenate dimethyl (octyloxy) sulfonium, hexafluoroarsenate dimethyl (octadecane oxygen base) sulfonium, hexafluoroarsenate dimethyl (isopropoxy) sulfonium, hexafluoroarsenate dimethyl (tert-butoxy) sulfonium, hexafluoroarsenate dimethyl (cyclopentyloxy) sulfonium, hexafluoroarsenate dimethyl (cyclohexyloxy) sulfonium, hexafluoroarsenate dimethyl (fluorine methoxyl) sulfonium, hexafluoroarsenate dimethyl (2-chloroethoxy) sulfonium, hexafluoroarsenate dimethyl (3-bromine propoxyl group) sulfonium, hexafluoroarsenate dimethyl (4-cyano group butoxy) sulfonium, hexafluoroarsenate dimethyl (8-nitro octyloxy) sulfonium, hexafluoroarsenate dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium, hexafluoroarsenate dimethyl (2-hydroxyl isopropoxy) sulfonium, hexafluoroarsenate dimethyl (three (trichloromethyl) methyl) sulfonium

Hexafluoro-antimonic acid diphenyl iodine, hexafluoro-antimonic acid two (p-methylphenyl) iodine, hexafluoro-antimonic acid two (to tert-butyl-phenyl) iodine, hexafluoro-antimonic acid two (to octyl phenyl) iodine, hexafluoro-antimonic acid two (to the octadecyl phenyl) iodine, hexafluoro-antimonic acid two (to octyloxyphenyl) iodine, hexafluoro-antimonic acid two (to octadecane oxygen base phenyl) iodine, hexafluoro-antimonic acid phenyl (to octadecane oxygen base phenyl) iodine, hexafluoro-antimonic acid (p-methylphenyl) (p-isopropyl phenyl) iodine, hexafluoro-antimonic acid methyl naphthalene iodide, hexafluoro-antimonic acid ethyl naphthalene iodide, the hexafluoro-antimonic acid triphenylsulfonium, hexafluoro-antimonic acid three (p-methylphenyl) sulfonium, hexafluoro-antimonic acid three (p-isopropyl phenyl) sulfonium, hexafluoro-antimonic acid three (2, the 6-3,5-dimethylphenyl) sulfonium, hexafluoro-antimonic acid three (to tert-butyl-phenyl) sulfonium, hexafluoro-antimonic acid three (to cyano-phenyl) sulfonium, hexafluoro-antimonic acid three (rubigan) sulfonium, hexafluoro-antimonic acid dimethyl naphthyl sulfonium, hexafluoro-antimonic acid diethyl naphthyl sulfonium, hexafluoro-antimonic acid dimethyl (methoxyl) sulfonium, hexafluoro-antimonic acid dimethyl (ethoxy) sulfonium, hexafluoro-antimonic acid dimethyl (propoxyl group) sulfonium, hexafluoro-antimonic acid dimethyl (butoxy) sulfonium, hexafluoro-antimonic acid dimethyl (octyloxy) sulfonium, hexafluoro-antimonic acid dimethyl (octadecane oxygen base) sulfonium, hexafluoro-antimonic acid dimethyl (isopropoxy) sulfonium, hexafluoro-antimonic acid dimethyl (tert-butoxy) sulfonium, hexafluoro-antimonic acid dimethyl (cyclopentyloxy) sulfonium, hexafluoro-antimonic acid dimethyl (cyclohexyloxy) sulfonium, hexafluoro-antimonic acid dimethyl (fluorine methoxyl) sulfonium, hexafluoro-antimonic acid dimethyl (2-chloroethoxy) sulfonium, hexafluoro-antimonic acid dimethyl (3-bromine propoxyl group) sulfonium, hexafluoro-antimonic acid dimethyl (4-cyano group butoxy) sulfonium, hexafluoro-antimonic acid dimethyl (8-nitro octyloxy) sulfonium, hexafluoro-antimonic acid dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium, hexafluoro-antimonic acid dimethyl (2-hydroxyl isopropoxy) sulfonium, hexafluoro-antimonic acid dimethyl (three (trichloromethyl) methyl) sulfonium

