CN102445844B

CN102445844B - Photosensitive composition

Info

Publication number: CN102445844B
Application number: CN201110292441.XA
Authority: CN
Inventors: 宫芳子; 三浦洋之; 白川政和
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2010-10-05
Filing date: 2011-09-30
Publication date: 2016-09-28
Anticipated expiration: 2031-09-30
Also published as: KR20120035868A; JP5892760B2; TWI570509B; KR101777426B1; TW201232174A; JP2012098711A; CN102445844A

Abstract

Offer can obtain the photosensitive composition of the good pattern of resolution, this photosensitive composition, containing (A), (B1), (B2), (C), and (E) (D), (A) coloring agent, (B1) containing coming from the construction unit of at least one selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides, with come from the monomer with cyclic ether that carbon number is 2～4 and ethylenic unsaturated bond construction unit copolymer (wherein, side chain does not have ethylenic unsaturated bond), (B2) side chain has the resin of ethylenic unsaturated bond, (C) polymerizable compound, (D) polymerization initiator, (E) solvent.

Description

Photosensitive composition

Technical field

The present invention relates to suitably form the color-patch map constituting the color filter used in liquid crystal display cells, solid-state imager The photosensitive composition of picture.

Background technology

The color filter used in the display devices such as display panels, electroluminescence panel, plasma display can Photosensitive composition is used to manufacture.As this photosensitive composition, it is known to following compositions, It contains pigment, resin, photopolymerizable compound, Photoepolymerizationinitiater initiater and solvent, and resin is methacrylic acid and have epoxy The copolymer (patent documentation 1) of the unsaturated compound of ethyl group.

Patent documentation 1: Japanese Unexamined Patent Publication 2007-333847 publication.

Summary of the invention

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

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

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

(A) coloring agent,

(B1) containing coming from the construction unit of at least one selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides, and come from (wherein, side chain is not to have the copolymer of construction unit of the monomer of cyclic ether that carbon number is 2～4 and ethylenic unsaturated bond There is ethylenic unsaturated bond),

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

(C) polymerizable compound,

(D) polymerization initiator,

(E) solvent.

[2] above-mentioned [1] photosensitive composition recorded, wherein, (B2) obtains with (c) copolymerization for making following (a) To copolymer further with (b) reaction and the resin that obtains,

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

(b): there is cyclic ether and the monomer of ethylenic unsaturated bond that carbon number is 2～4,

(c): having can be with the monomer of the unsaturated bond of (a) and (b) copolymerization.

The photosensitive composition that [2-2] above-mentioned [1] is recorded, wherein, (B2) is for making following (a) and (c) copolymerization The resin that the copolymer obtained reacts with (b) further and obtains,

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

[3] photosensitive composition that above-mentioned [1] or [2] are recorded, wherein, the content of (B1), relative to (B1) (B2) total amount, is 10 mass %～95 mass %.

[4] pattern, its photosensitive composition recorded by any one in above-mentioned [1]～[3] is formed.

[5] color filter, it contains the pattern that above-mentioned [4] are recorded.

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

(1) by the photosensitive composition that any one in above-mentioned [1]～[3] is recorded is coated on substrate On obtain the step of coated film,

(2) coated film is exposed via mask, the step of coated film after thus being exposed,

(3) after exposing, coated film alkaline developer develops, and thus obtains the step of pattern,

(4) pattern is bakeed, thus obtain the step of the pattern of solidification.

[7] manufacture method of above-mentioned [6] color filter recorded, wherein, step (4) is at a temperature of 25 DEG C～120 DEG C Carry out the step bakeed.

The manufacture method of the color filter that [8] above-mentioned [6] or [7] are recorded, wherein, the substrate in step (1) is plastics base Plate.

[invention effect]

According to the photosensitive composition of the present invention, the pattern that resolution is good can be obtained.

Detailed description of the invention

The photosensitive composition of the present invention, containing coloring agent (A), resin (B), polymerizable compound (C), gathers Closing initiator (D) and solvent (E), resin (B) is for containing

(B1) containing coming from the construction unit of at least one selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides, and come from (wherein, side chain is not to have the copolymer of construction unit of the monomer of cyclic ether that carbon number is 2～4 and ethylenic unsaturated bond There is ethylenic unsaturated bond) (hereinafter sometimes referred to " resin (B1) "), and

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

The photosensitive composition of the present invention contains coloring agent (A).As coloring agent (A), pigment can be enumerated And dyestuff, but from the standpoint of thermostability, light resistance, preferably comprise pigment.

As pigment, organic pigment and inorganic pigment can be enumerated, can enumerate at Colour Index (The Society of Dyers and Colourists publishes) in be categorized as the compound of pigment.

As organic pigment, specifically, such as C.I. pigment yellow 1, C.I. pigment yellow 3, C.I. pigment yellow can be enumerated 12, C.I. pigment yellow 13, C.I. pigment Yellow 14, C.I. pigment yellow 15, C.I. pigment yellow 16, C.I. pigment yellow 17, C.I. pigment Huang 20, C.I. pigment yellow 24, C.I. pigment yellow 31, C.I. pigment yellow 53, C.I. pigment yellow 83, C.I. pigment yellow 86, C.I. face Material is yellow 93, C.I. pigment yellow 94, C.I. pigment yellow 109, C.I. pigment yellow 110, C.I. pigment yellow 117, C.I. pigment Yellow 12 5, C.I. pigment Yellow 12 8, C.I. pigment yellow 13 7, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 147, C.I. face Material Huang 148, C.I. pigment yellow 150, C.I. pigment yellow 153, C.I. pigment yellow 154, C.I. pigment yellow 166, C.I. pigment yellow 173, the yellow uitramarine such as C.I. pigment yellow 194, C.I. pigment yellow 214,

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

C.I. Pigment Red 9, C.I. Pigment Red 97, C.I. paratonere 105, C.I. pigment red 122, C.I. pigment red 123, C.I. paratonere 144, C.I. pigment red 149, C.I. paratonere 166, C.I. paratonere 168, C.I. paratonere 176, C.I. face Expect red 177, C.I. paratonere 180, C.I. paratonere 192, C.I. paratonere 209, C.I. pigment red 21 5, C.I. paratonere 216, C.I. paratonere 224, C.I. paratonere 242, C.I. paratonere 254, C.I. paratonere 255, C.I. paratonere 264, C.I. the red pigment such as paratonere 265,

C.I. pigment blue 15, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6, C.I. alizarol saphirol 60 blue pigments such as grade,

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

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

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

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

Wherein, preferably C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. paratonere 177, C.I. paratonere 242, C.I. paratonere 254, C.I. pigment purple 23, C.I. pigment blue 15: 3, C.I. pigment blue 15: 6 and C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 58.These pigment can individually or mix two or more and use.

Above-mentioned pigment, as required, it is possible to implement Colophonium processes, uses the pigment being imported with acidic-group or basic group The surface that derivant, pigment dispersing agent etc. are carried out processes, and the grafting carried out surface of pigments by macromolecular compound etc. is processed, The micronized carried out by sulfuric acid particles method etc. is processed, or utilizes what organic solvent, water etc. carried out to wash for remove impurity Wash process, ionic impurity utilize the removing process etc. that ion exchange etc. carries out.Additionally, pigment preferable particle size is homogeneous.Logical Cross and carry out dispersion process containing pigment dispersing agent, the pigment dispersion of the most uniformly dispersing state of pigment can be obtained Liquid.

As above-mentioned pigment dispersing agent, it is possible to use commercially available surfactant.As surfactant, example can be enumerated Such as type siloxane, fluorine class, esters, cationic, anionic species, nonionic class, both sexes, polyesters, many amines and acrylic acid The surfactant of class.As above-mentioned surfactant, except polyoxyethylene alkyl ether class, polyoxyethylene alkyl phenyl ether class, Polyethylene glycol di class, sorbitan fatty acid esters class, fatty acid modified polyesters, tertiary-amine modified polyurethanes, poly-second Outside alkene imines etc., it is also possible to enumerate the KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system) with trade name name, Off ロレ Application (common prosperity Society chemistry (strain) system), ソ Le スパス (ゼネカ (strain) system), EFKA (CIBA society system), アジスパ (gourmet powder Off ァイ Application テ Network ノ (strain) makes), Disperbyk (PVC ッ Network ケミ society system) etc..They can individually or combine two or more come Use.

When using pigment dispersing agent, its consumption is relative to the weight of pigment, below preferably 100 mass %, and more preferably 5 ～50 mass %.If the consumption of pigment dispersing agent in above-mentioned scope, then has the becoming of dispersible pigment dispersion obtaining homogeneous dispersity Gesture.

The content of coloring agent (A), relative to the amount of the solid composition of photosensitive composition, preferably 5～60 Quality %, more preferably 5～45 mass %.If the content of coloring agent (A) in above-mentioned scope, then can obtain required light splitting, face Colour saturation.Wherein, the solid composition in this specification refers to be removed solvent by photosensitive composition and obtain The total amount of composition.

The photosensitive composition of the present invention contains the resin (B) of resinous (B1).Resin (B1) is containing active In the construction unit of at least one (hereinafter sometimes referred to " (a) ") selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides, and come from There is the construction unit of the monomer (hereinafter sometimes referred to " (b) ") of cyclic ether that carbon number is 2～4 and ethylenic unsaturated bond Copolymer (wherein, side chain does not have ethylenic unsaturated bond).

Contain resin (B1) by photosensitive composition, there is the thermostability of the pattern of gained, resistance to chemical reagents The best trend is become etc. reliability.

As resin (B1), can enumerate such as,

Resin (B1-1): the copolymer that (a) and (b) are polymerized, and

Resin (B1-2): by (a), (b) with have can be (following with the monomer (c) of the unsaturated bond of (a) and (b) copolymerization It is sometimes referred to as " (c) ") copolymer that is polymerized.As resin (B1), it is preferably (B1-1).

As (a), specifically, acrylic acid, methacrylic acid .beta.-methylacrylic acid, adjacent vinyl benzoic acid, a second can be enumerated Alkenyl benzene formic acid, to unsaturated monocarboxylic classes such as vinyl benzoic acids,

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalandione, 4-vinylphthalic acid, 3, 4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid, 1,4-ring The unsaturated dicarboxylic classes such as hexene dicarboxylic acid,

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

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

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

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

Wherein, acrylic acid, methacrylic acid, maleic anhydride etc. are examined from the viewpoint of the viewpoint of copolyreaction, alkali-solubility Worry is preferably used.

Wherein, in this specification, " (methyl) acrylic acid " represents at least one in acrylic acid and methacrylic acid. The statement of " (methyl) acryloyl group " and " (methyl) acrylate " etc. has same meaning.

As (b), can enumerate and such as there is the monomer (b-1) of Oxyranyle and ethylenic unsaturated bond (the most sometimes Referred to as " (b-1) "), there is monomer (b-2) (hereinafter sometimes referred to " (b-2) ") and the tool of oxetanylmethoxy and ethylenic unsaturated bond There is the monomer (b-3) (hereinafter sometimes referred to " (b-3) ") of tetrahydrofuran base and ethylenic unsaturated bond.

As (b-1), can enumerate and such as have the structure of chain type alkene epoxidation and ethylenic unsaturated bond Monomer (b-11) (hereinafter sometimes referred to " (b-11) ") and having the structure of cycloolefin epoxidation and ethylenic unsaturated bond Monomer (b-12) (hereinafter sometimes referred to " (b-12) ").

As (b-1), it is however preferred to have Oxyranyle and the monomer of (methyl) acryloxy, more preferably have There is (b-12) of (methyl) acryloxy.

As (b-11), specifically, (methyl) glycidyl acrylate, (methyl) propenoic acid beta-first can be enumerated Base glycidyl esters, (methyl) propenoic acid beta-ethyl glycidyl base ester, glycidyl vinyl ether, adjacent vinyl benzyl Glycidyl ether, a vinylbenzyl glycidyl base ether, to vinylbenzyl glycidyl base ether, Alpha-Methyl-neighbour's ethylene Base benzyl glycidyl ether, an Alpha-Methyl-vinylbenzyl glycidyl base ether, Alpha-Methyl-vinyl benzyl is shunk sweet Double (glycidyl oxy methyl) styrene of oleyl ether, 2,3-, 2,4-double (glycidyl oxy methyl) styrene, 2,5- Double (glycidyl oxy methyl) styrene of double (glycidyl oxy methyl) styrene, 2,6-, 2,3,4-tri-(shrink sweet Oil base epoxide methyl) styrene, 2,3,5-tri-(glycidyl oxy methyl) styrene, 2,3,6-tri-(glycidyl oxygen Ylmethyl) styrene, 3,4,5-tri-(glycidyl oxy methyl) styrene, 2,4,6-tri-(glycidyl oxy methyl) Compound etc. described in styrene, Japanese Unexamined Patent Publication 7-248625 publication.

