CN103034056A

CN103034056A - Colored photosensitive resin composition

Info

Publication number: CN103034056A
Application number: CN201210391755XA
Authority: CN
Inventors: 城内公之
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Dongwoo Fine Chem Co Ltd
Priority date: 2011-10-07
Filing date: 2012-09-29
Publication date: 2013-04-10
Also published as: JP6091831B2; TW201321893A; TWI610134B; KR20130038172A; KR101974965B1; JP2013092759A

Abstract

The invention provides a colored photosensitive resin composition containing (A), (B1), (B2), (C), and (D). (A) is a colorant; (B1) is resin containing the following structure units: structure units derived from at least one of a group formed by compounds selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydride, and structure units derived from monomers with cyclic ether structures with a carbon atom number of 2-4 and ethylene unsaturated bonds; (B2) is resin containing the following structure units: structure units derived from at least one of a group formed by compounds selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydride, and structure units derived from monomers with alicyclic hydrocarbon structures (wherein the resin does not contain structure units derived from monomers with a cyclic ether structure with a carbon atom number of 2-4 and ethylene unsaturated bonds); (C) is a polymerized compound; and (D) is a polymerization initiator.

Description

Photosensitive composition

Technical field

The present invention relates to photosensitive composition.

Background technology

Photosensitive composition is used to make the color filter that uses in the display device such as display panels, electroluminescence panel and plasm display panel.As such photosensitive composition, known have a kind of photosensitive composition (JP2010-211198-A), and as resin, it only contains methacrylic acid and acrylic acid 3,4 _-Epoxy three ring [5.2.1.0 ^2.6] multipolymer of decyl ester.

When forming pattern by photoetching process, photosensitive composition is coated substrate make its drying and the composition layer of formation, peel off and flow into the words of developer solution if when developing, produce, then exist its stripping film to be attached on the pattern with the form of foreign matter, or stop up the situation of the developer solution waste liquid pipe arrangement in the developing machine.Known above-mentioned photosensitive composition is for above-mentioned development now, and existing may not necessarily abundant gratifying situation.

Summary of the invention

The present invention comprises following invention.

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

(A) colorant

(B1) contain the resin of following structural unit: derive from least a kind the structural unit that is selected among the group that unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides consist of, and derive from the structural unit of the monomer of cyclic ether structure with carbon number 2～4 and ethene unsaturated link

(B2) contain the resin of following structural unit: derive from least a kind the structural unit that is selected among the group that unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides consist of, with the structural unit that derives from the monomer with the ester ring type hydrocarbon structure (structural unit that wherein, does not contain the monomer that derives from cyclic ether structure with carbon number 2～4 and ethene unsaturated link.)

(C) polymerizable compound

(D) polymerization initiator

[2] [1] described photosensitive composition wherein, (B2) further contains the structural unit that derives from the monomer with aromatic hydrocarbyl.

[3] [1] or [2] described photosensitive composition, wherein, content (B2) is 10～90 quality % with respect to (B1) and total amount (B2).

[4] color filter that is formed by the described photosensitive composition of any one of [1]～[3].

[5] display device that possesses [4] described color filter.

According to photosensitive composition of the present invention, in the developer solution after development, seldom produce the stripping film that derives from photosensitive composition.

Description of drawings

[Fig. 1] illustrates the skeleton diagram of the manufacture method of color filter of the present invention.

[Fig. 2] illustrates the skeleton diagram of the manufacture method of color filter of the present invention.

[Fig. 3] illustrates the skeleton diagram of the manufacture method of color filter of the present invention.

Symbol description

21 glass substrates

22 TFT (on-off element)

The 22a gate electrode

The 22b gate insulating film

The 22c polysilicon film

The 22d diaphragm

23 color-filter layers

23A photosensitive composition layer (color filter)

The 23a Red lightscreening plate

The 23b green color filter

The 23c blue color filter

24 pixel electrodes

27 signal wires

29 photosensitive resin films (diaphragm)

201,202 connecting holes

Embodiment

Photosensitive composition of the present invention contains following (A), (B1), (B2), (C) reaches (D).