Four (pentafluorophenyl group) boric acid diphenyl iodine, four (pentafluorophenyl group) boric acid two (p-methylphenyl) iodine, four (pentafluorophenyl group) boric acid two (to tert-butyl-phenyl) iodine, four (pentafluorophenyl group) boric acid two (to octyl phenyl) iodine, four (pentafluorophenyl group) boric acid two (to the octadecyl phenyl) iodine, four (pentafluorophenyl group) boric acid two (to octyloxyphenyl) iodine, four (pentafluorophenyl group) boric acid two (to octadecane oxygen base phenyl) iodine, four (pentafluorophenyl group) boric acid phenyl (to octadecane oxygen base phenyl) iodine, four (pentafluorophenyl group) boric acid (p-methylphenyl) (p-isopropyl phenyl) iodine, four (pentafluorophenyl group) boric acid methyl naphthalene iodide, four (pentafluorophenyl group) boric acid ethyl naphthalene iodide, four (pentafluorophenyl group) boric acid triphenylsulfonium, four (pentafluorophenyl group) boric acid three (p-methylphenyl) sulfonium, four (pentafluorophenyl group) boric acid three (p-isopropyl phenyl) sulfonium, four (pentafluorophenyl group) boric acid three (2, the 6-3,5-dimethylphenyl) sulfonium, four (pentafluorophenyl group) boric acid three (to tert-butyl-phenyl) sulfonium, four (pentafluorophenyl group) boric acid three (to cyano-phenyl) sulfonium, four (pentafluorophenyl group) boric acid three (rubigan) sulfonium, four (pentafluorophenyl group) boric acid dimethyl naphthyl sulfonium, four (pentafluorophenyl group) boric acid diethyl naphthyl sulfonium, four (pentafluorophenyl group) boric acid dimethyl (methoxyl) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (ethoxy) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (propoxyl group) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (butoxy) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (octyloxy) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (octadecane oxygen base) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (isopropoxy) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (tert-butoxy) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (cyclopentyloxy) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (cyclohexyloxy) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (fluorine methoxyl) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (2-chloroethoxy) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (3-bromine propoxyl group) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (4-cyano group butoxy) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (8-nitro octyloxy) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (2-hydroxyl isopropoxy) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (three (trichloromethyl) methyl) sulfonium etc., be preferably hexafluorophosphoric acid two (p-methylphenyl) iodine, hexafluorophosphoric acid (p-methylphenyl) (p-isopropyl phenyl) iodine, hexafluorophosphoric acid two (to tert-butyl-phenyl) iodine, the hexafluorophosphoric acid triphenylsulfonium, hexafluorophosphoric acid three (to tert-butyl-phenyl) sulfonium, hexafluoroarsenate two (p-methylphenyl) iodine, hexafluoroarsenate (p-methylphenyl) (p-isopropyl phenyl) iodine, hexafluoroarsenate two (to tert-butyl-phenyl) iodine, the hexafluoroarsenate triphenylsulfonium, hexafluoroarsenate three (to tert-butyl-phenyl) sulfonium, hexafluoro-antimonic acid two (p-methylphenyl) iodine, hexafluoro-antimonic acid (p-methylphenyl) (p-isopropyl phenyl) iodine, hexafluoro-antimonic acid two (to tert-butyl-phenyl) iodine, the hexafluoro-antimonic acid triphenylsulfonium, hexafluoro-antimonic acid three (to tert-butyl-phenyl) sulfonium, four (pentafluorophenyl group) boric acid two (p-methylphenyl) iodine, four (pentafluorophenyl group) boric acid (p-methylphenyl) (p-isopropyl phenyl) iodine, two (to tert-butyl-phenyl) iodine, four (pentafluorophenyl group) boric acid triphenylsulfonium, four (pentafluorophenyl group) boric acid three (to tert-butyl-phenyl) sulfonium etc., more preferably hexafluoro-antimonic acid two (p-methylphenyl) iodine, hexafluoro-antimonic acid (p-methylphenyl) (p-isopropyl phenyl) iodine, hexafluoro-antimonic acid two (to tert-butyl-phenyl) iodine, the hexafluoro-antimonic acid triphenylsulfonium, hexafluoro-antimonic acid three (to tert-butyl-phenyl) sulfonium, four (pentafluorophenyl group) boric acid two (p-methylphenyl) iodine, four (pentafluorophenyl group) boric acid (p-methylphenyl) (p-isopropyl phenyl) iodine, four (pentafluorophenyl group) boric acid two (to tert-butyl-phenyl) iodine, four (pentafluorophenyl group) boric acid triphenylsulfonium or four (pentafluorophenyl group) boric acid three (to tert-butyl-phenyl) sulfonium etc.

In addition, under the degree of not damaging effect of the present invention, can also in Photoepolymerizationinitiater initiater (D), use by combined light polymerization initiation auxiliary agent (D-1), can make up multiple polymerization initiation auxiliary agent and use.

Cause auxiliary agent (D-1) as photopolymerization, can enumerate the compound shown in the compound shown in amines, carboxylic acid compound, multi-functional thiol's compound, the formula (III), formula (A-1) or the formula (A-2) etc.

As above-mentioned amines, can enumerate fatty amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, 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, N-dimethyl-p-toluidine, 4, aromatic amines compounds such as 4 '-two (dimethylamino) benzophenone (common name Michler's keton) or 4,4 '-two (diethylamino) benzophenone.

As above-mentioned carboxylic acid compound, can enumerate assorted acetate (acid of the aromatic series ヘテロ jealous woman) class of aromatics such as thioacetic acid phenyl ester, thioacetic acid methyl phenyl ester, thioacetic acid ethyl phenyl ester, thioacetic acid Methylethyl phenyl ester, thioacetic acid dimethyl phenyl ester, thioacetic acid methoxyl phenyl ester, thioacetic acid dimethoxy phenyl ester, thioacetic acid chlorobenzene ester, thioacetic acid Dichlorfop, N-phenylglycine, phenoxyacetic acid, thioacetic acid naphthalene ester, N-naphthyl glycocoll or naphthoxy acetic acid.

Above-mentioned multi-functional thiol's compound is the compound that has two above mercaptos in the molecule.Wherein, have the compound of two above analiphatic sulphur alcohol radicals since improve photosensitive polymer combination of the present invention sensitivity and more preferably.

As multi-functional thiol's compound, specifically, can enumerate ethanthiol, the last of the ten Heavenly stems two mercaptan, 1,4-dimethyl sulfydryl benzene, butylene glycol two thiopropionates, butylene glycol dimercapto acetic acid esters, ethylene glycol dimercapto acetate, the trimethylolpropane tris mercaptoacetate, butylene glycol two thiopropionates, the trimethylolpropane tris thiopropionate, the trimethylolpropane tris mercaptoacetate, pentaerythrite tetrathio propionic ester, pentaerythrite four mercaptoacetates, trihydroxyethyl three sulfo-propionic esters, pentaerythrite four (3-sulfydryl butyric ester) or 1,4-two (3-sulfydryl butyryl acyloxy) butane etc.

The content of multi-functional thiol's compound is preferably 0.5～20 quality % with respect to the total amount of Photoepolymerizationinitiater initiater (D) according to massfraction, more preferably 1～15 quality %.If the content of multi-functional thiol's compound is in above-mentioned scope, then sensitivity raises, and so the trend that exists development to become good in addition is preferred.

