CN106030407A

CN106030407A - Photosensitive resin composition

Info

Publication number: CN106030407A
Application number: CN201480076369.9A
Authority: CN
Inventors: 河西裕; 井上裕康; 山下和贵
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2014-02-28
Filing date: 2014-06-06
Publication date: 2016-10-12
Anticipated expiration: 2034-06-06
Also published as: JP5598621B1; TWI650610B; WO2015129059A1; TW201546542A; KR102008050B1; CN106030407B; JP2015161895A; KR20160119682A

Abstract

A photosensitive resin composition containing (A), (B), (C), and (D), the amount of (A) being 45-80% by mass in relation to the total amount of (A) and (C): (A) a polymer that contains a structural unit derived from an aromatic carboxylic acid having an ethylenically unsaturated bond and a structural unit derived from an unsaturated compound having a C2-4 cyclic ether structure, said polymer having no structural units that have a C4-6 perfluoroalkyl group; (B) a polymer containing structural unit that has a C4-6 perfluoroalkyl group; (C) a polymeric compound; and (D) a polymerization initiator.

Description

Photosensitive polymer combination

Technical field

The present invention relates to photosensitive polymer combination.

Background technology

In recent years display devices etc. show with ink-jet method making colored filter, the ITO electrode of liquid crystal display cells, organic EL Show element, wiring substrate etc..It addition, ink-jet method utilizes the next door using photosensitive polymer combination to be formed.

This photosensitive polymer combination is known to be had such as containing methacrylic acid and acrylic acid 3,4-epoxy three ring [5.2.1.0^2.6] last of the ten Heavenly stems ester copolymer as the photosensitive polymer combination (patent documentation 1) of resin.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2012-73603 publication

Summary of the invention

Use ink discharge device will contain organofunctional in the recess being divided into by the next door formed on substrate and substrate During the Ink Application of material, preferable substrate wettability of the surface is high so that recess substrate surface is the most coating by ink, and In order to prevent ink for spilling the wettability above further preferably next door low (lyophobicity is high) beyond target area.But, use The wettability of the recess substrate surface that the next door that the photosensitive polymer combination in the past proposed is formed is divided into substrate has Situation about cannot meet.

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

[1] a kind of photosensitive polymer combination, it contains (A), (B), (C) and (D), and the content of (A) relative to (A) with (C) total content is below more than 45 mass % 80 mass %, and (A) is containing being derived from the aromatic series carboxylic with ethylenic unsaturated bond The construction unit of acid, it is derived from the construction unit of the unsaturated compound of the cyclic ether structure with carbon number 2～4, and does not have and contain The polymer of the construction unit of the perfluoroalkyl of carbon number 4～6, (B) construction unit containing the perfluoroalkyl with carbon number 4～6 Polymer, (C) polymerizable compound, (D) polymerization initiator.

[2] photosensitive polymer combination as described in [1], wherein (D) is for containing choosing free united imidazole, alkyl The polymerization initiator of at least one in the group that phenyl ketone compound and O-acyl group oxime compound are formed.

[3] a kind of pattern, it is formed by the photosensitive polymer combination described in [1] or [2].

[4] a kind of ink-jet next door, it is formed by the photosensitive polymer combination described in [1] or [2].

[5] a kind of display device, it comprises the pattern described in [3].

[6] a kind of display device, it comprises the ink-jet next door described in [4].

According to the photosensitive polymer combination of the present invention, the pattern that wettability is excellent can be obtained, i.e. drawn with substrate by next door The wettability of the recess substrate surface being divided into is high, the pattern that lyophobicity above next door is high.

Accompanying drawing explanation

Fig. 1 is a profile part for display device 1 being amplified and schematically showing.

Fig. 2 is a top view part for the display device 1 of an embodiment of the present invention being amplified and schematically showing.

Detailed description of the invention

The photosensitive polymer combination of the present invention is containing (A), (B), (C) and the photosensitive polymer combination of (D).

(A) containing being derived from the construction unit of the aromatic carboxylic acid with ethylenic unsaturated bond, being derived from there is carbon number 2～4 The construction unit of the unsaturated compound of cyclic ether structure, and not there is construction unit poly-of perfluoroalkyl containing carbon number 4～6 Compound (hereinafter sometimes referred to " resin (A) ")

(B) polymer (hereinafter sometimes referred to " resin of the construction unit containing the perfluoroalkyl with carbon number 4～6 (B)”)

(C) polymerizable compound

(D) polymerization initiator.

And then, the photosensitive polymer combination of the present invention preferably comprises solvent (E).

The photosensitive polymer combination of the present invention also can be containing by the resin beyond resin (A) and resin (B) (the most sometimes Referred to as " resin (A1) "), polymerization causes the group that auxiliary agent (D1), multi-functional thiol's compound (T) and surfactant (F) are formed In at least one selected.

It should be noted that in this specification, as long as the compound illustrated as each composition is without specializing, then can be independent Or be applied in combination.

Can enumerate as the resin (A) contained by the photosensitive polymer combination of the present invention:

Resin (A-1): containing being derived from the aromatic carboxylic acid (a) (hereinafter sometimes referred to " (a) ") with ethylenic unsaturated bond Construction unit, with the unsaturated compound (b) (hereinafter sometimes referred to " (b) ") being derived from the cyclic ether structure with carbon number 2～4 The polymer of construction unit,

Resin (A-2): make can be polymerized with (a) and (b) and not have the cyclic ether structure of carbon number 2～4 monomer (c) (with Under be sometimes referred to as " (c) "), (a) and (b) polymer of being polymerized.Wherein, (a), (b) and (c) does not the most have carbon number 4～6 Perfluoroalkyl.

A () is for by having the aromatic carboxylic acid of ethylenic unsaturated bond and having the aromatic carboxylic acid acid anhydride institute of ethylenic unsaturated bond At least one monomer of selecting in the group of composition, specifically, can enumerate o-vinyl benzoic acid, m-vinyl benzoic acid, The aromatic carboxylic acid such as p-vinyl benzoic acid, 3-vinylphthalic acid, 4-vinylphthalic acid；3-vinyl The aromatic carboxylic acid anhydrides such as phthalic anhydride, 4-vinylphthalic acid acid anhydride.

B () is for have the cyclic ether structure of carbon number 2～4 (such as, by oxirane ring, oxetanes ring and tetrahydrochysene furan At least one selected in the group that ring of muttering is formed) monomer, it is however preferred to have the cyclic ether structure of carbon number 2～4 and ethylene are not The monomer of saturated double bond, more preferably has the cyclic ether structure of carbon number 2～4 and the monomer of (methyl) acryloxy.

In this specification, so-called " (methyl) acrylic acid " is to represent in the group being made up of acrylic acid and methacrylic acid to select At least one gone out.The statement of " (methyl) acryloyl group " and " (methyl) acrylate " etc. also has same meaning.

As (b), such as, can enumerate and there is the monomer (b1) (following sometimes referred to as " (b1) ") of epoxy ethyl, there is oxa-ring The monomer (b2) of butyl (following sometimes referred to as " (b2) "), there is the monomer (b3) (following sometimes referred to as " (b3) ") of tetrahydrofuran base Deng.

As (b1), can enumerate and there is the monomer (b1-1) of the structure that unsaturated fatty hydrocarbons is at least partially epoxidized (the most sometimes Claim " (b1-1) "), there is the monomer (b1-2) (sometimes referred to as following " (b1-2) ") of the structure that unsaturated lipid ring type hydrocarbon is at least partially epoxidized.

As (b1), preferably there is the monomer of epoxy ethyl and (methyl) acryloyl group epoxide, more preferably there is unsaturation The structure that ester ring type hydrocarbon is at least partially epoxidized and the monomer of (methyl) acryloyl group epoxide.If these preferred monomer, then photonasty The excellent storage stability of resin combination.

As (b1-1), glycidyl (methyl) acrylate, Beta-methyl glycidyl (methyl) specifically can be enumerated Acrylate, β-ethyl glycidyl base (methyl) acrylate, glycidyl vinyl ether, adjacent vinyl benzyl shrink sweet Oleyl ether, a vinylbenzyl glycidyl base ether, to vinylbenzyl glycidyl base ether, Alpha-Methyl-neighbour's vinyl benzyl Glycidyl ether, an Alpha-Methyl-vinylbenzyl glycidyl base ether, Alpha-Methyl-to vinylbenzyl glycidyl base ether, 2,3-double (glycidyl oxy methyl) styrene, 2, double (glycidyl oxy methyl) styrene of 4-, 2,5-is double (to shrink Glyceryl epoxide methyl) styrene, 2,6-double (glycidyl oxy methyl) styrene, 2,3,4-tri-(glycidyl oxygen Ylmethyl) styrene, 2,3,5-tri-(glycidyl oxy methyl) styrene, 2,3,6-tri-(glycidyl oxy methyl) Styrene, 3,4,5-tri-(glycidyl oxy methyl) styrene, 2,4,6-tri-(glycidyl oxy methyl) styrene, The compound etc. that Japanese Unexamined Patent Publication 7-248625 publication is recorded.

As (b1-2), can enumerate VCH list oxide, 1,2-epoxy-4-vinyl cyclohexane is (such as Celloxide (registered trade mark) 2000；Daisel chemical industry Co., Ltd's system), acrylic acid 3,4-epoxycyclohexanecarboxylate (example Such as Cyclomer (registered trade mark) A400；Daisel chemical industry Co., Ltd's system), methacrylic acid 3,4-epoxycyclohexyl first Ester (such as Cyclomer (registered trade mark) M100；Daisel chemical industry Co., Ltd's system), compound represented by formula (I), Compound etc. represented by formula (II).

[in formula (I) and formula (II), R¹And R²Represent hydrogen atom or the alkyl of carbon number 1～4 independently of one another, this alkyl institute The hydrogen atom comprised can replace with hydroxyl.

X¹And X²Represent singly-bound, *-R independently of one another³-、*-R³-O-、*-R³-S-or *-R³-NH-。

R³Represent the alkane diyl of carbon number 1～6.

* represent with O be bonded key.]

As R¹And R²The alkyl of represented carbon number 1～4, such as, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, just Butyl, sec-butyl, the tert-butyl group etc..

As the alkyl being optionally substituted by a hydroxyl group, such as, can enumerate hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxyl Propyl group, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyl-1-Methylethyl, 2-hydroxyl-1-Methylethyl, 1-hydroxybutyl, 2- Hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl etc..

