CN102385248B

CN102385248B - Photosensitive polymer combination

Info

Publication number: CN102385248B
Application number: CN201110250770.8A
Authority: CN
Inventors: 井上胜治; 村上元彦
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2010-09-01
Filing date: 2011-08-29
Publication date: 2016-12-14
Anticipated expiration: 2031-08-29

Abstract

The present invention provides a kind of pattern, and its use comprises following (A), (B), (C), (D) and the photosensitive polymer combination of (E) and obtains, and has both high-fire resistance and high water proofing property.Described photosensitive polymer combination comprises: (A) copolymer, described copolymer comprises: come from the construction unit (wherein, the construction unit without the unsaturated compound coming from the perfluoroalkyl with carbon number 4～6) of the construction unit of at least one in the group selecting free unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides to constitute and the unsaturated compound coming from the cyclic ether structure with carbon number 2～4；(B) polymer, described polymer comprises the construction unit of the unsaturated compound coming from the perfluoroalkyl with carbon number 4～6；(C) polymerizable compound；(D) polymerization initiator；(E) solvent.

Description

Photosensitive polymer combination

Technical field

The present invention relates to a kind of photosensitive polymer combination.

Background technology

In display device in recent years etc., colored filter, the ITO electrode of liquid crystal display cells, organic EL display element, Circuit layout substrate etc. utilizes ink-jet method to prepare.It addition, in ink-jet method utilize use photosensitive polymer combination formed every Off member.

As this photosensitive polymer combination, it is known to such as comprise fluoro-alkyl by having carbon number 4～6 A position substitutional crylic acid polyisocyanate polyaddition and photosensitive polymer combination (the Japanese Unexamined Patent Publication 2008-287251 public affairs of polymer that obtain Report).

Summary of the invention

But, in the photosensitive polymer combination of existing institute motion, for the thermostability of obtained pattern, sometimes Not necessarily can be the most satisfied.

The present invention provides following (1)-(6) aspect.

(1), a kind of photosensitive polymer combination, it comprises following (A), (B), (C), (D) and (E),

(A) copolymer, it comprises at least come from the group selecting free unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides to constitute The construction unit planted and the construction unit of the unsaturated compound coming from the cyclic ether structure with carbon number 2～4, and do not wrap Construction unit containing the unsaturated compound coming from the perfluoroalkyl with carbon number 4～6；

(B) polymer, it comprises the structure list of the unsaturated compound coming from the perfluoroalkyl with carbon number 4～6 Unit；

(C) polymerizable compound；

(D) polymerization initiator；

(E) solvent.

(2) photosensitive polymer combination, as described in (1), wherein, (B) comes from the free unsaturated carboxylic acid of choosing for also comprising And the copolymer of the construction unit of at least one in the group of unsaturated carboxylic acid anhydrides composition.

(3) photosensitive polymer combination, as described in (1) or (2), wherein, (C) is that the polymerization comprising oxime compound causes Agent.

(4), a kind of pattern, it is to be formed by the photosensitive polymer combination described in any one of (1)～(3).

(5), a kind of ink-jet separator, it is to be formed by the photosensitive polymer combination described in any one of (1)～(3) 's.

(6), a kind of display device, it comprises the choosing freely pattern described in (4) and the ink-jet separator described in (5) and constitutes Group at least one.

According to the photosensitive polymer combination of the present invention, the pattern of excellent heat resistance can be obtained.

Accompanying drawing explanation

Fig. 1 is the profile of the part schematically showing the display device 1 amplifying the example as display device of the present invention.

Fig. 2 is the plane graph of the part schematically showing the display device 1 amplifying the example as display device of the present invention.

Fig. 3 is the shape using the observable pattern of scanning electron microscope.

Symbol description

1 display device

2 supporting substrates

3 separators

4 organic EL element

5 recesses

6 the 1st electrodes

7 first organic EL layers (hole injection layer)

9 second organic EL layers (luminescent layer)

10 the 2nd electrodes

Detailed description of the invention

The photosensitive polymer combination of the present invention is to comprise following (A), (B), (C), the photoresist group of (D) and (E) Compound.

(A) copolymer, it comprises at least come from the group selecting free unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides to constitute The construction unit of the construction unit planted and the unsaturated compound coming from the cyclic ether structure with carbon number 2～4 is (wherein, Do not comprise the construction unit of the unsaturated compound coming from the perfluoroalkyl with carbon number 4～6) (following, it is sometimes referred to as " resin (A) ")；

(B) polymer, it comprises the structure list of the unsaturated compound coming from the perfluoroalkyl with carbon number 4～6 Unit (hereinafter sometimes referred to " resin (B) ")；

(C) polymerizable compound；

(D) polymerization initiator；

(E) solvent.

It addition, the photosensitive polymer combination of the present invention can also be different from resin (A) and resin (B) containing choosing freedom Resin (hereinafter sometimes referred to " resin (A1) "), polymerization initiator (D1), multi-functional thiol's compound (T) and surfactant (F) at least one in the group constituted.

It should be noted that in this manual, the compound illustrated as each composition, as long as no particularly explanation, Just may be used singly or in combin.

The photosensitive polymer combination of the present invention comprises resin (A).As resin (A), can enumerate:

Resin (A-1): will select free unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides composition group at least one (a) (with Under be sometimes referred to as " (a) ") with have carbon number 2～4 cyclic ether structure unsaturated compound (b) (hereinafter sometimes referred to " (b) ") polymerization and the copolymer that formed；

Resin (A-2): (wherein, can not there is the ring-type of carbon number 2～4 with the monomer (c) of (a) and (b) copolymerization Ether structure) (hereinafter sometimes referred to " (c) ") copolymer of being polymerized with (a) and (b) and being formed.Wherein, (a), (b) and (c) does not has There is the perfluoroalkyl of carbon number 4～6.

As resin (A) preferred resin (A-1).

As (a), specifically, can enumerate: acrylic acid, methacrylic acid, butenoic acid, adjacent vinyl benzoic acid, Vinyl benzoic acid, to unsaturated monocarboxylic classes such as vinyl benzoic acids；

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinyl neighbour's benzene two Formic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid, Isosorbide-5-Nitrae- The unsaturated dicarboxylic classes such as cyclohexene dicarboxylic acid；

Methyl-5-norborene-2,3-dicarboxylic acids, 5-carboxyl dicyclo [2.2.1] hept-2-ene", 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl dicyclo [2.2.1] hept-2- Alkene, 5-carboxyl-6-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-6-ethyl dicyclo [2.2.1] hept-2-ene" etc. are containing carboxyl Dicyclo unsaturated compound class；

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic acid acid anhydride, 4-vinylphthalic acid acid anhydride, 3,4,5,6-tetrabydrophthalic anhydrides, 1,2,3,6-tetrabydrophthalic anhydrides, dimethyl tetrahydro phthalic anhydride, 5,6- The unsaturated dicarboxylic class acid anhydrides such as dicarboxyl dicyclo [2.2.1] hept-2-ene" dicarboxylic anhydride (Himic anhydride)；

Mono succinate [2-(methyl) acryloyl-oxyethyl] ester, phthalic acid list [2-(methyl) acryloxy second Base] unsaturated single [(methyl) acryloxyalkyl] esters of more than divalent such as ester polybasic carboxylic acid；

Containing hydroxyl and the unsaturated esters of acrylic acid of carboxyl in same a part as α-(methylol) acrylic acid Deng.

Wherein, from the standpoint of copolyreaction and alkali-solubility, acrylic acid, methacrylic acid, Malaysia are preferably used Anhydride etc..

In this specification, so-called " (methyl) acrylic acid " refers to select in the group that free acrylic acid and methacrylic acid are constituted At least one." (methyl) acryloyl " and " (methyl) acrylate " etc. are recorded also has the same meaning.

B () is for have the cyclic ether structure of carbon number 2～4 (such as: select free oxirane ring, oxetanes ring And oxolane ring constitute group at least one) unsaturated compound, preferably there is the cyclic ether of carbon number 2～4 Structure and the monomer of ethylene unsaturated double-bond, more preferably have cyclic ether structure and (methyl) acryloyl of carbon number 2～4 The monomer of epoxide.

As (b), such as, can enumerate: there is the unsaturated compound (b1) of Oxyranyle (hereinafter sometimes referred to " (b1) "), there is the unsaturated compound (b2) (hereinafter sometimes referred to " (b2) ") of oxetanyl, there is tetrahydrofuran base Unsaturated compound (b3) (hereinafter sometimes referred to " (b3) ") etc..

As (b1), can enumerate: there is the structure that the unsaturated fatty hydrocarbons base of straight-chain or branched is at least partially epoxidized Unsaturated compound (b1-1) (hereinafter sometimes referred to " (b1-1) "), there is the structure that unsaturated lipid ring type hydrocarbon is at least partially epoxidized Unsaturated compound (b1-2) (hereinafter sometimes referred to " (b1-2) ").

As (b1), preferably there is the monomer of oxetanyl and (methyl) acryloxy, more preferably have not The epoxidised structure of saturated fat ring type hydrocarbon and the monomer of (methyl) acryloxy.During for these monomers, photosensitive resin composition The excellent storage stability of thing.

As (b1-1), specifically, can enumerate: (methyl) glycidyl acrylate, (methyl) propenoic acid beta-first Base ethylene oxidic ester, (methyl) propenoic acid beta-ethyl glycidyl ester, glycidyl vinyl ether, adjacent vinyl benzyl shrink Glycerin ether, a vinylbenzyl glycidyl ether, vinylbenzyl glycidyl ether, Alpha-Methyl-neighbour's vinyl benzyl are shunk Glycerin ether, an Alpha-Methyl-vinylbenzyl glycidyl ether, Alpha-Methyl-to vinylbenzyl glycidyl ether, 2, the double (contracting of 3- Water glycerol epoxide methyl) styrene, 2, double (glycidoxypropyl methyl) styrene of 4-, 2,5-is double (glycidoxypropyl methyl) Styrene, 2, double (glycidoxypropyl methyl) styrene of 6-, 2,3,4-tri-(glycidoxypropyl methyl) styrene, 2,3,5- Three (glycidoxypropyl methyl) styrene, 2,3,6-tri-(glycidoxypropyl methyl) styrene, 3,4,5-tri-((+)-2,3-Epoxy-1-propanols Epoxide methyl) styrene, 2,4,6-tri-(glycidoxypropyl methyl) styrene, Japanese Unexamined Patent Publication 7-248625 publication is remembered The compound etc. carried.

As (b1-2), can enumerate: a vinylcyclohexene oxide, 1,2-epoxy radicals-4-vinyl cyclohexane (example As: CELLOXIDE (セロキサイ De) 2000；Daicel chemical industry (Co., Ltd.) make), acrylic acid 3,4-epoxy basic ring Hexyl methyl ester is (such as: CYCLOMER (サイ Network ロマ mono-) A400；Daicel chemical industry (Co., Ltd.) make), acrylic acid- 3,4-expoxycyclohexyl methyl ester are (such as: CYCLOMER M100；Daicel chemical industry (Co., Ltd.) make), formula (I) represent Compound, the compound etc. that represents of formula (II).

(in formula (I) and formula (II), R¹And R²Represent hydrogen atom or the alkyl of carbon number 1～4, contained in this alkyl Hydrogen atom can be optionally substituted by a hydroxyl group.

X¹And X²Represent singly-bound ,-R³-、*-R³-O-、*-R³-S-、*-R³-NH-。

R³Represent the alkane diyl of carbon number 1～6.

* the connecting key with O is represented.)

As the alkyl of carbon number 1～4, specifically, can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, positive fourth Base, sec-butyl, the tert-butyl group etc..

As the alkyl being optionally substituted by a hydroxyl group, can enumerate: methylol, 1-ethoxy, 2-ethoxy, 1-hydroxypropyl, 2-hydroxyl Propyl group, 3-hydroxypropyl, 1-hydroxyl-1-Methylethyl, 2-hydroxyl-1-Methylethyl, 1-hydroxyl butyl, 2-hydroxyl butyl, 3-hydroxyl butyl, 4-hydroxyl butyl etc..

As R¹And R², preferably can enumerate: hydrogen atom, methyl, methylol, 1-ethoxy, 2-ethoxy, more preferably may be used To enumerate: hydrogen atom, methyl.

As alkane diyl, can enumerate: methylene, ethylidene, propane-1,2-diyl, propane-1,3-diyl, butane- Isosorbide-5-Nitrae-diyl, pentane-1,5-diyl, hexane-1,6-diyl etc..

As X¹And X², preferably can enumerate: singly-bound, methylene, ethylidene, *-CH₂-O-(* represents the connecting key with O) Base, *-CH₂CH₂-O-base, more preferably can enumerate: singly-bound, *-CH₂CH₂-O-base.

The compound represented as formula (I), can enumerate the compound that in formula (I-1)～formula (I-15), arbitrary formula represents Deng.Preferably can enumerate in formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) and formula (I-11)～formula (I-15) The compound that arbitrary formula represents, more preferably can enumerate arbitrary formula table in formula (I-1), formula (I-7), formula (I-9) and formula (I-15) The compound shown.