The content of multi-functional thiol's compound is preferably 0.1～20 quality % with respect to the total amount of adhesive resin (A) and optical polymerism compound (C) according to massfraction, more preferably 1～10 quality %.If the content of multi-functional thiol's compound is in above-mentioned scope, then sensitivity raises, and so the trend that exists development to become good in addition is preferred.

Cause auxiliary agent (D-1) as photopolymerization, can use the compound shown in the following formula (III).

In the formula (III), the dotted line shown in the X represents that the carbon number that can be replaced by halogen atom is 6～12 aromatic ring.

Y represents oxygen atom, sulphur atom.

R ²¹The expression carbon number is 1～6 alkyl.

R ²²The carbon number that expression can be replaced by halogen atom is 1～12 the alkyl or the aryl that can be replaced by halogen atom.

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

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

As the carbon number that can be replaced by halogen atom is 6～12 aromatic ring, 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.

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

It as the carbon number that can be replaced 1～12 alkyl by halogen atom, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, 1-methyl n-pro-pyl, 2-methyl n-pro-pyl, the tert-butyl group, n-pentyl, 1-methyl normal-butyl, 2-methyl normal-butyl, 3-methyl normal-butyl, 1,1-dimethyl n propyl group, 1,2-dimethyl n propyl group, 2,2-dimethyl n propyl group, n-hexyl, cyclohexyl, 1-chloro-n-butyl, 2-chloro-n-butyl, 3-chloro-n-butyl etc.

As the aryl that can be replaced by halogen atom, can enumerate 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.

As the compound shown in the formula (III); specifically; can enumerate 2-benzoyl methylene-3-methyl-naphtho-[2; 1-d] thiazoline; 2-benzoyl methylene-3-methyl-naphtho-[1; 2-d] thiazoline; 2-benzoyl methylene-3-methyl-naphtho-[2; 3-d] thiazoline; 2-(2-naphthoyl methylene)-3-methylbenzothiazole quinoline; 2-(1-naphthoyl methylene)-3-methylbenzothiazole quinoline; 2-(2-naphthoyl methylene)-3-methyl-5-phenyl benzothiazole quinoline; 2-(1-naphthoyl methylene)-3-methyl-5-phenyl benzothiazole quinoline; 2-(2-naphthoyl methylene)-3-methyl-5-fluoro benzothiazole quinoline; 2-(1-naphthoyl methylene)-3-methyl-5-fluoro benzothiazole quinoline; 2-(2-naphthoyl methylene)-3-methyl-5-chloro benzothiazole quinoline; 2-(1-naphthoyl methylene)-3-methyl-5-chloro benzothiazole quinoline; 2-(2-naphthoyl methylene)-3-methyl-5-bromo benzothiazole quinoline; 2-(1-naphthoyl methylene)-3-methyl-5-bromo benzothiazole quinoline; 2-(4-dibenzoyl methylene)-3-methylbenzothiazole quinoline; 2-(4-dibenzoyl methylene)-3-methyl-5-phenyl benzothiazole quinoline; 2-(2-naphthoyl methylene)-3-methyl-naphtho-[2; 1-d] thiazoline; 2-(2-naphthoyl methylene)-3-methyl-naphtho-[1; 2-d] thiazoline; 2-(4-dibenzoyl methylene)-3-methyl-naphtho-[2; 1-d] thiazoline; 2-(4-dibenzoyl methylene)-3-methyl-naphtho-[1; 2-d] thiazoline; 2-(to the fluorobenzoyl methylene)-3-methyl-naphtho-[2; 1-d] thiazoline; 2-(to the fluorobenzoyl methylene)-3-methyl-naphtho-[1; 2-d] thiazoline; 2-benzoyl methylene-3-methyl-naphtho-[2; 1-d] oxazoline; 2-benzoyl methylene-3-methyl-naphtho-[1; 2-d] oxazoline; 2-benzoyl methylene-3-methyl-naphtho-[2; 3-d] oxazoline; 2-(2-naphthoyl methylene)-3-Jia base benzoxazole quinoline; 2-(1-naphthoyl methylene)-3-Jia base benzoxazole quinoline; 2-(2-naphthoyl methylene)-3-methyl-5-Ben base benzoxazole quinoline; 2-(1-naphthoyl methylene)-3-methyl-5-Ben base benzoxazole quinoline; 2-(2-naphthoyl methylene)-3-methyl-5-Fu benzoxazole quinoline; 2-(1-naphthoyl methylene)-3-methyl-5-Fu benzoxazole quinoline; 2-(2-naphthoyl methylene)-3-methyl-5-chloro benzoxazole quinoline; 2-(1-naphthoyl methylene)-3-methyl-5-chloro benzoxazole quinoline; 2-(2-naphthoyl methylene)-3-methyl-5-bromoxynil oxazoline quinoline; 2-(1-naphthoyl methylene)-3-methyl-5-bromoxynil oxazoline quinoline; 2-(4-dibenzoyl methylene)-3-Jia base benzoxazole quinoline; 2-(4-dibenzoyl methylene)-3-methyl-5-Ben base benzoxazole quinoline; 2-(2-naphthoyl methylene)-3-methyl-naphtho-[2; 1-d] oxazoline; 2-(2-naphthoyl methylene)-3-methyl-naphtho-[1; 2-d] oxazoline; 2-(4-dibenzoyl methylene)-3-methyl-naphtho-[2; 1-d] oxazoline; 2-(4-dibenzoyl methylene)-3-methyl-naphtho-[1; 2-d] oxazoline; 2-(to the fluorobenzoyl methylene)-3-methyl-naphtho-[2; 1-d] oxazoline; 2-(to the fluorobenzoyl methylene)-3-methyl-naphtho-[1,2-d] oxazoline etc.