As R¹And R², preferably can enumerate hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, more preferably Hydrogen atom, methyl can be enumerated.

As R³Represented alkane diyl, such as, 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-(* be with O be bonded key) base, *- CH₂CH₂-O-base, more preferably can enumerate singly-bound, *-CH₂CH₂-O-base.

As the compound represented by formula (I), such as, can enumerate the compound etc. represented by formula (I-1)～formula (I-15). Wherein preferred formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11)～the change represented by formula (I-15) Compound, more preferably formula (I-1), formula (I-7), formula (I-9) or the compound represented by formula (I-15).

As the compound represented by formula (II), the compound etc. represented by formula (II-1)～formula (II-15) can be enumerated.Its Middle preferred formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11)～formula (II-15) institute table The compound shown, more preferably formula (II-1), formula (II-7), formula (II-9) or the compound represented by formula (II-15).

Compound represented by formula (I) and the compound represented by formula (II) can each be used alone or two kinds or more thereof. And during with the compound represented by formula (I) and the compound represented by formula (II), they containing ratio (represented by formula (I) Compound: the compound represented by formula (II)) with molar basis, preferably 5: 95～95: 5, more preferably 20: 80～80: 20。

As (b2), preferably there is the monomer of oxetanylmethoxy and (methyl) acryloyl group epoxide.As (b2), such as may be used Enumerate 3-methyl-3-(methyl) acryloyl group epoxide methy oxetane, 3-ethyl-3-(methyl) acryloyl group epoxide methyl Oxetanes, 3-methyl-3-(methyl) acryloyl group epoxide Ethyloxetane, 3-ethyl-3-(methyl) acryloyl group Epoxide Ethyloxetane etc..

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

As (b3), tetrahydrofurfuryl acrylate (such as VISCOATV#150, Osaka organic chemistry work specifically can be enumerated Industry Co., Ltd. system), tetrahydrofurfuryl methacrylate etc..

As (c), (methyl) esters of acrylic acid, the substituted maleimide of N-, unsaturated dicarboxylic diester can be enumerated Class, ester ring type unsaturated compound class, unsaturated carboxylic acid class, unsaturated carboxylic acid anhydride, phenylethylene, other vinyl compounds Deng.

As (methyl) esters of acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (first can be enumerated Base) alkyl esters such as n-butylacrylate, (methyl) acrylic acid sec-butyl ester, (methyl) acrylate tert-buthyl；

Cyclohexyl (methyl) acrylate, 2-methylcyclohexyl (methyl) acrylate, three ring [5.2.1.0^2,6] decane- 8-base (methyl) acrylate (in this technical field, usual entitled bicyclopentane base (methyl) acrylate), bicyclopentane base Epoxide ethyl (methyl) acrylate, three ring [5.2.1.0^2,6] decene-8-base (methyl) acrylate is (in this technical field, used With entitled " dicyclopentenyl (methyl) acrylate "), the cycloalkyl esters such as isobornyl (methyl) acrylate；

The hydroxy alkyl esters such as (methyl) acrylic acid 2-hydroxyethyl ester, (methyl) acrylic acid 2-hydroxy-propyl ester；

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

As N-substituted maleimide, N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl can be enumerated Base maleimide, N-butanimide-3-maleimidobenzoyl ester, N-butanimide-4-maleimidobutyrate Ester, N-butanimide-6-maleimidohexanoic acid ester, N-butanimide-3-maleimidopropionic acid ester, N-(9-acridine Base) maleimide etc..

As unsaturated dicarboxylic two esters, maleic acid diethyl ester, fumaric acid diethyl ester, itaconic acid diethyl can be enumerated Base ester etc..

As ester ring type unsaturated compound class, dicyclo [2.2.1] hept-2-ene", 5-methyl bicycle [2.2.1] can be enumerated Hept-2-ene", 5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxyl dicyclo [2.2.1] hept-2-ene", 5-hydroxymethyl dicyclo [2.2.1] hept-2-ene", 5-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5-methoxyl 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-(hydroxymethyl) dicyclo [2.2.1] hept-2-ene", 5,6-bis-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5,6-dimethoxy dicyclo [2.2.1] Hept-2-ene", 5,6-diethoxy dicyclo [2.2.1] hept-2-ene", 5-hydroxy-5-methyl base dicyclo [2.2.1] hept-2-ene", 5-hydroxyl Base-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxymethyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-tert-butoxy carbonyl Base dicyclo [2.2.1] hept-2-ene", 5-cyclohexyl epoxide carbonyl dicyclo [2.2.1] hept-2-ene", 5-phenyloxycarbonyl dicyclo [2.2.1] hept-2-ene", 5, double (tert-butoxycarbonyl) dicyclo [2.2.1] hept-2-ene" of 6-, 5,6-is double (cyclohexyl epoxide carbonyl) The dicyclo unsaturated compound classes etc. such as dicyclo [2.2.1] hept-2-ene".

As unsaturated carboxylic acid class, the unsaturated monocarboxylic classes such as acrylic acid, methacrylic acid .beta.-methylacrylic acid can be enumerated；

Maleic acid, fumaric acid, citraconic acid, paraconic acid (mesaconicacid), itaconic acid, 3,4,5,6-tetrahydrochysene neighbour's benzene two The unsaturated dicarboxyl such as formic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid, Isosorbide-5-Nitrae-cyclohexene dicarboxylic acid Acids；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 carboxylic Dicyclo unsaturated compound class；

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

Containing hydroxyl and unsaturation (methyl) acrylate of carboxyl in same a part of α-(hydroxymethyl) acrylic acid etc. Class etc..

As unsaturated carboxylic acid anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl O-phthalic can be enumerated Anhydride, 4-vinylphthalic acid acid anhydride, 3,4,5,6-tetrabydrophthalic anhydrides, 1,2,3,6-tetrabydrophthalic anhydrides, Dimethyl tetrahydro phthalic anhydride, 5, the unsaturated two acids anhydride etc. such as 6-dicarboxyl dicyclo [2.2.1] hept-2-ene" anhydride.

Styrene, α-methyl styrene, m-methyl styrene, p-methylstyrene, second can be enumerated as phenylethylene Thiazolinyl toluene, p-methoxystyrene etc..

As other vinyl compounds can enumerate (methyl) acrylonitrile, vinyl chloride, vinylidene chloride, (methyl) acrylamide, Vinyl acetate, 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene etc..

As (c), from the viewpoint of polymerisation reactivity 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), it is derived from the ratio of construction unit of each monomer relative to the construction unit constituting resin (A-1) Add up to molal quantity, following scope.

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

It is derived 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) when above-mentioned scope, have photosensitive polymer combination storage stability, Developability during pattern and gained film and the solvent resistance of pattern, thermostability and machine is formed by photosensitive polymer combination Tool intensity becomes good tendency.

Resin (A-1) preferably (b) be the resin (A-1) of (b1), more preferably (b) be the resin (A-1) of (b1-2).

Resin (A-1) refers to such as document " laboratory method of Polymer Synthesizing ", and (the grand row in big Tianjin writes sale room (strain) chemistry With people the 1st edition the 1st printing distribution on March 1st, 1972) document of quoting recorded of the method recorded and the document manufactures.

Specifically, such as the specified quantitative of (a) and (b), polymerization initiator and solvent etc. are put in reaction vessel, example As replaced by the oxygen in air with nitrogen, thus set de-oxidizing environment, and the method heating while stirring and being incubated.It addition, at this To the polymerization initiator used and solvent etc. without particular limitation of, in this field, normally used material all can use.Such as conduct Polymerization initiator, (2,2 '-azobis isobutyronitrile, 2,2 '-azo is double (2,4-methyl pentane nitrile) such as can to enumerate azo-compound Deng) or organic peroxide (benzoyl peroxide etc.), as long as solvent is the solvent dissolving each monomer, as photosensitive The solvent (E) of property resin combination can use aftermentioned solvent etc..In order to adjust the molecular weight of the resin obtained, during polyreaction, Chain-transferring agent can be added.As chain-transferring agent, normal butane mercaptan, tertiary butane thiol, n-dodecane mercaptan, 2-sulfydryl second can be enumerated The acid of alcohol, ethyl mercaptan, ethyl mercaptan acid ethyl ester, ethyl mercaptan acid 2-ethyl hexyl ester, ethyl mercaptan acid methoxy butyl acrylate, 3-sulfydryl third Sour, containing thio-alcohols such as sulfydryl silicone (KF-2001: SHIN-ETSU HANTOTAI's chemistry system)；The halogen substituted alkyls such as chloroform, carbon tetrachloride, carbon tetrabromide Esters etc..

It should be noted that the polymer obtained, reacted solution be can be used directly, be used as concentrating or through dilute The solution released, it is used as taking out as solid the material of (powder body) with methods such as reprecipitations.Particularly, during this polymerization, as molten Agent is by using and aftermentioned solvent (E) same solvent, and reacted solution can be used directly, and can simplify manufacturing process.

In resin (A-2), it is derived from the ratio of construction unit of each monomer relative to the entire infrastructure list constituting resin (A-2) The total molal quantity of unit, following scope.

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

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

It is derived 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) when above-mentioned scope, have photosensitive polymer combination storage stability, Developability during pattern and gained film and the solvent resistance of pattern, thermostability and machine is formed by photosensitive polymer combination Tool intensity becomes good tendency.

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

Resin (A-2) can be by the method manufacture identical with resin (A-1).

The weight average molecular weight of the polystyrene conversion of resin (A), preferably 3,000～100,000, more preferably 5,000 ～50,000.If the weight average molecular weight of resin (A) is within the above range, then there is the tendency that coating is excellent, and be difficult to during development The film producing exposure portion reduces, and further non-exposed portion easily removes in development.

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

The acid number of resin (A), usually 20～150mgKOH/g, be preferably 40～135mgKOH/g, more preferably 50～ 135mgKOH/g.This acid number be neutralize resin 1g required for the value that measures of the amount (mg) of potassium hydroxide, can be by using hydrogen Potassium oxide aqueous solution carries out titration and obtains.

The content of resin (A) is more than 45 mass % 80 relative to the total content of resin (A) Yu polymerizable compound (C) Below quality %, more than preferably 48 mass % below 75 mass %, more than more preferably 50 mass % below 70 mass %.