(A) colorant;

(B1) contain the resin of following structural unit: derive from least a kind the structural unit that is selected among the group that unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides consist of, and derive from the structural unit (below be also referred to as " resin (B1) ") of the monomer of cyclic ether structure with carbon number 2～4 and ethene unsaturated link;

(B2) contain the resin of following structural unit: derive from least a kind the structural unit that is selected among the group that unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides consist of, with the structural unit that derives from the monomer with ester ring type hydrocarbon structure (structural unit that wherein, does not comprise the monomer that derives from cyclic ether structure with carbon number 2～4 and ethene unsaturated link) (below be also referred to as " resin (B2) ");

(C) polymerizable compound;

(D) polymerization initiator.

Preferred photosensitive composition of the present invention further contains solvent (E).

In addition, photosensitive composition of the present invention can also contain at least a kind among the group who is selected from polymerization initiation auxiliary agent (D1) and surfactant (F) formation as required.

In addition, if each composition without special declaration, all can be independent a kind use or more than 2 kinds and use.

＜colorant (A) 〉

Colorant (A) can be enumerated dyestuff (A1) and pigment (A2).

Dyestuff (A1) is not particularly limited, and can use known dyestuff, has enumerated such as solvent dye, acid dyes, direct dyes, mordant dye etc., preferably can be dissolved in the dyestuff of organic solvent.

Dyestuff (A1) can be enumerated, for example classify as the compound of dyestuff in the Colour Index (Britain dyeing association of man (The Society of Dyers and Colourists) publishes), or the known dyestuff of record in the dyeing handbook (look dyes society).In addition, can enumerate azo dyes, cyanine dye, triphenhlmethane dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dyestuff, quinoneimine dye, methine type dye, azomethine dyes, squaraine dye, acridine dye, styryl dye, coumarine dye, quinoline dye, nitro dye etc. according to chemical constitution.Wherein, preferred organic solvent-soluble dye.

Can enumerate particularly C.I. solvent yellow 4 (narration of following omission C.I. solvent yellow, only record numbering), 14,15,23,24,38,62,63,68,82,94,98,99,117,162,163,167,189;

C.I. solvent red 45,49,111,125,130,143,145,146,150,151,155,168,169,172,175,181,207,218,222,227,230,245,247;

C.I. solvent orange 2,7,11,15,26,56,77,86;

C.I. solvent violet 11,13,14,26,31,36,37,38,45,47,48,51,59,60;

C.I. solvent blue 4,5,14,18,35,36,37,45,58,59,59:1,63,67,68,69,70,78,79,83,90,94,97,98,100,101,102,104,105,111,112,122,128,132,136,139;

C.I. the C.I. solvent dye such as solvent green 1,3,4,5,7,28,29,32,33,34,35,

C.I. Indian yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112,113,114,116,119,123,128,134,135,138,139,140,144,150,155,157,160,161,163,168,169,172,177,178,179,184,190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251;

C.I. azogeramine, 4,8,14,17,18,26,27,29,31,33,34,35,37,40,42,44,50,51,52,57,66,73,76,80,87,88,91,92,94,95,97,98,103,106,111,114,129,133,134,138,143,145,150,151,155,158,160,172,176,182,183,195,198,206,211,215,216,217,227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,289,308,312,315,316,339,341,345,346,349,382,383,388,394,401,412,417,418,422,426;

C.I. acid orange 6,7,8,10,12,26,50,51,52,56,62,63,64,74,75,94,95,107,108,169,173;

C.I. acid violet 6B, 7,9,17,19,30,34,102;