Wherein, be preferably the 2-benzoyl methylene-3-methyl-naphtho-[1 shown in the 2-shown in the formula (III-1) (2-naphthoyl methylene)-3-methylbenzothiazole quinoline, the formula (III-2); 2-d] 2-(4-dibenzoyl methylene)-3-methyl-naphtho-[1, the 2-d] thiazoline shown in thiazoline and the formula (III-3).

Cause auxiliary agent (D-1) as photopolymerization, can also use the compound shown at least a kind in formula of being selected from (A-1) and the formula (A-2).

[in formula (A-1) and the formula (A-2), ring X ³¹With ring X ³²Represent independently that respectively carbon number is 6～12 aromatic ring.Y ³¹And Y ³²Expression oxygen atom or sulphur atom.R ³¹And R ³²The expression carbon number is that 1～12 alkyl or carbon number are 6～12 aryl.

The carbon atom that contains in this aromatic ring, this alkyl or aryl can be replaced by oxygen atom, nitrogen-atoms, sulphur atom or halogen atom.]

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

As carbon number is 6～12 aromatic ring, 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, phenanthrene ring,

Ring, fluoranthene ring, benzo [a] pyrene ring, benzo [e] pyrene Huan, perylene ring and their derivant etc.

It as carbon number 1～12 alkyl, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, 1-methyl n-pro-pyl, 2-methyl n-pro-pyl, the tert-butyl group, n-pentyl, 1-methyl normal-butyl, 2-methyl normal-butyl, 3-methyl normal-butyl, 1,1-dimethyl n propyl group, 1,2-dimethyl n propyl group, 2,2-dimethyl n propyl group, n-hexyl, cyclohexyl, 1-chloro-n-butyl, 2-chloro-n-butyl, 3-chloro-n-butyl etc.

As carbon number is 6～12 aryl, can enumerate phenyl, chlorphenyl, dichlorophenyl, bromophenyl, dibromo phenyl, chloro-bromobenzene base, hydroxy phenyl, alkoxyl phenyl, xenyl, chlorodiphenyl, DCBP base, bromophenyl, dibromo phenyl, naphthyl, chloronaphthyl, methylnaphthyl, dichloro naphthyl, bromonaphthalene base, dibromo naphthyl, hydroxyl naphthyl etc.

As the compound shown in formula (A-1) or the formula (A-2), can enumerate particularly:

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

Dialkoxy anthracene classes such as dimethoxy anthracene, diethoxy anthracene, dipropoxy anthracene, diisopropoxy anthracene, dibutoxy anthracene, two amoxy anthracenes, two own oxygen base anthracenes, 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., but be not limited thereto.

The content of Photoepolymerizationinitiater initiater (D) according to massfraction, is preferably 0.1～40 quality %, more preferably 1～30 quality % with respect to the total amount of adhesive resin (A) and optical polymerism compound (C).

In addition, photopolymerization causes the content of auxiliary agent (D-1) according to benchmark same as described above, is preferably 0.01～50 quality %, more preferably 0.1～40 quality %.

The content that is selected from the compound shown at least a kind in formula (A-1) and the formula (A-2) causes the content of auxiliary agent (D-1) with respect to photopolymerization, is preferably 50～100%, and more preferably 60～100%, more preferably 65～100%.If the content that is selected from the compound shown at least a kind in formula (A-1) and the formula (A-2) in above-mentioned scope, then uses the photosensitive polymer combination that contains it to form when filming, the transparency of filming is good, so preferred.

If the total amount of Photoepolymerizationinitiater initiater (D) is in above-mentioned scope, then photosensitive polymer combination is highly sensitive, the intensity of filming of using that above-mentioned photosensitive polymer combination forms or pattern, above-mentioned filming or trend that the flatness of patterned surfaces becomes good are arranged, so preferred.In addition, if photopolymerization causes the amount of auxiliary agent (D-1) in above-mentioned scope, the sensitivity of the photosensitive polymer combination that then obtains further improves, and the trend of the productivity raising of the pattern that uses above-mentioned photosensitive polymer combination formation is arranged, so preferred.

Photosensitive polymer combination of the present invention can contain solvent (E) as required.As this solvent (E), can enumerate the various organic solvents that use in the photosensitive polymer combination field, as its object lesson, can enumerate ethylene glycol monoalkyl ether classes such as glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl propyl ether and ethylene glycol monobutyl ether

Diglycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diglycol ethyl-methyl ether, diglycol dipropyl ether, diglycol dibutyl ethers,

Ethylene glycol alkyl ether acetate esters such as methylcellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetic acid esters, ethylene glycol monomethyl ether acetate,

Aklylene glycol alkyl ether acetate esters such as propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, propylene glycol list propyl ether acetic acid esters, methoxyl butylacetic acid ester, methoxyl amyl group acetic acid esters,

Propylene-glycol monoalky lether classes such as propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list propyl ether, propylene glycol single-butyl ether,

Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol Anaesthetie Ether, propylene glycol ethyl-methyl ether, propylene glycol dipropyl ether, propylene glycol propyl group methyl ether, propylene glycol ethyl propyl ether,

Propylene glycol alkyl ether propionic acid esters such as methyl proxitol propionic ester, propylene glycol ethylether propionic ester, propylene glycol propyl ether propionic ester, propylene glycol butyl ether propionic ester,

Butylene glycol monoalkyl ethers such as methoxybutanol, ethoxy butanols, propoxyl group butanols, butoxy butanols,