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

[in formula (I) and formula (II), R¹And R²Represent hydrogen atom or the alkyl that carbon number is 1～4 independently of each other, should The hydrogen atom contained in alkyl can be optionally substituted by a hydroxyl group.

X¹And X²Represent singly-bound ,-R independently of each other³-, *-R³-O-, *-R³-S-, *-R³-NH-。

R³Represent the alkane diyl that carbon number is 1～6.

* represent with O be bonded key.]

As the alkyl that carbon number is 1～4, specifically, methyl, ethyl, n-pro-pyl, isopropyl, just can be enumerated Butyl, sec-butyl, the tert-butyl group etc..

As hydroxy alkyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxyl can be enumerated Propyl group, 3-hydroxypropyl, 1-hydroxyl-1-Methylethyl, 2-hydroxyl-1-Methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3- Hydroxybutyl, 4-hydroxybutyl etc..

As R¹And R², preferably enumerate hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, more preferably lift Go out hydrogen atom, methyl.

As alkane diyl, methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, fourth can be enumerated Alkane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl etc..

As X¹And X², preferably enumerate singly-bound, methylene, ethylene, *-CH₂-O-(* represent with O be bonded key) Base, *-CH₂CH₂-O-base, more preferably enumerates singly-bound, *-CH₂CH₂-O-base.

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

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

Compound shown in formula (I) and the compound shown in formula (II) can individually use.Additionally, they can also Mix with arbitrary ratio.During mixing, its blending ratio, according to mol ratio, preferably formula (I): formula (II) is 5:95～95:5, more excellent Elect 10:90～90:10 as, particularly preferably 20:80～80:20.

As (b-2), it is however preferred to have oxetanylmethoxy and the monomer of (methyl) acryloxy.As (b-2), permissible Enumerate such as 3-methyl-3-(methyl) acryloyloxymethyl oxetanes, 3-ethyl-3-(methyl) acryloyloxymethyl Oxetanes, 3-methyl-3-(methyl) acryloyl-oxyethyl oxetanes and 3-ethyl-3-(methyl) acryloxy Ethyloxetane.

As (b-3), more preferably there is the monomer of tetrahydrofuran base and (methyl) acryloxy.As (b-3), tool Say body, acrylic acid tetrahydro furfuryl ester (such as PVC ス U ト V#150, Osaka Organic Chemical Industry (strain) system), first can be enumerated Base acrylic acid tetrahydro furfuryl ester etc..

As (c), (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) acrylic acid can enumerated such as just (methyl) alkyl-acrylates such as butyl ester, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate,

(methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methyl cyclohexyl, (methyl) acrylic acid three ring [5.2.1.0² ^,6] decane-8-base ester (in this technical field, as trivial name, be referred to as (methyl) acrylic acid Bicvclopentyl ester), (methyl) propylene Acid (methyl) acrylic acid cyclic alkyl esters such as Bicvclopentyl epoxide ethyl ester, (methyl) isobornyl acrylate,

(methyl) benzyl acrylate or the aralkyl esters such as (methyl) phenyl acrylate, (methyl) benzyl acrylate,

The dicarboxylic diesters such as ethyl maleate., DEF, diethyl itaconate,

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

Dicyclo [2.2.1] hept-2-ene", 5-methyl bicycle [2.2.1] hept-2-ene", 5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxyl dicyclo [2.2.1] hept-2-ene", 5-hydroxymethyl dicyclo [2.2.1] hept-2-ene", 5-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5-methoxyl group dicyclo [2.2.1] hept-2-ene", 5-ethyoxyl dicyclo [2.2.1] hept-2-ene", 5,6-dihydroxy Base dicyclo [2.2.1] hept-2-ene", 5,6-bis-(hydroxymethyl) dicyclo [2.2.1] hept-2-ene", 5,6-bis-(2 '-hydroxyethyl) are double Ring [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- Alkene, 5-hydroxy-5-methyl base dicyclo [2.2.1] hept-2-ene", 5-hydroxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxyl first Base-5-methyl bicycle [2.2.1] hept-2-ene", 5-tert-butoxycarbonyl dicyclo [2.2.1] hept-2-ene", 5-cyclohexyloxy carbonyl are double Double (tert-butoxycarbonyl) dicyclo of ring [2.2.1] hept-2-ene", 5-phenyloxycarbonyl dicyclo [2.2.1] hept-2-ene", 5,6- [2.2.1] hept-2-ene", 5, the dicyclo unsaturated compound class such as double (cyclohexyloxy carbonyl) dicyclo [2.2.1] hept-2-ene"s of 6-,

N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, N-succinimido- 3-maleimidobenzoyl ester, N-succinimido-4-malimidobutanoate, N-succinimido-6-Malaysia The dicarbapentaborane such as acid imide alkyl caproate, N-succinimido-3-maleimidopropionic acid ester, N-(9-acridinyl) maleimide Imide derivative class,

Styrene, α-methyl styrene, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxybenzene second Alkene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1,3- Butadiene, isoprene and 2,3-dimethyl-1,3-butadiene etc..

Wherein, styrene, N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, dicyclo [2.2.1] hept-2-ene"s etc. are preferred from the viewpoint of copolyreaction and alkali-solubility.

In resin (B1-1), as the ratio of the construction unit coming from each monomer, relative to the knot constituting resin (B1-1) The total mole number of structure unit, preferably in following scope.

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

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

If the ratio of the construction unit of resin (B1-1) is in above-mentioned scope, then there is storage stability, developability, solvent resistant Property, thermostability and mechanical strength become good trend.

Being the resin of (b-1) as resin (B1-1), preferably (b), more preferably (b-1) is the resin of (b-12).

Resin (B1-1) is such as referred to document " Polymer Synthesizing method ", and (the grand row in big Tianjin writes sale room (strain) Chemistry is with people the 1st edition the 1st printing distribution on March 1st, 1972) described in method and citation described in the document Offer and prepare.

Specifically, can enumerate and (a) and the ormal weight of (b), polymerization initiator and solvent etc. are joined reaction vessel In, utilize nitrogen to replace oxygen, thus carry out deoxidation, and the method being stirred, heating, be incubated.And, to the polymerization wherein used Initiator and solvent etc. without particular limitation of, it is possible to use normally used arbitrary polymerization initiator and solvent in this field.Make For polymerization initiator, can enumerate such as azo-compound (2,2 '-azobis isobutyronitrile, 2, double (2, the 4-dimethyl of 2 '-azo Valeronitrile) etc.) and organic peroxide (benzoyl peroxide etc.), as solvent, as long as the solvent of each monomer of solubilized, The solvent of photosensitive composition can use solvent described later etc..

And, obtained copolymer can directly use reacted solution, it is possible to use concentrate or dilute molten Liquid, it is also possible to use the copolymer taken out by methods such as reprecipitations in solid (powder) mode.Particularly during this polymerization, as Solvent, by using the solvent identical with solvent described later (E), can directly use reacted solution, such that it is able to simplify Preparation process.

In resin (B1-2), as the ratio of the construction unit coming from each monomer, relative to constituting the complete of resin (B1-2) The total mole number of portion's construction unit, preferably in following scope.

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

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

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

If the ratio of the construction unit of resin (B1-2) is in above-mentioned scope, then there is storage stability, developability, solvent resistant Property, thermostability and mechanical strength become good trend.

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

Resin (B1-2) can be prepared by the method identical with resin (B1-1).

The weight average molecular weight (Mw) of the polystyrene conversion of resin (B1) is preferably 3000～100000, more preferably 5000 ～50000.If the weight average molecular weight of resin (B1) is in above-mentioned scope, then there is the trend that coating becomes good, additionally, development Time be difficult to produce film and reduce, and then during development, there is the trend that the deciduous of non-pixel portion becomes good.

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

The acid number of resin (B1) is 20～150mg-KOH/g, preferably 30～135mg-KOH/g, more preferably 40～ 125mg-KOH/g.Wherein, acid number is as measuring for neutralizing the amount (mg) of resin (B1) 1g and required potassium hydroxide Value, can try to achieve by using potassium hydroxide aqueous solution to carry out titration.

The content of resin (B1), relative to resin (B1) and the total amount of resin (B2), preferably 10～95 mass %, more excellent Elect 10～85 mass %, particularly preferably 10～80 mass % as.If the content of resin (B1) is in above-mentioned scope, then developability, close Conjunction property, solvent resistance, mechanical property have the trend becoming good.

The resin (B) contained in the photosensitive composition of the present invention contains resin (B2) further.Resin (B2) for having the resin of ethylenic unsaturated bond at side chain, can enumerate the copolymer making (a) and (c) copolymerization obtain further with B resin (B2-1) that () is reacted and obtained, the tree that the copolymer making (b) and (c) copolymerization obtain reacts with (a) further and obtains Fat (B2-2) etc..Wherein, as resin (B2), preferably resin (B2-1).

As (a), (b) and (c) of composition resin (B2), the material identical with above-mentioned resin (B1) can be enumerated, as C (), particularly preferably has at least one skeleton selected from tricyclodecane skeleton and tricyclo decene skeleton and ethylenic unsaturated bond Compound (c1) (hereinafter sometimes referred to " (c1) ").C () is (c1) in the case of, the figure caused due to development can be suppressed The film of case reduces.

Wherein, " tricyclodecane skeleton " in this specification and " tricyclo decene skeleton " refer respectively to following structure (in Ge Zi, arbitrary carbon atom has bonding key).

As (c1), specifically, (methyl) acrylic acid Bicvclopentyl ester, (methyl) acrylic acid dicyclo amylene can be enumerated Base ester, (methyl) acrylic acid Bicvclopentyl epoxide ethyl ester, (methyl) acrylic acid double cyclopentenyl epoxide ethyl ester.They are permissible Individually or two or more combination uses.

Resin (B2-1) and resin (B2-2) such as can be prepared through two stage step.At this point it is possible to reference to upper (the grand row in big Tianjin writes sale room (strain) chemistry with the 1st edition the 1st printing 1972 of people to state document " Polymer Synthesizing method " Distribution on March 1) described in method, prepared by method etc. described in Japanese Unexamined Patent Publication 2001-89533 publication.

For resin (B2-1), first as the first stage, obtain in the same manner as the preparation method of above-mentioned resin (B1-1) The copolymer of (a) and (c).

Now, as described above, the copolymer of gained, can directly use reacted solution, it is possible to use dense Contracting or the solution of dilution, it is also possible to use the copolymer obtained by methods such as reprecipitations in solid (powder) mode.

As the ratio of the construction unit coming from (a) and (c), relative to the entire infrastructure unit constituting above-mentioned copolymer Total mole number, preferably in following scope.

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

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

Then, as second stage, the part coming from the carboxylic acid of (a) of the copolymer of gained and carboxylic acid anhydrides and (b) are made Cyclic ether reaction.The reactive height of cyclic ether, it is difficult to (b) of remained unreacted, accordingly, as (b), is preferably (b-1), enters One step is preferably (b-11).

Specifically, after the above, atmosphere in flask is replaced into air by nitrogen, adds relative to (a) in flask (b) that molal quantity is 5～80 moles of %, relative to (a), (b) and (c) the carboxyl that total amount is 0.001～5 mass % with ring-type The catalysts (such as three (dimethylaminomethyl) phenol) of ether, it is 0.001～5 relative to the total amount of (a), (b) and (c) The polymerization inhibitor (such as hydroquinone) of quality %, reacts 1～10 hour at 60～130 DEG C, can obtain resin (B2-1).And And, in the same manner as polymerizing condition, it is contemplated that Preparation equipment, the thermal discharge etc. that caused of polymerization, can suitably adjust adding method, Reaction temperature.