The content of resin (A) relative to the total content of resin (A) and polymerizable compound (C) more than 80 mass % time, The tendency that developing time when having the film making to be formed by photosensitive polymer combination to develop is elongated.

The content of resin (A) above-mentioned preferably in the range of time, by warp in the next door that photosensitive polymer combination is formed The basal disc wettability of the surface of patterning is good.

The photosensitive polymer combination of the present invention contains resin (B).Resin (B) is for having the complete of carbon number 4～6 containing being derived from The polymer of the construction unit of the unsaturated compound (d) (hereinafter sometimes referred to " (d) ") of fluoroalkyl.

As (d), the compound represented by formula (d-0) can be enumerated.

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

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

X^dRepresent singly-bound, the divalent aliphatic alkyl of carbon number 1～10, the divalent ester ring type alkyl of carbon number 3～10 or carbon number 6～ -the CH that the divalent aromatic hydrocarbyl of 12, this aliphatic alkyl and this ester ring type alkyl are comprised₂-can be by-O-,-CO-,-NR^e-、- S-or-SO₂-replaced.]

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

R^dIn the alkyl of carbon number 1～21, methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, just can be enumerated The straight-chain alkyl such as heptyl, n-octyl, n-nonyl, positive decyl；Isopropyl, isobutyl group, sec-butyl, isopentyl, 1-methyl amyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 1-ethyl-butyl, 2-ethyl-butyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethyl pentyl group, 2-ethyl pentyl group, 3-ethyl pentyl group, 1-butyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-propylpentyl, 1-butyl, 1-butyl-2-methyl butyl, 1-fourth Base-3-methyl butyl, the tert-butyl group, 1,1-dimethyl propyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethyl Butyl, 2,3-dimethylbutyl, 1-Ethyl-2-Methyl propyl group, 1,1-dimethyl amyl group, 1,2-dimethyl amyl group, 1,3-diformazan Base amyl group, Isosorbide-5-Nitrae-dimethyl amyl group, 2,2-dimethyl amyl group, 2,3-dimethyl amyl group, 2,4-dimethyl amyl group, 3,3-dimethyl Amyl group, 3, the branched-chain alkyl etc. such as 4-dimethyl amyl group, 1-ethyl-1-methyl butyl, 2-ethyl-3-methyl butyl.

As R^dIt is preferably hydrogen atom, halogen atom and methyl.

As X^dIn the divalent aliphatic alkyl 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-diyl, hexane-1, 6-diyl, heptane-1,7-diyl, octane-1, the alkane diyl such as 8-diyl.

As X^dIn the divalent ester ring type alkyl of carbon number 3～10, cyclopropane diyl, Tetramethylene. diyl, Pentamethylene. can be enumerated Diyl, hexamethylene diyl, cycloheptane diyl, cyclodecane diyl etc..

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

-the CH comprised as the divalent aliphatic alkyl of carbon number 1～10 and the divalent ester ring type alkyl of carbon number 3～10₂- By-O-,-CO-,-NR^e-,-S-or SO₂-replaced obtained by X^d, such as, can enumerate formula (xd-1)～formula (xd-10) is represented Group etc..

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

As the compound represented by (d) preferred formula (d-0 ').

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

R^gRepresent hydrogen atom, halogen atom or methyl.]

As the compound represented by formula (d-0), such as, can enumerate compound (d-1)～compound (d-94) etc..In table, X^dThe formula numbering of the numbered above-mentioned illustration group of formula shown in hurdle.It addition, such as compound (d-1) is following formula (d-1) institute table The compound shown.

[table 1]

[table 2]

It is preferably containing by being derived from the construction unit of (d), being derived from the construction unit of aforementioned (a), Yi Jiyuan as resin (B) From unsaturated carboxylic acid and/or the construction unit institute of unsaturated carboxylic acid anhydrides (e) (but different from (a)) (hereinafter sometimes referred to " (e) ") The resin of at least one selected in the group of composition, more preferably containing being derived from the construction unit of (d) and being derived from the structure list of (e) The resin of unit, more preferably contains the construction unit being derived from (d) and is derived from the construction unit of (e) and is derived from the structure of (b) The resin of unit.By by making resin (B) containing being derived from the construction unit of (a) and/or (e), owing to developability is excellent, therefore having Suppress the uneven tendency from residue or development.By by making resin (B) containing being derived from the construction unit of (b), thus having resistance to The tendency that solvent borne is excellent.It should be noted that resin (B) also can contain other construction units.Import other construction units Monomer (hereinafter sometimes referred to " (c ') ") such as can enumerate in the monomer that above-mentioned (c) represents, unsaturated carboxylic acid and unsaturated carboxylic acid Monomer beyond acid anhydride.

When resin (B) is the polymer of (a) and/or (e) and (d), it is derived from the ratio of the construction unit of each monomer, relative structure The total molal quantity of the construction unit of resin (B), is preferably in following scope.

It is derived from the construction unit of (a) and/or (e)；5～40 mass % (more preferably 10～30 mass %)

It is derived from the construction unit of (d)；60～95 mass % (more preferably 70～90 mass %)

When resin (B) is the polymer of (a) and/or (e), (b) and (d), it is derived from the ratio of the construction unit of each monomer, phase Total molal quantity to the construction unit constituting resin (B), is preferably in following scope.

It is derived from the construction unit of (b)；5～80 mass % (more preferably 10～70 mass %)

It is derived from the construction unit of (d)；10～80 mass % (more preferably 20～70 mass %)

When resin (B) is the polymer of (a) and/or (e), (b), (c ') and (d), it is derived from the ratio of the construction unit of each monomer Rate, relatively constitutes the total molal quantity of the construction unit of resin (B), is preferably in following scope.

It is derived from the construction unit of (b)；5～70 mass % (more preferably 10～60 mass %)

It is derived from the construction unit of (c ')；10～50 mass % (more preferably 20～40 mass %)

When the ratio of each construction unit is in above-mentioned scope, there is the tendency that lyophobicity, developability are excellent.

The weight average molecular weight of the polystyrene conversion of resin (B), preferably 3000～20000, more preferably 5000～ 15000.If the weight average molecular weight of resin (B) is in above-mentioned preferred scope, then it is difficult to produce when having tendency and the development of coating excellence The film of raw exposure portion reduces, and further non-exposed portion is prone in development remove.

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

Relative to total amount 100 mass parts of resin (A), resin (A1) and polymerizable compound (C), resin (B) contains Amount is preferably 0.001～10 mass parts, more preferably 0.01～5 mass parts.If the content of resin (B) is in above-mentioned preferred scope In, then when pattern is formed, developability is excellent, and the pattern obtained has the tendency that lyophobicity is excellent.

The photosensitive polymer combination of the present invention can contain resin (A1).As resin (A1), such as, can enumerate

Resin (A1-1): polymer that (e) and (b) carry out being polymerized,

Resin (A1-2): polymer that (e) and (b) and (c ') carry out being polymerized,

Resin (A1-3): polymer that (e) and (c ') carry out being polymerized,

Resin (A1-4): resin that (e) and (' c) carry out the polymer that is polymerized and (b) reaction and obtain,

Resin (A1-5): the resin that (b) and (c ') carry out the polymer that is polymerized and (a) and/or (e) reaction and obtain Deng.

In resin (A1-1), it is derived from the ratio of the construction unit of each monomer, relatively constitutes the entire infrastructure of resin (A1-1) The total molal quantity of unit, is preferably in following scope.

It is derived from the construction unit of (e)；5～60 moles of % (more preferably 10～50 moles %)

It is derived from the construction unit of (b)；40～95 moles of % (more preferably 50～90 moles %)

If the ratio of the construction unit of resin (A1-1) is in above-mentioned scope, then the preservation having photosensitive polymer combination is steady The solvent resistance of qualitative, developability when being formed pattern by photosensitive polymer combination and the film obtained and pattern becomes Good tendency.

In resin (A1-2), it is derived from the ratio of the construction unit of each monomer, relatively constitutes the entire infrastructure of resin (A1-2) The total molal quantity of unit is preferably in following scope.

It is derived from the construction unit of (e)；2～45 moles of % (more preferably 5～40 moles %)

It is derived from the construction unit of (b)；2～95 moles of % (more preferably 5～80 moles %)

It is derived from the construction unit of (c ')；1～65 mole of % (more preferably 5～60 moles %)

If the ratio of the construction unit of resin (A1-2) is in above-mentioned scope, then the preservation having photosensitive polymer combination is steady The solvent resistance of qualitative, developability when being formed pattern by photosensitive polymer combination and the film obtained and pattern becomes Good tendency.

In resin (A1-3), it is derived from the ratio of the construction unit of each monomer, relatively constitutes the entire infrastructure of resin (A1-3) The total molal quantity of unit, is preferably in following scope.

It is derived from the construction unit of (e)；2～40 moles of % (more preferably 5～35 moles %)

It is derived from the construction unit of (c ')；60～98 moles of % (more preferably 65～95 moles %)

The polymer that resin (A1-4) is (e) and (c ') and (b) reaction and the resin that obtains.

Resin (A1-4) can manufacture through such as two-stage operation.The most also the above-mentioned document " reality of Polymer Synthesizing is referred to Test method " (the grand row in big Tianjin writes sale room (strain) chemistry with people the 1st edition the 1st printing distribution on March 1st, 1972) record method, The methods that Japanese Unexamined Patent Publication 2001-89533 publication is recorded etc. manufacture.

First, as the first stage, with the manufacture method of above-mentioned resin (A-1) in the same manner, being polymerized of (e) and (c ') is obtained Thing.

Now, as described above, the polymer obtained can be used directly reacted solution, be used as concentrated or The solution of person's dilution, it is used as the material that takes out with methods such as reprecipitations with solid (powder body).Additionally, it is preferred that it is same as described above The weight average molecular weight of polystyrene conversion and molecular weight distribution [weight average molecular weight (Mw)/number-average molecular weight (Mn)].

But, it is derived from the ratio of the construction unit of (e) and (c '), relatively constitutes the entire infrastructure unit of above-mentioned polymer Add up to molal quantity, be preferably in following scope.