Butylene glycol monoalky lether acetate esters such as methoxyl butylacetic acid ester, ethoxy butylacetic acid ester, propoxyl group butylacetic acid ester, butoxy butylacetic acid ester,

Butylene glycol monoalky lether propionic acid esters such as methoxyl butyl propionic ester, ethoxy butyl propionic ester, propoxyl group butyl propionic ester, butoxy butyl propionic ester,

Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol Anaesthetie Ether, dipropylene glycol methyl ethyl ether,

Aromatic hydrocarbons such as benzene,toluene,xylene, sym-trimethyl benzene,

Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone,

Alcohols such as ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, glycerine,

Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, the 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy methyl acetate, hydroxyl ethyl acetate, the glycolic acid butyl ester, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, the 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-hydracrylic acid propyl ester, 3-hydracrylic acid butyl ester, 2-hydroxy-3-methyl methyl butyrate, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid propyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, the ethoxyacetic acid propyl ester, the ethoxyacetic acid butyl ester, the propoxyl group methyl acetate, propoxyl group ethyl acetate, the propoxyl group propyl acetate, the propoxyl group butyl acetate, the butoxy acetic acid methyl esters, the butoxy acetic acid ethyl ester, the butoxy acetic acid propyl ester, the butoxy acetic acid butyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2-butoxy methyl propionate, 2-butoxy ethyl propionate, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxyl group methyl propionate, 3-propoxyl group ethyl propionate, 3-propoxyl group propyl propionate, 3-propoxyl group butyl propionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate, ester classes such as 3-butoxy butyl propionate

Cyclic ether such as tetrahydrofuran, pyrans base class,

Cyclic ester classes such as gamma-butyrolacton etc.

In the above-mentioned solvent, consider, preferably enumerate boiling point in the above-mentioned solvent and be 100～200 ℃ organic solvent from coating, drying property aspect.It as boiling point 100～200 ℃ organic solvent, specifically, ester classes such as ketones such as alcohols, cyclohexanone such as aklylene glycol alkyl ether acetate esters, methoxybutanol and ethoxy butanols, 3-ethoxyl ethyl propionate and 3-methoxypropionic acid methyl esters be can enumerate, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, cyclohexanone, methoxybutanol, methoxyl butylacetic acid ester, 3-ethoxyl ethyl propionate and 3-methoxypropionic acid methyl esters further preferably enumerated.

These solvents (E) can be distinguished use separately or will mix more than 2 kinds and use.

The content of the solvent in the photosensitive polymer combination of the present invention (E) is preferably 60～90 quality % with respect to photosensitive polymer combination according to massfraction, more preferably 65～85 quality %.If the content of solvent (E) is in above-mentioned scope, then by spin coater, Xia Feng ﹠amp; During the coating of apparatus for coating such as spin coater, slit coater (be also referred to as mould sometimes and be coated with machine, curtain coater), ink-jet, roll coater, dip coater, coating might become well, so preferred.

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 is with respect to the content of composition in its entirety, for example according to massfraction less than 10 quality %, preferably less than 1 quality %.

In the photosensitive polymer combination of the present invention, as required, can also and with filling agent, other adjuvants (F) such as macromolecular compound, levelling agent, adhesion promotor, antioxidant, ultraviolet light absorber, light stability, deflocculation material, chain-transferring agent.

As filling agent, specifically, can enumerate glass, silicon dioxide, aluminium oxide etc.

As other macromolecular compound, specifically, can enumerate curable resins such as epoxy resin, maleimide resin, or thermoplastic resins such as polyvinyl alcohol (PVA), polyacrylic acid, polyalkylene glycol monoalkyl ether, poly-fluoroalkyl acrylate, polyester, polyurethane etc.

As levelling agent, can use commercially available surfactant, specifically, can enumerate for example surfactants such as type siloxane, fluorine class, ester class, cationic, anionic species, nonionic class, both sexes etc., can use separately respectively or will be used in combination more than 2 kinds.As above-mentioned surfactant, can enumerate the polyoxyethylene alkyl ether class, the polyoxyethylene alkyl phenyl ether class, the polyethylene glycol di class, the sorbitan fatty acid esters class, fatty acid modified polyesters, the tertiary amine modified polyurethane, outside polyethylene imine based (Port リェチレ Application ィミ Application) class etc., can also enumerate for example commodity KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system) by name, Port リ Off ロ one (common prosperity chemistry (strain) system), ェ Off トップ (ト one ケ system プロダ Network ッ society system), メガ Off ァッ Network (big Japanese ィ Application キ chemical industry (strain) system), Off ロラ one De (Sumitomo スリ one ェ system (strain) system), ァサヒガ one De, サ one Off ロ Application (above) by Asahi Glass (strain) system, ソ Le スパ one ス (ゼネカ (strain) system), EFKA (EFKA CHEMICALS corporate system), PB821 (monosodium glutamate (strain) system) etc.

As adhesion promotor, the preferred silane compounds, specifically, can enumerate vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-methacryloxypropyl trimethoxy silane, 3-sulfydryl propyl trimethoxy silicane etc.