The compound represented as formula (II), can enumerate the chemical combination that in formula (II-1)～formula (II-15), arbitrary formula represents Thing etc..Preferably can enumerate formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) and formula (II-11)～formula (II-15) compound that in, arbitrary formula represents, more preferably can enumerate formula (II-1), formula (II-7), formula (II-9) and formula (II- 15) compound that in, arbitrary formula represents.

Compound that formula (I) represents and the compound that formula (II) represents can individually use.It addition, these can also Mix with arbitrary ratio.During mixing, its blending ratio with molar ratio computing, preferably formula (I)/formula (II)=5/95～95/5, more It is preferably 10/90～90/10, especially preferably 20/80～80/20.

As (b2), preferably there is the monomer of oxetanyl and (methyl) acryloxy.As (b2), such as may be used To enumerate: 3-methyl-3-(methyl) acryloyloxymethyl oxetanes, 3-ethyl-3-(methyl) acryloyloxymethyl Oxetanes, 3-methyl-3-(methyl) acryloyl-oxyethyl oxetanes, 3-ethyl-3-(methyl) acryloxy Ethyloxetane etc..

As (b3), preferably there is the monomer of tetrahydrofuran base and (methyl) acryloxy.

As (b3), specifically, can enumerate: acrylic acid tetrahydrofuran ester is (such as: Viscoat V#50, Osaka have Chemical machine industry (Co., Ltd.) system), THFMA etc..

As (c), can enumerate: (methyl) esters of acrylic acid, N-substituted maleimide, unsaturated dicarboxylic diester Class, ester ring type unsaturated compound class, phenylethylene, other vinyl compound etc..

As (methyl) esters of acrylic acid, can enumerate: (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (first Base) alkyl esters such as n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate；

(methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methyl cyclohexyl, (methyl) acrylic acid three ring [5.2.1.0² ^{, 6}] decyl-8-base ester (in this technical field, as trivial name, be referred to as (methyl) acrylic acid bicyclo-pentyl ester), (methyl) acrylic acid two Cyclopentyloxy ethyl ester, (methyl) acrylic acid three ring [5.2.1.0^2,6] decyl-8-base ester (in this technical field, as trivial name, claims For " (methyl) acrylic acid dicyclopentenyl ester "), the cycloalkyl esters such as (methyl) isobornyl acrylate；

The hydroxy alkyl esters such as (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate；

Aryl and the aralkyl esters etc. such as (methyl) phenyl acrylate, (methyl) benzyl acrylate.

As unsaturated dicarboxylic two esters, can enumerate: ethyl maleate., DEF, itaconic acid diethyl Ester etc..

As N-substituted maleimide, can enumerate: N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, N-succinimido-3-maleimidobenzoyl ester, N-succinimido-4-maleoyl Imines butyrate, N-succinimido-6-maleimidohexanoic acid ester, N-succinimido-3-maleimidopropionic acid Ester, N-(9-acridinyl) maleimide etc..

As ester ring type unsaturated compound class, can enumerate: dicyclo [2.2.1] hept-2-ene", 5-methyl bicycle [2.2.1] hept-2-ene", 5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxyl dicyclo [2.2.1] hept-2-ene", 5-methylol dicyclo [2.2.1] hept-2-ene", 5-(2 '-ethoxy) dicyclo [2.2.1] hept-2-ene", 5-methoxyl group dicyclo [2.2.1] hept-2-ene", 5- Ethyoxyl dicyclo [2.2.1] hept-2-ene", 5,6-dihydroxy dicyclo [2.2.1] hept-2-ene", 5,6-bis-(methylol) dicyclo [2.2.1] hept-2-ene", 5,6-bis-(2 '-ethoxy) dicyclo [2.2.1] hept-2-ene", 5,6-dimethoxy dicyclo [2.2.1] hept- 2-alkene, 5,6-diethoxy dicyclo [2.2.1] hept-2-ene", 5-hydroxy-5-methyl base dicyclo [2.2.1] hept-2-ene", 5-hydroxyl-5- Ethyl dicyclo [2.2.1] hept-2-ene", 5-methylol-5-methyl bicycle [2.2.1] hept-2-ene", 5-tert-butoxycarbonyl dicyclo [2.2.1] hept-2-ene", 5-cyclohexyloxy carbonyl dicyclo [2.2.1] hept-2-ene", 5-phenyloxycarbonyl dicyclo [2.2.1] hept-2- Alkene, 5, double (tert-butoxycarbonyl) dicyclo [2.2.1] hept-2-ene" of 6-, 5, double (cyclohexyloxy carbonyl) dicyclo [2.2.1] hept-of 6- The dicyclo unsaturated compound classes etc. such as 2-alkene.

As phenylethylene, can enumerate: styrene, α-methyl styrene, a methyl styrene, p-methylstyrene, Vinyltoluene, to methoxy styrene etc..

As other vinyl compound, can enumerate: (methyl) acrylonitrile, vinyl chloride, vinylidene chloride, (methyl) third Acrylamide, vinylacetate, 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene etc..

As (c), from the standpoint of copolyreaction and alkali-solubility, optimization styrene, N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide and dicyclo [2.2.1] hept-2-ene" etc..

In resin (A-1), come from the ratio of construction unit of each monomer relative to the construction unit constituting resin (A-1) Total molal quantity, preferably in following scope:

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

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

The ratio of the construction unit of resin (A-1) is when above-mentioned scope, and the preservation with photosensitive polymer combination is stable Property, photosensitive polymer combination developability when forming pattern and the film obtained and the solvent resistance of pattern, thermostability And mechanical strength becomes good tendency.

It is the resin (A-1) of (b1-2) as the resin (A-1) that resin (A-1), preferably (b) are (b1), more preferably (b).

Resin (A-1) is such as referred to document " laboratory method of Polymer Synthesizing ", and (the grand row in big Tianjin writes sale room (strain formula meeting Society) chemistry is with distribution in people's first edition first impression on March 1st, 1972) described in method and the document described in quote Document manufactures.

Specifically, the method that such as can illustrate is, the ormal weight of (a) and (b), polymerization initiator and solvent etc. is added In reaction vessel, form deoxidation atmosphere gas by the oxygen replaced in air with nitrogen, stir and heat and be incubated Method.It should be noted that polymerization initiator as used herein and solvent etc. are not particularly limited, it is possible to use logical in this field Any polymerization initiator often used and solvent.Such as: as polymerization initiator, can enumerate: azo-compound (2, 2 '-azodiisobutyronitrile, 2,2 '-azo double (2,4-methyl pentane nitrile) etc.) and organic peroxide (benzoyl peroxide etc.), As solvent, as long as dissolve the solvent of each monomer, as the solvent (E) of photosensitive polymer combination, it is possible to use after The solvent etc. stated.In order to adjust the molecular weight of the resin obtained, chain-transferring agent can be added when polyreaction.As chain tra nsfer Agent, can enumerate: n-butyl mercaptan, tert-butyl mercaptan, n-dodecyl mercaptan, 2-thioglycol (2-sulfanyl ethanol), Thioglycolic acid, ethyl thloylyllate, thioglycolic acid 2-Octyl Nitrite, thioglycolic acid methoxybutyl, 3-sulfur generation third The thio-alcohols such as acid, silicone (KF-2001: SHIN-ETSU HANTOTAI's chemistry system) containing sulfenyl；The haloalkyls such as chloroform, carbon tetrachloride, carbon tetrabromide Class etc..

It should be noted that for obtained copolymer, can directly use reacted solution, it is possible to use Solution that is concentrated or that dilute, it is also possible to use the copolymer separated out by methods such as reprecipitations with the form of solid (powder body). When particularly carrying out this polymerization, as solvent, by using the solvent identical with solvent described later (E) can directly use reaction After solution, manufacturing process can be simplified.

In resin (A-2), come from the ratio of construction unit of each monomer relative to all structures constituting resin (A-2) The total molal quantity of unit, preferably in following scope.

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

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

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

The ratio of the construction unit of resin (A-2) is when above-mentioned scope, and the preservation with photosensitive polymer combination is stable Property, photosensitive polymer combination developability when forming pattern and the film obtained and the solvent resistance of pattern, thermostability And mechanical strength has the tendency becoming good.

It is the resin (A-2) of (b1-2) as the resin (A-2) that resin (A-2), preferably (b) are (b1), more preferably (b).

Resin (A-2) can manufacture by the method as resin (A-1).

The weight average molecular weight of the polystyrene conversion of resin (A) is preferably 3,000～100,000, more preferably 5,000～ 50,000.The weight average molecular weight of resin (A), when above-mentioned scope, has the tendency that coating is excellent, it addition, be difficult to when development Produce the membrane damage of exposure portion, and then, non-exposed portion is easily removed by development.

The molecular weight distribution [weight average molecular weight (Mw)/number-average molecular weight (Mn)] of resin (A) preferably 1.1～6.0, more excellent Elect 1.2～4.0 as.Molecular weight distribution, when above-mentioned scope, has the tendency that developability is excellent.

The acid number of resin (A) is 20～150mgKOH/g, preferably 40～135mgKOH/g, more preferably 50～ 135mgKOH/g.Here, acid number is the value measured as the amount (mg) neutralizing the necessary potassium hydroxide of 1g resin, can pass through Obtain with potassium hydroxide aqueous solution titration.

The content of resin (A) relative to the total amount of resin (A), resin (A1) and polymerizable compound (C) be preferably 5～ 95 mass %, more preferably 20～80 mass %, particularly preferably 40～60 mass %.The content of resin (A) is in above-mentioned scope Time, the developability with photosensitive polymer combination, the adaptation of pattern, solvent resistance and the mechanical property obtained become good Tendency.

The photosensitive polymer combination of the present invention comprises resin (B).Resin (B) has carbon number 4～6 for comprising to come from The polymer of construction unit of unsaturated compound (d) (hereinafter sometimes referred to " (d) ") of perfluoroalkyl.

As (d), the compound that formula (d-0) represents can be enumerated.

[in formula (d-0), R^fRepresent the perfluoroalkyl of carbon number 4～6.

R^dRepresent hydrogen atom, halogen atom, cyano group, phenyl, benzyl or the alkyl of carbon number 1～21.Contained by this alkyl Hydrogen atom can be replaced by halogen atom or hydroxyl.

X^dRepresent the aliphatic alkyl of the divalent of singly-bound, carbon number 1～10, the ester ring type of the divalent of carbon number 3～10 -CH contained in the aromatic hydrocarbyl of the divalent of alkyl or carbon number 6～12, this aliphatic alkyl and this ester ring type alkyl₂- Can be by-O-,-CO-,-NR^e-,-S-or-SO₂-replace.]

R^fFor the perfluoroalkyl of carbon number 4～6, preferably perfluoro butyl and perfluoro hexyl.

As R^dIn the alkyl of carbon number 1～21, can enumerate: methyl, ethyl, n-pro-pyl, normal-butyl, positive penta The straight-chain alkyl such as base, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl；

Isopropyl, isobutyl group, sec-butyl, isopentyl, 1-methyl amyl, 2-methyl amyl, 3-methyl amyl, 4-methylpent Base, 1-ethyl-butyl, 2-ethyl-butyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methyl are own Base, 1-ethyl pentyl group, 2-ethyl pentyl group, 3-ethyl pentyl group, 1-butyl, 1-methylheptyl, 2-methylheptyl, 3-methyl heptan Base, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethyl hexyl Base, 2-propylpentyl, 1-butyl, 1-butyl-2-methyl butyl, 1-butyl-3-methyl butyl, the tert-butyl group, 1,1-diformazan Base propyl group, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1-ethyl-2- Methyl-propyl, 1,1-dimethyl amyl group, 1,2-dimethyl amyl group, 1,3-dimethyl amyl group, Isosorbide-5-Nitrae-dimethyl amyl group, 2,2-diformazan Base amyl group, 2,3-dimethyl amyl group, 2,4-dimethyl amyl group, 3,3-dimethyl amyl group, 3,4-dimethyl amyl group, 1-ethyl-1- The branched-chain alkyls etc. such as methyl butyl, 2-ethyl-3-methyl butyl.

As R^dPreferably hydrogen atom, halogen atom and methyl.

As X^dIn the aliphatic alkyl of divalent of carbon number 1～10, can enumerate: methylene, ethylidene, propane- 1,3-diyl, propane-1,2-diyl, butane-Isosorbide-5-Nitrae-diyl, butane-1,3-diyl, butane-1,2-diyl, pentane-1,5-bis- Base, hexane-1,6-diyl, heptane-1,7-diyl, octane-1, the alkane diyl such as 8-diyl.

As X^dIn the ester ring type alkyl of divalent of carbon number 3～10, can enumerate: cyclopropane diyl, Tetramethylene. two Base, Pentamethylene. diyl, hexamethylene diyl, cycloheptane diyl, cyclodecane diyl etc..