It is derived from the construction unit of (e)；5～50 moles of % (more preferably 10～45 moles %)

It is derived from the construction unit of (c ')；50～95 moles of % (more preferably 55～90 moles %)

Then, as second stage, make to be derived from the carboxylic acid of (e) of the polymer obtained and a part for carboxylic acid anhydrides with above-mentioned The cyclic ether reaction of (b).Owing to the reactivity of cyclic ether is high, unreacted (b) is difficult to remaining, therefore as resin (A1-2) institute (b) used preferably (b1) or (b2), more preferably (b1-1).

Specifically, connect above-mentioned, atmosphere in flask is substituted by air by nitrogen, be 5～80 to rub by the molal quantity of relatively (e) The carboxyl that total amount is 0.001～5 mass % of (b) of you %, relatively (a), (b) and (c) and the catalysts of cyclic ether (such as three (dimethylaminomethyl) phenol etc.) and relatively (e), the resistance that total amount is 0.001～5 mass % of (b) and (c ') Poly-agent (such as hydroquinone etc.) is inserted in flask, carries out reaction in 1～10 hour at 60～130 DEG C, it is possible to obtain resin (A1- 4).It addition, in the same manner as polymerizing condition, it is contemplated that manufacture the caloric value etc. caused by equipment or polymerization, suitably adjust adding method Or reaction temperature.

It addition, now, the molal quantity of (e) relatively, the molal quantity of (b) be preferably 10～75 moles of %, more preferably 15～ 70 moles of %.By in above-mentioned preferred scope, the storage stability of photosensitive polymer combination, by photosensitive polymer combination shape Developability when becoming pattern and the film obtained and the balance of the solvent resistance of pattern, thermostability, mechanical strength and sensitivity There is the tendency becoming good.

About resin (A1-5), as the first stage, can obtain (b) with the manufacture method of above-mentioned resin (A-1) in the same manner Polymer with (c ').

Now, as described above, the polymer obtained, can be used directly reacted solution, be used as concentrated Or the solution of dilution, it is used as the material that takes out with methods such as reprecipitations with solid (powder body).

It is derived from the ratio of the construction unit of (b) and (c '), relatively constitutes the total of the entire infrastructure unit of above-mentioned polymer Molal quantity, is preferably in following scope.

It is derived from the construction unit of (b)；5～95 moles of % (more preferably 10～90 moles %)

It is derived from the construction unit of (c ')；5～95 moles of % (more preferably 10～90 moles %)

Further, in the same manner as the manufacture method of resin (A1-4), (b) polymer with (c ') can be derived from by making B carboxylic acid or carboxylic acid anhydrides that the cyclic ether of () and (a) and/or (e) are had react and obtain.Cyclic ether and carboxylic acid or carboxylic acid can be made The hydroxyl that the reaction of acid anhydride produces reacts with carboxylic acid anhydrides further.

With the usage amount of (a) and/or (e) of above-mentioned polymer reaction, the relatively molal quantity of (b), preferably 5～80 rub You are %.Because the reactivity of cyclic ether is high, unreacted (b) is difficult to remaining, pretend as (b) preferably (b1), further preferably (b1- 1)。

The weight average molecular weight of the polystyrene conversion of resin (A1), preferably 3,000～100,000, more preferably 5,000 ～50,000.If the weight average molecular weight of resin (A) in above-mentioned preferred scope, then has a tendency that coating is excellent, and during development not Be easily generated the film minimizing of exposure portion, further non-exposed portion easily removes in 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.If molecular weight distribution is in above-mentioned preferred scope, then there is the tendency that developability is excellent.

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

During containing resin (A1), its content, relative resin (A) and the total amount of resin (A1), preferably 1～80 matter Amount %, more preferably 1～50 mass %.If the content of resin (A1) is in above-mentioned preferred scope, then pattern can be made with high sensitivity Formed, and developability is excellent.

Polymerizable compound (C) is for carrying out, by living radical produced by polymerization initiator (D), the change being polymerized Compound, for example, has the compound etc. of ethylenic unsaturated bond, is preferably (methyl) acrylate compounds.

As having the polymerizable compound (C) of 1 ethylenic unsaturated bond, such as, can enumerate and above-mentioned (a), (b) and (c) The compound that cited compound is identical, wherein preferred (methyl) esters of acrylic acid.

As having the polymerizable compound (C) of 2 ethylenic unsaturated bonds, such as, can enumerate 1,3 butylene glycol two (methyl) Acrylate, 1,3 butylene glycol (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) third Olefin(e) acid ester, diethylene glycol two (methyl) acrylate, dimethyltrimethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) third Olefin(e) acid ester, TEG two (methyl) acrylate, polyethyleneglycol diacrylate, double (acryloyl-oxyethyl) of bisphenol-A Ether, Ethoxylated bisphenol A bis-(methyl) acrylate, propoxylation dimethyltrimethylene glycol two (methyl) acrylate, ethoxylation Dimethyltrimethylene glycol two (methyl) acrylate, 3-methylpentane glycol two (methyl) acrylate etc..

As having the polymerizable compound (C) of more than 3 ethylenic unsaturated bonds, such as, can enumerate trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, three (2-hydroxyethyl) 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 the reactant of anhydride, caprolactone modification trimethylolpropane tris (methyl) acrylate, caprolactone Modified tetramethylolmethane three (methyl) acrylate, caprolactone modification three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylic acid Ester, caprolactone modification tetramethylolmethane four (methyl) acrylate, caprolactone modification dipentaerythritol five (methyl) acrylate, oneself Lactone-modified dipentaerythritol six (methyl) acrylate, caprolactone modification tripentaerythritol four (methyl) acrylate, in oneself Ester modified tripentaerythritol five (methyl) acrylate, caprolactone modification tripentaerythritol six (methyl) acrylate, caprolactone Modified tripentaerythritol seven (methyl) acrylate, caprolactone modification tripentaerythritol eight (methyl) acrylate, caprolactone change Property tetramethylolmethane three (methyl) acrylate and the reactant of anhydride, caprolactone modification dipentaerythritol five (methyl) acrylate Reactant etc. with reactant, caprolactone modification tripentaerythritol seven (methyl) acrylate and the anhydride of anhydride.

The most preferably there is the polymerizable compound (C) of more than 3 ethylenic unsaturated bonds, more preferably dipentaerythritol six (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate.

The content of polymerizable compound (C), relative resin (A), resin (A1) and the total amount of polymerizable compound (C), It is preferably 20～55 mass %, more preferably 30～45 mass %.

If the content of polymerizable compound (C) is in above-mentioned scope, then sensitivity or the intensity of pattern obtained, flatness, Reliability has the tendency becoming good.

The photosensitive polymer combination of the present invention contains polymerization initiator (D).As polymerization initiator (D) as long as being can be because of The effect of light or heat starts the compound of polymerization and is then not specifically limited, and can use known polymerization initiator.

As polymerization initiator (D), such as can enumerate alkyl phenyl ketonic compound, united imidazole, triaizine compounds, Acylphosphine oxide compound O-acyl group oxime compound.It addition, be used as described in Japanese Unexamined Patent Publication 2008-181087 publication Light and/or hot cationic polymerization initiators (such as by cation be derived from the initiation that lewis acidic anion is constituted Agent).Wherein it is preferably selected from the group being made up of united imidazole, alkyl phenyl ketonic compound and O-acyl group oxime compound At least one, particularly preferred alkyl phenyl ketonic compound.If containing the polymerization initiator of these compounds, then having and become special Highly sensitive tendency, thus preferably.

Above-mentioned O-acyl group oxime compound is for having the compound of the partial structurtes represented by formula (d1).Hereinafter, * is bonding Key.

As above-mentioned O-acyl group oxime compound, such as, can enumerate N-benzoyl Oxy-1-(4-phenylmercapto phenyl) fourth Alkane-1-ketone-2-imines, N-benzoyl Oxy-1-(4-phenylmercapto phenyl) octane-1-ketone-2-imines, N-benzoyl oxygen Base-1-(4-phenylmercapto phenyl)-3-cyclopenta propane-1-ketone-2-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methyl Benzoyl)-9H-carbazole-3-base] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-{2-methyl-4-(3,3-diformazans Base-2,4-dioxolane ylmethyl epoxide) benzoyl-9H-carbazole-3-base] ethane-1-imines, N-acetoxyl group- 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-3-cyclopenta propane-1-imines, N-benzoyl oxygen Base-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-3-cyclopenta propane-1-ketone-2-imines etc..Also may be used Use IRGACURE (registered trade mark) OXE01, OXE02 (above, BASF AG's system), N-1919 (ADEKA company system) etc. commercially available Product.

Abovementioned alkyl phenyl ketone compound is for having the partial structurtes represented by formula (d2) or the local represented by formula (d3) The compound of structure.In these partial structurtes, phenyl ring can have substituent group.

As the compound of the partial structurtes having represented by formula (d2), such as, can enumerate 2-methyl-2-morpholino-1- (4-methyl mercapto phenyl) propane-1-ketone, 2-dimethylamino-1-(4-morphlinophenyl)-2-benzyl butane-1-ketone, 2-(two Methylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl] butane-1-ketone etc..It is used as The commercially available products such as IRGACURE (registered trade mark) 369,907,379 (above, BASF AG's system).

As the compound of the partial structurtes having represented by formula (d3), such as, can enumerate 2-hydroxy-2-methyl-1-phenyl Propane-1-ketone, 2-hydroxy-2-methyl-1-(4-(2-hydroxyl-oxethyl) phenyl propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(the 4-isopropenyl phenyl) oligomer of propane-1-ketone, α, α-diethoxy acetophenone, benzil two Methyl ketal etc..

From the viewpoint of sensitivity, as alkyl phenyl ketonic compound, preferably there is the local knot represented by formula (d2) The compound of structure.

As above-mentioned united imidazole, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5 can be enumerated, 5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2,3-Dichlorobenzene base)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline (referring for example 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 '-bis- (2-chlorphenyl)-4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxaline, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-four (dioxane Phenyl) bisglyoxaline, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxalines are (referring for example to day This examined patent publication 48-38403 publication, Japanese Laid-Open Patent Publication 62-174204 publication etc..), 4,4 ', 5, the phenyl of 5 '-position is by carbonyl The substituted imidazolium compounds of alkoxyl institute is (referring for example to Japanese Unexamined Patent Publication 7-10913 publication etc..) etc..Preferably can enumerate 2, 2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2,3-Dichlorobenzene base)-4,4 ', 5,5 '-tetraphenyl Bisglyoxaline, 2,2 '-bis-(2,4-Dichlorobenzene base)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline.