As antioxidant, can enumerate the 2-tert-butyl group-6-(the 3-tert-butyl group-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate particularly, 2-[1-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl) ethyl]-4,6-di-tert-pentyl-phenyl acrylate, 6-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propoxyl group]-2,4,8,10-tetra-tert dibenzo [d, f] [1,3,2] two oxa-phosphorus heterocycle heptane (ジォキサ Off ォス Off ェピ Application), 3,9-two [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1, the 1-dimethyl ethyl]-2,4,8,10-four oxaspiros [5,5] undecane, 2,2 '-methylene two (the 6-tert-butyl group-4-methylphenol), 4,4 '-butylidene two (the 6-tert-butyl group-3-methylphenol), 4,4 '-sulfo-two (the 2-tert-butyl group-5-methylphenol), 2,2 '-sulfo-two (the 6-tert-butyl group-4-methylphenol), dilauryl 3,3 ' thiodipropionate, myristyl 3,3 '-thiodipropionate, distearyl 3,3 '-thiodipropionate, pentaerythrite base four (3-lauryl thiopropionate), 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-triketone, 3,3 '; 3 " 5,5 ', 5 "-and six tert-butyl groups-a; a '; a "-(sym-trimethyl benzene-2,4,6-three bases) three paracresol, [3-(3 for pentaerythrite four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], 2,6 di tert butyl 4 methyl phenol etc.

As ultraviolet light absorber, can enumerate 2-(2-hydroxyl-5-tert-butyl-phenyl)-2H-benzotriazole particularly, octyl group-3-[3-tertiary butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2-yl) phenyl] propionic ester, 2-[4-[(2-hydroxyl-3-dodecyloxy propyl group) oxygen base]-the 2-hydroxy phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2-[4-[(2-hydroxyl-3-(2 '-ethyl) hexyl) oxygen base]-the 2-hydroxy phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2,4-two (2-hydroxyl-4-butoxy phenyl)-6-(2,4-two-butoxy phenyl)-1,3, the 5-triazine, 2-(2-hydroxyl-4-[1-carbonyl octyloxy ethoxy] phenyl)-4,6-two (4-phenyl)-1,3, the 5-triazine, 2-(2H-benzotriazole-2-yl)-4,6-two (1-methyl isophthalic acid-phenylethyl) phenol, 2-(2H-benzotriazole-2-yl)-6-(1-methyl isophthalic acid-phenylethyl)-4-(1,1,3, the 3-tetramethyl butyl) phenol, 2-(the 3-tert-butyl group-2-hydroxy-5-methyl base phenyl)-5-chlorobenzotriazole or alkoxy benzophenone etc.

As light stabilizer, specifically, can enumerate by succinic acid and (4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-yl) macromolecule that forms of ethanol, N, N '; N ", N ' " and-four (4,6-two (butyl-(N-methyl-2; 2,6,6-tetramethyl piperidine-1-yl) amino) triazine-2-yl)-4; 7-diaza decane-1,10-diamines, decanedioic acid; two (2; 2,6,6-tetramethyl-1-(octyloxy)-4-piperidyl) ester and 1; 1-dimethyl ethyl hydroperoxides, two (1,2,2,6,6-pentamethyl-4-piperidyl)-[[3,5-two (1, the 1-dimethyl ethyl)-4-hydroxy phenyl] methyl] the butylmalonic acid ester, 2,4-two [N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl) amino]-6-(2-hydroxyethyl amine)-1,3,5-triazines, two (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate or methyl (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate etc.

As the deflocculation material, can enumerate sodium polyacrylate etc.

In addition, as chain-transferring agent, can enumerate dodecyl mercaptans, 2,4-diphenyl-4-methyl-1-pentene etc.

Photosensitive polymer combination of the present invention uses spectrophotometer if be filled in the quartz cell of optical path length 1cm, measures transmittance under the condition of measuring wavelength 400～700nm, and then transmittance is more than 70%, to be preferably more than 80%.

Method to coating photosensitive polymer combination of the present invention on substrate surface does not limit especially, for example, can pass through spin coater, Xia Feng ﹠amp; The coating of apparatus for coating such as spin coater, slit coater (be also referred to as mould sometimes and be coated with machine, curtain coater), ink-jet, roll coater, dip coater.

If photosensitive polymer combination of the present invention is filming for 3 μ m thickness after be heating and curing (for example, 100～250 ℃, 5 minutes～3 hours), use spectrophotometer, measure transmittance under the condition of measuring wavelength 400～700nm, then transmittance is more than 90%, to be preferably more than 95%.Thus, can provide the transparency excellent filming.

Photosensitive polymer combination of the present invention is following to be coated on glass substrate or film substrate, form on the base material of color filter or driving circuit, carries out photocuring and development, can form and film or pattern.

At first, with this photosensitive polymer combination be coated on that substrate (being generally glass) or the previous solid constituent by photosensitive polymer combination that forms form layer on, remove volatile ingredient such as desolvate by preceding baking by the photosensitive polymer combination layer of coating, obtain level and smooth uncured filming.The uncured thickness of filming of this moment is about 1～6 μ m.To uncured the filming that so obtains, by being used to form the mask of purpose pattern, the ultraviolet ray that irradiation is produced by mercury lamp or light emitting diode.

In addition, in pattern formed, its live width can suitably be controlled by mask size.

Utilize exposure machine in recent years, to use the filtrator that blocks this wavelength region may to block less than the light of 350nm, use the bandpass filter of taking out this wavelength region may optionally to take out near near near the light of the wavelength the 436nm, the 408nm, the 365nm, exposure portion integral body is shone parallel rays equably.This moment, preferred mask alignment instrument or the ledex devices such as (ステッパ) of using cooperated with the correct position of substrate to carry out mask.Further, after this make filming and the non-exposure of aqueous alkali contact lysis portion of rayed end, develop, obtain filming or pattern of purpose thus.Developing method can be in liquid pool method, infusion process or the spray-on process etc. any one.Further can when developing, make the substrate angle arbitrarily that tilts.

Form the developer solution that uses in the development after pattern also exposes and be generally the aqueous solution that contains alkali compounds and surfactant.

Alkali compounds can be in the inorganic or organic alkali compounds any one.

As the object lesson of inorganic alkaline compound, 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, sodium bicarbonate, saleratus, sodium borate, potassium borate or ammonia etc.