As X^dIn the aromatic hydrocarbyl of divalent of carbon number 6～12, can enumerate: phenylene, naphthalene-diyl etc..

As-CH₂-by-O-,-CO-,-NR^e-,-S-or-SO₂-substituted X^d, such as formula (xd-1)～formula can be enumerated (xd-10) group etc. represented.

As X^d, the preferably alkane diyl of carbon number 1～6, more preferably ethylidene.

As (d), the compound that preferred formula (d-1) represents.

[in formula (d-1), R^hRepresent the perfluoroalkyl of carbon number 4～6.R^gRepresent hydrogen atom, halogen atom or methyl.]

The compound represented as formula (d-0), can enumerate such as: compound (d-1)～compound (d-94) etc..Table In, X^dThe chemical formula numbering of display in hurdle represents the chemical formula numbering of foregoing illustrative group.It addition, such as: compound (d-1) The compound represented for following formula (d-1).

[table 1]

[table 2]

The resin of the construction unit coming from (d) and the construction unit coming from (a) is preferably comprised as resin (B), more excellent Elect as to comprise and come from the construction unit of (d), come from the construction unit of (a) and come from the resin of construction unit of (b).Resin (B) By comprising the construction unit coming from (a), developability is excellent, therefore has suppression and comes from the uneven tendency of residue and development. Resin (B) is by comprising the construction unit coming from (b), and has the tendency of excellent solvent resistance.It addition, resin (B) can also Comprise the construction unit coming from (c).Can enumerate and above-mentioned identical material as (a), (b) and (c).

When resin (B) is the copolymer of (a) and (d), come from the ratio of construction unit of each monomer relative to constituting resin (B) the total molal quantity of construction unit, preferably in following scope.

Come from the construction unit of (a): 5～40 mass % (more preferably 10～30 mass %)

Come from the construction unit of (d): 60～95 mass % (more preferably 70～90 mass %)

When resin (B) is the copolymer of (a), (b) and (d), come from the ratio of construction unit of each monomer relative to composition The total mass number of the construction unit of resin (B), preferably in following scope.

Come from the construction unit of (b): 5～80 mass % (more preferably 10～70 mass %)

Come from the construction unit of (d): 10～80 mass % (more preferably 20～70 mass %)

When resin (B) is the copolymer of (a), (b), (c) and (d), come from each monomer construction unit ratio relative to Constitute the total molal quantity of the construction unit of resin (B), preferably in following scope.

Come from the construction unit of (b): 5～70 mass % (more preferably 10～60 mass %)

Come from the construction unit of (c): 10～50 mass % (more preferably 20～40 mass %)

The ratio of each construction unit, when above-mentioned scope, has water proofing property, the tendency of developability excellence.

The weight average molecular weight of the polystyrene conversion of resin (B) is preferably 3,000～20,000, more preferably 5,000～ 15,000.The weight average molecular weight of resin (A), when above-mentioned scope, has the tendency that coating is excellent, it addition, be difficult to when development Produce the membrane damage of exposure portion, and then, can easily remove non-exposed portion by development.

The acid number of resin (B) is 20～200mgKOH/g, preferably 40～150mgKOH/g.

The content of resin (B) is relative to total amount 100 mass parts of resin (A), resin (A1) and polymerizable compound (C) It is preferably 0.001～10 mass parts, more preferably 0.01～5 mass parts.The content of resin (B), when above-mentioned scope, has shape When becoming pattern, developability is excellent, and the tendency that the pattern water proofing property obtained is excellent.

The photosensitive polymer combination of the present invention can comprise resin (A1).As resin (A1), can enumerate:

Resin (A1-1): polymerization (a) and (c) obtained by copolymer,

Resin (A1-2): the resin that makes (b) be polymerized copolymer reaction obtained by (a) and (c) and obtain,

Resin (A1-3): make (a) and be polymerized the resin etc. that copolymer reaction obtained by (b) and (c) obtains.

In resin (A1-1), come from the ratio of construction unit of each monomer relative to all knots constituting resin (A1-1) The total molal quantity of structure unit, preferably in following scope.

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

The ratio of the construction unit of resin (A1-1) is when above-mentioned scope, and the preservation with photosensitive polymer combination is stable The solvent resistance of property, photosensitive polymer combination developability when forming pattern and the film obtained and pattern becomes good Tendency.

Resin (A1-1) can utilize and manufacture with above-mentioned same method.

Resin (A1-2) is the resin making the copolymer reaction of (b) and (a) and (c) obtain.

Resin (A1-2) such as can manufacture through two procedures.In this case, it is also possible to " high with reference to above-mentioned document The laboratory method of molecule synthesis " (the grand row in big Tianjin writes sale room (Co., Ltd.) chemistry with people's first edition first impression in March, 1972 Distribution on the 1st) described in method and method described in Japanese Unexamined Patent Publication 2001-89533 publication manufacture.

First, as first operation, carry out the operation same with the manufacture method of above-mentioned resin (A-1), obtain (a) and The copolymer of (c).

In this case, copolymer that is identical with above-mentioned, that obtain, can directly use reacted solution, it is possible to so that With the concentrated or solution of dilution, it is also possible to use the copolymerization separated out by methods such as reprecipitations with the form of solid (powder body) Thing.Additionally, it is preferred that be set as the weight average molecular weight with above-mentioned same polystyrene conversion and molecular weight distribution [weight average molecular weight (Mw)/number-average molecular weight (Mn)].

Wherein, the ratio of construction unit of (a) and (c) is come from relative to all construction units constituting above-mentioned copolymer Add up to molal quantity, preferably in following scope.

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

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

Secondly, as second operation work, make to come from a part for the carboxylic acid of (a) of obtained copolymer and carboxylic acid anhydrides and The cyclic ether reaction of above-mentioned (b).From the reactive height of cyclic ether, from the standpoint of being difficult to (b) of remained unreacted, as resin (A1-2) (b) used in preferably (b1) or (b2), more preferably (b1-1).

Specifically, then aforesaid operations, atmosphere gas in flask is replaced to air from nitrogen, adds relatively in flask Molal quantity in (a) is (b) of 5～80 moles of %, is 0.001～5 mass % relative to the total amount of (a), (b) and (c) The catalysts (such as: three (dimethylamino methyl) phenol etc.) of carboxyl and cyclic ether and the conjunction relative to (a), (b) and (c) Metering is the polymerization inhibitor (such as: benzoquinone etc.) of 0.001～5 mass %, makes it react at 60～130 DEG C 1～10 hour, Resin (A1-2) can be obtained.It should be noted that as polymerizing condition, it is contemplated that manufacture equipment and the calorific value etc. of polymerization, Can suitably adjust feeding method and reaction temperature.

It addition, in this case, the molal quantity of (b) is preferably 10～75 moles of % relative to the molal quantity of (a), more preferably It is 15～70 moles of %.By being set in this scope, there is the storage stability of photosensitive polymer combination, by photoresist Developability when compositions forms pattern and the film obtained and the solvent resistance of pattern, thermostability, mechanical strength and sensitive The balance of degree becomes good tendency.

For resin (A1-3), first operation carries out the operation as the manufacture method of above-mentioned resin (A-1), Obtain the copolymer of (b) and (c).

It addition, in this case, identical with above-mentioned, the copolymer obtained can directly use reacted solution, it is possible to To use the concentrated or solution of dilution, it is also possible to use by methods such as reprecipitations with being total to that the form of solid (powder body) separates out Polymers.

Come from the ratio of construction unit of (b) and (c) relative to the total of all construction units constituting above-mentioned copolymer Molal quantity, preferably in following scope.

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

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

And then, carry out the operation as the manufacture method of resin (A1-2), carboxylic acid or the carboxylic making (a) to have can be passed through Reaction in anhydride and the cyclic ether coming from (b) in the copolymer of (b) and (c) and obtain.Can also make further carboxylic acid anhydrides with The hydroxyl reaction reacting by cyclic ether and carboxylic acid or carboxylic acid anhydrides and producing.

The usage amount of (a) carrying out in above-mentioned copolymer reacting is preferably 5～80 moles of % relative to the molal quantity of (b). From the reactive height of cyclic ether, from the standpoint of being difficult to (b) of remained unreacted, (b) is preferred (b1), further preferably (b1- 1)。

The weight average molecular weight of the polystyrene conversion of resin (A1) is preferably 3,000～100, and 000, more preferably 5,000 ～50,000.The weight average molecular weight of resin (A), when above-mentioned scope, has the tendency that coating is excellent, it addition, when development not It is easily generated the membrane damage of exposure portion, and then, non-exposed portion can be easily removed by development.

The molecular weight distribution [weight average molecular weight (Mw)/number-average molecular weight (Mn)] of resin (A1) preferably 1.1～6.0, more It is preferably 1.2～4.0.Molecular weight distribution, when above-mentioned scope, has the tendency that developability is excellent.

The acid number of resin (A1) is 20～150mgKOH/g, preferably 40～135mgKOH/g, more preferably 50～ 135mgKOH/g。

The content of resin (A1) is preferably 0～80 mass % relative to the total amount of resin (A) and resin (A1), more preferably It is 0～50 mass %.The content of resin (A1) is when above-mentioned scope, it is possible to form pattern with high sensitivity, and developability is also Excellent.

The photosensitive polymer combination of the present invention comprises polymerizable compound (C).

Polymerizable compound (C) is for can utilize the living radical produced by polymerization initiator (D) to carry out the change being polymerized Compound, such as: for having the compound etc. of ethylene unsaturated bond, is preferably (methyl) acrylate compounds.

As having the polymerizable compound (C) of 1 ethylene unsaturated bond, can enumerate with as above-mentioned (a), (b) (c) compound that the compound enumerated is same, wherein, preferably (methyl) esters of acrylic acid.

As having the polymerizable compound (C) of two ethylene unsaturated bonds, can enumerate: 1,3 butylene glycol two (first Base) acrylate, 1,3 butylene glycol (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, ethylene glycol bisthioglycolate (first Base) acrylate, diethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (first Base) acrylate, TEG two (methyl) acrylate, Polyethylene Glycol two (methyl) acrylate, two (propylene of bisphenol-A Trimethylammonium) ether, Ethoxylated bisphenol A bis-(methyl) acrylate, ethoxylated neopentylglycol two (methyl) acrylate, Ethoxylation neopentyl glycol two (methyl) acrylate, 3-methyl pentanediol two (methyl) acrylate etc..

As having the polymerizable compound (C) of more than 3 ethylene unsaturated bonds, can enumerate: trimethylolpropane Three (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, three (2-ethoxy) isocyanuric acid ester three (methyl) propylene Acid esters, ethoxylated trimethylolpropane three (methyl) acrylate, propoxylation trimethylolpropane tris (methyl) acrylic acid Ester, tetramethylolmethane four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) propylene Acid esters, tripentaerythritol four (methyl) acrylate, tripentaerythritol five (methyl) acrylate, tripentaerythritol six (methyl) Acrylate, tripentaerythritol seven (methyl) acrylate, tripentaerythritol eight (methyl) acrylate, tetramethylolmethane three (first Base) acrylate and the reactant of anhydride, dipentaerythritol five (methyl) acrylate and the reactant of anhydride, tripentaerythritol Seven (methyl) acrylate and caprolactone modification trimethylolpropane tris (methyl) acrylate of anhydride, caprolactone modification season penta Tetrol three (methyl) acrylate, caprolactone modification three (2-ethoxy) isocyanuric acid ester three (methyl) acrylate, caprolactone Modified tetramethylolmethane four (methyl) acrylate, caprolactone modification dipentaerythritol five (methyl) acrylate, caprolactone modification Dipentaerythritol six (methyl) acrylate, caprolactone modification tripentaerythritol four (methyl) acrylate, caprolactone modification three Tetramethylolmethane five (methyl) acrylate, caprolactone modification tripentaerythritol six (methyl) acrylate, caprolactone modification three season Penta tetrol seven (methyl) acrylate, caprolactone modification tripentaerythritol eight (methyl) acrylate, caprolactone modification Ji Wusi Alcohol three (methyl) acrylate and the reactant of anhydride, caprolactone modification dipentaerythritol five (methyl) acrylate and anhydride Reactant, caprolactone modification tripentaerythritol seven (methyl) acrylate and the reactant etc. of anhydride.Wherein, preferably 3 officials can be with On photopolymerizable compound (C), more preferably dipentaerythritol six (methyl) acrylate.

The content of polymerizable compound (C) is relative to resin (A), resin (A1) and the total amount of polymerizable compound (C) It is preferably 5～95 mass %, more preferably 20～80 mass %.The content of polymerizable compound (C), when above-mentioned scope, has Sensitivity and the intensity of pattern obtained, flatness, reliability become good tendency.

The photosensitive polymer combination of the present invention comprises polymerization initiator (D).As polymerization initiator (D) as long as can The compound of polymerization is caused just to be not particularly limited by the effect of light or heat, it is possible to use known polymerization initiator.