C.I. Blue VRS, 7,9,15,18,22,23,25,27,29,40,41,42,43,45,51,54,59,60,62,70,72,74,78,80,82,83,86,87,90,92,93,96,100,102,103,104,112,113,117,120,126,127,129,130,131,138,140,142,143,147,150,151,154,158,161,166,167,168,170,171,175,182,183,184,187,192,199,203,204,205,210,229,234,236,242,243,256,259,267,278,280,285,290,296,315,324:1,335,340;

C.I. acid green 1,3,5,9,16,25,27,28,41,50,58,63,65,80,104,105,106, the C.I. acid dyess such as 109,

C.I. directly yellow 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129,136,138,141;

C.I. directly red 79,82,83,84,91,92,96,97,98,99,105,106,107,172,173,176,177,179,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246,250;

C.I. direct orange 26,34,39,41,46,50,52,56,57,61,64,65,68,70,96,97,106,107;

C.I. directly purple 47,52,54,59,60,65,66,79,80,81,82,84,89,90,93,95,96,103,104;

C.I. directly blue 1,2,6,8,15,22,25,40,41,57,71,76,77,78,80,81,84,85,86,90,93,94,95,97,98,99,100,101,106,107,108,109,113,114,115,117,119,120,137,149,150,153,155,156,158,159,160,161,162,163,164,165,166,167,168,170,171,172,173,188,189,190,192,193,194,195,196,198,199,200,201,202,203,207,209,210,212,213,214,222,225,226,228,229,236,237,238,242,243,244,245,246,247,248,249,250,251,252,256,257,259,260,268,274,275,293;

C.I. direct green 25,27,31,32,34,37,63,65,66,67,68,69,72,77,79, the C.I. direct dyess such as 82,

C.I. disperse yellow 51,54,76;

C.I. disperse violet 26,27;

C.I. disperse blue 1,14,56, the C.I. disperse dyes such as 60,

C.I. alkali red 1:1,10;

C.I. alkali blue 1,3,5,7,9,19,21,22,24,25,26,28,29,40,41,45,47,54,58,59,60,64,65,66,67,68;

C.I. Viride Nitens 1; Deng the C.I. basic-dyeable fibre,

C.I. reactive yellow 2,76, and 116;

C.I. reactive orange 16;

C.I. reactive red 36; Deng the C.I. reactive dye,

C.I. mordant yellow 5,8,10,16,20,26,30,31,33,42,43,45,56,61,62,65;

C.I.

mordant rouge

1,2,3,4,9,11,12,14,17,18,19,22,23,24,25,26,27,30,32,33,36,37,38,39,41,43,45,46,48,53,56,63,71,74,85,86,88,90,94,95;

C.I.

mordant dyeing orange

3,4,5,8,12,13,14,20,21,23,24,28,29,32,34,35,36,37,42,43,47,48;

C.I. mordant dyeing purple 1,2,4,5,7,14,22,24,30,31,32,37,40,41,44,45,47,48,53,58;

C.I. mordant

dyeing indigo plant

1,2,3,7,8,9,12,13,15,16,19,20,21,22,23,24,26,30,31,32,39,40,41,43,44,48,49,53,61,74,77,83,84;

C.I. viridon 1,3,4,5,10,15,19,26,29,33,34,35,41,43, the C.I. mordant dyes such as 53,

C.I. vat green 1 reducing dye such as C.I. such as grade etc.

These dyestuffs are suitably selected to get final product according to the spectrophotometric spectra of desired color filter.

The preferred xanthene dye (Aa) of dyestuff (A1).

Xanthene dye (Aa) is the dyestuff that contains the compound that has the xanthene skeleton in the molecule.Xanthene dye (Aa) can be enumerated, for example C.I. CI 45430 (narration of following omission C.I. acid red, only record numbering.Other too.), 52,87,92,94,289,388, C.I. acid violet 9,30,102, C.I. alkali red 1:1 (rhodamine 6G), 2,3,4,8, C.I. alkali red 1:1 0 (rhodamine B), 11, C.I. alkaline purple 10,11,25, C.I. solvent red 218, C.I. mordant rouge 27, C.I. reactive red 36 (rose red b), sulfo group rhodamine G, the described xanthene dye of Japanese Patent Laid-Open 2010-32999-A and the described xanthene dye of Jap.P. 4492760-B etc.Be preferably dissolved in the dyestuff of organic solvent.