In addition, as the object lesson of organic basic compound, can enumerate Tetramethylammonium hydroxide, 2-hydroxyethyl trimethylammonium hydroxide, monomethyl amine, dimethyl amine, Trimethylamine, single ethylamine, diethylamide, triethylamine, single isopropylamine, diisopropylamine or monoethanolamine etc.These inorganic and organic basic compounds can use separately respectively or will be used in combination more than 2 kinds.The concentration of the alkali compounds in the alkaline developer is preferably 0.01～10 quality %, more preferably 0.03～5 quality %.

In addition, the surfactant in the alkaline developer can be in nonionic class surfactant, anionic species surfactant or the cationic surfactant any one.

Object lesson as nonionic class surfactant, can enumerate polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other polyoxyethylene deriv, the 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.

Object lesson as the anionic species surfactant, can enumerate higher alcohol sulfuric ester salts such as lauryl alcohol sodium sulfovinate, oleyl alcohol sodium sulfovinate, alkylsurfuric acid such as NaLS or Texapon Special salt, alkyl aryl sulfonate classes such as neopelex or dodecyl sodium naphthalene sulfonate etc.

As the object lesson of cationic surfactant, can enumerate amine salt such as stearyl amine hydrochloride or DTAC or quaternary ammonium salt etc.

These surfactants can use separately respectively or will be used in combination more than 2 kinds.

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

After the development, wash, further, as required can be 150～230 ℃ of back bakings of implementing 10 minutes～180 minutes down.

Use photosensitive polymer combination of the present invention, through above steps, can film or pattern forming on the substrate or on the filter substrate.This is filmed or pattern is useful as the finishing coat (ォ one バ one コ one ト) that the light interval body that uses in the liquid crystal indicator maybe can form pattern.In addition, if, then can form the hole, be used as interlayer dielectric in that uncured filming formed pattern and when exposing, use the hole to form and use photomask.Further, filming when exposing to uncured, can not use photomask and carry out overall exposing and be heating and curing or only form hyaline membrane by being heating and curing, this hyaline membrane can be used as finishing coat, can be used for touch-screen in addition.

Go into by filming of will so obtaining or pattern groups in the display device such as liquid crystal indicator, can make the display device of superior quality with high yield.

According to photosensitive polymer combination of the present invention, can form the pattern of the high transmittance that shows sufficient resolution.

Embodiment

By the following examples the present invention is carried out specific description, but the present invention is not limited by these embodiment.In the example, the % of expression content or consumption and part only otherwise specify and then refer to quality criteria.

[synthesis example 1]

0.02L/ minute nitrogen of circulation adds 3-methoxyl-1-butanols 200 mass parts and 3-methoxyl butylacetic acid ester 105 mass parts as atmosphere gas in the flask of the 1L with reflux condenser, tap funnel and stirring machine, is heated to 70 ℃ in the time of stirring.Then, be dissolved in methacrylic acid 60 mass parts, 3,4-epoxy radicals three ring [5.2.1.0 ^2.6] prepare solution in decyl acrylate (compound shown in compound shown in the formula (I-1) and the formula (II-1) mixes with 50: 50 according to mol ratio) 240 mass parts and 3-methoxyl butylacetic acid ester 140 mass parts, use tap funnel with 4 hours this lysate, be added drop-wise to insulation in 70 ℃ flask.On the other hand, with polymerization initiator 2,2 '-azo two (2, the 4-methyl pentane nitrile), 30 mass parts are dissolved in the solution that obtains in 3-methoxyl butylacetic acid ester 225 mass parts, use other tap funnel to be added drop-wise in the flask with 4 hours.Drip after polymerization initiator solution finishes, remain on 70 ℃ 4 hours, be cooled to room temperature then, obtain multipolymer (Resin A solution a) of solid constituent 32.6 quality %, acid number 110mg-KOH/g (being scaled solid constituent).The weight-average molecular weight Mw of the Resin A a that obtains is 1.3 * 10 ⁴, molecular weight distribution (Mw/Mn) is 2.50.

(mensuration of molecular weight)

For the weight-average molecular weight (Mw) of Resin A a and the mensuration of number-average molecular weight (Mn), use the GPC method, under following condition, carry out.

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

Chromatographic column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ℃

Solvent: THF (tetrahydrofuran)

Flow velocity: 1.0ml/min

Detecting device: RI

The weight-average molecular weight and the likening to of number-average molecular weight of the above-mentioned polystyrene conversion that obtains are molecular weight distribution (Mw/Mn).

[embodiment 1]

With 153 parts of the resin solutions that contains Resin A a (A) (being scaled 50 parts of solid constituents) that obtain in the synthesis example 1; 3 parts of phthalic anhydrides (B); 50 parts of dipentaerythritol acrylates (C); 2; 2 '-two (2-chlorphenyls)-4; 4 '; 5; 4 parts of 5 '-tetraphenyl bisglyoxalines (D); 0.5 part of 2-(2-naphthoyl methylene)-3-methylbenzothiazole quinoline (D); 3 parts of pentaerythrite tetrathio propionic esters (D); (F) 0.8 part of IRGANOX3114 (Ciba Specialty Chemicals corporate system); 58 parts of propylene glycol monomethyl ether; 42 parts of 3-ethoxyethyl group propionic esters; 7 parts in 3-methoxyl 1-butanols and 9 parts of mixing of 3-methoxyl butylacetic acid ester obtain photosensitive polymer combination 1.

The average transmittance of＜composition 〉

For photosensitive polymer combination 1, use ultraviolet-visible pectrophotometer (V-650DS, Japanese beam split (strain) system) (quartz cell, optical path length: 1cm), measure the average transmittance (%) under 400～700nm.