Additionally, now, the molal quantity of (b), relative to the molal quantity of (a), preferably 10～75 moles %, more preferably 15 ～70 moles of %.By making the molal quantity of (b) in this scope, the balance of storage stability, solvent resistance and thermostability has and becomes good Good trend.

As the concrete example of resin (B2-1), can enumerate and make (methyl) acrylic acid/(methyl) acrylic acid Bicvclopentyl ester Copolymer react with (methyl) glycidyl acrylate and obtain resin, make (methyl) acrylic acid/(methyl) propylene Resin that the copolymer of acid benzyl ester reacts with (methyl) glycidyl acrylate and obtains, make (methyl) acrylic acid/(first Base) copolymer of cyclohexyl acrylate react with (methyl) glycidyl acrylate and obtain resin, make (methyl) Resin that the copolymer of acrylic/styrene reacts with (methyl) glycidyl acrylate and obtains, make (methyl) propylene Resin that the copolymer of acid/(methyl) acrylic acid methyl ester. reacts with (methyl) glycidyl acrylate and obtains, make (first Base) copolymer of the acrylic acid/N-N-cyclohexylmaleimide tree that reacts with (methyl) glycidyl acrylate and obtain Fat, the copolymer of .beta.-methylacrylic acid/(methyl) acrylic acid Bicvclopentyl ester is made to react with (methyl) glycidyl acrylate and obtain The resin arrived,

The copolymer making .beta.-methylacrylic acid/(methyl) benzyl acrylate reacts with (methyl) glycidyl acrylate and obtains To resin, make the copolymer of .beta.-methylacrylic acid/(methyl) cyclohexyl acrylate react with (methyl) glycidyl acrylate And the resin obtained, make the tree that .beta.-methylacrylic acid/cinnamic copolymer reacts with (methyl) glycidyl acrylate and obtain Fat, make resin that the copolymer of .beta.-methylacrylic acid/Methyl crotonate reacts with (methyl) glycidyl acrylate and obtain, make bar The resin that the copolymer of bean acid/N-N-cyclohexylmaleimide reacts with (methyl) glycidyl acrylate and obtains,

The copolymer making maleic acid/(methyl) acrylic acid Bicvclopentyl ester reacts with (methyl) glycidyl acrylate And the resin obtained, make maleic acid/(methyl) benzyl acrylate copolymer anti-with (methyl) glycidyl acrylate The resin answered and obtain, copolymer and (methyl) glycidyl base of making maleic acid/(methyl) cyclohexyl acrylate Ester reaction and obtain resin, make maleic acid/cinnamic copolymer react with (methyl) glycidyl acrylate and obtain To resin, make the tree that the copolymer of maleic acid/methyl maleate reacts with (methyl) glycidyl acrylate and obtain Fat, the copolymer of maleic acid/N-N-cyclohexylmaleimide is made to react with (methyl) glycidyl acrylate and obtain Resin,

Make copolymer and (methyl) acrylic acid of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid Bicvclopentyl ester Glycidyl esters reaction and the resin obtained, the copolymerization that makes (methyl) acrylic acid/maleic anhydride/(methyl) benzyl acrylate Resin that thing reacts with (methyl) glycidyl acrylate and obtains, make (methyl) acrylic acid/maleic anhydride/(methyl) third Resin that the copolymer of olefin(e) acid cyclohexyl ester reacts with (methyl) glycidyl acrylate and obtains, make (methyl) propylene Resin that acid/maleic anhydride/cinnamic copolymer reacts with (methyl) glycidyl acrylate and obtains, make (methyl) The copolymer of acrylic acid/maleic anhydride/(methyl) acrylic acid methyl ester. reacts with (methyl) glycidyl acrylate and obtains Resin, make the copolymer of (methyl) acrylic acid/maleic anhydride/N-N-cyclohexylmaleimide shrink sweet with (methyl) acrylic acid The resin that oil base ester reacts and obtains,

Make copolymer and the methacrylic acid 3,4-epoxy hexamethylene of (methyl) acrylic acid/(methyl) acrylic acid Bicvclopentyl ester Ylmethyl ester reacts and the resin obtained, the copolymer making (methyl) acrylic acid/(methyl) benzyl acrylate and metering system Acid 3,4-epoxycyclohexyl-methyl ester reaction and obtain resin, make (methyl) acrylic acid/(methyl) cyclohexyl acrylate Resin that copolymer reacts with methacrylic acid 3,4-epoxycyclohexyl-methyl ester and obtains, make (methyl) acrylic/styrene Copolymer react with methacrylic acid 3,4-epoxycyclohexyl-methyl ester and obtain resin, make (methyl) acrylic acid/(first Base) copolymer of acrylic acid methyl ester. react with methacrylic acid 3,4-epoxycyclohexyl-methyl ester and obtain resin, make (first Base) copolymer of acrylic acid/N-N-cyclohexylmaleimide reacts with methacrylic acid 3,4-epoxycyclohexyl-methyl ester and obtains The resin arrived,

Make copolymer and the methacrylic acid 3,4-epoxycyclohexyl-methyl of .beta.-methylacrylic acid/(methyl) acrylic acid Bicvclopentyl ester The resin that ester reacts and obtains, the copolymer making .beta.-methylacrylic acid/(methyl) benzyl acrylate and methacrylic acid 3,4-epoxide ring Hexyl methyl ester reacts and the resin obtained, the copolymer making .beta.-methylacrylic acid/(methyl) cyclohexyl acrylate and methacrylic acid The reaction of 3,4-epoxycyclohexyl-methyl ester and obtain resin, make .beta.-methylacrylic acid/cinnamic copolymer and methacrylic acid 3,4- The resin that epoxycyclohexyl-methyl ester reacts and obtains, the copolymer making .beta.-methylacrylic acid/Methyl crotonate and methacrylic acid 3,4- Epoxycyclohexyl-methyl ester reacts and the resin obtained, the copolymer making .beta.-methylacrylic acid/N-N-cyclohexylmaleimide and methyl-prop Olefin(e) acid 3, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains,

Make copolymer and the methacrylic acid 3,4-epoxycyclohexyl-methyl of maleic acid/(methyl) acrylic acid Bicvclopentyl ester The resin that ester reacts and obtains, the copolymer making maleic acid/(methyl) benzyl acrylate and methacrylic acid 3,4-epoxide ring Hexyl methyl ester reacts and the resin obtained, the copolymer making maleic acid/(methyl) cyclohexyl acrylate and methacrylic acid The reaction of 3,4-epoxycyclohexyl-methyl ester and obtain resin, make maleic acid/cinnamic copolymer and methacrylic acid 3,4- The resin that epoxycyclohexyl-methyl ester reacts and obtains, the copolymer making maleic acid/methyl maleate and methacrylic acid 3,4- Epoxycyclohexyl-methyl ester reacts and the resin obtained, the copolymer making maleic acid/N-N-cyclohexylmaleimide and methyl-prop Olefin(e) acid 3, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains,

Make copolymer and the methacrylic acid 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid Bicvclopentyl ester, 4-epoxycyclohexyl-methyl ester reaction and obtain resin, make (methyl) acrylic acid/maleic anhydride/(methyl) benzyl acrylate Copolymer react with methacrylic acid 3,4-epoxycyclohexyl-methyl ester and obtain resin, make (methyl) acrylic acid/Malaysia The copolymer of anhydride/(methyl) cyclohexyl acrylate reacts with methacrylic acid 3,4-epoxycyclohexyl-methyl ester and obtains Resin, make (methyl) acrylic acid/maleic anhydride/cinnamic copolymer anti-with methacrylic acid 3,4-epoxycyclohexyl-methyl ester The resin answered and obtain, the copolymer and the methacrylic acid 3 that make (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid methyl ester., 4-epoxycyclohexyl-methyl ester reaction and obtain resin, make (methyl) acrylic acid/maleic anhydride/N-N-cyclohexylmaleimide Copolymer react with methacrylic acid 3,4-epoxycyclohexyl-methyl ester and the resin etc. that obtains.

Further, as resin (B2-1), more preferably make what (c) copolymerization beyond (a), (c1) and (c1) obtained to be total to The resin that polymers reacts with (b) and obtains.By making resin (B2-1) be above-mentioned composition, the pattern existence of gained is close with substrate Conjunction property and the trend of excellent solvent resistance.

When the copolymer of () and (c) comprises (c) beyond (a), (c1) and (c1) a, come from (c) beyond (c1) and (c1) The ratio of construction unit be preferably 10:90～60:40, more preferably 10:90～40:60, more preferably 10:90～ 30:70。

The resin reacted with (b) as the copolymer making (c) copolymerization beyond (a), (c1) and (c1) obtain and obtain, tool Say body, the copolymerization making (methyl) acrylic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate can be enumerated Resin that thing reacts with (methyl) glycidyl acrylate and obtains, make (methyl) acrylic acid/(methyl) acrylic acid dicyclo The tree that the copolymer of amyl group ester/(methyl) cyclohexyl acrylate reacts with (methyl) glycidyl acrylate and obtains Fat, make (methyl) acrylic acid/(methyl) acrylic acid Bicvclopentyl ester/cinnamic copolymer and (methyl) glycidyl Base ester reaction and obtain resin, make (methyl) acrylic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) acrylic acid methyl ester. Resin that copolymer reacts with (methyl) glycidyl acrylate and obtains, make (methyl) acrylic acid/(methyl) acrylic acid The tree that the copolymer of Bicvclopentyl ester/N-N-cyclohexylmaleimide reacts with (methyl) glycidyl acrylate and obtains Fat,

Make copolymer and (methyl) third of .beta.-methylacrylic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate Olefin(e) acid glycidyl esters reaction and obtain resin, make .beta.-methylacrylic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) acrylic acid Resin that the copolymer of cyclohexyl ester reacts with (methyl) glycidyl acrylate and obtains, make .beta.-methylacrylic acid/(methyl) third Resin that olefin(e) acid Bicvclopentyl ester/cinnamic copolymer reacts with (methyl) glycidyl acrylate and obtains, make bar The copolymer of bean acid/(methyl) acrylic acid Bicvclopentyl ester/Methyl crotonate reacts with (methyl) glycidyl acrylate And the resin obtained, the copolymer making .beta.-methylacrylic acid/(methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide and (first Base) glycidyl acrylate reaction and the resin that obtains,

Make copolymer and (methyl) third of maleic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate Olefin(e) acid glycidyl esters reaction and obtain resin, make maleic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) acrylic acid Resin that the copolymer of cyclohexyl ester reacts with (methyl) glycidyl acrylate and obtains, make maleic acid/(methyl) third Resin that olefin(e) acid Bicvclopentyl ester/cinnamic copolymer reacts with (methyl) glycidyl acrylate and obtains, make horse The copolymer carrying out sour/(methyl) acrylic acid Bicvclopentyl ester/methyl maleate reacts with (methyl) glycidyl acrylate And the resin obtained, the copolymer making maleic acid/(methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide and (first Base) glycidyl acrylate reaction and the resin that obtains,

Make being total to of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate Resin that polymers reacts with (methyl) glycidyl acrylate and obtains, make (methyl) acrylic acid/maleic anhydride/(methyl) The copolymer of acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate and (methyl) glycidyl acrylate react and The resin that obtains, make (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid Bicvclopentyl ester/cinnamic copolymer and (first Base) glycidyl acrylate reaction and obtain resin, make (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid double Resin that the copolymer of cyclopentyl ester/(methyl) acrylic acid methyl ester. reacts with (methyl) glycidyl acrylate and obtains, Make the copolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide with The resin that (methyl) glycidyl acrylate reacts and obtains,

Make copolymer and the first of (methyl) acrylic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate Base acrylic acid 3,4-epoxycyclohexyl-methyl ester reaction and obtain resin, make (methyl) acrylic acid/(methyl) acrylic acid dicyclo The copolymer of amyl group ester/(methyl) cyclohexyl acrylate reacts with methacrylic acid 3,4-epoxycyclohexyl-methyl ester and obtains Resin, make (methyl) acrylic acid/(methyl) acrylic acid Bicvclopentyl ester/cinnamic copolymer and methacrylic acid 3,4-ring Oxygen cyclohexyl methyl ester reaction and obtain resin, make (methyl) acrylic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) third Resin that the copolymer of e pioic acid methyl ester reacts with methacrylic acid 3,4-epoxycyclohexyl-methyl ester and obtains, make (methyl) propylene The copolymer of acid/(methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide and methacrylic acid 3,4-epoxy hexamethylene The resin that ylmethyl ester reacts and obtains,