Wherein, xanthene dye (Aa) preferably contains the dyestuff of compound shown in the formula (1a) (below be also referred to as " compound (1a) ").When using compound (1a), more than the preferred 50 quality % of the content of the compound (1a) in the xanthene dye (Aa), more preferably more than the 70 quality %, further more than the preferred 90 quality %.Especially, preferably only use compound (1a) as xanthene dye (Aa).

[in the formula (1a), R ¹～R ⁴Represent independently of one another hydrogen atom ,-R ⁸The 1 valency aromatic hydrocarbyl that maybe can have substituent carbon number 6～10.R ¹And R ²Can form with nitrogen-atoms the ring of nitrogen atom, R ³And R ⁴Can form with nitrogen-atoms the ring of nitrogen atom.

R ⁵Expression-OH ,-SO ₃ ^-,-SO ₃H ,-SO ₃ ^-Z ⁺,-CO ₂H ,-CO ₂ ^-Z ⁺,-CO ₂R ⁸,-SO ₃R ⁸Or-SO ₂NR ⁹R ¹⁰

R ⁶And R ⁷The alkyl that represents independently of one another hydrogen atom or carbon number 1～6.

M represents 0～5 integer.When m is integer more than 2, a plurality of R ⁵Identical or different.Wherein, work as R ⁵For-SO ₃ ^-The time, m is 1.

A represents 0 or 1 integer.

X represents halogen atom.

R ⁸1 valency saturated hydrocarbyl of expression carbon number 1～20, the contained hydrogen atom of this saturated hydrocarbyl can be replaced by halogen atom.

Z ⁺Expression ⁺N (R ¹¹) ₄, Na ⁺Or K ⁺

R ⁹And R ¹⁰The 1 valency saturated hydrocarbyl that represents independently of one another hydrogen atom or carbon number 1～20, R ⁹And R ¹⁰Can be in key and form 3～10 yuan of nitrogenous heterocycles with nitrogen-atoms.

R ¹¹Represent independently of one another 1 valency saturated hydrocarbyl of hydrogen atom, carbon number 1～20 or the aralkyl of carbon number 7～10.]

Represent R ¹～R ⁴1 valency aromatic hydrocarbyl of carbon number 6～10 can enumerate for example phenyl, tolyl, xylyl, sym-trimethyl benzene base, propyl phenyl and butylbenzene base.

For R ¹～R ⁴In 1 valency aromatic hydrocarbyl of carbon number 6～10, the contained hydrogen atom of this aromatic hydrocarbyl can by halogen atom ,-R ⁸,-OH ,-OR ⁸,-SO ₃ ^-,-SO ₃H ,-SO ₃ ^-Z ⁺,-CO ₂H ,-CO ₂R ⁸,-SR ⁸,-SO ₃R ⁸,-SO ₂NR ⁹R ¹⁰Deng replacement.Among these substituting groups, be preferably selected from-SO ₃ ^-,-SO ₃H ,-SO ₃ ^-Z ⁺And-SO ₂NR ⁹R ¹⁰Among the group who consists of at least a kind more preferably is selected from-SO ₃ ^-Z ⁺And-SO ₂NR ⁹R ¹⁰Among the group who consists of at least a kind.As this moment-SO ₃ ^-Z ⁺, preferred-SO ₃ ^-+N (R ¹¹) ₄Work as R ¹～R ⁴During for these groups, the photosensitive composition that contains compound (1a) can form the foreign matter generation and lack, and the color filter of excellent heat resistance.