The average transmittance of＜film 〉

Usability photosensitive resin composition 1 is made cured film under following condition, make that the thickness after solidifying is 3 μ m.

2 inches square glass substrates (#1737, コ one ニ Application グ society system) are dry with neutral lotion, water and alcohol washing back successively.Spin coating photosensitive polymer combination 1 on this glass substrate makes and uses 200mJ/cm ²Exposure (405nm) expose, develop, wash, the thickness after the baking of back is 3.0 μ m, then in cleaning oven, dried by the fire 3 minutes before down at 90 ℃.

For the cured film that obtains, use micro-spectral light measurer (OSP-SP200, OLYMPUS corporate system), measure the average transmittance (%) under 400～700nm.

The transmittance raising means that absorption reduces.

[manufacturing of pattern 1]

2 inches square glass substrates (#1737, コ one ニ Application グ society system) are dry with neutral lotion, water and alcohol washing back successively.Spin coating photosensitive polymer combination 1 on this glass substrate makes and uses 200mJ/cm ²Exposure (405nm) expose, develop, wash, the thickness after the baking of back is 3.0 μ m, then in cleaning oven, dried by the fire 3 minutes before down at 90 ℃.After the cooling, make this photosensitive polymer combination 1 of coating substrate and quartz glass system photomask be spaced apart 10 μ m, the use exposure machine (TEM-150RSK, make, light source: ultrahigh pressure mercury lamp), use 100mJ/cm under atmospheric atmosphere gas by トプコ Application (strain) ²Exposure (405nm benchmark) carry out rayed.And make radiating light from ultrahigh pressure mercury lamp pass through optical filter (LU0400, Korean and Japanese beam split (strain) system) to the irradiation of photosensitive polymer combination 1 this moment, the light below the 400nm blocked use.In addition, as photomask, use pattern (having the length of side is the foursquare transmittance section of 20 μ m, these foursquare 100 μ m that are spaced apart) formation photomask at grade.

After the rayed, will above-mentionedly film down at 25 ℃ is immersed in the water system developer solution that contains nonionic class surfactant 0.12% and potassium hydroxide 0.04% 100 seconds and develops, and after washing, dries by the fire after carrying out 20 minutes under 220 ℃ in baking oven, obtains pattern 1.

＜live width 〉

The pattern that obtains is measured with three-dimensional noncontact surface shape measuring system (MicromapMM527N-PS-M100, (strain) water chestnutization システ system society system).For pattern height, will be apart from the part of real estate 5% as live width.

The more little then resolution of the numerical value of live width is high more and preferred.

[embodiment 2]

Obtain the photosensitive polymer combination of composition shown in the table 1, similarly to Example 1 it is estimated.The result is as shown in table 1.

[embodiment 3]

[comparative example 1]

[table 1]

By the result of the embodiment shown in the table 1 1～3 as can be known, by using specific compound, can form the pattern that shows excellent resolution.And in the comparative example 1, can not obtain having the pattern of sufficient resolution.

Industrial applicability

Photosensitive polymer combination of the present invention, owing to can form the pattern of the high light transmittance that shows excellent resolution ratio, can be used for suitably finishing coat, photomask, dielectric film, liquid crystal aligning control with projection, for the formation of filming of using of the display unit such as coating of the thickness of cooperation colored pattern or pattern.

Claims

1. photosensitive polymer combination, it contains adhesive resin (A), be selected from carboxylic acid anhydrides and have at least a kind of compound (B), optical polymerism compound (C) and Photoepolymerizationinitiater initiater (D) in the compound of at least 2 carboxyls,

2. photosensitive polymer combination as claimed in claim 1, wherein, adhesive resin (A) will be for being selected from least a kind of monomer in unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides (A-a), being the adhesive resin that the monomer (A-c) of 2～4 ring-type ether is polymerized with having carbon number.

3. photosensitive polymer combination as claimed in claim 1 or 2 wherein, has carbon number and is the monomer of monomer (A-c) for having epoxy radicals of 2～4 ring-type ether.

4. photosensitive polymer combination as claimed in claim 3, wherein, the monomer with epoxy radicals is to have the monomer that aliphatics is encircled epoxy radicals more.

5. photosensitive polymer combination as claimed in claim 4 wherein, has monomer that aliphatics encircles epoxy radicals more for being selected from least a kind of compound in the compound shown in compound shown in the formula (I) and the formula (II),

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

6. as any described photosensitive polymer combination in the claim 1～5, wherein, at least a kind of monomer that is selected from unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides (A-a) is aliphatics unsaturated carboxylic acid, aliphatics unsaturated carboxylic acid anhydrides or aliphatics unsaturated carboxylic acid and aliphatics unsaturated carboxylic acid anhydrides.

7. as claim 5 or 6 described photosensitive polymer combinations, wherein, be selected from least a kind of compound in the compound shown in compound shown in the formula (I) and the formula (II) for being selected from least a kind of compound in the compound shown in compound shown in the formula (I ') and the formula (II ')

[formula (I ') and formula (II ') in, R ₁' and R ₂' represent independently that respectively hydrogen atom or carbon number are 1～4 alkyl, the hydrogen atom that contains in this alkyl can be replaced by hydroxyl].

8. as any described photosensitive polymer combination in the claim 1～7, wherein, be selected from carboxylic acid anhydrides and at least a kind of compound (B) of having in the compound of at least 2 carboxyls is a carboxylic acid anhydrides.

9. be used to form film or the claim 1～8 of pattern in the application of any described photosensitive polymer combination.

10. film or pattern, it forms for any described photosensitive polymer combination in the use claim 1～8.

11. display device, it contains, and claim 10 is described films or pattern.