Make copolymer and the metering system of .beta.-methylacrylic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate Acid 3,4-epoxycyclohexyl-methyl ester reaction and obtain resin, make .beta.-methylacrylic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) Resin that the copolymer of cyclohexyl acrylate reacts with methacrylic acid 3,4-epoxycyclohexyl-methyl ester and obtains, make Fructus Crotonis Acid/(methyl) acrylic acid Bicvclopentyl ester/cinnamic copolymer reacts with methacrylic acid 3,4-epoxycyclohexyl-methyl ester And the resin obtained, the copolymer making .beta.-methylacrylic acid/(methyl) acrylic acid Bicvclopentyl ester/Methyl crotonate and methacrylic acid 3, 4-epoxycyclohexyl-methyl ester reaction and obtain resin, make .beta.-methylacrylic acid/(methyl) acrylic acid Bicvclopentyl ester/N-cyclohexyl horse Come imido copolymer and methacrylic acid 3, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains,

Make copolymer and the metering system of maleic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate Acid 3,4-epoxycyclohexyl-methyl ester reaction and obtain resin, make maleic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) Resin that the copolymer of cyclohexyl acrylate reacts with methacrylic acid 3,4-epoxycyclohexyl-methyl ester and obtains, make Malaysia Acid/(methyl) acrylic acid Bicvclopentyl ester/cinnamic copolymer reacts with methacrylic acid 3,4-epoxycyclohexyl-methyl ester And the resin obtained, the copolymer making maleic acid/(methyl) acrylic acid Bicvclopentyl ester/methyl maleate and methacrylic acid 3, 4-epoxycyclohexyl-methyl ester reaction and obtain resin, make maleic acid/(methyl) acrylic acid Bicvclopentyl ester/N-cyclohexyl horse Come imido copolymer and methacrylic acid 3, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains,

Make being total to of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate Resin that polymers reacts with methacrylic acid 3,4-epoxycyclohexyl-methyl ester and obtains, make (methyl) acrylic acid/maleic anhydride/ The copolymer of (methyl) acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate and methacrylic acid 3,4-epoxycyclohexyl Methyl ester reaction and obtain resin, make (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid Bicvclopentyl ester/styrene Copolymer react with methacrylic acid 3,4-epoxycyclohexyl-methyl ester and obtain resin, make (methyl) acrylic acid/Malaysia The copolymer of anhydride/(methyl) acrylic acid Bicvclopentyl ester/(methyl) acrylic acid methyl ester. and methacrylic acid 3,4-epoxy hexamethylene Ylmethyl ester reaction and obtain resin, make (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid Bicvclopentyl ester/N-ring The resin etc. that the copolymer of hexyl maleimide reacts with methacrylic acid 3,4-epoxycyclohexyl-methyl ester and obtains.

For resin (B2-2), as the first stage, obtain in the same manner as the preparation method of above-mentioned resin (B1-1) (b) with The copolymer of (c).

Now, as described above, the copolymer of gained, can directly use reacted solution, it is possible to use dense Contracting or the solution of dilution, it is also possible to the copolymer that the methods such as use reprecipitation obtain in solid (powder) mode.

As the ratio of the construction unit coming from (b) and (c), relative to the entire infrastructure unit constituting above-mentioned copolymer Total mole number, preferably in following scope.

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

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

Further, with the preparation method of resin (B2-1) likewise it is possible to by making in the copolymer of (b) and (c) Come from carboxylic acid that the cyclic ether of (b) has with (a) or carboxylic acid anhydrides reacts and obtains.Can also make by cyclic ether and carboxylic acid or carboxylic The reaction of anhydride and the hydroxyl that produces react with carboxylic acid anhydrides further.

With the consumption of (a) of above-mentioned copolymer reaction, relative to the molal quantity of (b), preferably 5～80 moles %.Cyclic ether Reactive high, be difficult to (b) of remained unreacted, accordingly, as (b), be preferably (b-1), more preferably (b-11).

As the concrete example of resin (B2-2), can enumerate and make (methyl) acrylic acid Bicvclopentyl ester/(methyl) acrylic acid Resin that the copolymer of glycidyl esters reacts with (methyl) acrylic acid and obtains, make (methyl) benzyl acrylate/(first Base) copolymer of glycidyl acrylate react with (methyl) acrylic acid and obtain resin, make (methyl) acrylic acid ring Resin that the copolymer of hexyl ester/(methyl) glycidyl acrylate reacts with (methyl) acrylic acid and obtains, make benzene second Resin that the copolymer of alkene/(methyl) glycidyl acrylate reacts with (methyl) acrylic acid and obtains, make (methyl) third Resin that the copolymer of e pioic acid methyl ester/(methyl) glycidyl acrylate reacts with (methyl) acrylic acid and obtains, make N- The tree that the copolymer of N-cyclohexylmaleimide/(methyl) glycidyl acrylate reacts with (methyl) acrylic acid and obtains Fat, make the copolymerization of (methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate/(methyl) glycidyl acrylate Resin that thing reacts with (methyl) acrylic acid and obtains, make (methyl) acrylic acid Bicvclopentyl ester/(methyl) acrylate base Resin that the copolymer of ester/(methyl) glycidyl acrylate reacts with (methyl) acrylic acid and obtains, make (methyl) third The copolymer of olefin(e) acid Bicvclopentyl ester/styrene/(methyl) glycidyl acrylate reacts with (methyl) acrylic acid and obtains To resin, make (methyl) acrylic acid Bicvclopentyl ester/(methyl) acrylic acid methyl ester ./(methyl) glycidyl acrylate Resin that copolymer reacts with (methyl) acrylic acid and obtains, make (methyl) acrylic acid Bicvclopentyl ester/N-cyclohexyl maleoyl The resin that the copolymer of imines/(methyl) glycidyl acrylate reacts with (methyl) acrylic acid and obtains,

The copolymer making (methyl) acrylic acid Bicvclopentyl ester/(methyl) glycidyl acrylate reacts with .beta.-methylacrylic acid And the resin obtained, make (methyl) benzyl acrylate/(methyl) glycidyl acrylate copolymer anti-with .beta.-methylacrylic acid Answer and the resin obtained, the copolymer making (methyl) cyclohexyl acrylate/(methyl) glycidyl acrylate and Fructus Crotonis Acid reaction and the resin, the copolymer that makes styrene/(methyl) glycidyl acrylate that obtain react with .beta.-methylacrylic acid and obtain To resin, make the copolymer of Methyl crotonate/(methyl) glycidyl acrylate react with .beta.-methylacrylic acid and the tree that obtains Fat, the copolymer of N-N-cyclohexylmaleimide/(methyl) glycidyl acrylate is made to react with .beta.-methylacrylic acid and obtain Resin, make being total to of (methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate/(methyl) glycidyl acrylate Resin that polymers reacts with .beta.-methylacrylic acid and obtains, make (methyl) acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate/ Resin that the copolymer of (methyl) glycidyl acrylate reacts with .beta.-methylacrylic acid and obtains, make (methyl) acrylic acid dicyclo penta Resin that the copolymer of base ester/styrene/(methyl) glycidyl acrylate reacts with .beta.-methylacrylic acid and obtains, make (methyl) The copolymer of acrylic acid Bicvclopentyl ester/Methyl crotonate/(methyl) glycidyl acrylate reacts with .beta.-methylacrylic acid and obtains To resin, make (methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide/(methyl) glycidyl acrylate Copolymer react with .beta.-methylacrylic acid and the resin that obtains,

The copolymer making (methyl) acrylic acid Bicvclopentyl ester/(methyl) glycidyl acrylate reacts with maleic acid And the resin obtained, make (methyl) benzyl acrylate/(methyl) glycidyl acrylate copolymer anti-with maleic acid Answer and the resin obtained, the copolymer making (methyl) cyclohexyl acrylate/(methyl) glycidyl acrylate and Malaysia Acid reaction and the resin, the copolymer that makes styrene/(methyl) glycidyl acrylate that obtain react with maleic acid and obtain To resin, make the copolymer of methyl maleate/(methyl) glycidyl acrylate react with maleic acid and the tree that obtains Fat, the copolymer of N-N-cyclohexylmaleimide/(methyl) glycidyl acrylate is made to react with maleic acid and obtain Resin, make being total to of (methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate/(methyl) glycidyl acrylate Resin that polymers reacts with maleic acid and obtains, make (methyl) acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate/ Resin that the copolymer of (methyl) glycidyl acrylate reacts with maleic acid and obtains, make (methyl) acrylic acid dicyclo penta Resin that the copolymer of base ester/styrene/(methyl) glycidyl acrylate reacts with maleic acid and obtains, make (methyl) The copolymer of acrylic acid Bicvclopentyl ester/methyl maleate/(methyl) glycidyl acrylate reacts with maleic acid and obtains To resin, make (methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide/(methyl) glycidyl acrylate Copolymer react with maleic acid and the resin that obtains,

Make copolymer and (methyl) propylene of (methyl) acrylic acid Bicvclopentyl ester/(methyl) glycidyl acrylate Acid and maleic anhydride reaction and obtain resin, make (methyl) benzyl acrylate/(methyl) glycidyl acrylate Resin that copolymer reacts with (methyl) acrylic acid and maleic anhydride and obtains, make (methyl) cyclohexyl acrylate/(methyl) Resin that the copolymer of glycidyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and obtains, make styrene/ Resin that the copolymer of (methyl) glycidyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and obtains, make The copolymer of (methyl) acrylic acid methyl ester ./(methyl) glycidyl acrylate reacts with (methyl) acrylic acid and maleic anhydride And the resin obtained, the copolymer making N-N-cyclohexylmaleimide/(methyl) glycidyl acrylate and (methyl) third Olefin(e) acid and maleic anhydride reaction and obtain resin, make (methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate/ Resin that the copolymer of (methyl) glycidyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and obtains, make The copolymer of (methyl) acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate/(methyl) glycidyl acrylate The resin that reacts and obtain with (methyl) acrylic acid and maleic anhydride, make (methyl) acrylic acid Bicvclopentyl ester/styrene/(first Base) copolymer of glycidyl acrylate react with (methyl) acrylic acid and maleic anhydride and obtain resin, make (first Base) copolymer and (methyl) of acrylic acid Bicvclopentyl ester/(methyl) acrylic acid methyl ester ./(methyl) glycidyl acrylate Acrylic acid and maleic anhydride reaction and obtain resin, make (methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide/ The resin that the copolymer of (methyl) glycidyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and obtains,

Make copolymer and the (first of (methyl) acrylic acid Bicvclopentyl ester/methacrylic acid 3,4-epoxycyclohexyl-methyl ester Base) acrylic acid reaction and obtain resin, make (methyl) benzyl acrylate/methacrylic acid 3,4-epoxycyclohexyl-methyl ester Copolymer react with (methyl) acrylic acid and obtain resin, make (methyl) cyclohexyl acrylate/methacrylic acid 3,4- Resin that the copolymer of epoxycyclohexyl-methyl ester reacts with (methyl) acrylic acid and obtains, make styrene/methacrylic acid 3, Resin that the copolymer of 4-epoxycyclohexyl-methyl ester reacts with (methyl) acrylic acid and obtains, make (methyl) acrylic acid methyl ester ./ Resin that the copolymer of methacrylic acid 3,4-epoxycyclohexyl-methyl ester reacts with (methyl) acrylic acid and obtains, make N-hexamethylene The copolymer of base maleimide/methacrylic acid 3,4-epoxycyclohexyl-methyl ester reacts with (methyl) acrylic acid and obtains Resin, make (methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate/methacrylic acid 3,4-epoxycyclohexyl-methyl Resin that the copolymer of ester reacts with (methyl) acrylic acid and obtains, make (methyl) acrylic acid Bicvclopentyl ester/(methyl) propylene The tree that the copolymer of acid cyclohexyl ester/methacrylic acid 3,4-epoxycyclohexyl-methyl ester reacts with (methyl) acrylic acid and obtains Fat, make the copolymer of (methyl) acrylic acid Bicvclopentyl ester/styrene/methacrylic acid 3,4-epoxycyclohexyl-methyl ester with (methyl) acrylic acid reaction and obtain resin, make (methyl) acrylic acid Bicvclopentyl ester/(methyl) acrylic acid methyl ester ./methyl-prop Resin that the copolymer of olefin(e) acid 3,4-epoxycyclohexyl-methyl ester reacts with (methyl) acrylic acid and obtains, make (methyl) acrylic acid The copolymer of Bicvclopentyl ester/N-N-cyclohexylmaleimide/methacrylic acid 3,4-epoxycyclohexyl-methyl ester and (methyl) The resin that acrylic acid reacts and obtains,