R ¹And R ²Can form with nitrogen-atoms the ring of nitrogen atom, R ³And R ⁴Can form with nitrogen-atoms the ring of nitrogen atom.Contain the ring of nitrogen-atoms as this, can enumerate for example as follows.

Represent R ⁸～R ¹¹1 valency saturated hydrocarbyl of carbon number 1～20 can enumerate the straight chain shape alkyl of the carbon numbers 1～20 such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, cetyl, eicosyl; The branched-chain alkyl of the carbon numbers 3～20 such as isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl; The ester ring type saturated hydrocarbyl of the carbon numbers 3～20 such as cyclopropyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, three ring decyls.

-OR ⁸Can enumerate, for example, methoxyl, ethoxy, propoxyl group, butoxy, amoxy, own oxygen base, heptan oxygen base, octyloxy, 2-ethyl hexyl oxy and eicosane oxygen base.

-CO ₂R ⁸Can enumerate, for example, methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxy carbonyl and eicosane oxygen base carbonyl.

_-SR ⁸Can enumerate, such as, methyl mercapto, ethylmercapto group, butylthio, own sulfenyl, the last of the ten Heavenly stems sulfenyl and eicosane sulfenyl etc.

-SO ₂R ⁸Can enumerate, for example, methyl sulphonyl, ethylsulfonyl, butyl sulfonyl, hexyl sulfonyl, decyl sulfonyl and eicosyl sulfonyl.

-SO ₃R ⁸Can enumerate, for example, methoxyl sulfonyl, ethoxy sulfonyl, propoxyl group sulfonyl, tert-butoxy sulfonyl, own oxygen base sulfonyl and eicosane oxygen base sulfonyl.

-SO ₂NR ⁹R ¹⁰Can enumerate, for example, sulfamoyl;

N-methyl sulfamoyl, N-ethyl sulfamoyl, N-propyl group sulfamoyl, N-isopropyl sulfamoyl, N-butyl sulfamoyl, N-isobutyl sulfamoyl, N-sec-butyl sulfamoyl, N-tert-butyl group sulfamoyl, N-amyl group sulfamoyl, N-(1-ethyl propyl) sulfamoyl, N-(1, the 1-dimethyl propyl) sulfamoyl, N-(1, the 2-dimethyl propyl) sulfamoyl, N-(2, the 2-dimethyl propyl) sulfamoyl, N-(1-methyl butyl) sulfamoyl, N-(2-methyl butyl) sulfamoyl, N-(3-methyl butyl) sulfamoyl, N-cyclopentyl sulfamoyl, N-hexyl sulfamoyl, N-(1, the 3-dimethylbutyl) sulfamoyl, N-(3, the 3-dimethylbutyl) sulfamoyl, N-heptyl sulfamoyl, N-(1-methyl hexyl) sulfamoyl, N-(1,4-dimethyl amyl group) sulfamoyl, N-octyl group sulfamoyl, N-(2-ethylhexyl) sulfamoyl, N-(1, the 5-dimethyl) hexyl sulfamoyl, N-(1,1,2,2-tetramethyl butyl) N-1 such as sulfamoyl replaces sulfamoyl;

N; N-dimethylamino sulfonyl, N; N-ethyl-methyl sulfamoyl, N, N-diethyl amino sulfonyl, N, N-propyl group methyl sulfamoyl, N; N-isopropyl methyl sulfamoyl, N; N-tert-butyl group methyl sulfamoyl, N, N-butyl ethyl sulfamoyl, N, N-two (1-methyl-propyl) sulfamoyl, N; the N such as N-heptyl methyl sulfamoyl, N-2 replaces sulfamoyl etc.

In addition for representing R ⁹And R ¹⁰1 valency saturated hydrocarbyl of carbon number 1～20, the contained hydrogen atom of this saturated hydrocarbyl can be replaced by-OH or halogen atom, this saturated hydrocarbyl is contained-CH ₂-can by-O-,-CO-,-NH-or-NR ⁸-replace.