As polymerization initiator (D), can enumerate such as: alkyl phenyl ketonic compound, united imidazole, triazine chemical combination Thing, acylphosphine oxide compound and oxime compound.Alternatively, it is also possible to use described in Japanese Unexamined Patent Publication 2008-181087 publication Light and/or hot cationic polymerization initiators (such as: by cation and come from the material that lewis acidic anion is constituted). Wherein, at least in the group being made up of united imidazole, alkyl phenyl ketonic compound and oxime ester compound it is preferably selected from Kind, particularly preferably oxime ester compound.During for comprising the polymerization initiator of these compounds, especially have and become highly sensitive Tendency, it is advantageous to.

As abovementioned alkyl phenyl ketone compound, can enumerate: diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl Propane-1-ketone, benzyl dimethyl ketal, 2-hydroxyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-2-methylpropane-1-ketone, 2-hydroxyl Base-1-{4-[4-(2-hydroxy-2-methyl-propiono)-benzyl] phenyl }-2-methyl-propan-1-ketone, 1-hydroxy-cyclohexyl benzene Base ketone, 2-morpholinyl-1-(4-methylsulfanylphenyl)-2-methylpropane-1-ketone, 2-dimethylamino-2-benzyl-1-(4-morpholine Base phenyl) butane-1-ketone, 2-dimethylamino-2-(2-methyl-benzyl)-1-(4-morpholino phenyl) butane-1-ketone, 2-diformazan ammonia Base-2-(3-methyl-benzyl)-1-(4-morpholino phenyl) butane-1-ketone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4- Quinoline base phenyl) butane-1-ketone, 2-dimethylamino-2-(2-Ethylbenzyl)-1-(4-morpholino phenyl) butane-1-ketone, 2-diformazan Amino-2-(2-benzyl)-1-(4-morpholino phenyl) butane-1-ketone, 2-dimethylamino-2-(2-butyl benzyl)-1-(4- Morpholino phenyl) butane-1-ketone, 2-dimethylamino-2-(2,3-dimethyl benzyl)-1-(4-morpholino phenyl) butane-1-ketone, 2-dimethylamino-2-(2,4-dimethyl benzyl)-1-(4-morpholino phenyl) butane-1-ketone, 2-dimethylamino-2-(2-benzyl chloride Base)-1-(4-morpholino phenyl) butane-1-ketone, 2-dimethylamino-2-(2-bromobenzyl)-1-(4-morpholino phenyl) butane-1- Ketone, 2-dimethylamino-2-(3-chlorobenzyl)-1-(4-morpholino phenyl) butane-1-ketone, 2-dimethylamino-2-(4-chlorobenzyl)- 1-(4-morpholino phenyl) butane-1-ketone, 2-dimethylamino-2-(3-bromobenzyl)-1-(4-morpholino phenyl) butane-1-ketone, 2-dimethylamino-2-(4-bromobenzyl)-1-(4-morpholino phenyl) butane-1-ketone, 2-dimethylamino-2-(2-methoxybenzyl Base)-1-(4-morpholino phenyl) butane-1-ketone, 2-dimethylamino-2-(3-methoxy-benzyl)-1-(4-morpholino phenyl) fourth Alkane-1-ketone, 2-dimethylamino-2-(4-methoxy-benzyl)-1-(4-morpholino phenyl) butane-1-ketone, 2-dimethylamino-2- (2-methyl-4-methoxy-benzyl)-1-(4-morpholino phenyl) butane-1-ketone, 2-dimethylamino-2-(2-methyl-4-bromobenzyl Base)-1-(4-morpholino phenyl) butane-1-ketone, 2-dimethylamino-2-(2-bromo-4-methoxy-benzyl)-1-(4-morpholinyl benzene Base) butane-1-ketone, the oligomer etc. of 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] propane-1-ketone.

As above-mentioned united imidazole, can enumerate: 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl connection miaow Azoles, 2,2 '-bis-(2,3-Dichlorobenzene base)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline is (such as: with reference to Japanese Unexamined Patent Publication 6-75372 Publication, Japanese Unexamined Patent Publication 6-75373 publication etc.), 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2, 2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxaline, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (dialkoxy phenyl) bisglyoxaline, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxaline (such as: With reference to Japanese Patent Publication 48-38403 publication, Japanese Laid-Open Patent Publication 62-174204 publication etc..), 4,4 ', 5, the phenyl of 5 '-position The united imidazole replaced by alkoxy carbonyl group is (such as: with reference to Japanese Unexamined Patent Publication 7-10913 publication etc..) etc..Preferably 2,2 '- Double (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,3-Dichlorobenzene base)-4,4 ', 5,5 '-tetraphenyl joins Imidazoles, 2,2 '-two (2,4-Dichlorobenzene base)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline.

As above-mentioned triaizine compounds, can enumerate: 2,4-double (trichloromethyl)-6-(4-methoxyphenyl)-1,3,5- Triazine, 2, double (trichloromethyl)-6-(4-methoxyl group the naphthyl)-1,3,5-triazines of 4-, 2, double (the trichloromethyl)-6-piperonyl of 4-- 1,3,5-triazines, 2, double (trichloromethyl)-6-(4-the methoxyl-styrene)-1,3,5-triazines of 4-, 2,4-double (trichloromethyl)- 6-[2-(5-methylfuran-2-base) vinyl]-1,3,5-triazines, 2, double (trichloromethyl)-6-[2-(furan-2-base) second of 4- Thiazolinyl]-1,3,5-triazines, 2, double (the trichloromethyl)-6-[2-(4-lignocaine-2-aminomethyl phenyl) vinyl]-1,3,5-of 4- Triazine, 2, double (trichloromethyl)-6-[2-(3,4-Dimethoxyphenyl) the vinyl]-1,3,5-triazines of 4-etc..

As above-mentioned acylphosphine oxide compound, TMDPO etc. can be enumerated.

As above-mentioned oxime ester compound, can enumerate: N-benzoyloxy-1-(4-phenylsulfartyl phenyl) butane-1-ketone- 2-imines, N-ethoxy carbonyl Oxy-1-phenyl-propane-1-ketone-2-imines, N-benzoyloxy-1-(4-phenylsulfartyl benzene Base) octane-1-ketone-2-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base] second Alkane-1-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methyl-4-(3,3-dimethyl-2,4-dioxolyl methyl oxygen Base) benzoyl)-9H-carbazole-3-base] ethane-1-imines etc..Can also use Irgacure (registered trade mark) OXE-01, Sales on the markets such as OXE-02 (be above Ciba Japan company system), N-1919 (ADEKA company system).

It addition, as polymerization initiator (D), can enumerate: benzoin, benzoin methylether, benzoin ethyl ether, benzoin are different The benzoin compounds such as propyl ether, benzoin isobutyl ether；Benzophenone, methyl o-benzoylbenzoate, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl thioether, 3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 2,4,6-front threes The benzophenone compounds such as base benzophenone；The quinoness such as 9,10-phenanthrenequione, 2-ethyl-anthraquinone, camphorquinone；10-butyl- 2-chloro-acridine ketone, benzyl, phenylglyoxalates methyl ester, titanocenes compound etc..These polymerization initiators preferably with following polymerization Auxiliary agent (D1) is caused to be applied in combination.

It addition, as the polymerization initiator with the group that can cause chain tra nsfer, it is possible to use Japanese Unexamined Patent Application Publication 2002- Photoepolymerizationinitiater initiater described in No. 544205 publications.

As the polymerization initiator of the above-mentioned group having and can causing chain tra nsfer, can enumerate such as: following formula (a)～ The compound of (f).

The above-mentioned polymerization initiator with the group that can cause chain tra nsfer can also be as the composition (c) constituting resin (A) Use.

In the photosensitive polymer combination of the present invention, polymerization can be caused auxiliary agent (D1) and above-mentioned polymerization initiator (D) used along.Polymerization causes auxiliary agent (D1) can be applied in combination with polymerization initiator (D), is to cause by polymerization for promotion Agent causes the compound used in the polymerization of the polymerizable compound of polymerization or sensitizer.Auxiliary agent (D1) is caused as polymerization, Following formula (III) can be enumerated～compound, thioxanthone compounds, amines and carboxylic acid compound etc. that formula (V) represents.

[in formula (III), W¹The dotted line represented represents the aromatic rings of the carbon number 6～12 that can be replaced by halogen atom.

Y¹Represent-O-or-S-.

R⁴Represent the saturated hydrocarbyl of 1 valency of carbon number 1～6.

R⁵The saturated hydrocarbyl of 1 valency of the carbon number 1～12 that expression can be replaced by halogen atom or can be taken by halogen atom The aryl of the carbon number 6～12 in generation.]

As halogen atom, can enumerate: fluorine atom, chlorine atom, bromine atoms etc..Aromatic rings as carbon number 6～12 Can enumerate: phenyl ring, naphthalene nucleus etc..

As the aromatic rings of the carbon number 6～12 that can be replaced by halogen atom, such as, can enumerate: phenyl ring, methylbenzene 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..

As the saturated hydrocarbyl of 1 valency of carbon number 1～6, such as, can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, Normal-butyl, 1-methyl-propyl, 2-methyl-propyl, the tert-butyl group, n-pentyl, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 1,1-dimethyl propyl, 1,2-dimethyl propyl, 2,2-dimethyl propyl, n-hexyl, cyclohexyl etc..

As the saturated hydrocarbyl of 1 valency of the carbon number 1～12 that can be replaced by halogen atom, such as except above-mentioned carbon atom Outside the saturated hydrocarbyl of 1 valency of several 1～6, it is also possible to enumerate: heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, 1- Chlorobutyl, 2-chlorobutyl, 3-chlorobutyl etc..

As the aryl of the carbon number 6～12 that can be replaced by halogen atom, can enumerate: phenyl, chlorphenyl, dichloro-benzenes Base, bromophenyl, dibromo phenyl, chloro-bromobenzene base, xenyl, chlorodiphenyl, DCBP base, bromophenyl, dibromo phenyl, naphthyl, Chloronaphthyl, methylnaphthyl, dichloro naphthyl, bromonaphthalene base, dibromo naphthyl etc..

The compound represented as formula (III), specifically, can enumerate: 2-[the sub-second of 2-oxo-2-(2-phenyl) Base]-3-methyl naphtho-[2,1-d] thiazoline, 2-[2-oxo-2-(2-phenyl) ethylidene]-3-methyl naphtho-[1,2-d] thiazole [2-oxo-2-(2-naphthyl) is sub-for quinoline, 2-[2-oxo-2-(2-phenyl) ethylidene]-3-methyl naphtho-[2,3-d] thiazoline, 2- Ethyl]-3-methylbenzothiazole quinoline, 2-[2-oxo-2-(1-naphthyl) ethylidene]-3-methylbenzothiazole quinoline, 2-[2-oxygen Generation-2-(2-naphthyl) ethylidene]-3-methyl-5-phenylbenzothiazol quinoline, 2-[2-oxo-2-(1-naphthyl) ethylidene]-3-first Base-5-phenylbenzothiazol quinoline, 2-[2-oxo-2-(2-naphthyl) ethylidene]-3-methyl-5-fluoro benzothiazole quinoline, 2-[2-oxygen Generation-2-(1-naphthyl) ethylidene]-3-methyl-5-fluoro benzothiazole quinoline, 2-[2-oxo-2-(2-naphthyl) ethylidene]-3-first Base-5-chloro benzothiazole quinoline, 2-[2-oxo-2-(1-naphthyl) ethylidene]-3-methyl-5-chloro benzothiazoline, 2-[2-oxygen Generation-2-(2-naphthyl) ethylidene]-3-methyl-5-bromo benzothiazole quinoline, 2-[2-oxo-2-(1-naphthyl) ethylidene]-3-first Base-5-bromo benzothiazole quinoline, 2-[2-oxo-2-(4-phenyl) ethylidene]-3-methylbenzothiazole quinoline, 2-[2-oxo- 2-(4-phenyl h) ethylidene]-3-methyl-5-phenyl thiazoline, 2-[2-oxo-2-(2-naphthyl) ethylidene]-3-first Base naphtho-[2,1-d] thiazoline, 2-[2-oxo-2-(2-naphthyl) ethylidene]-3-methyl naphtho-[1,2-d] thiazoline, 2-[2- Oxo-2-(4-phenyl) ethylidene]-3-methyl naphthalene [2,1-d] thiazoline, 2-[the sub-second of 2-oxo-2-(4-phenyl) Base]-3-methyl naphtho-[1,2-d] thiazoline, 2-[2-oxo-2-(4-fluorophenyl) ethylidene]-3-methyl naphtho-[2,1-d] thiophene Oxazoline, 2-[2-oxo-2-(4-fluorophenyl) ethylidene]-3-methyl naphtho-[1,2-d] thiazoline, 2-[2-oxo-2-(2-benzene Base) ethylidene]-3-methyl naphtho-[2,1-d] oxazoline, 2-[2-oxo-2-(2-phenyl) ethylidene]-3-methyl naphtho-[1, 2-d] oxazoline, 2-[2-oxo-2-(2-phenyl) ethylidene]-3-methyl naphtho-[2,3-d] oxazoline, 2-[2-oxo-2- (2-naphthyl) ethylidene]-3-methyl benzo oxazoline, 2-[2-oxo-2-(1-naphthyl) ethylidene]-3-methyl benzothiazole [2-oxo-2-(1-naphthyl) is sub-for quinoline, 2-[2-oxo-2-(2-naphthyl) ethylidene]-3-methyl-5-phenyl benzo oxazoline, 2- Ethyl]-3-methyl-5-phenyl benzo oxazoline, 2-[2-oxo-2-(2-naphthyl) ethylidene]-3-methyl-5-fluorine benzothiazole Quinoline, 2-[2-oxo-2-(1-naphthyl) ethylidene]-3-methyl-5-fluorobenzene oxazoline, 2-[the sub-second of 2-oxo-2-(2-naphthyl) Base]-3-methyl-5-chloro benzo oxazoline, 2-[2-oxo-2-(1-naphthyl) ethylidene]-3-methyl-5-chloro benzo oxazoline, 2-[2-oxo-2-(2-naphthyl) ethylidene]-3-methyl-5-bromobenzene oxazoline, 2-[the sub-second of 2-oxo-2-(1-naphthyl) Base]-3-methyl-5-bromobenzene oxazoline, 2-[2-oxo-2-(4-phenyl) ethylidene]-3-methyl benzo oxazoline, 2- [2-oxo-2-(1-naphthyl) is sub-for [2-oxo-2-(4-phenyl) ethylidene]-3-methyl-5-phenyl benzo oxazoline, 2- Ethyl]-3-methyl naphtho-[2,1-d] oxazoline, 2-[2-oxo-2-(1-naphthyl) ethylidene]-3-methyl naphtho-[1,2-d] Oxazoline, 2-[2-oxo-2-(4-phenyl) ethylidene]-3-methyl naphtho-[2,1-d] oxazoline, 2-[2-oxo-2-(4- Phenyl) ethylidene]-3-methyl naphtho-[1,2-d] oxazoline, 2-[2-oxo-2-(4-difluorophenyl) ethylidene]-3-first Base naphtho-[2,1-d] oxazoline, 2-[2-oxo-2-(4-difluorophenyl) ethylidene]-3-methyl naphtho-[1,2-d] oxazoline Deng.