Make copolymer and the Fructus Crotonis of (methyl) acrylic acid Bicvclopentyl ester/methacrylic acid 3,4-epoxycyclohexyl-methyl ester Acid reaction and the resin obtained, the copolymerization that makes (methyl) benzyl acrylate/methacrylic acid 3,4-epoxycyclohexyl-methyl ester Resin that thing reacts with .beta.-methylacrylic acid and obtains, make (methyl) cyclohexyl acrylate/methacrylic acid 3,4-epoxycyclohexyl first Resin that the copolymer of base ester reacts with .beta.-methylacrylic acid and obtains, make styrene/methacrylic acid 3,4-epoxycyclohexyl-methyl ester Copolymer react with .beta.-methylacrylic acid and obtain resin, make Methyl crotonate/methacrylic acid 3,4-epoxycyclohexyl-methyl ester Copolymer react with .beta.-methylacrylic acid and obtain resin, make N-N-cyclohexylmaleimide/methacrylic acid 3,4-epoxy hexamethylene Resin that the copolymer of ylmethyl ester reacts with .beta.-methylacrylic acid and obtains, make (methyl) acrylic acid Bicvclopentyl ester/(methyl) propylene Acid benzyl ester/methacrylic acid 3,4-epoxycyclohexyl-methyl ester copolymer react with .beta.-methylacrylic acid and obtain resin, make (first Base) copolymerization of acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate/methacrylic acid 3,4-epoxycyclohexyl-methyl ester Resin that thing reacts with .beta.-methylacrylic acid and obtains, make (methyl) acrylic acid Bicvclopentyl ester/styrene/methacrylic acid 3,4-epoxy Resin that the copolymer of cyclohexyl methyl ester reacts with .beta.-methylacrylic acid and obtains, make (methyl) acrylic acid Bicvclopentyl ester/.beta.-methylacrylic acid Resin that the copolymer of methyl ester/methacrylic acid 3,4-epoxycyclohexyl-methyl ester reacts with .beta.-methylacrylic acid and obtains, make (methyl) The copolymer of acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide/methacrylic acid 3,4-epoxycyclohexyl-methyl ester with The resin that .beta.-methylacrylic acid reacts and obtains,

Make copolymer and the Malaysia of (methyl) acrylic acid Bicvclopentyl ester/methacrylic acid 3,4-epoxycyclohexyl-methyl ester Acid reaction and the resin obtained, the copolymerization that makes (methyl) benzyl acrylate/methacrylic acid 3,4-epoxycyclohexyl-methyl ester Resin that thing reacts with maleic acid and obtains, make (methyl) cyclohexyl acrylate/methacrylic acid 3,4-epoxycyclohexyl first Resin that the copolymer of base ester reacts with maleic acid and obtains, make styrene/methacrylic acid 3,4-epoxycyclohexyl-methyl ester Copolymer react with maleic acid and obtain resin, make methyl maleate/methacrylic acid 3,4-epoxycyclohexyl-methyl ester Copolymer react with maleic acid and obtain resin, make N-N-cyclohexylmaleimide/methacrylic acid 3,4-epoxy hexamethylene Resin that the copolymer of ylmethyl ester reacts with maleic acid and obtains, make (methyl) acrylic acid Bicvclopentyl ester/(methyl) propylene Acid benzyl ester/methacrylic acid 3,4-epoxycyclohexyl-methyl ester copolymer react with maleic acid and obtain resin, make (first Base) copolymerization of acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate/methacrylic acid 3,4-epoxycyclohexyl-methyl ester Resin that thing reacts with maleic acid and obtains, make (methyl) acrylic acid Bicvclopentyl ester/styrene/methacrylic acid 3,4-epoxy Resin that the copolymer of cyclohexyl methyl ester reacts with maleic acid and obtains, make (methyl) acrylic acid Bicvclopentyl ester/maleic acid Resin that the copolymer of methyl ester/methacrylic acid 3,4-epoxycyclohexyl-methyl ester reacts with maleic acid and obtains, make (methyl) The copolymer of acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide/methacrylic acid 3,4-epoxycyclohexyl-methyl ester with The resin that maleic acid reacts and obtains,

Make copolymer and the (first of (methyl) acrylic acid Bicvclopentyl ester/methacrylic acid 3,4-epoxycyclohexyl-methyl ester Base) acrylic acid and maleic anhydride reaction and obtain resin, make (methyl) benzyl acrylate/methacrylic acid 3,4-epoxide ring Resin that the copolymer of hexyl methyl ester reacts with (methyl) acrylic acid and maleic anhydride and obtains, make (methyl) acrylate The copolymer of base ester/methacrylic acid 3,4-epoxycyclohexyl-methyl ester reacts with (methyl) acrylic acid and maleic anhydride and obtains Resin, make the copolymer of styrene/methacrylic acid 3,4-epoxycyclohexyl-methyl ester and (methyl) acrylic acid and maleic acid Anhydride reactant and the resin obtained, the copolymer that makes (methyl) acrylic acid methyl ester ./methacrylic acid 3,4-epoxycyclohexyl-methyl ester The resin that reacts and obtain with (methyl) acrylic acid and maleic anhydride, make N-N-cyclohexylmaleimide/methacrylic acid 3,4- Resin that the copolymer of epoxycyclohexyl-methyl ester reacts with (methyl) acrylic acid and maleic anhydride and obtains, make (methyl) propylene The copolymer of acid Bicvclopentyl ester/(methyl) benzyl acrylate/methacrylic acid 3,4-epoxycyclohexyl-methyl ester and (first Base) acrylic acid and maleic anhydride reaction and obtain resin, make (methyl) acrylic acid Bicvclopentyl ester/(methyl) acrylate The copolymer of base ester/methacrylic acid 3,4-epoxycyclohexyl-methyl ester reacts with (methyl) acrylic acid and maleic anhydride and obtains Resin, make the copolymer of (methyl) acrylic acid Bicvclopentyl ester/styrene/methacrylic acid 3,4-epoxycyclohexyl-methyl ester The resin that reacts and obtain with (methyl) acrylic acid and maleic anhydride, make (methyl) acrylic acid Bicvclopentyl ester/(methyl) propylene The copolymer of acid methyl ester/methacrylic acid 3,4-epoxycyclohexyl-methyl ester reacts with (methyl) acrylic acid and maleic anhydride and obtains To resin, make (methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide/methacrylic acid 3,4-epoxycyclohexyl The resin etc. that the copolymer of methyl ester reacts with (methyl) acrylic acid and maleic anhydride and obtains.

The weight average molecular weight (Mw) of the polystyrene conversion of resin (B2) is preferably 3000～100000, more preferably 5000 ～50000.If the weight average molecular weight of resin (B2) is in above-mentioned scope, then there is the trend that coating becomes good, additionally, development Time be difficult to produce film and reduce, and then during development, there is the trend that the deciduous of non-pixel portion becomes good.

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

The acid number of resin (B2) is 20～150mg-KOH/g, preferably 50～135mg-KOH/g, more preferably 65～ 135mg-KOH/g.Acid number is as neutralizing the value that the amount (mg) of resin (B2) 1g and required potassium hydroxide measures, can With by using potassium hydroxide aqueous solution to carry out titration and try to achieve.

The content of resin (B2), relative to resin (B1) and the total amount of resin (B2), preferably 5～90 mass %, more preferably It is 15～90 mass %, particularly preferably 20～90 mass %.If the content of resin (B2) is in above-mentioned scope, then developability, closely sealed Property, solvent resistance, mechanical property have the trend becoming good.

The photosensitive composition of the present invention, can be containing the resin different from resin (B1) and resin (B2) (BX) as resin (B).As resin (BX), the copolymer of such as (a) and (c) can be enumerated.The content of resin (BX), relatively In the gross mass of resin (B), preferably 0～50 mass %, more preferably 0～30 mass %.

The gross mass of the resin (B) contained in the photosensitive composition of the present invention, relative to coloring phototonus The amount of the solid composition of resin combination, preferably 20～70 mass %, more preferably 25～50 mass %.

Additionally, the total amount of resin (B), relative to resin (B) and the total amount of polymerizable compound (C), preferably 20～80 Quality %, more preferably 40～60 mass %.

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

Polymerizable compound (C) is can be polymerized by the living radical produced by polymerization initiator (D) and acid etc. Compound, the compound such as with ethylenic unsaturated bond can be enumerated, preferably enumerate (methyl) acrylate compounds.

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

As having the polymerizable compound (C) of 2 ethylenic unsaturated bonds, 1,3 butylene glycol two (methyl) third can be enumerated Olefin(e) acid ester, 1,3 butylene glycol (methyl) acrylate, 1,6-HD two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) propylene Acid esters, diethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylic acid Ester, TEG two (methyl) acrylate, polyethyleneglycol diacrylate, double (acryloyl-oxyethyl) ether, the second of bisphenol-A Epoxide bisphenol-A two (methyl) acrylate, ethoxylated neopentylglycol two (methyl) acrylate, ethoxylation neopentyl glycol Two (methyl) acrylate, 3-methyl pentanediol two (methyl) acrylate etc..

As having the polymerizable compound (C) of more than 3 ethylenic unsaturated bonds, trimethylolpropane tris can be enumerated (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.Wherein, preferably Be 3 officials can above monomer, more preferably dipentaerythritol six (methyl) acrylate.

The content of polymerizable compound (C), relative to the amount of the solid composition of photosensitive composition, is preferably 5～50 mass %, more preferably 10～45 mass %.Additionally, relative to resin (B) and the total amount of polymerizable compound (C), preferably It is 20～80 mass %, more preferably 40～60 mass %.If the content of polymerizable compound (C) is in above-mentioned scope, then there is spirit Sensitivity, the intensity of pattern or flatness, reliability become good trend.

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

As polymerizing initiator (D), as long as produced living radical and acid etc. by the effect of light, cause polymerization The compound of the polymerization of property compound (C), is not particularly limited, it is possible to use known polymerization initiator.

As polymerization initiator (D), preferably united imidazole, benzene alkyl ketone compound, triaizine compounds, acyl group oxygen Change phosphine compound, oxime compound.In addition it is possible to use the light cation described in Japanese Unexamined Patent Publication 2008-181087 publication is gathered Close initiator (such as byCation and the material coming from lewis acidic anion composition).Wherein, examine from sensitivity viewpoint Consider, preferably oxime compound.

As above-mentioned united imidazole, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl connection miaow can be enumerated Azoles, 2,2 '-bis-(2,3-Dichlorobenzene base)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline is (referring for example to Japanese Unexamined Patent Publication 6-75372 public affairs Report and Japanese Unexamined Patent Publication 6-75373 publication), 2,2 '-bis-(2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis- (2-chlorphenyl)-4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxaline, 2,2 '-bis-(2-chlorphenyls)-4,4 ', 5,5 '-four (dioxanes Phenyl) bisglyoxaline, 2,2 '-bis-(2-chlorphenyls)-4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxaline is (referring for example to day This examined patent publication 48-38403 publication and Japanese Laid-Open Patent Publication 62-174204 publication), the phenyl of 4,4 ' 5,5 '-position is by alcoxyl carbonyl The substituted imidazolium compounds of base (referring for example to Japanese Unexamined Patent Publication 7-10913 publication) etc..Preferably enumerate 2,2 '-bis-(2-chlorobenzenes Base)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2,3-Dichlorobenzene base)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '- Double (2,4 dichloro benzene bases)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline.