As above-mentioned triaizine compounds, 2 can be enumerated, double (the trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri-of 4- Piperazine, 2, double (trichloromethyl)-6-(4-methoxyl group the naphthyl)-1,3,5-triazines of 4-, 2, double (trichloromethyl)-6-piperonyl-1 of 4-, 3,5-triazines, 2, double (trichloromethyl)-6-(4-the methoxyl-styrene)-1,3,5-triazines of 4-, 2, double (the trichloromethyl)-6-of 4- (2-(5-methylfuran-2-base) vinyl)-1,3,5-triazines, 2, double (trichloromethyl)-6-(2-(furan-2-base) ethylene of 4- Base)-1,3,5-triazines, 2, double (the trichloromethyl)-6-(2-(4-diethylamino-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, such as, can enumerate 2,4,6-trimethylbenzoyldiphenyl oxidations Thing etc..

Further, as polymerization initiator (D), benzoin, benzoin methyl ether, benzoin ethyl ether, benzene can be enumerated occasionally The benzoin based compounds such as relation by marriage isopropyl ether, benzoin isobutyl ether；Benzophenone, o-benzoyl yl benzoic acid methyl ester, 4- Phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl sulfide, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) hexichol The benzophenone based compounds such as ketone, 2,4,6-tri-methyl benzophenones；The quinone systems such as 9,10-phenanthrenequione, 2-ethyl-anthraquinone, camphorquinone Compound；10-butyl-2-chloro-acridine ketone, benzil, phenylglyoxalates methyl ester, titanocenes compound etc..Preferably they with after Stating polymerization causes auxiliary agent (D1) to be applied in combination.

It addition, as having the polymerization initiator of the group that can cause chain tra nsfer, Japanese Unexamined Patent Application Publication 2002-544205 can be used The polymerization initiator that number publication is recorded.

The above-mentioned polymerization initiator with the group that can cause chain tra nsfer, it is also possible to as the composition constituting resin (A) (c)。

In the photosensitive polymer combination of the present invention, above-mentioned polymerization initiator (D) can be used simultaneously and be polymerized initiation and help Agent (D1).Polymerization causes auxiliary agent (D1) to be applied in combination with polymerization initiator (D), is to promote to cause polymerization due to polymerization initiator The compound that used of the polymerization of polymerizable compound or sensitizer.Polymerization causes auxiliary agent (D1), such as, can enumerate thioxanthene Ketonic compound, amines, carboxylic acid compound, Japanese Unexamined Patent Publication 2008-65319 publication and Japanese Unexamined Patent Publication 2009-139932 The compound etc. that publication is recorded.

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

As amines, can enumerate the aliphatic amine compound such as triethanolamine, methyl diethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl ester, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid 2-ethyl hexyl ester, benzoic acid 2-dimethyl aminoethyl ester, N, N-dimethyl-p-toluidine, 4, (the common name of 4 '-bis-(dimethylamino) benzophenone；Michaelis ketone), 4,4 '-bis-(diethylamino) the such fragrance of benzophenone Race's amines.

As carboxylic acid compound, can enumerate phenylmercapto acetic acid, aminomethyl phenyl TGA, ethylphenyl TGA, Methylethyl phenyl TGA, 3,5-dimethylphenyl TGA, methoxyphenyl TGA, Dimethoxyphenyl sulfydryl second Acid, chlorphenyl TGA, Dichlorobenzene base TGA, N-phenyl glycine, phenoxyacetic acid, naphthyl sulfur acetic acid, N-naphthyl The aromatic series such as glycine, naphthoxy acetic acid miscellaneous acetic acid class.

As polymerization initiator (D) and the combination being polymerized initiation auxiliary agent (D1), alkyl phenyl ketonic compound and thiophene can be enumerated Ton ketonic compound, alkyl phenyl ketonic compound and aromatic amines compound, specifically, can enumerate 2-methyl-2-morpholino-1- (4-methyl mercapto phenyl) propane-1-ketone and 2,4-diethyl thioxanthone, 2-dimethylamino-2-benzyl-1-(4-morpholino benzene Base) butane-1-ketone and 2,4-diethyl thioxanthone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morphlinophenyl) fourth Alkane-1-ketone and 2,4-diethyl thioxanthone, 2-morpholino-1-(4-methyl mercapto phenyl)-2-methylpropane-1-ketone and 2-isopropyl Base thiaxanthone and ITX, 2-morpholino-1-(4-methyl mercapto phenyl)-2-methylpropane-1-ketone and 4,4 '-bis- (diethylamino) benzophenone, 2-dimethylamino-2-benzyl-1-(4-morphlinophenyl) butane-1-ketone and 4,4 '-bis- (diethylamino) benzophenone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morphlinophenyl) butane-1-ketone with 4,4 '-bis-(diethylamino) benzophenone etc..

Wherein, preferably alkyl phenyl ketonic compound and the combination of thioxanthone compounds, more preferably 2-methyl-2-morpholino- 1-(4-methyl mercapto phenyl) propane-1-ketone and 2,4-diethyl thioxanthone, 2-methyl-2-morpholino-1-(4-methyl mercapto benzene Base) propane-1-ketone and ITX and ITX.If these combination, then can get high sensitivity and The pattern that transmission of visible light is high.

The content of polymerization initiator (D), relative resin (A), resin (A1) and the total amount 100 of polymerizable compound (C) Mass parts, preferably 0.5～30 mass parts, more preferably 1～20 mass parts, more preferably 1～10 mass parts.If polymerization The content of initiator (D) in above-mentioned preferred scope, then can obtain pattern with high sensitivity.

Polymerization causes the usage amount of auxiliary agent (D1), relative resin (A), resin (A1) and the total of polymerizable compound (C) Measure 100 mass parts, preferably 0.1～10 mass parts, more preferably 0.3～7 mass parts.If the amount that polymerization causes auxiliary agent (D1) exists Above-mentioned preferred scope, then can obtain pattern with high sensitivity, and the shape of the pattern obtained is good.

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

As solvent spendable in the present invention, such as can by ester solvent (intramolecular contains-COO-, without the solvent of-O-), Ether solvents (intramolecular contains-O-, without the solvent of-COO-), ether-ether solvent (intramolecular is containing the solvent of-COO-and-O-), ketone solvent Choosing in (intramolecular contains-CO-, without the solvent of-COO-), alcoholic solvent, aromatic hydrocarbon solvents, amide solvent, dimethyl sulfoxide etc. Select use.

As ester solvent, such as, can enumerate lactic acid methyl ester, lactic acid ethyl ester, lactic acid butyl ester, 2-hydroxy-isobutyric alkanoic acid Methyl ester, ethyl acetate, ro-butyl acetate, Sucrose Acetate base ester, formic acid amyl group ester, acetic acid isopentyl ester, propanoic acid butyl Ester, butanoic acid isopropyl esters, butanoic acid ethyl ester, butanoic acid butyl ester, acetone acid methyl ester, acetone acid ethyl ester, acetone acid propyl diester, Acetoacetic acid methyl ester, ethyl acetoacetate, adnoral acetate, gamma-butyrolacton etc..

As ether solvents, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol can be enumerated Single-butyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, third Glycol list ethylether, propylene glycol monopropyl ether, glycol monobutyl ether, 3-methoxyl group-n-butyl alcohol, 3-methoxyl group-3-methyl fourth Alcohol, oxolane, Pentamethylene oxide., Isosorbide-5-Nitrae-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol first Benzyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, methyl phenyl ethers anisole, ethyl phenyl ether, methylanisole etc..

As ether-ether solvent, such as, can enumerate 2-Methoxyacetic acid methyl ester, 2-Methoxyacetic acid ethyl ester, 2-Methoxyacetic acid fourth Base ester, ethoxyacetic acid methyl ester, ethoxyacetic acid ethyl ester, 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxy-propionic acid methyl ester, 3-ethyl-ethoxypropionate, 2-methoxypropionic acid methyl ester, 2-methoxypropionic acid ethyl ester, 2-methoxypropionic acid propyl diester, 2-ethoxy-propionic acid methyl ester, 2-ethyl-ethoxypropionate, 2-methoxyl group-2 Methylpropionic acid Methyl ester, 2-ethyoxyl-2 Methylpropionic acid ethyl ester, 3-methoxybutyl acetas, 3-methyl-3-methoxybutyl acetic acid Ester, propylene glycol monomethyl ether, propylene glycol monoethyl acetas, propylene glycol monopropyl ether acetas, ethylene glycol list first Base ether acetic acid ester, ethylene glycol monomethyl ether acetate, TC acetas, diethylene glycol monobutyl ether acetas Deng.

As ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptan can be enumerated Ketone, 4-methyl-2 pentanone, Ketocyclopentane, Ketohexamethylene, isophorone etc..

As alcoholic solvent, such as, can enumerate methanol, ethanol, propanol, butanol, hexanol, Hexalin, ethylene glycol, propylene glycol, sweet Oil etc..

As aromatic hydrocarbon solvents, such as, can enumerate benzene,toluene,xylene, sym-trimethylbenzene. etc..

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

These solvents can be used singly or two or more kinds in combination.

In above-mentioned solvent, it it is more than 120 DEG C less than 180 DEG C from the boiling point of coating, drying property viewpoint, preferably 1atm Organic solvent.Wherein preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-ethyl-ethoxypropionate, two Ethylene Glycol Methyl ethylether, 3-methoxybutyl acetas, 3-methoxyl group-n-butyl alcohol etc..If solvent (E) is that these are the most molten Agent, then can suppress inequality during coating, and the flatness that can make film is good.

The content of the solvent (E) in the photosensitive polymer combination of the present invention, the total amount of relative photosensitive polymer combination, It is preferably 60～95 mass %, more preferably 70～90 mass %.

In other words, the solid constituent of photosensitive polymer combination is preferably 5～40 mass %, more preferably 10～30 matter Amount %.If the content of solvent (E) is in above-mentioned preferred scope, then the flatness of the film of photosensitive resin coating compositions is had to carry High tendency.Here, solid constituent refers to remove the amount of solvent (E) from photosensitive polymer combination.

It addition, the photosensitive polymer combination of the present invention, multi-functional thiol's compound (T) can be contained further.Multifunctional Mercaptan compound (T) refers to that intramolecular has the compound of the sulfydryl (-SH) of more than 2.Have if particularly using and be derived from The compound of the sulfydryl of more than 2 of the carbon atom bonding of aliphatic alkyl, then have the photosensitive polymer combination of the present invention The tendency that sensitivity improves.