[in formula (IV) and (V), ring W²、W³And W⁴Represent aromatic rings or the carbon atom of carbon number 6～12 independently of each other Hydrogen atom contained in the heterocycle of several 2～10, this aromatic rings and this heterocycle can be replaced by halogen atom.Y²～Y⁵Independently of each other Represent-O-or-S-.R⁶～R⁹Representing saturated hydrocarbyl or the aryl of carbon number 6～12 of 1 valency of carbon number 1～12, this is satisfied Can be replaced by the alkoxyl of halogen atom, hydroxyl or carbon number 1～6 with hydrogen atom contained in alkyl and this aryl.]

As the aromatic rings of carbon number 6～12, the fragrance identical with the aromatic rings enumerated in formula (III) can be enumerated Ring, hydrogen atom contained in this aromatic rings at random can also be replaced by the above-mentioned halogen atom enumerated.

As the heterocycle of the carbon number 2～10 that can be replaced by halogen atom, can enumerate: pyridine ring, pyrimidine ring, pyridazine Ring, pyrazine ring, pyranoid ring etc..

As the substituted saturated hydrocarbyl of hydroxyl of 1 valency, can enumerate: methylol, ethoxy, hydroxypropyl, hydroxyl butyl etc..

As the substituted aryl of hydroxyl, can enumerate: hydroxy phenyl, hydroxynaphenyl etc..

As the substituted saturated hydrocarbyl of alkoxyl of 1 valency, can enumerate: methoxy, methoxy ethyl, methoxy propyl Base, methoxybutyl, butoxymethyl, ethoxyethyl group, ethoxycarbonyl propyl, propyloxybutyl etc..

As the substituted aryl of alkoxyl, methoxyphenyl, ethoxynaphthyl etc. can be enumerated.

The compound represented as formula (IV) and formula (V), specifically, can enumerate: dimethoxy-naphthalene, diethoxy The dialkoxy naphthalenes such as naphthalene, dipropoxy naphthalene, diisopropoxy naphthalene, dibutoxy naphthalene；

9,10-dimethoxy anthracenes, EDMO, 9,10-diethoxy anthracene, 2-ethyl-9,10-bis- Ethyoxyl anthracene, dipropoxy anthracene, diisopropoxy anthracene, dibutoxy anthracene, two amoxy anthracenes, two hexyloxy anthracenes, methoxyl group ethoxy Base anthracene, methoxy propoxy anthracene, methoxyl group isopropoxy anthracene, methoxybutoxy anthracene, ethoxy-c epoxide anthracene, ethyoxyl isopropyl The dioxanes such as epoxide anthracene, ethyoxyl butoxy anthracene, propoxyl group isopropoxy anthracene, propoxyl group butoxy anthracene, isopropoxy butoxy anthracene Epoxide anthracene class；

Dimethoxy aphthacene, diethoxy aphthacene, dipropoxy aphthacene, diisopropoxy aphthacene, two fourth oxygen The dialkoxy aphthacene classes etc. such as base aphthacene.

As thioxanthone compounds, such as, can enumerate: ITX, ITX, 2,4-diethyl Base thiaxanthone, 2,4-bis-clopenthixal ketone, 1-chloro-4-propoxythioxanthone etc..

As amines, can enumerate: the aliphatic amine chemical combination such as triethanolamine, methyl diethanolamine, triisopropanolamine Thing；4-dimethylaminobenzoic acid methyl ester, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid isopentyl ester, 4-diformazan ammonia Yl benzoic acid 2-Octyl Nitrite, benzoic acid 2-dimethylaminoethyl, N, N-dimethyl-p-toluidine, 4,4 '-bis-(dimethylaminos) The aromatic amines compound of benzophenone (common name: tetramethyldiaminobenzophenone .), 4,4 '-bis-(lignocaine) benzophenone etc.

As carboxylic acid compound, can enumerate: benzene thiacetic acid., methylbenzene thiacetic acid., ethylo benzene thiacetic acid., methyl Ethylo benzene thiacetic acid., dimethyl benzene thiacetic acid., methoxybenzene thiacetic acid., dimethoxy benzene thiacetic acid., chlorobenzene sulfur generation Acetic acid, dichloro-benzenes thiacetic acid., N-phenylglycine, phenoxyacetic acid, naphthylthio acetic acid, N-naphthyl glycine, naphthoxy The aromatic series such as acetic acid miscellaneous acetic acid class.

Cause the combination of auxiliary agent (D1) as polymerization initiator (D) and polymerization, can enumerate: acetophenone compound and thioxanthene Ketonic compound, acetophenone compound and aromatic amines compound, specifically, can enumerate: 2-morpholinyl-1-(4-methyl sulfur Base phenyl)-2-methylpropane-1-ketone and 2,4-diethyl thioxanthone, 2-dimethylamino-2-benzyl-1-(4-morpholino phenyl) Butane-1-ketone and 2,4-diethyl thioxanthone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholino phenyl) butane-1- Ketone and 2,4-diethyl thioxanthone, 2-morpholinyl-1-(4-methylsulfanylphenyl)-2-methylpropane-1-ketone and 2-isopropyl thiophene Ton ketone and ITX, 2-morpholinyl-1-(4-methylsulfanylphenyl)-2-methylpropane-1-ketone and 4,4 '-bis-(two Ethylamino) benzophenone, 2-dimethylamino-2-benzyl-1-(4-morpholino phenyl) butane-1-ketone and 4,4 '-bis-(diethylaminos Base) benzophenone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholino phenyl) butane-1-ketone and 4,4 '-two (diethyls Amino) benzophenone etc..

Wherein, the preferably combination of acetophenone compound and thioxanthone compounds, more preferably 2-morpholinyl-1-(4-methyl sulfur Base phenyl)-2-methylpropane-1-ketone and 2,4-diethyl thioxanthone, 2-morpholinyl-1-(4-methylsulfanylphenyl)-2-methyl Propane-1-ketone and ITX and ITX.During for these combination, high sensitivity and can be obtained See the pattern that light transmission is high.

The content of polymerization initiator (D) is relative to resin (A), resin (A1) and the total amount 100 of polymerizable compound (C) Mass parts is preferably 0.5～30 mass parts, more preferably 1～20 mass parts, more preferably 1～10 mass parts.Polymerization is drawn Send out the content of agent (D) when above-mentioned scope, it is possible to obtain pattern with high sensitivity.

Polymerization causes the usage amount of auxiliary agent (D1) relative to resin (A), resin (A1) and the total of polymerizable compound (C) Measure 100 mass parts and be preferably 0.1～10 mass parts, more preferably 0.3～7 mass parts.Polymerization causes the amount of auxiliary agent (D1) upper When stating scope, it is possible to obtain pattern with high sensitivity, and the shape of the pattern obtained is good.

The photosensitive polymer combination of the present invention comprises solvent (E).

As the solvent used in the present invention, such as, (-COO-can be comprised in intramolecular from ester solvent and not comprise-O- Solvent), the ether solvents (intramolecular comprises the solvent that-O-does not comprise-COO-) beyond ester solvent, ether-ether solvent (intramolecular bag Solvent containing-COO-and-O-), the ketone solvent (intramolecular comprises-CO-and do not comprises the solvent of-COO-) beyond ester solvent, alcohol Solvent, aromatic hydrocarbon solvents, amide solvent, dimethyl sulfoxide etc. select use.

As ester solvent, can enumerate: methyl lactate, ethyl lactate, butyl lactate, 2-hydroxyisophthalic acid methyl ester, second Acetoacetic ester, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, butanoic acid second Ester, butyl butyrate, methyl pyruvate, ethyl pyruvate, Propyl 2-oxopropionate, methyl acetoacetate, ethyl acetoacetate, Hexalin Acetas, gamma-butyrolacton etc..

As ether solvents, can enumerate: glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol only son Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, third Glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxyl group-n-butyl alcohol, 3-methoxyl group-3-methyl butanol, oxolane, tetrahydrochysene pyrrole Mutter, Isosorbide-5-Nitrae-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl Ether, dibutyl ethylene glycol ether, methyl phenyl ethers anisole, ethyl phenyl ether, methylanisole etc..

As ether-ether solvent, can enumerate: methoxy menthyl acetate, ethyl methoxyacetate, 2-Methoxyacetic acid butyl ester, second Ethoxyacetic acid methyl ester, ethoxy ethyl acetate, 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxy-propionic acid first Ester, 3-ethoxyl ethyl propionate, 2-methoxy methyl propionate, 2-methoxypropionate, 2-methoxy propyl propyl propionate, 2-ethoxy Base methyl propionate, 2-ethoxyl ethyl propionate, 2-methoxyl group-2 Methylpropionic acid methyl ester, 2-ethyoxyl-2 Methylpropionic acid ethyl ester, 3-2-Methoxyacetic acid butyrate, 3-methyl-3-methoxybutyl acetas, propylene glycol methyl ether acetate, dihydroxypropane single-ether Acetas, propylene glycol monopropyl ether acetas, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, diethylene glycol list second Ether acetic acid ester, butyl carbitol acetate etc..

As ketone solvent, can enumerate: 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4- Heptanone, 4-methyl-2 pentanone, Ketocyclopentane, Ketohexamethylene, isophorone etc..

As alcoholic solvent, can enumerate: methanol, ethanol, propanol, butanol, hexanol, Hexalin, ethylene glycol, propylene glycol, third Triol etc..

As aromatic hydrocarbon flux, can enumerate: benzene,toluene,xylene, sym-trimethylbenzene. etc..

As amide solvent, can enumerate: DMF, N,N-dimethylacetamide, N-crassitude Ketone etc..

These solvents may be used singly or in combination of two or more use.

In above-mentioned solvent, from the standpoint of coating, drying property, it it is preferably more than 120 DEG C 180 at 1atm mid-boiling point Organic solvent below DEG C.Wherein, preferably propylene glycol monomethyl ether, propylene glycol methyl ether acetate, 3-ethoxyl ethyl propionate, two Ethylene Glycol Methyl ethylether, 3-methoxybutyl acetas, 3-methoxyl group-n-butyl alcohol etc..When solvent (E) is these solvent, Inequality during coating can be suppressed, and the flatness of film can be made good.

In the photosensitive polymer combination of the present invention, the content of solvent (E) is excellent relative to the total amount of photosensitive polymer combination Elect 60～95 mass %, more preferably 70～90 mass % as.In other words, the solid constituent of photosensitive polymer combination is preferably 5～40 mass %, more preferably 10～30 mass %.The content of solvent (E), when above-mentioned scope, has and is coated with photonasty tree The tendency that the flatness of the film of oil/fat composition is high.Here, so-called solid constituent refers to eliminate from photosensitive polymer combination molten Amount after agent (E).