As above-mentioned benzene alkyl ketone compound, diethoxy acetophenone, 2-methyl-2-morpholino-1-(4-first can be enumerated Base methyldisulfanylphenyl) propane-1-ketone, 2-dimethylamino-1-(4-morphlinophenyl)-2-benzyl butane-1-ketone, 2-dimethyl Amino-1-(4-morphlinophenyl)-2-(4-methylphenylmethyl) butane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1- Ketone, benzyldimethylketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl] propane-1-ketone, 1-hydroxyl Cyclohexyl-phenyl ketone, the oligomer etc. of 2-hydroxy-2-methyl-1-(4-isopropenyl phenyl) propane-1-ketone, preferably enumerate 2-first Base-2-morpholino-1-(4-methylsulfanyl phenyl) propane-1-ketone, 2-dimethylamino-1-(4-morphlinophenyl)-2-benzyl Base butane-1-ketone etc..イ Le ガキュア 369, イ Le ガキュア 907 (above BASF ジャパ Application society system) can also be used Etc. commercially available product.

As above-mentioned triaizine compounds, 2 can be enumerated, double (the trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri-of 4- Double (trichloromethyl)-6-(4-methoxyl group the naphthyl)-1,3,5-triazine of piperazine, 2,4-, double (trichloromethyl)-6-piperonyl-1 of 2,4-, Double (trichloromethyl)-6-(4-the methoxyl-styrene)-1,3,5-triazine of 3,5-triazine, 2,4-, double (the trichloromethyl)-6-of 2,4- Double (trichloromethyl)-6-[2-(furan-2-base) ethylene of [2-(5-methylfuran-2-base) vinyl]-1,3,5-triazine, 2,4- Base]-1,3,5-triazine, double (trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) the vinyl]-1,3,5-of 2,4- Double (trichloromethyl)-6-[2-(3,4-Dimethoxyphenyl) the vinyl]-1,3,5-triazines of triazine, 2,4-etc..

As above-mentioned acylphosphine oxide initiator, TMDPO etc. can be enumerated. The commercially available products such as イ Le ガキュア 819 (チバジャパ Application society system) can also be used.

As above-mentioned oxime compound, can enumerate N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) butane-1-ketone- 2-imines, N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) octane-1-ketone-2-imines, N-acetoxyl group-1-[9-second Base-6-(2-methyl benzoyl)-9H-carbazole-3-base] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-[2-first Base-4-(3,3-dimethyl-2,4-dioxolyl methyl epoxide) benzoyl]-9H-carbazole-3-base] ethane-1-imines Deng.イ Le ガキュア OXE-01, OXE-02 (above BASF ジャパ Application society system), N-1919 (ADEKA society can also be used System) etc. commercially available product.

And then, as polymerization initiator (D), benzoin, benzoin methyl ether, benzoin ethyl ether, benzene can be enumerated occasionally The benzoin 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 '-dimethyl diphenyl sulfide, 3,3 ', 4,4 '-four (tert-butyl peroxide carbonyl) benzophenone, The benzophenone cpds such as 2,4,6-tri-methyl benzophenones, the naphtoquinone compounds such as 9,10-phenanthrenequione, 2-ethyl-anthraquinone, camphorquinone, 10-butyl-2-chloro-acridine ketone, dibenzoyl, phenylglyoxylic acid methyl ester, titanocenes compound etc..They are preferably polymerized with described later Auxiliary agent (D1) (particularly amine) combination is caused to use.

It is possible to further cause auxiliary agent (D1) containing polymerization.Polymerization initiation auxiliary agent (D1) can be with polymerization initiator (D) group Incompatible use, its be the compound used to promote to be caused the polymerization of polymerizable compound of polymerization by polymerization initiator or Sensitizer.

Cause auxiliary agent (D1) as polymerization, amines, thiazolinium compounds, alkoxy anthracene compound, thiophene can be enumerated Ton ketonic compound, carboxylic acid compound etc..

As amines, triethanolamine, methyl diethanolamine, triisopropanolamine, 4-dimethylamino benzene can be enumerated Methyl formate, EDMAB, 4-dimethylaminobenzoic acid isopentyl ester, benzoic acid 2-dimethylaminoethyl Ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, N, N-dimethyl-p-toluidine, 4,4 '-bis-(dimethylamino) hexichol first Ketone, 4,4 '-bis-(diethylamino) benzophenone, 4,4 '-bis-(ethylmethylamino) benzophenone etc., wherein, preferably 4, 4 '-bis-(diethylamino) benzophenone.The commercially available product of EAB-F (hodogaya chemical industry (strain) system) etc. can also be used.

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

As alkoxy anthracene compound, 9 can be enumerated, 10-dimethoxy anthracene, EDMO, 9, 10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene, 9,10-dibutoxy anthracene, 2-ethyl-9,10-dibutoxy anthracene Deng.

As thioxanthone compounds, can enumerate ITX, ITX, 2,4-diethyl thioxanthene Ketone, 2,4-bis-clopenthixal ketone, 1-chloro-4-propoxythioxanthone etc..

As carboxylic acid compound, Phenylsulfanyl acetic acid, methyl phefzylsulfanyl acetic acid, ethylphenyl sulfane can be enumerated Guanidine-acetic acid, Methylethyl phenyl sulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenyl sulfanyl acetic acid, diformazan Phenyl sulfanyl acetic acid, chlorophenylsulfanyl acetic acid, Dichlorobenzene base sulfanyl acetic acid, N-phenylglycine, phenoxy group second Acid, naphthylthio acetic acid, N-naphthyl glycine, naphthoxy acetic acid etc..

The content of polymerization initiator (D), relative to total amount 100 mass parts of resin (B) and polymerizable compound (C), excellent Elect 0.1～40 mass parts, more preferably 1～30 mass parts as.If the content of polymerization initiator (D) is in this scope, then can be with High sensitivity forms pattern, there is the resistance to chemical reagents of pattern, mechanical strength, surface smoothness become good trend.

When using polymerization to cause auxiliary agent (D1), its consumption, relative to resin (B) and the total amount 100 of polymerizable compound (C) Mass parts, preferably 0.01～50 mass parts, more preferably 0.1～40 mass parts.Additionally, rub relative to polymerization initiator (D) 1 You, preferably 0.01～10 mole, more preferably 0.01～5 mole.If polymerization causes the amount of auxiliary agent (D1) in this scope, then may be used To form pattern with the highest sensitivity, there is the trend that the productivity of pattern improves.

Additionally, the photosensitive composition of the present invention, multi-functional thiol's compound (T) can be contained further. This multi-functional thiol's compound (T) is the compound that intramolecular has more than 2 sulfanyls.Wherein, if using and there are more than 2 The compound of the sulfanyl adjacent with aliphatic alkyl, then can form pattern with high sensitivity, it is advantageous to.

As multi-functional thiol's compound (T), ethanthiol, mercaptan in the last of the ten Heavenly stems two, Isosorbide-5-Nitrae-bis-(methylsulfanyl) can be enumerated Benzene, butanediol double (3-sulfanyl propionic ester), butanediol double (3-sulfanyl acetas), ethylene glycol bis (3-sulfanyl acetic acid Ester), trimethylolpropane tris (3-sulfanyl acetas), butanediol double (3-sulfanyl propionic ester), trimethylolpropane tris (3- Sulfanyl propionic ester), trimethylolpropane tris (3-sulfanyl acetas), tetramethylolmethane four (3-sulfanyl propionic ester), season penta Tetrol four (3-sulfanyl acetas), trihydroxyethyl three (3-sulfanyl propionic ester), tetramethylolmethane four (3-sulfanyl butyrate), Double (3-sulfanyl butoxy) butane of 1,4-etc..

The content of multi-functional thiol's compound (T), relative to polymerization initiator (D) 100 mass parts, preferably 0.5～20 Mass parts, more preferably 1～15 mass parts.If the content of multi-functional thiol's compound (T) is in this scope, then sensitivity improves, In addition there is the trend that developability becomes good.

To solvent (E) without particular limitation of, it is possible to use the most normally used solvent.Such as can be from ester solvent Ether solvents beyond (intramolecular contains-COO-, do not contains the solvent of-O-), ester solvent (intramolecular contain-O-, do not contain- The solvent of COO-), the ether-ether solvent solvent of-COO-and-O-(intramolecular contain), (intramolecular contains for ketone solvent beyond ester solvent Have-CO-, do not contain the solvent of-COO-), alcoholic solvent, aromatic hydrocarbon solvents, amide solvent and dimethyl sulfoxide select to make With.These solvents can individually or two or more combination uses.

As ester solvent, methyl lactate, ethyl lactate, butyl lactate, 2-hydroxy-methyl isobutyl acid, acetic acid second can be enumerated Ester, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl n-butyrate., fourth Acid butyl ester, methyl pyruvate, ethyl pyruvate, Propyl 2-oxopropionate, methyl acetoacetate, ethyl acetoacetate, Hexacyclonic Acid Ester, gamma-butyrolacton etc..

As ether solvents, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, second two can be enumerated Alcohol single-butyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, Propylene glycol monoethyl, propylene glycol monopropyl ether, glycol monobutyl ether, 3-methoxyl group-n-butyl alcohol, 3-methoxyl group-3-methyl Butanol, oxolane, Pentamethylene oxide., 1,4-bis-Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, methyl phenyl ethers anisole, ethyl phenyl ether, methylanisole etc..

As ether-ether solvent, methoxy menthyl acetate, ethyl methoxyacetate, 2-Methoxyacetic acid butyl ester, second can be enumerated Ethoxyacetic acid methyl ester, ethoxy ethyl acetate, 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxy-propionic acid first Ester, 3-ethoxyl ethyl propionate, 2-methoxy methyl propionate, 2-methoxypropionate, 2-methoxy propyl propyl propionate, 2-ethoxy Base methyl propionate, 2-ethoxyl ethyl propionate, 2-methoxyl group-2 Methylpropionic acid methyl ester, 2-ethyoxyl-2 Methylpropionic acid ethyl ester, 3-methoxybutyl acetas, 3-methyl-3-methoxybutyl acetas, propylene glycol monomethyl ether, propylene glycol list second Base ether acetic acid ester, propylene glycol monopropyl ether acetas, ethylene glycol monomethyl ether acetic acid ester, ethylene glycol monomethyl ether acetate, two Ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetas etc..

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

As alcoholic solvent, methanol, ethanol, propanol, butanol, hexanol, Hexalin, ethylene glycol, propylene glycol, glycerol can be enumerated Deng.

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

As amide solvent, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone can be enumerated Deng.

In above-mentioned solvent, from the viewpoint of coating, drying property, the boiling point under preferably 1atm is 120 DEG C～180 DEG C Organic solvent.Wherein, preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether etc..

The content of solvent (E), relative to photosensitive composition total amount, preferably 60～95 mass %, more preferably It is 70～90 mass %.In other words, the solid composition of photosensitive composition, preferably 5～40 mass %, more preferably It is 10～30 mass %.If the content of solvent (E) has, at above-mentioned scope, then flatness when being coated with, the trend becoming good.

The photosensitive composition of the present invention preferably comprises surfactant (F).As surfactant, permissible Enumerate such as siloxane type surfactants, fluorine class surfactant and there is the siloxane type surfactants of fluorine atom.Logical Crossing containing surfactant, flatness during coating has the trend becoming good.

As siloxane type surfactants, the surfactant with siloxane bond can be enumerated.Specifically, permissible Enumerate トレシリ U Application DC3PA, トレシリ U Application SH7PA, トレシリ U Application DC11PA, トレシリ U Application SH21PA, トレシリ U Application SH28PA, トレシリ U Application SH29PA, トレシリ U Application SH30PA, polyethers Modified silicon oil SH8400 (trade name: east レダウ conning (strain) system), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445、TSF-4446、TSF4452、TSF4460(モメンティブ·パフォーマンス·マテリアルズ·ジャパ Application contract commercial firm system) etc..