Multi-functional thiol's compound (T), particularly can enumerate hexanedithiol, decanedithiol, Isosorbide-5-Nitrae-bis-(methyl sulfur Base) benzene, butanediol double (3-thiohydracrylic acid ester), butanediol double (3-ethyl thioglycollic acid ester), ethylene glycol bis (3-ethyl thioglycollic acid ester), three Hydroxymethyl-propane three (3-ethyl thioglycollic acid ester), butanediol double (3-thiohydracrylic acid ester), trimethylolpropane tris (3-thiohydracrylic acid Ester), trimethylolpropane tris (3-ethyl thioglycollic acid ester), tetramethylolmethane four (3-thiohydracrylic acid ester), tetramethylolmethane four (3-sulfenyl second Acid esters), trihydroxy ethyl three (3-thiohydracrylic acid ester), tetramethylolmethane four (3-sulfenyl butyrate), Isosorbide-5-Nitrae-bis-(3-sulfenyl butyl oxygen Base) butane etc..

The content of multi-functional thiol's compound (T), relative polymerization initiator (D) 100 mass parts, preferably 0.1～10 matter Amount part, more preferably 0.5～7 mass parts.If the content of multi-functional thiol's compound (T) is in above-mentioned preferred scope, then have photosensitive Property resin combination sensitivity improve, and developability becomes good tendency, the most preferably.

The photosensitive polymer combination of the present invention, can contain surfactant (F) (but different from resin (B).).As table Face activating agent, such as, can enumerate silicone-based surfactant, fluorine system surfactant, have the silicone-based surface activity of fluorine atom Agent etc..

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

Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray can be enumerated 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 Chemial Co., Ltd's system), TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF4446、TSF4452、TSF4460 (Momentive Performance Materials Japan contract commercial firm system) etc..

As fluorine system surfactant, such as, can enumerate the surfactant with fluorocarbon chain.

Specifically, Fluorinert (registered trade mark) FC430, Fluorinert FC431 (Sumitomo 3M strain formula can be enumerated Commercial firm's system), MEGAFAC (registered trade mark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC R30 (Dainippon Ink Chemicals's system), EFTOP (registered trade mark) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (Mitsubishi Materials electronization becomes Co., Ltd.'s system), Surflon (registered trade mark) S381, Surflon S382, Surflon SC101, SurflonSC105 (Asahi Glass Co., Ltd's system), E5844 (Co., Ltd. Daikin Fine Chemical research is made) etc..

As having the silicone-based surfactant of fluorine atom, the surface activity with siloxane bond and fluorocarbon chain can be enumerated Agent.Specifically, MEGAFAC (registered trade mark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC can be enumerated F477, MEGAFAC F443 (Dainippon Ink Chemicals's system) etc..Preferably can enumerate MEGAFAC (registered trade mark) F475.

The content of surfactant (F), the total amount of relative photosensitive polymer combination, is more than 0.001 mass % 0.2 matter 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 scope below 0.2 mass % more than 0.001 mass %, the flatness of film can be made For well.

The photosensitive polymer combination of the present invention, can contain filler, other macromolecular compound, closely sealed as required The various additives such as accelerator, antioxidant, UV absorbent, light stabilizer, chain-transferring agent.

As closely sealed accelerator, such as, can enumerate vinyltrimethoxy silane, VTES, vinyl Three (2-methoxy ethoxy) silane, 3-aoxidize glycidylpropyl trimethoxy silane, 3-glycidoxypropyl Dimethoxysilane, 3-glycidoxypropyl dimethoxysilane, 3-glycidoxypropyl diethoxy silicon Alkane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyl trimethoxy Base silane, 3-methacryloxypropyl trimethoxy silane, 3-mercaptopropyi trimethoxy silane, 3-mercaptopropyi front three TMOS, 3-isocyanates propyl-triethoxysilicane, N-2-(amino-ethyl)-3-amino propyl methyl dimethoxy silicon Alkane, N-2-(amino-ethyl)-3-amino propyl methyl diethoxy silane, N-2-(amino-ethyl)-3-aminopropyl trimethoxy Base silane, N-2-(amino-ethyl)-3-amino propyl methyl diethoxy silane, 3-TSL 8330,3-ammonia Base propyl-triethoxysilicane, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyl triethoxysilicane Alkane etc..

The photosensitive polymer combination of the present invention, contains substantially no the coloring agent such as pigment and dyestuff.That is, the sense of the present invention In photosensitive resin composition, the colorant content that relative combinations thing is all, the most preferably less than 1 mass %, more preferably less than 0.5 mass %.

The photosensitive polymer combination of the present invention, is filled in the quartz colorimetric utensil of a length of 1cm of light path, uses spectrophotometric Meter, is preferably more than 70%, more preferably measuring average transmittance when measuring absorbance under conditions of wavelength 400～700nm It is more than 80%.

The photosensitive polymer combination of the present invention, when making film, the average transmittance of film preferably more than 90%, enters One step more preferably more than 95%.This average transmittance is will be heating and curing (such as 100～250 DEG C, 5 minutes～the condition of 3 hours Solidification) after the film that thickness is 3 μm, use spectrophotometer, measuring when measuring under conditions of wavelength 400～700nm Meansigma methods.Thus may be provided in the film that the transparency of visible regime is excellent.

The photosensitive polymer combination of the present invention, such as, can coat the substrates such as glass, metal, plastics or be formed On the above-mentioned substrate of color filter, various insulation or conducting film, drive circuit etc., it is patterned as after desired shape formation figure again Case.And then, it is possible to make a part for the member of formation that this pattern is formed as display device etc. use.

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

Coating, as above-mentioned, can use spin coater, slit spin coater, slit coater, ink jet printing, roller coat The various apparatus for coating such as cloth machine, dip coaterd are carried out.

The most preferably it is dried or prebake conditions, is dried after the volatile ingredients such as solvent are removed.Thus, can be put down Sliding uncured film.

The thickness of film now is not particularly limited, and suitably can adjust according to the material used, purposes etc., for example, 1 ～6 μm degree.

And then, to the uncured film obtained, irradiate light through the mask forming purpose pattern, such as from mercury lamp, send out Ultraviolet etc. produced by optical diode.Mask shape now is not particularly limited, and shape or size are according to the purposes of pattern Needs select.

Utilize exposure machine in recent years can not reach the light of 350nm, use the color filter intercepting this wavelength domain to carry out intercepting or By the light near 436nm, near 408nm, near 365nm, the band filter selectivity taking out these wavelength domains is used to take out After, plane of exposure entirety is irradiated almost parallel light equably.If using the devices such as mask registration exposure machine, stepper, then Now can be masked the correct position alignment with base material.

Make the film after exposure contact developer solution, specific part, such as non-exposed portion (i.e. non-image portion) are dissolved, logical Cross development, available purpose pattern form.

Developing method can be the either method such as liquid pool method, infusion process, nebulization.Base material can be made further during development to tilt to appoint Meaning angle.

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

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

As the concrete example of inorganic alkali compounds, such as can enumerate sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, Sodium dihydrogen phosphate, diammonium phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, carbonic acid Hydrogen sodium, potassium bicarbonate, sodium borate, potassium borate, ammonia etc..

As organic alkali compounds, such as, can enumerate Tetramethylammonium hydroxide, 2-hydroxyethyl trimethyl hydroxide Ammonium, monomethyl amine, dimethyl amine, Trimethylamine, MEA, diethylamide, triethylamine, single isopropylamine, diisopropyl Amine, ethanolamine etc..

Concentration in the aqueous solution of these inorganic and organic alkali compoundss, preferably 0.01～10 mass %, more excellent Elect 0.03～5 mass % as.

Above-mentioned developer solution can contain surfactant.

As surfactant, can be nonionic system surfactant, anion system surfactant or cation system table Any one of face activating agent.

As nonionic system surfactant, such as, can enumerate polyethylene oxide alkyl ethers, polyoxyethylene aryl ethers, gather Ethylene oxide alkyl aryl ether, other polyethylene oxide derivatives, ethylene oxide/propylene oxide block copolymer, sorbose Alcohol acid anhydride fatty acid ester, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol candy alcohol fatty acid ester, glycerin fatty Acid esters, polyoxyethylene fatty acid esters, polyoxyethylene etc..

As anion system surfactant, such as, can enumerate lauryl alcohol sodium sulfovinate or oleyl sulfate sodium is such Higher alcohol sulfate salt, sodium lauryl sulfate or ammonium lauryl sulfate such alkylsurfuric acid salt, DBSA Sodium or dodecyl sodium naphthalene sulfonate such alkylaryl sulfonates class etc..

As cation system surfactant, such as, can enumerate stearyl amine hydrochlorate or lauryl trimethyl ammonium chloride Such amine salt or quaternary ammonium salt etc..

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

By washing after development, available pattern.The most also can toast after being exposed.After exposure Baking, the most preferably 150～240 DEG C temperature range, within 10～180 minutes, carry out.

When being exposed by uncured film, by not using the figuratum mask of formation, carry out light irradiation and/or province by entire surface Show slightly shadow, do not had figuratum film.

As an example of the display device as the present invention, organic EL (electroluminescent) display device is carried out following theory Bright.

Fig. 1 is the sectional view schematically shown of the part expansion of the display device 1 by display device one example of the present invention. Fig. 2 is the top view schematically shown of the part expansion of the display device 1 by display device one example of the present invention.Display device 1 mainly by containing supporting substrates 2, on this supporting substrates 2, zoning goes out the next door 3 in region set in advance, is arranged at by next door 3 Multiple organic EL element 4 in the region that institute's zoning goes out and constitute.The ink jet printing next door of the suitable present invention in next door 3.

Next door 3 is on supporting substrates 2, for example formed as clathrate or striated.The most in fig. 2, as a reality Execute mode, it is shown that be provided with the display device 1 in clathrate next door 3.In the region being provided with next door 3 in this figure, impose hachure.

On supporting substrates 2, set the multiple recesses 5 limited with next door 3 and supporting substrates 2.This recess 5 quite by every The region that 3 zonings of wall go out.