It addition, the photosensitive polymer combination of the present invention can also comprise multi-functional thiol's compound (T) further.So-called Multi-functional thiol's compound (T) refer to the compound in intramolecular with more than 2 sulfydryls (-SH).Particularly make apparatus During the compound of more than 2 sulfydryls that the carbon atom having and come from aliphatic alkyl is combined, there is the photoresist of the present invention The tendency that the sensitivity of compositions is increased.

As multi-functional thiol's compound (T), specifically, can enumerate: ethanthiol, mercaptan in the last of the ten Heavenly stems two, Isosorbide-5-Nitrae-bis-(first Base sulfenyl) benzene, butanediol double (3-thiopropionate), butanediol double (3-thiacetate), ethylene glycol bis (3-thiacetic acid. Ester), trimethylolpropane tris (3-thiacetate), butanediol double (3-thiopropionate), trimethylolpropane tris (3-sulfur generation Propionic ester), trimethylolpropane tris (3-thiacetate), tetramethylolmethane four (3-thiopropionate), tetramethylolmethane four (3-sulfur For acetas), trihydroxyethyl three (3-thiopropionate), tetramethylolmethane four (3-Thiobutyric acid ester), Isosorbide-5-Nitrae-bis-(3-sulfenyl fourth oxygen Base) butane etc..

The content of multi-functional thiol's compound (T) is preferably 0.1～10 matter relative to polymerization initiator (D) 100 mass parts Amount part, more preferably 0.5～7 mass parts.The content of multi-functional thiol's compound (T), when above-mentioned scope, has photonasty tree The sensitivity of oil/fat composition is increased and developability becomes good tendency, the most preferably.

The photosensitive polymer combination of the present invention can also contain surfactant (F) (but, different from resin (B)). As surfactant, such as, can enumerate: silicone-based surfactant, fluorine system surfactant, there is the silicone of fluorine atom It it is surfactant etc..

The surfactant with siloxane bond can be enumerated as silicone-based surfactant.

Specifically, as Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA、Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、 Toray Silicone SH30PA, polyether-modified silicone oil SH8400 (trade name: Dow Corning Toray Co., Ltd System), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (Co., Ltd.) system), TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF-4446、TSF4452、TSF4460、 (Momentive Performance Materials Japan contract company system) etc..

As fluorine system surfactant, the surfactant with fluorocarbon chain can be enumerated.

Specifically, can enumerate: Fluorinert (registered trade mark) FC430, Fluorinert FC431 (Sumitomo 3M (strain) make), Megafac (registered trade mark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac R30 (DIC (strain) system), FTOP (エ Off ト Star プ) (registered trade mark) EF301, FTOP EF303, FTOP EF351, FTOP EF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd System), Surflon (registered trade mark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass (strain) System), E5844 ((strain) ダイキ Application Off アイ Application ケミカ Le research made) etc..

As having the silicone-based surfactant of fluorine atom, can enumerate and there is the surface of siloxane bond and fluorocarbon chain live Property agent.Specifically, can enumerate: Megafac (registered trade mark) R08, Megafac BL20, Megafac F475, Megafac F477, Megafac F443 (DIC (Co., Ltd.) system) etc..Preferably enumerate Megafac (registered trade mark) F475.

The content of surfactant (F) is more than 0.001 mass % 0.2 matter relative to the total amount of photosensitive polymer combination Amount below %, more than preferably 0.002 mass % below 0.1 mass %, more than more preferably 0.01 mass % 0.05 mass % Below.By containing surfactant within the range, the flatness that can make film is good.

In the photosensitive polymer combination of the present invention, filler, other macromolecular compound, close can be contained as required Close the various additives such as accelerator, antioxidant, UV absorbent, light stabilizer, chain-transferring agent.

The photosensitive polymer combination of the present invention contains substantially no the coloring agent such as pigment and dyestuff.That is, the present invention's In photosensitive polymer combination, relative to total composition, the content of coloring agent is such as preferably less than 1 mass %, more preferably For less than 0.5 mass %.

For the photosensitive polymer combination of the present invention, it is filled with in the quartzy box of a length of 1cm of light path, uses The spectrophotometer average transmittance when measuring mensuration absorbance under conditions of wavelength 400～700nm is preferably more than 70%, More preferably more than 80%.

For the photosensitive polymer combination of the present invention, when making film, the average transmittance of film is preferably More than 90%, yet more preferably more than 95%.This average transmittance is measuring wavelength 400～700nm for using spectrophotometer Under conditions of to measure and be heating and curing the thickness after (such as: solidify under conditions of 100～250 DEG C, 5 minutes～3 hours) be 3 μm Meansigma methods during film.Thus, it is possible to provide the film that the transparency in a kind of visible regime is excellent.

For the photosensitive polymer combination of the present invention, can be coated on such as: the substrate of glass, metal, plastics etc. Or define on these substrates of colored filter, various insulation or conducting film, drive circuit etc., it is patterned into desired shape also Form pattern.Further, it is also possible to these films or pattern are formed the part use of the constituent parts such as display device.

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

As it has been described above, coating can use spin coater, slit and spin coater, slit coater, ink-jet, roll coater, dipping The various apparatus for coating such as coating machine is carried out.

Then, preferably it is dried or prebake, removes the volatile ingredients such as solvent and be dried.Thus, it is possible to obtain smoothing Uncured film.

The thickness of film in this case is not particularly limited, and suitably can adjust according to the material used, purposes etc. Whole, about for example, 1～6 μm.

Further, to the uncured film obtained via the photomask for forming target pattern, irradiate light, such as, irradiate The ultraviolet etc. produced by finsen lamp, light emitting diode.The shape of photomask now is not particularly limited, and form and dimension can Select with the purposes according to pattern.

In exposure machine in recent years, it is possible to use the light less than 350nm sheared by the wave filter shearing this wavelength region, or makes With the band filter of these wavelength region of taking-up, optionally take out the light near 436nm, near 408nm, near 365nm, Plane of exposure entirety is irradiated almost parallel light equably.If using the device such as mask aligner, step-by-step exposure machine, this Time can carry out the correct para-position of mask and base material.

By making the contact developer solution of the mask after exposure, make non-exposed part (that is, non-pixel portion) dissolve, and show Shadow, it is possible to obtain target pattern shape.

Developing method can be any one method in liquid pool method, infusion process, spraying process etc..And can be by when development Base material is inclined to arbitrarily angled.

The aqueous solution of the preferred alkali compounds of developer solution used during development.

Alkali compounds can be inorganic and any one in organic basic compound.

As the concrete example of inorganic alkaline compound, can enumerate: sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, phosphorus Acid dihydride sodium, diammonium phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, bicarbonate Sodium, potassium bicarbonate, sodium borate, potassium borate, ammonia etc..

As organic basic compound, such as, can enumerate: Tetramethylammonium hydroxide, 2-ethoxy trimethyl hydroxide Ammonium, MMA, dimethylamine, trimethylamine, mono aminoethane, diethylamine, triethylamine, single 2-aminopropane., diisopropylamine, ethanolamine etc..

These inorganic and organic alkali compounds concentration in aqueous are preferably 0.01～10 mass %, more preferably It is 0.03～5 mass %.

Above-mentioned developer solution can also contain surfactant.

Surfactant can be to live in nonionic system surfactant, anion system surfactant or cation system surface Any one in property agent.

As nonionic system surfactant, such as, can enumerate: polyoxyethylene alkyl ether, polyoxyethylene aryl ether, poly- Oxygen vinyl alkyl aryl ether, other polyoxyethylene deriv, oxygen ethylene/oxypropylene block copolymer, sorbitan fatty acid Ester, polyoxyethylene sorbitan carboxylic ester, Polyoxyethylene Sorbitol Fatty Acid Esters, (+)-2,3-Epoxy-1-propanol fatty acid ester, polyoxyethylene Fatty acid ester, polyoxyethylene alkyl amine etc..

As anion system surfactant, such as, can enumerate: sodium lauryl sulfate and oleyl sulfate sodium etc The alkylsurfuric acid salt of higher alcohol sulfate salt, sodium lauryl sulfate and ammonium lauryl sulfate etc, detergent alkylate sulphur The alkylaryl sulfonates class etc. of acid sodium and dodecyl sodium naphthalene sulfonate etc.

As cation system surfactant, such as, can enumerate: stearmide hydrochlorate and lauryl trimethyl chlorination The amine salt of ammonium etc or quaternary ammonium salt etc..

The concentration of the surfactant in alkaline-based developer is preferably the scope of 0.01～10 mass %, and more preferably 0.05 ～8 mass %, more preferably 0.1～5 mass %.

After development, i.e. can get pattern by carrying out washing.Can toast after carrying out further as required.After bake is preferred Such as carry out within the temperature range of 150～240 DEG C 10～180 minutes.

When exposing uncured film, by the case of not using the photomask defining pattern, whole face is carried out Light irradiates and/or omits development, can obtain not having figuratum film.

As an example of the display device of the present invention, below organic EL (electroluminescent) display device is illustrated.

Fig. 1 is the section of the part schematically showing the display device 1 amplifying the example as display device of the present invention Figure.Fig. 2 is the plane graph of the part schematically showing the display device 1 amplifying the example as display device of the present invention.Aobvious Showing device 1 mainly include supporting substrates 2, the separator 3 dividing section set in advance on this supporting substrates 2 and utilize every Off member 3 divide section in arrange multiple organic EL element 4 and constitute.Separator 3 is equivalent to the separator of the present invention.

Separator 3 forms such as clathrate or striated on supporting substrates 2.It should be noted that Fig. 2 is denoted as one The display device 1 being provided with cancellate separator 3 of embodiment.With in figure, can set in the region being provided with separator 3 Put hachure.

Supporting substrates 2 utilize separator 3 and supporting substrates 2 set multiple recesses 5 of regulation.This recess 5 is equivalent to The interval divided with separator 3.

Separator 3 in display device 1 is set as clathrate.Therefore, in terms of a side of the thickness direction Z of supporting substrates 2 (with Under, it is sometimes referred to as " looking squarely "), multiple recesses 5 are configured to rectangular.I.e. recess 5 along line direction X separate regulation interval, And it is spaced setting along what column direction Y separated regulation.The shape that each recess 5 is looked squarely is not particularly limited.Such as recess 5 is looked squarely Time be formed as a generally rectangular shape, generally oblong shape and elliptical shape.In present embodiment, being provided with when looking squarely is substantially rectangular shape Recess 5.It should be noted that in this manual, above-mentioned line direction X and column direction Y refers to and the thickness side of supporting substrates To the direction that Z is vertical, and mutually orthogonal direction.

It addition, as other embodiment, in the case of arranging the separator of striated, separator is configured to such as be expert at Multiple spacer parts that direction X extends separate predetermined distance configuration on column direction Y.In which, by striated every Off member and supporting substrates carry out the recess of regulation striated.

Separator is formed according to the mode narrowed along with the fabric width away from supporting substrates.Such as, will extend on column direction Y Separator by be perpendicular to its bearing of trend (column direction Y) plane cut off time section shape according to along with away from supporting base The mode that plate fabric width narrows is formed.Fig. 1 represents the separator of isosceles-trapezium-shaped, by the upper end and the phase of going to the bottom of supporting substrates side Ratio, goes to the bottom than upper bottom width.It should be noted that the section of the separator being actually formed differs is set to trapezoidal shape, the most trapezoidal The straight line portion of shape and angle part are with circularity.

The end face of separator 3 preferably has water proofing property.It should be noted that so-called end face refers to the table at separator 3 The plane on the farthest position of distance supporting substrates 2 it is present on face.Due to the end face display water proofing property of separator 3, therefore, Being prevented from supplying to being isolated ink that the region (recess 5) that part 3 surrounds the supplies end face along separator 3 spills into neighbouring Region.

Organic EL element 4 is arranged on the interval (i.e. recess 5) divided by separator 3.Grid in display device 1 is set During the separator 3 of shape, each organic EL element 4 is separately positioned on each recess 5.That is, organic EL element 4 and each recess 5 is similarly joined Being set to rectangular, on supporting substrates 2, X separates the interval of regulation, is also separated by between regulation along column direction Y simultaneously in the row direction Every spread configuration.

Shape and the configuration of separator 3 can be according to the specification of the display device such as pixel count and resolution and the difficulty or ease of manufacture Degree etc. sets aptly.The fabric width of the line direction X or column direction Y of such as separator 3 is about 5 μm～50 μm, the height of separator 3 Degree is about 0.5 μm～5 μm, and the interval between the adjacent separator 3 of line direction X or column direction Y, i.e. the line direction X of recess 5 Or the width of column direction Y is about 10 μm～200 μm.It addition, the width of the line direction X or column direction Y of the 1st electrode 6 is respectively About 10 μm～200 μm.

Separator 3 can be formed by above-mentioned pattern formation method by the photosensitive polymer combination of the present invention.