As fluorine class surfactant, the surfactant with fluorocarbon chain can be enumerated.Specifically, Off can be enumerated ロリ Na ト (registered trade mark) FC430, Off ロリ Na ト FC431 (Sumitomo スリエ system (strain) system), (registration of メガ Off ァッ Network Trade mark) F142D, メガ Off ァッ Network F171, メガ Off ァッ Network F172, メガ Off ァッ Network F173, メガ Off ァッ Network F177, メガ Off ァッ Network F183, メガ Off ァッ Network R30 (DIC (strain) system), エ Off トップ (registered trade mark) EF301, エ Off トップ EF303, エ Off トップ EF351, エ Off トップ EF352 (Rhizoma Sparganii マテリア Le electronics chemical conversion (strain) system), サ Off ロ Application (note Volume trade mark) S381, サ Off ロ Application S382, サ Off ロ Application SC101, サ Off ロ Application SC105 (Asahi Glass (strain) system), E5844 (research of (strain) ダイキ Application Off ァイ Application ケミカ Le is made) etc..

As having the siloxane type surfactants of fluorine atom, the surface with siloxane bond and fluorocarbon chain can be enumerated Activating agent.Specifically, メガ Off ァッ Network (registered trade mark) R08, メガ Off ァッ Network BL20, メガ Off ァッ Network can be enumerated F475, メガ Off ァッ Network F477, メガ Off ァッ Network F443 (DIC (strain) system) etc..It is preferably メガ Off ァッ Network (registered trade mark) F475。

Surfactant (F), relative to the photosensitive composition total amount of the present invention, be 0.001 mass %～ 0.2 mass %, preferably 0.002 mass %～0.1 mass %, more preferably 0.01 mass %～0.05 mass %.By making surface live The content of property agent is in this scope, and the flatness that can make film is good.

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

The photosensitive composition of the present invention such as can be prepared as follows.

First, the pigment of coloring agent (A) is mixed with solvent (E), use ball mill etc. to be dispersed to the mean diameter of pigment It it is below 0.2 μm left and right.Can coordinate the most as required pigment dispersing agent, resin (B) part or all.At gained In dispersible pigment dispersion, add remaining resin (B), polymerizable compound (C) and polymerization initiator (D), root with the concentration of regulation According to needing other the composition used and then the solvent added as required, the coloring phototonus resin group of purpose can be obtained Compound.

The photosensitive composition of the present invention such as through the step shown in following (1)～(4), is processed as colour filter Device.

(1) by the photosensitive composition of the present invention being coated on substrate the step obtaining coated film,

(4) pattern is bakeed, thus obtain the step of the pattern of solidification.

As the method obtaining pattern, photoetching process, ink-jet method, print process etc. can be enumerated.Wherein, preferably photoetching process. Photoetching process is to be coated on substrate by above-mentioned photosensitive composition and be dried, and via photomask exposure, carries out Development, the method thus obtaining pattern.

As aforesaid substrate, such as glass, metal and plastics can be enumerated, can be tabular, it is also possible to for membranaceous.

As plastics, the polyolefin such as such as polyethylene, polypropylene, norbornene polymer can be enumerated, polyvinyl alcohol, Polyethylene terephthalate, PEN, poly-(methyl) acrylate, cellulose esters, Merlon, poly- Sulfone, polyether sulfone, polyether-ketone, polyphenylene sulfide and polyphenylene oxide.Wherein, (methyl) acrylic acid refers to selected from acrylic acid and metering system At least one of acid.These substrates can be formed color filter, various insulation or the structure such as conducting film, drive circuit.

According to the photosensitive composition of the present invention, the pattern solidified at lower temperatures can be formed.Therefore, When plastic base forms pattern, particularly useful.

As the coating process for substrate, can enumerate such as, extrusion coating methods, direct heliogravure rubbing method, anti- To type heliogravure rubbing method, lid coating and metal mold rubbing method.In addition it is possible to use dip coater, roll coater, bar coater, rotation Painting machine, slit & spin coater, slit coater (being sometimes referred to as metal mold coating machine, curtain flow coater, non-rotating coating machine), ink-jet It is coated Deng apparatus for coating.Wherein, slit coater, spin coater, roll coater etc. are preferably used be coated.

As the drying means of the film being coated on substrate, such as heat drying, natural drying, aeration-drying can be enumerated Method with drying under reduced pressure.Multiple method can be combined carry out.

As baking temperature, preferably 10～120 DEG C, more preferably 25～100 DEG C.Additionally, as heat time heating time, preferably It is 10 seconds～60 minutes, more preferably 30 seconds～30 minutes.

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

To the thickness of dried coated film without particular limitation of, suitably can adjust according to the material used, purposes etc. Whole, usually 0.1～20 μm, preferably 1～6 μm.

For dried coated film, it is exposed via the photomask being used for being formed purpose pattern.Light now is covered Pattern form on mould is without particular limitation of, it is possible to use the pattern form adapted with purpose purposes.

As the light source used in exposure, preferably produce the light source of the light that wavelength is 250～450nm.Such as can use The light filter stoping the wavelength light less than 350nm stops the light of this wavelength region, or use obtains near 436nm, 408nm is attached Closely, the band filter of the light near 365nm optionally obtains the light of these wavelength region.Specifically, hydrargyrum can be enumerated Lamp, light emitting diode, metal halide lamp and halogen lamp.

In order to whole plane of exposure be irradiated equably parallel rays, or it is masked the correct position with base material Join, the device such as mask aligner, stepper during exposure, is preferably used.

After exposure, make coated film contact with developer solution, established part such as unexposed portion is dissolved, develops, by This can obtain pattern.As developer solution, it is possible to use organic solvent, but in order to make the exposure portion of coated film be difficult to by developing Liquid and produce dissolving, swelling, the pattern of good shape can be obtained, the aqueous solution of alkali compounds is preferably used.

Developing method, can be any means in slurry processes, infusion process, nebulization etc..Further, during development, substrate can To tilt with arbitrary angle.

Preferably wash after development.

As above-mentioned alkali compounds, sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, phosphorus can be enumerated Acid hydrogen diammonium, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, The inorganic alkaline compounds such as sodium borate, potassium borate, ammonia, and Tetramethylammonium hydroxide, 2-hydroxyethyl trimethylammonium hydroxide, Monomethyl amine, dimethyl amine, Trimethylamine, MEA, diethylamide, triethylamine, single isopropylamine, diisopropylamine, The organic basic compounds such as ethanolamine.As above-mentioned alkali compounds, preferably potassium hydroxide, sodium bicarbonate and tetramethyl hydrogen-oxygen Change ammonium.

These alkali compoundss concentration in aqueous is preferably 0.01～10 mass %, more preferably 0.03～5 matter Amount %.

The aqueous solution of above-mentioned alkali compounds can contain surfactant.

As surfactant, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyxyethylated aryl can be enumerated Ether, other polyoxyethylene deriv, ethylene oxide/propylene oxide block copolymer, sorbitan fatty acid esters, polyoxy Ethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid ester, fatty acid glyceride, polyoxyethylene fatty acid The nonionic class surfactant such as ester, polyoxyethylene alkyl amine,

Dodecanol sodium sulfovinate, oleyl sulfate sodium, sodium lauryl sulphate, ammonium lauryl sulfate, dodecyl The anionic based surfactants such as benzene sulfonic acid sodium salt, dodecyl sodium naphthalene sulfonate, and stearic amine hydrochlorate, dodecyl front three The cationic based surfactants such as ammonium chloride.

The concentration of the surfactant in the aqueous solution of alkali compounds is preferably 0.01～10 mass %, more preferably 0.05～8 mass %, particularly preferably 0.1～5 mass %.

The pattern obtained as mentioned above is bakeed further, it is hereby achieved that the pattern of solidification.As bakeing temperature Degree, is 25 DEG C～230 DEG C, preferably 25 DEG C～200 DEG C, more preferably 25 DEG C～160 DEG C, more preferably 25 DEG C～120 ℃.As the time of baking, it is 1～300 minute, preferably 1～180 minute, more preferably 1～60 minute.

By the photosensitive composition of the present invention, suitably repeat the pattern manufacture carried out by said method, thus Color filter can be manufactured.The color filter of gained, can be by known method for having this color filter as the one of component parts The display device of part, such as liquid crystal indicator, organic el device, solid camera head, Electronic Paper etc. and rendered image phase In the instrument closed.

[embodiment]

By the following examples the present invention is carried out more specific description." % " and " part " in example as long as not illustrating, For quality % and mass parts.

Synthesis example 1

Appropriate person who lives in exile's nitrogen in the flask with reflux condenser, Dropping funnel and blender, forms nitrogen atmosphere, adds third Glycol monomethyl ether acetas 100 parts, is heated to 85 DEG C while stirring.Then, dropping pump is used to use about 5 hours, to this burning In bottle, dropping is by methacrylic acid 19 parts, acrylic acid 3,4-epoxy three ring [5.2.1.0^2.6] decyl ester is (shown in formula (I-1) Compound shown in compound and formula (II-1) mixes with mol ratio 50:50) 171 parts be dissolved in propylene glycol monomethyl ether Solution in 40 parts.On the other hand, use other dropping pump to drip polymerization initiator 2 in flask with about 5 hours, Double (2,4-methyl pentane nitrile) the 26 parts of solution being dissolved in propylene glycol monomethyl ether 120 parts of 2 '-azo.Polymerization After the completion of dropwise addition of initiator, keeping at that same temperature about 3 hours, be then cooled to room temperature, obtaining solid composition is 43.5%, acid number is the resin solution Ba of 53mgKOH/g (conversion of solid composition).Weight average molecular weight Mw of obtained resin B a Being 8000, molecular weight distribution (Mw/Mn) is 1.98.

Synthesis example 2

In the flask with blender, thermometer, reflux condensing tube, Dropping funnel and nitrogen ingress pipe, import propylene glycol Monomethyl ether acetate 123g, makes after atmosphere is by the spoiled nitrogen of air in flask, after being warming up to 100 DEG C, by Dropping funnel with 2 hours Drip in flask comprise benzyl methacrylate 72.6g (0.41 mole), methacrylic acid 42.0g (0.49 mole), three Monomethacrylates (Hitachi chemical conversion (strain) FA-513M processed) 23.0g (0.10 mole) of cyclodecane skeleton and propylene glycol list first The mixture of base ether acetic acid ester 137g adds the solution of azobis isobutyronitrile 3.6g, stirs continuously at 100 DEG C further Mix 5 hours.Then in making flask, atmosphere is become air from nitrogen, adds methyl propenoic acid glycidyl base ester 21.3g in flask [0.15 mole, (being 31 moles of % relative to the carboxyl of methacrylic acid used in this reaction)], three (dimethylaminomethyls) Phenol 0.9g and hydroquinone 0.145g, 110 DEG C of successive reactions 6 hours, obtain solid composition be 38.3%, acid number be The resin solution Bb of 120.1mgKOH/g (conversion of solid composition).By the weight average molecular weight of the polystyrene conversion that GPC measures Being 10500, molecular weight distribution (Mw/Mn) is 2.1.

Synthesis example 3

In the flask with blender, thermometer, reflux condensing tube, Dropping funnel and nitrogen ingress pipe, import propylene glycol Monomethyl ether acetate 125.1g, makes the atmosphere in flask be become after nitrogen from air, after being warming up to 100 DEG C, by Dropping funnel with 2 Hour drip comprising benzyl methacrylate 96.0g (0.55 mole) in flask, (0.36 rubs methacrylic acid 30.6g You), the monomethacrylates of tricyclodecane skeleton (Hitachi chemical conversion (strain) FA-513M processed) 22.0g (0.10 mole) and the third two The mixture of alcohol monomethyl ether acetate 149g adds the solution of azobis isobutyronitrile 3.6g, further in 100 DEG C of companies Continuous stirring 5 hours.Then in making flask, atmosphere is become air from nitrogen, adds methyl propenoic acid glycidyl base ester in flask 21.3g [0.15 mole, (being 42 moles of % relative to the carboxyl of methacrylic acid used in this reaction)], three (dimethylaminos Methyl) phenol 0.9g and hydroquinone 0.145g, 110 DEG C of successive reactions 6 hours, obtain solid composition be 37.8%, acid number be The resin solution Bc of 67.7mgKOH/g (conversion of solid composition).The weight average molecular weight of the polystyrene conversion measured by GPC is 9400, molecular weight distribution (Mw/Mn) is 2.0.