Next door 3 in display device 1 is set to clathrate.Therefore from the point of view of by a side of the thickness direction Z of supporting substrates 2 (following sometimes referred to as " to overlook ".), multiple recesses 5 are configured to rectangular.I.e. be set to recess 5 X in the row direction separate have specific Interval, has been also separated by specific interval at column direction Y simultaneously, thus has carried out permutation.Shape in the vertical view of each recess 5 is the most especially Limit.Such as recess 5 forms substantially rectangular shape, the slightly shape such as ellipticity and ellipse to overlook.In present embodiment, to overlook It is provided with the recess 5 of substantially rectangular shape.Additionally, above-mentioned line direction X and thickness that column direction Y is vertical support substrate in this specification Degree direction Z and mutually orthogonal direction.

It addition, as other embodiment, when being provided with the next door of striated, next door X the most in the row direction prolongs The partition wall member of many stretched, by separate on column direction Y have specific interval in the way of and be configured and constituted.In which In, the recess of striated is gone out by the next door of striated and the common zoning of supporting substrates.

Next door is formed in the way of the narrowest further away from supporting substrates width.Such as by column direction Y extend next door with It is perpendicular to the cross sectional shape when plane of its bearing of trend (column direction Y) is cut off, with along with width is more further away from supporting substrates Narrow mode is formed.In FIG, for the next door of isosceles-trapezium-shaped, relatively the going to the bottom of the upper end and supporting substrates side, ratio of going to the bottom is upper Bottom width.The cross section in the next door being additionally actually formed not necessarily must trapezoidal shape, the straight line portion of trapezoidal shape and angle are sometimes With fillet.

Next door 3 its end face preferred has lyophobicity.Additionally, end face refers in the surface of next door 3, it is present in farthest away from propping up Hold the plane of the position of substrate 2.By the end face in next door 3, there is lyophobicity, supply can be prevented to next door 3 area encompassed The black liquid of (recess 5) is delivered to the end face in next door 3 and is spilled over to adjacent area.

Organic EL element 4 is arranged at the region (i.e. recess 5) that 3, next door zoning goes out.Clathrate in display device 1 is set Next door 3 time, each organic EL element 4 is respectively arranged at each recess 5.I.e. organic EL element 4 is configured to square in the same manner as each recess 5 Battle array shape, and on supporting substrates 2, separate on X in the row direction and have specific interval, on column direction Y, it has been also separated by specific simultaneously Every, thus carry out permutation and arrange.

The shape in next door 3 and configuration thereof are according to the specification of the display device such as pixel count and resolution or the difficulty etc. of manufacture Suitable setting.Such as about a width of 5 μm of the line direction X or column direction Y in next door 3～50 μm, the height in next door 3 be 0.5 μm～5 The line direction X's or column direction Y at interval about μm and between the adjacent next door 3 of line direction X or column direction Y, i.e. recess 5 is a width of About 10 μm～200 μm.Additionally, the wide of the line direction X or column direction Y of the 1st electrode 6 is respectively about 10 μm～200 μm.

Next door 3, can be by being formed with the forming method of above-mentioned pattern by the photosensitive polymer combination of the present invention.

Additionally, as other embodiment, when being provided with the next door of striated, organic EL element 4 X in the row direction extends Each recess in, X has been each spaced apart by specific interval and has configured in the row direction.

Display device 1 is provided with 3 kinds of organic EL element 4.I.e. it is provided with (1) and launches the red organic EL element of red light Blue organic EL element 4B of blue light is launched in 4R, green organic EL element 4G of light of (2) transmitting green and (3).

Organic EL element 4, supporting substrates side stack gradually the 1st electrode, organic EL layer, the 2nd electrode and constitute.In this theory The one or more layers being arranged between the 1st electrode the 6 and the 2nd electrode 10 are called organic EL layer by bright book.Organic EL element 4 Possess at least 1 layer of luminescent layer as organic EL layer.Additionally, organic EL element, in addition to 1 layer of luminescent layer, the most also have also Possesses the situation of the organic EL layer different from luminescent layer.Such as between the 1st electrode the 6 and the 2nd electrode 10, as organic EL layer, Hole injection layer, hole transporting layer, electron-blocking layer, electron supplying layer and electron injecting layer etc. are set.Additionally, at the 1st electrode Also the situation of the luminescent layer arranging more than 2 layers is had between the 6 and the 2nd electrode 10.

Organic EL element 4, as the pair of electrodes being made up of anode and negative electrode, possesses the 1st electrode the 6 and the 2nd electrode 10. An electrode in 1st electrode the 6 and the 2nd electrode 10 is provided as anode, and another electrode is provided as negative electrode.At display device 1, according to stacking gradually the 1st electrode 6 as anode function on supporting substrates 2, as hole injection layer function The 1st organic EL layer 7, the 2nd organic EL layer 9 as luminescent layer function, the 2nd electrode 10 as negative electrode function Mode is constituted.

1st electrode 6 is respectively provided with organic EL element 4.I.e. organic EL element 4 be arranged at supporting with the 1st electrode 6 of number On substrate 2.The configuration of the 1st corresponding organic EL element 4 of electrode 6 and arrange, be assigned to as rectangular in the same manner as organic EL element 4. Additionally, next door 3, be mainly formed as clathrate in the region not including the 1st electrode 6, but further to cover the week of the 1st electrode 6 The mode of edge forms (with reference to Fig. 1).

1st organic EL layer 7 suitable with hole injection layer, is respectively arranged on the 1st electrode 6 in recess 5.1st is organic EL layer 7, as required according to organic EL element kind and its material or thickness are arranged differently.Additionally, it is organic by the 1st From the viewpoint of the difficulty of the formation process of EL layer 7, it is also possible to identical material, identical thickness form the 1st whole organic EL Layer 7.

1st organic EL layer 7, is formed by the following method: make the black liquid containing the material becoming the 1st organic EL layer 7 with spray Method of the use of ink and water supply, to by next door 3 area encompassed (recess 5), is then dried, heats and/or light irradiation, make black liquid-solidization.

As the 2nd organic EL layer 9 of luminescent layer function, it is arranged in recess 5 on the 1st organic EL layer 7.Above-mentioned that The luminescent layer of sample is arranged according to the kind of organic EL element.Therefore red light emitting layer 9R is arranged at and arranges red organic EL element The recess 5 of 4R, green light emitting layer 9G is arranged at the recess 5 arranging green organic EL element 4G, and blue light-emitting layer 9B is arranged at Put the recess 5 of blue organic EL element 4B.

2nd electrode 10 is formed in the viewing area arranging organic EL element 4 comprehensively.I.e. the 2nd electrode 10 is not made only in On 2nd organic EL layer 9, it is also formed on next door 3, and is continuously formed throughout multiple organic EL element.

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

By the pattern obtained by the photosensitive polymer combination of the present invention, for the recess base gone out with next door and substrate institute zoning The pattern that plate wettability of the surface is high, the lyophobicity of next door upper surface is high, therefore makes color filter, liquid crystal as with ink-jet method Show next door that the ITO electrode of element, organic EL display element and wiring substrate etc. used and particularly useful.And then conduct Such as constitute filter substrate and/or the photonasty separating material (Photo Spacer) of a part of array board, patternable The contact panels such as the coating layer that protecting film, interlayer dielectric, liquid crystal aligning control projection, lenticule, thickness adjust Component and useful, above-mentioned obtain do not have figuratum film, can be used as constituting filter substrate and/or array board The protecting film of a part.Above-mentioned filter substrate and array base palte be suitable for liquid crystal display, organic EL display apparatus and Electronic Paper etc..

Embodiment

With embodiment, the present invention is described in more detail below." % " and " part " in example in the case of not illustrating, For quality % and mass parts.

(synthesis example 1)

In the flask possessing reflux condenser, Dropping funnel and blender, appropriate inflow nitrogen also replaces with blanket of nitrogen, adds Enter propylene glycol monomethyl ether 166 parts, methoxypropanol 52 parts, be heated to 85 DEG C while stirring.The most time-consuming 4 hours will 3,4-epoxy three ring [5.2.1.0^2,6] decane-8 or/and 233 parts of the mixture of 9-base acrylate, to vinyl benzoic acid 77 Part, propylene glycol monomethyl ether 125 parts, the mixed solution of methoxypropanol 115 parts drip.On the other hand, used time 5 hours Dropping makes 2, and 2-azo double (2,4-methyl pentane nitrile) 32 parts is dissolved in the mixing of propylene glycol monomethyl ether 210 parts Solution.After completion of dropwise addition, keep at the same temperature after 3 hours, be cooled to room temperature, it is thus achieved that be Type B viscosity (23 DEG C) 46mPas, solid Body composition 33.7%, the polymer (Resin A a) solution of solution acid number 83mgKOH/g.The weight average molecular weight of gained Resin A a Mw is 7.7 × 10³, molecular weight distribution is 1.90.

Resin A a has following construction unit.

(synthesis example 2)

Nitrogen is made to become nitrogen flowed into the flask possessing reflux condenser, Dropping funnel and blender with 0.02L/ minute in Atmosphere is enclosed, and puts into 3-methoxyl group-n-butyl alcohol 200 mass parts and acetic acid 3-methoxybutyl 105 mass parts, is heated to while stirring 70℃.Then, by methacrylic acid 60 mass parts, acrylic acid 3,4-epoxy three ring [5.2.1.0^2.6] last of the ten Heavenly stems ester (with molar ratio computing with 50: 50 compounds that represent with formula (I-1) of mixing and the compound represented with formula (II-1)) 240 mass parts are dissolved in 140 mass In part acetic acid 3-methoxybutyl, modulate solution, use Dropping funnel, this lysate was dripped in 4 hours in 70 DEG C of guarantors In the flask of temperature.

On the other hand, use another Dropping funnel, polymerization initiator 2 will be made in 4 hours, double (2, the 4-diformazans of 2 '-azo Base valeronitrile) 30 mass parts are dissolved in the solution of 225 mass parts acetic acid 3-methoxybutyl and drip in flask.Polymerization initiator After solution completion of dropwise addition, maintain 70 DEG C 4 hours, be then cooled to room temperature, it is thus achieved that solid constituent 32.6 mass %, acid number The solution of the polymer (Resin A 1a) of 110mgKOH/g (solid constituent conversion).Weight average molecular weight Mw of gained Resin A 1a It is 1.3 × 10⁴, molecular weight distribution is 2.50.Resin A 1a has following construction unit.