It addition, as other embodiment, in the case of arranging the separator of striated, organic EL element 4 is along row In each recess that direction X extends, X is spaced one from the interval configuration of regulation in the row direction.

Display device 1 is provided with 3 kinds of organic EL element 4.I.e. (1) send red organic EL element 4R of red light；(2) send out Go out green organic EL element 4G of green light；And (3) send blue organic EL element 4B of blue light.

Organic EL element 4 stack gradually from supporting substrates side the 1st electrode, organic EL layer, the 2nd electrode and constitute.This In description, the one or more layer being arranged between the 1st electrode the 6 and the 2nd electrode 10 is called organic EL layer.Organic EL element 4 possesses least one layer of luminescent layer as organic EL layer.It should be noted that organic EL element is sent out except possessing one layer Outside photosphere, it is also possible to there is the organic EL layer the most further different from luminescent layer.Such as at the 1st electrode the 6 and the 2nd electricity Hole injection layer, hole transporting layer, resistance electronic shell, electron supplying layer and electron injecting layer etc. are set between pole 10 as organic EL Layer.It addition, the luminescent layer of more than 2 layers can also be provided with between the 1st electrode the 6 and the 2nd electrode 10.

Organic EL element 4 possesses the 1st electrode the 6 and the 2nd electrode 10 as the pair of electrodes being made up of anode and negative electrode.By An electrode in 1 electrode the 6 and the 2nd electrode 10 is arranged as anode, and another electrode is arranged as negative electrode.Display device 1 is The first organic EL layer 7 of using the 1st electrode 6 played a role as anode, playing a role as hole injection layer, as luminescent layer The second organic EL layer 9 of playing a role, the 2nd electrode 10 played a role as negative electrode are laminated in that order on supporting substrates 2 Constitute.

1st electrode 6 is arranged in each organic EL element 4.That is, the 1st electrode 6 with organic EL element 4 equal number sets Put on supporting substrates 2.The configuration of the corresponding organic EL element 4 of the 1st electrode 6 is configured, and is configured as organic EL element 4 Become rectangular.It should be noted that separator 3 mainly forms clathrate in the field in addition to the 1st electrode 6, further with The mode of the periphery covering the 1st electrode 6 forms (with reference to Fig. 1).

The first organic EL layer 7 being equivalent to hole injection layer is respectively arranged on the 1st electrode 6 in recess 5.This first has Machine EL layer 7 makes its material or thickness differently be configured as required in every kind of organic EL element.It should be noted that from From the viewpoint of the ease of the formation process of the first organic EL layer 7, it is also possible to forming all first with same material with thickness has Machine EL layer 7.

First organic EL layer 7 is formed by the following method: utilize ink-jet method will to comprise the material becoming the first organic EL layer 7 Ink supply be isolated the region (recess 5) that part 3 surrounds, then, and be dried, heat and/or carry out light irradiation and make ink solid Change.

The second organic EL layer 9 played a role as luminescent layer is arranged on the first organic EL layer 7 in recess 5.As above Described, luminescent layer can be configured according to the kind of organic EL element.Therefore, red light emitting layer 9R is arranged on it is provided with redness On the recess 5 of organic EL element 4R, green light emitting layer 9G is arranged on the recess 5 being provided with green organic EL element 4G, by indigo plant Color luminescent layer 9B is arranged on the recess 5 being provided with blue organic EL element 4B.

2nd electrode 10 is formed at whole of the viewing area being provided with organic EL element 4.That is, the 2nd electrode 10 not only shape On Cheng Yu 2 organic EL layer 9, it is also formed on separator 3, and is continuously formed across multiple organic EL element.

As it has been described above, by covering, with sealant and hermetic sealing substrate, the multiple organic EL element 4 being formed on supporting substrates 2 (not shown), can manufacture organic EL display.

The pattern obtained by the photosensitive polymer combination of the present invention has high thermostability and water proofing property concurrently, therefore, especially It is to be used in as separator to utilize ink-jet method manufacture colored filter, the ITO electrode of liquid crystal display cells, organic EL to show unit Part and circuit layout substrate etc. are useful.Further, such as constituting colored filter substrate and/or the one of array base palte Part photosensitive separation material (Photo Spacer), can the external coating of composition, interlayer dielectric, liquid crystal aligning control projection, Lenticule, for adjusting the coating etc. of thickness, the parts of touch pad are useful, obtain by the way does not has Figuratum film is useful as the external coating of the part constituting colored filter substrate and/or array base palte.Above-mentioned Colored filter substrate and array base palte are suitable for liquid crystal indicator, organic EL display and Electronic Paper etc..

Embodiment

Below, the present invention is explained in more detail by embodiment." % " and " part " in example describes as long as no special, For quality % and mass parts.

(synthesis example 1)

In the flask possessing reflux condenser, Dropping funnel and agitator, flow through nitrogen with 0.02L/ minute and make nitrogen Atmosphere gas, adds 3-methoxyl group-n-butyl alcohol 200 mass parts and 3-methoxybutyl acetas 105 mass parts, stirs It is heated to 70 DEG C.Then, by methacrylic acid 60 mass parts, 3,4-epoxy radicals three ring [5.2.1.0^2.6] decyl acrylate (with Compound that the ratio hybrid (I-1) of mol ratio 50: 50 represents and the compound that formula (II-1) represents) 240 mass parts dissolve In 3-methoxybutyl acetas 140 mass parts, prepare solution, use Dropping funnel, through 4 hours, this solution is instilled temperature It is maintained in the flask of 70 DEG C.

On the other hand, will make polymerization initiator 2, double (2,4-methyl pentane nitrile) 30 mass parts of 2 '-azo are dissolved in 3-first Solution in epoxide butylacetic acid ester 225 mass parts uses other Dropping funnel to instill in flask through 4 hours.In polymerization After the instillation of initiator solution terminates, being cooled to room temperature after keeping 4 hours at 70 DEG C, obtaining solid constituent is 32.6 matter Amount %, acid number are the copolymer (solution of Resin A a) of 110mg-KOH/g (solid constituent conversion).The weight average of Resin A a obtained Molecular weight (Mw) is 1.3 × 10⁴, molecular weight distribution is 2.50.Resin A a is to have the copolymer of following construction unit.

(synthesis example 2)

In the flask possessing reflux condenser, Dropping funnel and agitator, flow through nitrogen with 0.02L/ minute and make nitrogen Atmosphere gas, adds 3-methoxyl group-n-butyl alcohol 59 mass parts and 3-methoxybutyl acetas 81 mass parts, stirs and add Heat is to 70 DEG C.

Then, by methacrylic acid 40 mass parts, 3,4-epoxy radicals three ring [5.2.1.0^2.6] decyl acrylate is (to rub The mixture of the compound that your compound of representing of ratio hybrid (I-1) than 50: 50 and formula (II-1) represent) 360 mass Part is dissolved in 3-methoxyl group-n-butyl alcohol 80 mass parts and 3-methoxybutyl acetas 110 mass parts prepares solution.Use This solution instillation temperature was maintained in the flask of 70 DEG C by Dropping funnel through 4 hours.

Another aspect, will make polymerization initiator 2, and double (2,4-methyl pentane nitrile) 36 mass parts of 2 '-azo are dissolved in 3- Solution in methoxyl group-n-butyl alcohol 101 mass parts and 3-methoxybutyl acetas 139 mass parts uses other dropping liquid Pump instilled in flask through 5 hours.After the instillation of polymerization initiator solution terminates, after keeping 4 hours at 70 DEG C, it is cooled to room Temperature, obtain solid constituent be 42.5 mass %, acid number be 56mg-KOH/g (solid constituent conversion) copolymer (Resin A b's) Solution.The weight average molecular weight (Mw) of Resin A b obtained is 7.6 × 10³, molecular weight distribution is 2.01.Resin A b is following for having The copolymer of construction unit.

(synthesis example 3)

In the 4 mouthfuls of flasks possessing reflux condenser, nitrogen ingress pipe, thermometer and agitator, add methacrylic acid 30 Part, HEMA 30 parts, isobornyl methacrylate 40 parts, 2-thioglycol 5.9 parts, propylene glycol monomethyl ether Acetas 163 parts, after being heated to 70 DEG C, stirring 30 minutes under nitrogen flowing.Add azodiisobutyronitrile 1.3 parts wherein, poly- Close 18 hours.Then, acrylic acid 2-isocyano group ethyl ester (currants AOI is added；Showa electrician (Co., Ltd.) makes) 29.3 Part, adding is the hydroquinone monomethyl ether of 50ppm relative to all compositionss, by reacting 1 hour at nitrogen stream, at 45 DEG C, obtains Solid constituent is the copolymer (solution of Resin A c) of 34 mass %.The weight average molecular weight (Mw) of Resin A c obtained is 4900. Resin A c is to have the copolymer of following construction unit.

(synthesis example 4)

In the flask possessing reflux condenser, Dropping funnel and agitator, flow through nitrogen with 0.02L/ minute and make nitrogen Atmosphere gas, adds 3-methoxyl group-n-butyl alcohol 200 mass parts and 3-methoxybutyl acetas 105 mass parts, stirs It is heated to 70 DEG C.Then, by methacrylic acid 55 mass parts, 3,4-epoxy radicals three ring [5.2.1.0^2.6] decyl acrylate (with Compound that the ratio hybrid (I-1) of mol ratio 50: 50 represents and the mixture of the compound that formula (II-1) represents) 175 matter Amount part and N-N-cyclohexylmaleimide 70 mass parts be dissolved in prepared by 3-methoxybutyl acetas 140 mass parts molten Liquid.Dropping liquid pump is used this solution instillation temperature to be maintained in the flask of 70 DEG C through 4 hours.On the other hand, polymerization will be made to cause Agent 2, double (2,4-methyl pentane nitrile) 30 mass parts of 2 '-azo are dissolved in 3-methoxybutyl acetas 225 mass parts and form Solution use other dropping liquid pump to instill in flask through 5 hours.After the instillation of polymerization initiator solution terminates, at 70 DEG C Be cooled to room temperature after keeping 4 hours, obtain solid constituent be 32.6 mass %, acid number be that (solid constituent changes 105mg-KOH/g Calculate) the copolymer (solution of Resin A d).The weight average molecular weight (Mw) of Resin A d obtained is 13,600, number-average molecular weight (Mn) Being 5,400, molecular weight distribution is 2.5.Resin A d has following construction unit.

(synthesis example 5)

In the flask possessing reflux condenser, Dropping funnel and agitator, flow through nitrogen with 0.02L/ minute and make nitrogen Atmosphere gas, adds diethylene glycol ethyl methyl ether 140 mass parts, stirs and be heated to 70 DEG C.

Then, by methacrylic acid 40 mass parts, 3,4-epoxy radicals three ring [5.2.1.0^2.6] decyl acrylate (formula (I- 1) mixture of the compound that the compound represented and formula (II-1) represent, mol ratio=50: 50) 340 mass parts, acrylic acid two Cyclopentenes ester (compound that following formula (x1) represents and the mixture of the compound that formula (x2) represents, mol ratio=50: 50) 20 Mass parts is dissolved in diethylene glycol ethyl methyl ether 190 mass parts prepares solution.

Dropping liquid pump is used the solution obtained instillation temperature to be maintained in the flask of 70 DEG C through 4 hours.

On the other hand, will make polymerization initiator 2, double (2,4-methyl pentane nitrile) 30 mass parts of 2 '-azo are dissolved in diethyl Solution in glycol ethyl methyl ether 240 mass parts uses other dropping liquid pump to instill in flask through 5 hours.

After the instillation of polymerization initiator solution terminates, after keeping 4 hours at 70 DEG C, it is cooled to room temperature, obtains solid It is divided into the copolymer (solution of Resin A e) of 41.8 mass %.The weight average molecular weight (Mw) of Resin A e obtained is 9.6 × 10³, Molecular weight distribution (Mw/Mn) is 2.02, and the acid number of solid constituent conversion is 60mg-KOH/g.Resin A e has following structure list Unit.

(synthesis example 6)

In possessing the flask of 1L of reflux condenser, Dropping funnel and agitator, flow through nitrogen system with 0.02L/ minute Become nitrogen atmosphere gas, add diethylene glycol ethyl methyl ether 140 mass parts, stir and be heated to 70 DEG C.

Then, by methacrylic acid 40 mass parts, 3,4-epoxy radicals three ring [5.2.1.0^2.6] decyl acrylate (formula (I- 1) mixture of the compound that the compound represented and formula (II-1) represent, mol ratio=50: 50) 320 mass parts, acrylic acid two Cyclopentenes ester 40 mass parts is dissolved in diethylene glycol ethyl methyl ether 190 mass parts prepares solution.

After the instillation of polymerization initiator solution terminates, after keeping 4 hours at 70 DEG C, it is cooled to room temperature, obtains solid It is divided into the copolymer (solution of Resin A f) of 41.8 mass %.The weight average molecular weight (Mw) of Resin A d obtained is 7.9 × 10³, Molecular weight distribution (Mw/Mn) is 1.82, and the acid number of solid constituent conversion is 60mg-KOH/g.Resin A f has following structure list Unit.