Synthesis example 4

In the flask with reflux condenser, Dropping funnel and blender, flow into nitrogen with 0.02L/ minute, form nitrogen atmosphere Enclose, add 3-methoxyl group-n-butyl alcohol 200 parts and acetic acid 3-methoxy butyl acrylate 100 parts, while stirring, be heated to 70 DEG C.Connect , by methacrylic acid 54 parts, acrylic acid 3,4-epoxy three ring [5.2.1.0^2.6] decyl ester is (by the compound shown in formula (I-1) Mixing with mol ratio 50:50 with the compound shown in formula (II-1)) 180 parts and N-N-cyclohexylmaleimide 67 parts be dissolved in 3- In methoxyl group-n-butyl alcohol 140 parts, preparing solution, using dropping pump to be added drop-wise to be incubated with 4 hours by this solution is the flask of 70 DEG C In.On the other hand, other dropping pump is used to drip polymerization initiator 2,2 '-azo double (2,4-bis-in flask with 4 hours Methyl valeronitrile) 20 parts be dissolved in the solution in acetic acid 3-methoxy butyl acrylate 240 parts.The dropping of the solution of polymerization initiator After end, 70 DEG C keep 4 hours, be then cooled to room temperature, obtain solid composition be 32.6%, solution acid number be 34.3mg- The solution of the resin solution Bd of KOH/g.Weight average molecular weight Mw of resin B d of gained is 9000, and molecular weight distribution (Mw/Mn) is 1.9。

Synthesis example 5

In the flask with blender, thermometer, reflux condensing tube, Dropping funnel and gas introduction tube, import the third two Alcohol monomethyl ether acetate 250 parts.Then, use gas introduction tube to import in flask by nitrogen, atmosphere in flask is replaced For nitrogen.Then, after the solution in flask is warming up to 100 DEG C, uses Dropping funnel to drip in flask with 2 hours and comprise first Base benzyl acrylate 152.6 parts, methacrylic acid 41.7 parts, azobis isobutyronitrile 1.5 parts and propylene glycol monomethyl ether The mixture of 150 parts, after being added dropwise to complete, further 100 DEG C of continuous stirring 2.5 hours, obtain weight average molecular weight Mw be 2.3 × 10⁴, solid composition be 34%, solution acid number be the resin solution Be of 47mg-KOH/g.

The weight average molecular weight (Mw) of the resin obtained in synthesis example and the mensuration of number-average molecular weight (Mn) use GPC method, Carry out under conditions of below.

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

Pillar: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 DEG C

Solvent: THF (oxolane)

Flow velocity, 1.0mL/min

Detector: RI

Using the weight average molecular weight of polystyrene conversion obtained above and the ratio (Mw/Mn) of number-average molecular weight as molecular weight Distribution.

Embodiment 1

[preparation of photosensitive composition 1]

By pigment: C.I. paratonere 177 49 parts

Polyesters pigment dispersing agent 16 parts

Resin solution Be 29 parts

Propylene glycol monomethyl ether 280 parts

Mixing, use ball mill by fully dispersed for pigment and form dispersible pigment dispersion A,

By pigment: C.I. paratonere 254 5.9 parts

Acrylic pigment dispersant 2.2 parts

Resin solution Be 4.9 parts

Propylene glycol monomethyl ether 29 parts

Mixing, use ball mill by fully dispersed for pigment and form dispersible pigment dispersion B,

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

Resin (B1): resin solution Ba 126 parts,

Resin (B2): resin solution Bb 72 parts,

Polymerizable compound: dipentaerythritol acrylate (KAYARAD DPHA, Japan's chemical medicine (strain) system) 63 parts,

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

Solvent: propylene glycol monomethyl ether 313 parts and

Surfactant: polyether modified silicon oil (トレシリ U Application SH8400, east レダウ conning (strain) System) 0.02 part

Mixing, obtains photosensitive composition 1.

Embodiment 2

[preparation of photosensitive composition 2]

By pigment: C.I. pigment yellow 13 9 18 parts

Polyesters pigment dispersing agent 7.2 parts

Resin solution Be 13 parts

Propylene glycol monomethyl ether 116 parts

By pigment: C.I. paratonere 177 72 parts

Polyesters pigment dispersing agent 20 parts

Resin solution Be 61 parts

Propylene glycol monomethyl ether 310 parts

Resin (B1): resin solution Ba 90 parts,

Resin (B2): resin solution Bc 78 parts,

Polymerizable compound: dipentaerythritol acrylate (KAYARAD DPHA, Japan's chemical medicine (strain) system) 40 parts,

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

Solvent: propylene glycol monomethyl ether 165 parts and

Mixing, obtains photosensitive composition 2.

Embodiment 3

[preparation of photosensitive composition 3]

To by pigment: C.I. paratonere 254 51 parts

Polyesters pigment dispersing agent 15 parts

Propylene glycol monomethyl ether 287 parts

Mixing, and use ball mill by dispersible pigment dispersion fully dispersed for pigment, then mix

Resin (B1): resin solution Ba 184 parts

Resin (B2): resin solution Bb 50 parts

Polymerizable compound: dipentaerythritol acrylate (KAYARAD DPHA, Japan's chemical medicine (strain) system) 64 parts

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

Solvent: propylene glycol monomethyl ether 336 parts

Surfactant: polyether modified silicon oil (トレシリ U Application SH8400, east レダウ conning (strain) System) 0.02 part,

Obtain photosensitive composition 3.

Embodiment 4

[preparation of photosensitive composition 4]

By pigment: C.I. pigment green 36 14 parts

Polyesters pigment dispersing agent 2.7 parts

Resin solution Be 4.0 parts

Propylene glycol monomethyl ether 56 parts

By pigment: C.I. pigment yellow 13 8 12 parts

Polyesters pigment dispersing agent 2.5 parts

Resin solution Be 1.9 parts

Propylene glycol monomethyl ether 66 parts

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

Resin (B2): resin solution Bc 41 parts,

Polymerizable compound: dipentaerythritol acrylate (KAYARAD DPHA, Japan's chemical medicine (strain) system) 80 parts,

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

Solvent: propylene glycol monomethyl ether 570 parts and

Mixing, obtains photosensitive composition 4.

Embodiment 5

[preparation of photosensitive composition 5]

By pigment: C.I. naphthol green 58 53 parts

Acrylic pigment dispersant 11 parts

Resin solution Be 62 parts

Propylene glycol monomethyl ether 251 parts

By pigment: C.I. pigment yellow 13 8 30 parts

Polyesters pigment dispersing agent 4.4 parts

Resin solution Be 31 parts

Propylene glycol monomethyl ether 136 parts

Resin (B1): resin solution Ba 18 parts,

Resin (B2): resin solution Bb 147 parts,

Polymerizable compound: dipentaerythritol acrylate (KAYARAD DPHA, Japan's chemical medicine (strain) system) 64 parts,

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

Solvent: propylene glycol monomethyl ether 181 parts and

Mixing, obtains photosensitive composition 5.

Embodiment 6

[preparation of photosensitive composition 6]

To by pigment: C.I. paratonere 177 28 parts

Pigment: C.I. paratonere 254 86 parts

Polyesters pigment dispersing agent 10 parts

Resin solution Be 27 parts

Propylene glycol monomethyl ether 403 parts

Resin (B1): resin solution Bd 87 parts

Resin (B2): resin solution Bb 99 parts

Polymerizable compound: dipentaerythritol acrylate (Japan's chemical medicine (strain) system) 33 parts

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

Polymerization initiation auxiliary agent: 4,4 '-bis-(diethylamino) benzophenone (EAB-F, hodogaya chemical industry (strain) system) 7.6 part

Solvent: propylene glycol monomethyl ether 294 parts,

Obtain photosensitive composition 6.

Comparative example 1

[preparation of photosensitive composition 7]

To by pigment: C.I. paratonere 177 28 parts

Pigment: C.I. paratonere 254 86 parts

Polyesters pigment dispersing agent 10 parts

Resin solution Be 27 parts

Propylene glycol monomethyl ether 404 parts

Resin: resin solution Bd 169 parts

Polymerizable compound: dipentaerythritol acrylate (Japan's chemical medicine (strain) system) 32 parts

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

Polymerization initiation auxiliary agent: 4,4 '-bis-(diethylamino) benzophenone (EAB-F, hodogaya chemical industry (strain) system) 7.4 part

Solvent: propylene glycol monomethyl ether 92 parts

3-methoxyl group-n-butyl alcohol 67 parts

Acetic acid 3-methoxy butyl acrylate 67 parts,

Obtain photosensitive composition 7.

PET film (east レ Le ミラ 75-T60) of fitting on the glass plate of 2 inch square manufactures substrate.At substrate PET film side, be coated with photosensitive composition by spin-coating method, on hot plate in 60 DEG C of preliminary dryings 2 minutes.Let cool After, make this be coated with 150 μm that are spaced apart of the substrate of photosensitive composition and quartz glass photomask, use and expose Ray machine (TME-150RSK, トプ U Application (strain) make), under atmospheric atmosphere, with 150mJ/cm²Light exposure (365nm benchmark) enter Row light irradiates.And, as photomask, use line and the photomask of space pattern defining 10～100 μm.After light irradiates, In the water system developer solution containing nonionic class surfactant 0.12% and potassium hydroxide 0.04%, within 40 seconds, carry out at 23 DEG C of dippings Development, washs with pure water, forms pattern.Determining film thickness device (DEKTAK3, Japan's vacuum technique (strain) system) is used to measure The thickness of gained pattern, result is 2 μm.

The pattern formed as described above is heated 5 minutes (after bake) at 50 DEG C further, obtains the pattern of solidification.This Outward, the pattern formed as described above is heated 5 minutes (after bake) at 100 DEG C further, obtain the pattern of solidification.Same with above-mentioned Sample ground measures the thickness of the pattern of the solidification of gained, and result is 2 μm.

To pattern dropping propylene glycol monomethyl ether 1ml formed on aforesaid substrate, after static 30 seconds, use rotation Painting machine rotates 10 seconds under conditions of rotating speed 1000rpm, gets rid of the propylene glycol monomethyl ether on pattern.

By the film thickness value measured before and after contacting with propylene glycol monomethyl ether, calculate thickness conservation rate by following formula. Thickness conservation rate is the highest, then curable is the best, when manufacturing color filter, is possible to prevent colour mixture.Result is as shown in table 1.

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

To the pattern obtained, seen by laser microscope (Axio Imager MAT カ Le Star ァイス society system) Examine, using the minimum dimension of resolution as resolution.Resolution is the highest, can manufacture the color filter of fine.Result such as table 1 Shown in.

[table 1]

Can confirm that the excellent in resolution of the pattern using the photosensitive composition of embodiment to be formed.Additionally, Even if when the high temperature more than 200 DEG C carries out baking step, it is also possible to confirm excellent solvent resistance.Even if it follows that using The substrate that thermostability is low, it is also possible to obtain the color filter of fine and high-quality.

Industry utilizability

According to the photosensitive composition of the present invention, the high pattern of resolution and the colour filter of high-quality can be obtained Device.

Claims

1. photosensitive composition, it contains:

(A) coloring agent,

(B1) containing coming from selected from the construction unit of at least one of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides and coming from there is carbon Atomic number is cyclic ether and the copolymer of construction unit of monomer of ethylenic unsaturated bond of 2～4, and it is that side chain does not have olefinic The resin of unsaturated bond,

(B2) side chain has the resin of ethylenic unsaturated bond, its be the copolymer making following (a) and (c) copolymerization obtain further with B resin that () is reacted and obtained,

A () is selected from least one of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides,

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

(c) be have can with the monomer of the unsaturated bond of (a) and (b) copolymerization,

(C) polymerizable compound,

(D) polymerization initiator, and

(E) solvent,

The content of resin (B2) is 5～90 mass % relative to the total amount of resin (B1) and resin (B2).

2. the photosensitive composition described in claim 1, wherein, the content of (B1) is total relative to (B1's) and (B2) Amount is 10 mass %～95 mass %.

3. color filter, it contains the photosensitive composition described in claim 1 or 2.

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

(1) obtain by the photosensitive composition described in any one in claim 1～2 is coated on substrate To the step of coated film,

(3) developed by coated film alkaline developer after exposing, obtain the step of pattern,

(4) by being bakeed by pattern, the step of the pattern of solidification is obtained.

5. the manufacture method of the color filter described in claim 4, wherein, step (4) is to dry in the temperature of 25 DEG C～120 DEG C The step of roasting.

6. the manufacture method of the color filter described in claim 4 or 5, wherein, the substrate in step (1) is plastic base.