(synthesis example 3)

α-chloropropene is put in the four-neck flask possessing reflux condenser, nitrogen ingress pipe, thermometer and agitating device 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, first Base glycidyl acrylate 13 parts, dodecyl mercaptans 12.7 parts, propylene glycol monomethyl ether 266 parts, be heated to 70 DEG C After, stirring 30 minutes under nitrogen flowing.Add azodiisobutyronitrile 1 part wherein, be polymerized 18 hours, it is thus achieved that solid constituent 33 matter Polymer (resin B a) the solution of amount %, acid number 68mgKOH/g (solid constituent conversion).The weight averaged molecular of gained resin B a Amount is 7500.Resin B a has following construction unit.

In synthesis example, the weight average molecular weight (Mw) of gained resin and the mensuration of number mean molecule quantity (Mn) use GPC Method, is carried out by following condition.

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

Chromatographic column；SHIMADZUShim-packGPC-80M

Column temperature；40℃

Solvent；THF (oxolane)

Flow velocity；1.0mL/min

Detector；RI

Using the ratio (Mw/Mn) of the weight average molecular weight of the polystyrene conversion of above-mentioned acquisition and number mean molecule quantity as Molecular weight distribution.

(embodiment 1～4 and comparative example 1～3)

The composition of mixture table 3 respectively, it is thus achieved that photosensitive polymer combination.

[table 3]

Each composition in table 3 is as follows.The number described in hurdle of resin (A) and resin (B) represents what solid constituent converted Mass parts.

Resin (A)；Resin A a obtained in Aa: synthesis example 1

Resin (A1)；Resin A 1a that A1a: synthesis example 1 obtains

Resin (A1)；Resin A 1b that A1b: synthesis example 2 obtains

Resin (B)；Resin B a that Ba: synthesis example 3 obtains

Polymerizable compound (C)；Ca: trimethylolpropane trimethacrylate (A-TMPT；Xin Zhong village chemical industry (strain) System)

Polymerizable compound (C)；Cb: dipentaerythritol acrylate (KAYARAD (registered trade mark) DPHA；Japanization Medicine (strain) is made)

Polymerization initiator (D)；Da:2-methyl-2-morpholino-1-(4-methylsulfanylphenyl) propane-1-ketone (IRGACURE (registered trade mark) 907；BASF AG's system)

Polymerization initiator (D)；Db: ethyl ketone, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-, 1- (O-acetyl group oxime) (IRGACURE (registered trade mark) OXE02；BASF AG's system)

Polymerization causes auxiliary agent (D1)；4,4 '-bis-(diethylamino) benzophenone (EAB-F；Hodogaya chemical industry (strain) System)

Solvent (E)；Ea；Propylene glycol monomethyl ether

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

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

Solvent (E)；Ed；3-methoxybutyl acetas

Solvent (E) is that the solid constituent amount of photosensitive polymer combination mixes like that with " solid constituent amount (%) " of table 3, Solvent composition (Ea)～the value of (Ed) in solvent (E) are the mass ratio in solvent (E).

Photosensitive polymer combination obtained by above-mentioned, each uses UV, visible light near infrared spectrometer (V-650； Japan's light splitting (strain) system) (quartz colorimetric utensil, optical path length；1cm), the average transmittance (%) in 400～700nm is measured.Result Such as table 3.

By 2 inch box glass substrate (EAGLEXG；Corning Incorporated's system) laggard with neutral lotion, water and alcohol washing successively Row is dried.On this glass substrate, make above-mentioned obtained photosensitive polymer combination each with the thickness after postexposure bake The mode becoming 3.0 μm carries out rotary coating, utilizes pressure Reduction Dryer (MICROTEK (strain) system) to make degree of decompression set to 66kPa After carrying out drying under reduced pressure, carry out 2 minutes prebake conditions with heating plate at 80 DEG C and make it be dried.After condensation, use exposure machine (TME- 150RSK；Open up Pu Kang (strain) system, light source: ultrahigh pressure mercury lamp), under atmospheric environment, irradiation exposure amount 50mJ/cm²(365nm benchmark) Light.It addition, now the irradiation to photosensitive polymer combination uses ultrahigh pressure mercury lamp.After light irradiates, containing nonionic system Surfactant 0.12%, with the water system developer solution of potassium hydroxide 0.04%, makes above-mentioned film carry out leaching in 60 seconds at 23 DEG C Stain, shake and be brought into contact with, then, in an oven 230 DEG C carry out 20 points of heating (postexposure bake) after, obtain film.

To the film obtained, use micro-spectral light measurer (OSP-SP200；OLYMPUS company system), measure 400～ Average transmittance (%) in 700nm.Absorbance uprises and refers to that absorption diminishes.Result such as table 3.

To the film obtained, use contact angle meter (DGDFast/60；GBX company system), measure the contact angle of methyl phenyl ethers anisole.

The most a height of lyophobicity of contact angle is the highest.If the contact angle in film is high, then use identical photosensitive polymer combination In the pattern formed, contact angle is the highest.Form next door with the high photosensitive polymer combination of contact angle, in this next door surrounds with During ink-jet printing apparatus printing (print is write) ink liquid, easily repel ink liquid.During it is thus possible, for instance make color filter with ink-jet method, it is difficult to produce Black liquid colour mixture between raw adjacent image-region.Result such as table 5.

Glass substrate (EAGLEXG at 2 inch square of surface evaporation ITO；Corning Incorporated's system) sequentially with neutral lotion, It is dried after water and 2-propanol rinse.Make the photosensitive polymer combination of above-mentioned acquisition respectively so that the thickness after rear baking becomes Be the mode rotary coating of 1.0 μm on this glass substrate, with pressure Reduction Dryer (Microtech (strain) system) drying under reduced pressure to subtracting After pressure degree is 66kPa, within 2 minutes, it is dried 90 DEG C of prebake conditions with heating plate.

After condensation, the substrate of this photosensitive resin coating compositions and the interval of quartz glass mask are set to 100 μm, And use exposure machine (TME-150RSK；TOPCON (strain) makes, light source；Ultrahigh pressure mercury lamp), under atmospheric atmosphere, irradiation exposure amount 200mJ/cm²The light of (365nm benchmark).Pattern (light shielding part is formed at grade it should be noted that use as mask Be shaped as being cut at four angles the shape (oval) of round shape from the rectangle of long axis direction 300 μm, short-axis direction 100 μm) Mask.

After illumination, with pure water, tetramethyl ammonium hydroxide aqueous solution (TOKUYAMA (strain) makes, TOKUSOSD25) is being diluted Become in 2.38% developer solution modulated to concentration, make above-mentioned film limit shake dipping limit development in 60 seconds at 23 DEG C, through water After washing, toast 20 minutes after carrying out at 230 DEG C in an oven, it is thus achieved that pattern.

[wettability assessment solution makes]

As the solvent of the wettability assessment implementing next door, select N,N-dimethylacetamide (with Guang Chun medicine joint-stock company System, more than 99.5%), 2 kinds of DMI (Tokyo chemical conversion Industry Stock Company system, more than 99.0%). The 2 kinds of solvents selected, owing to viscosity is low, are therefore fills up to next door for available ink-jet printing apparatus by liquid, add Hexalin (with Guang Chun medicine joint-stock company, more than 98.0%) adjust material as viscosity, use with mixed solvent form.

It addition, about solvent monomers, owing to being difficult to observe dried coating scope with microscope, therefore use Luo Dan Bright B (Tokyo chemical conversion Industry Stock Company system, purity more than 95%) is as solute.

Solution makes 3 kinds of table 4 below.

[table 4]

	Solution is 1.	Solution is 2.	Solution is 3.
				N,N-dimethylacetamide	50 parts
1,3-dimethyl-2-imidazoline		50 parts	60 parts
				Hexalin	50 parts	50 parts	40 parts
Rhodamine B	1%	1%	1%

[wettability evaluation]

Ink-jet printing apparatus (ULVAC company Litlex120L) is used, by the solution of above-mentioned record, with often in next door 200pL is filled in the mode in the next door at 1000 and is filled in each next door, uses microscope (OLIMPUS company system after drying MX61L, eyeglass LCPFLN20xLCD), carry out whether solute at 30 diffuses to the observation of end, next door.Whole shown in table 4 In solution, when all spreading at 30, wettability is well zero, beyond it be ×.Result such as table 5.

[table 5]

Embodiment 1

Embodiment 2

Embodiment 3

Embodiment 4

Comparative example 1

Comparative example 2

Comparative example 3

Contact angle

23

25

27

33

31

52

30

Wettability

○

×

X

×

From embodiment result, the photosensitive polymer combination of the present invention can get and do not produce ink liquid colour mixture in maintenance Contact angle in the case of the excellent film of wettability and pattern.

Industry utilizability

According to the photosensitive polymer combination of the present invention, can get the excellent pattern of wettability, i.e. with next door and substrate institute The pattern that high and next door upper surface the lyophobicity of the wettability of the recess substrate surface that zoning goes out is high.

Symbol description

1 display device

2 supporting substrates

3 next doors

4 organic EL element

5 recesses

6 the 1st electrodes

7 the 1st organic EL layers (hole injection layer)

9 the 2nd organic EL layers (luminescent layer)

10 the 2nd electrodes

Claims

1. a photosensitive polymer combination, it contains (A), (B), (C) and (D), and the content of (A) is relative to (A) and (C) Adding up to content is below more than 45 mass % 80 mass %,

(A) containing being derived from the construction unit of the aromatic carboxylic acid with ethylenic unsaturated bond, being derived from there is the ring-type of carbon number 2～4 The construction unit of the unsaturated compound of ether structure, and not there is the polymerization of the construction unit of perfluoroalkyl containing carbon number 4～6 Thing,

(B) containing have carbon number 4～6 perfluoroalkyl construction unit polymer,

(C) polymerizable compound,

(D) polymerization initiator.

2. photosensitive polymer combination as claimed in claim 1, wherein (D) is for containing choosing free united imidazole, alkyl The polymerization initiator of at least one in the group that phenyl ketone compound and O-acyl group oxime compound are formed.

3. a pattern, it is formed by the photosensitive polymer combination described in claim 1 or 2.

4. an ink-jet next door, it is formed by the photosensitive polymer combination described in claim 1 or 2.

5. a display device, it comprises the pattern described in claim 3.

6. a display device, it comprises the ink-jet next door described in claim 4.