(synthesis example 7)

In the 4 mouthfuls of flasks possessing reflux condenser, nitrogen ingress pipe, thermometer and agitator, add α-chloroacrylic acid 3, 3,4,4,5,5,6,6, the 6-nine own esters of fluorine 78 parts, methacrylic acid 19.5 parts, isobornyl methacrylate 19.5 parts, methyl-prop Olefin(e) acid ethylene oxidic ester 13 parts, lauryl mercaptan 12.7 parts, propylene glycol methyl ether acetate 266 parts, after being heated to 70 DEG C, at nitrogen Flow down stirring 30 minutes.Adding azodiisobutyronitrile 1 part wherein, be polymerized 18 hours, obtaining solid constituent is 33 mass %, acid Value is the copolymer (solution of resin B a) of 68mg-KOH/g (solid constituent conversion).The weight average molecular weight of resin B a obtained is 7500.Resin B a is to have the copolymer of following construction unit.

(synthesis example 8)

In the 4 mouthfuls of flasks possessing reflux condenser, nitrogen ingress pipe, thermometer and agitator, add α-chloroacrylic acid 3, 3,4,4,5,5,6,6,7,7,8,8,8-ten trifluoro monooctyl esters 78 parts, methacrylic acid 19.5 parts, isobornyl methacrylate 19.5 parts, glycidyl methacrylate 13 parts, lauryl mercaptan 12.7 parts, propylene glycol methyl ether acetate 266 parts, be heated to After 70 DEG C, stirring 30 minutes under nitrogen flowing.Add azodiisobutyronitrile 1 part wherein, be polymerized 18 hours, obtain solid constituent Be 33 mass %, acid number be the copolymer (solution of resin B b) of 65mg-KOH/g (solid constituent conversion).Resin B b obtained Weight average molecular weight be 6,800.Resin B b is to have the copolymer of following construction unit.Resin B b has following construction unit.

The weight average molecular weight (Mw) of the resin obtained in synthesis example 1～5 and the mensuration of number-average molecular weight (Mn) use GPC method And carry out under the following conditions.

Device: K2479 ((Co., Ltd.) Shimadzu Seisakusho Ltd. system)

Chromatographic column: SHIMADZU Shim-pack GPC-80M

Chromatogram column temperature: 40 DEG C

Solvent: THF (oxolane)

Flow velocity: 1.0mL/min

Detector: RI

The weight average molecular weight of polystyrene conversion obtained above and the ratio (Mw/Mn) of number-average molecular weight are set as molecule Amount distribution.

(embodiment 1～4 and comparative example 1)

The composition of mixture table 3, obtains photosensitive polymer combination 1～5 respectively.

[table 3]

In table 3, each composition is as shown below.Number described in resin (A) and resin (B) hurdle represents that solid constituent converts Mass parts.

Resin (A)；Resin A a that Aa: synthesis example 1 obtains

Resin (A)；Resin A b that Ab: synthesis example 2 obtains

Resin (A)；Resin A c that Ac: synthesis example 3 obtains

Resin (A)；Resin A d that Ad: synthesis example 4 obtains

Resin (A)；Resin A e that Ae: synthesis example 5 obtains

Resin (A)；Resin A f that Af: synthesis example 6 obtains

Resin (B)；Resin B a that Ba: synthesis example 7 obtains

Resin (B)；Resin B b that Bb: synthesis example 8 obtains

Polymerizable compound (C)；Ca: dipentaerythritol acrylate (KAYARAD (registered trade mark) DPHA；Japanization Medicine (Co., Ltd.) is made)

Polymerizable compound (C)；Cb: tetramethylol methane tetraacrylate (A-TMMT；Xin Zhong village chemical industry (Co., Ltd.) System)

Polymerization initiator (D)；Da:N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3- Base] ethane-1-imines (Irgacure (registered trade mark) OXE02；BASF Japan (Co., Ltd.) makes)

Polymerization initiator (D)；Db:2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl propiono) benzyl] phenyl }-2-first Base propane-1-ketone (Irgacure (registered trade mark) 127；BASF Japan (Co., Ltd.) makes)

Solvent (E)；Ea: propylene glycol methyl ether acetate

Solvent (E)；Eb:3-ethoxyl ethyl propionate

Solvent (E)；Ec:3-methoxyl group-n-butyl alcohol

Solvent (E)；Ed:3-methoxybutyl acetas

Solvent (E)；Ee: diethylene glycol MEE

The mode of " solid constituent amount (%) " that solvent (E) is table 3 with the solid constituent amount of photosensitive polymer combination is mixed Closing, solvent composition (Ea)～the value of (Ee) in solvent (E) represent the mass ratio in solvent (E).

Other composition；Za: thermal cross-linking agent Cymel 300 (three well cytec (Co., Ltd.) systems)

Other composition；Zb: tetrabydrophthalic anhydride (Rikacid TH；New Japan Chemical (Co., Ltd.) system)

To the photosensitive polymer combination obtained, use UV, visible light near infrared spectrometer (V-650 respectively；Japan Light splitting (Co., Ltd.) is made) (quartz box, optical length: 1cm), measure the average transmittance (%) in 400～700nm.By result It is shown in table 3.

By glass substrate (the Eagle XG of 2 inch square；Corning company system) use neutral detergent, water and alcohol successively It is dried after washing.Thickness after later baking is that the mode of 3.0 μm is by photosensitive polymer combination 1～4 obtained above difference It is spin-coated on this glass substrate, by pressure Reduction Dryer (Microtek (Co., Ltd.) system) drying under reduced pressure until degree of decompression reaches 66kPa, then uses heating plate to carry out 2 minutes prebakings at 80 DEG C and makes it be dried.After cooling, use exposure machine (TME- 150RSK；Topcon (Co., Ltd.) system, light source: extra-high-pressure mercury vapour lamp) irradiation exposure amount 50mJ/cm under atmospheric atmosphere² The light of (365nm standard).It should be noted that at this moment use extra-high-pressure mercury vapour lamp to the irradiation of photosensitive polymer combination.Light After irradiation, by above-mentioned film in comprising the water system developer solution of nonionic system surfactant 0.12% and potassium hydroxide 0.04% The dipping, the shake that carry out at 23 DEG C 60 seconds make it contact, and thereafter, heat 20 minutes (baking afterwards) in an oven at 230 DEG C, Obtain film.

For photosensitive polymer combination 5, except changing light exposure into 500mJ/cm²Outside (365nm standard), with upper State same method and obtain film.

To the film obtained, use microscope spectrophotometry device (OSP-SP200；OLYMPUS society system) measure 400 ～the average transmittance (%) of 700nm.Absorbance uprises and means that absorption diminishes.Show the result in table 3.

To the film obtained, use contact angle meter (DGD Fast/60；GBX society system) measure methyl phenyl ethers anisole contact angle.

Contact angle is the highest means that water proofing property is the strongest.If the contact angle in film is high, then use identical photonasty tree In the pattern that oil/fat composition is formed, contact angle is the highest.The photosensitive polymer combination that contact angle is high is used to form separator, with this When the scope that separator surrounds uses ink discharge device printing-ink, easy ink-jet.It is thus possible, for instance utilizing ink-jet method to make coloured silk During colo(u)r filter, between adjacent pixel region, it is not susceptible to the colour mixture of ink.

The film obtained is impregnated 40 minutes in the N-Methyl pyrrolidone of 40 DEG C, measures thickness and absorbance.Utilize Following formula is obtained rate of change respectively by the thickness before and after impregnating and the absorbance in 400nm.

Thickness (μm) before thickness (μm) after Thickness Variation rate (%)=dipping/dipping

Absorbance (%) before absorbance (%) after absorbance rate of change (%)=dipping/dipping

It addition, the film after dipping is carried out fitness test.Use cutting machine on film after impregnating and super cut Cutting mill guider (Super Cutter Guide) (Tai Youji material society system), with the incision of 1mm interval, makes 100 1mm × 1mm Grid.Then, the grid of the incision of film pastes (Nichiban (the strain formula meeting of adhesive tape (registered trade mark) 24mm fabric width Society) system), above adhesive tape, carry out wiping with eraser and make adhesive tape be attached to film, after 2 minutes, hold transparent adhesive tape The end of band, keeps and coated surface disposable stripping at a right angle.Then, do not peeled off by visually counting film and remain in base Grid number on plate.On substrate, the quantity of the grid number of residual is the most, and adaptation is the best.

If the solvent resistance of film is pattern that is good, that formed even with identical photosensitive polymer combination, resistance to Solvent borne is the best.Show the result in table 4.

The film obtained is heated 1 hour in cleaning oven at 240 DEG C, measures thickness and absorbance.Utilize following Formula is obtained rate of change respectively by the thickness before and after heating and the absorbance under 400nm.

Thickness (μm) before thickness (μm) after Thickness Variation rate (%)=heating/heating

Absorbance (%) before absorbance (%) after absorbance rate of change (%)=heating/heating

If the thermostability of film is good, then the pattern formed even with identical photosensitive polymer combination is heat-resisting Property is the best.Show the result in table 4.

By glass substrate (the Eagle XG of 2 inch square；Corning company system) use neutral detergent, water and alcohol successively It is dried after washing.Thickness after later baking is that the mode of 3.5 μm is by photosensitive polymer combination 1～4 and 6～8 spin coating respectively On this glass substrate, by pressure Reduction Dryer (Microtek (Co., Ltd.) system) drying under reduced pressure until degree of decompression reaches 66kPa, then uses heating plate to carry out 2 minutes prebakings at 80 DEG C and is dried.After cooling, this photoresist group will be coated with The substrate of compound and the interval of quartz glass photomask are set as 10 μm, use exposure machine (TME-150RSK；Topcon (strain formula Commercial firm) system, light source: extra-high-pressure mercury vapour lamp) irradiation exposure amount 50mJ/cm under atmospheric atmosphere²The light of (365nm standard).Need Illustrate, be at this moment to make the radiating light from extra-high-pressure mercury vapour lamp pass through optically filtering to the irradiation of photosensitive polymer combination Device (UV-33；Morning sun light splitting (Co., Ltd.) system) carry out.It addition, as photomask, use and formed in same level The light of pattern (have the foursquare transmittance section that 1 length of side is 13 μm, this foursquare be spaced apart 100 μm) (i.e. transmittance section) is covered Film.

After light irradiates, comprising nonionic system surfactant 0.12% and the aqueous developer solution of potassium hydroxide 0.04% In, above-mentioned film is carried out at 25 DEG C dipping, the shake of 100 seconds, after carrying out developing, washing, enters at 235 DEG C in an oven Row baked after 15 minutes, obtained pattern.

For photosensitive polymer combination 5, except light exposure is changed to 500mJ/cm²Beyond (365nm standard), with Above-mentioned same method obtains pattern.

Use scanning electron microscope (S-4000；Society of (Co., Ltd.) Hitachi system) observable pattern Shape.Using pattern as separator use time, the most positive taper (shape shown in Fig. 3).

[table 4]

From the result of embodiment, the photosensitive polymer combination of the present invention can obtain maintaining high contact angle State under the film of excellent heat resistance and pattern.

Industrial applicability

Photosensitive polymer combination according to the present invention can obtain the pattern of excellent heat resistance.

Claims

1. a photosensitive polymer combination, it comprises following A, A1, B, C, D and E,

Resin A is copolymer, its be comprise come from select free unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides composition group at least A kind of construction unit and come from being total to of construction unit of unsaturated compound of the cyclic ether structure with carbon number 2～4 Polymers,

The construction unit of the described unsaturated compound coming from the cyclic ether structure with carbon number 2～4 has not for coming from The unsaturated compound of the structure that saturated fat ring type hydrocarbon is at least partially epoxidized, there is the unsaturated compound of oxetanyl or have The construction unit of the unsaturated compound of tetrahydrofuran base,

And described Resin A does not comprise the construction unit of the unsaturated compound coming from the perfluoroalkyl with carbon number 4～6；

Resin B is polymer, and it comprises the structure list of the unsaturated compound coming from the perfluoroalkyl with carbon number 4～6 Unit；

Resin A 1 is the resin different from Resin A and resin B；

C is polymerizable compound；

D is polymerization initiator；

E is solvent,

The content of Resin A 1 is 0～80 mass % relative to the total amount of Resin A and Resin A 1,

The content of the Resin A total amount relative to Resin A, Resin A 1 and polymerizable compound C is 5～95 mass %,

The content of resin B total amount 100 mass parts relative to Resin A, Resin A 1 and polymerizable compound C is 0.001～10 Mass parts.

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

B is also to comprise the construction unit of at least one come from the group selecting free unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides to constitute Copolymer.

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

D is the polymerization initiator comprising oxime compound.

4. an ink-jet separator, it is to be formed by the photosensitive polymer combination described in claim 1.

5. a display device, it comprises the ink-jet separator described in claim 4.