R ⁹And R ¹⁰Can be in key and form 3～10 yuan of nitrogenous heterocycles with nitrogen-atoms.This heterocycle can be enumerated for example as follows.

Represent R ⁶And R ⁷The alkyl of carbon number 1～6 can enumerate the alkyl of the above-mentioned straight chain shape alkyl of enumerating and the carbon number 1～6 among the branched-chain alkyl.

Represent R ¹¹The aralkyl of carbon number 7～10 can enumerate benzyl, phenethyl, benzene butyl etc.

Z ⁺For ⁺N (R ¹¹) ₄, Na ⁺Or K ⁺, preferred ⁺N (R ¹¹) ₄

Above-mentioned ⁺N (R ¹¹) ₄Preferred 4 R ¹¹Among have at least 2 to be 1 valency saturated hydrocarbyl of carbon number 5～20.In addition, 4 R ¹¹Total carbon atom number preferred 20～80, more preferably 20～60.Work as R ¹¹During for these groups, the photosensitive composition that contains compound (1a) can form the color filter of few foreign.

M is preferred 1～4, and more preferably 1 or 2.

Xanthene dye (Aa) more preferably contains the dyestuff of compound shown in the formula (2a) (below be also referred to as " compound (2a) ").When using compound (2a), more than the preferred 50 quality % of the content of the compound (2a) in the xanthene dye (Aa), more preferably more than the 70 quality %, further more than the preferred 90 quality %.

[in the formula (2a), R ²¹～R ²⁴Represent independently of one another hydrogen atom ,-R ²⁶Or has a substituent aromatic hydrocarbyl of 1 valency of carbon number 6～10.R ²¹And R ²²Can form with nitrogen-atoms the ring of nitrogen atom, R ²³And R ²⁴Can form with nitrogen-atoms the ring of nitrogen atom.

R ²⁵Expression-SO ₃ ^-,-SO ₃H ,-SO ₃ ^-Z1 ⁺Or-SO ₂NHR ²⁶

M1 represents 0～5 integer.When m1 is integer more than 2, a plurality of R ²⁵Identical or different.Wherein work as R ²⁵For-SO ^3-The time, m1 is 1.

A1 represents 0 or 1 integer.

X1 represents halogen atom.

R ²⁶1 valency saturated hydrocarbyl of expression carbon number 1～20.

Z1 ⁺Expression ⁺N (R ²⁷) ₄, Na ⁺Or K ⁺

R ²⁷1 valency saturated hydrocarbyl or the benzyl that represents independently of one another carbon number 1～20.]

Represent R ²¹～R ²⁴1 valency aromatic hydrocarbyl of carbon number 6～10 can enumerate and above-mentioned R ¹～R ⁴In the identical group of aromatic hydrocarbyl enumerated.The contained hydrogen atom of this aromatic hydrocarbyl can be by-SO ₃ ^-,-SO ₃H ,-SO ₃ ^-Z1 ⁺,-SO ₃R ²⁶Or-SO ₂NHR ²⁶Replace.

R ²¹～R ²⁴Combinatorial optimization be R ²¹And R ²³Be hydrogen atom, R ²²And R ²⁴Be 1 valency aromatic hydrocarbyl of carbon number 6～10, the hydrogen atom quilt-SO that this aromatic hydrocarbyl is contained ₃ ^-,-SO ₃H ,-SO ₃ ^-Z1 ⁺,-SO ₃R ²⁶Or-SO ₂NHR ²⁶Replace.Further preferred combination is R ²¹And R ²³Be hydrogen atom, R ²²And R ²⁴Be 1 valency aromatic hydrocarbyl of carbon number 6～10, the hydrogen atom quilt-SO that this aromatic hydrocarbyl is contained ₃ ^-Z1 ⁺Or-SO ₂NHR ²⁶Replace.

In addition, preferred R ²¹And R ²²Form the aliphatics heterocycle of nitrogen atom and R with nitrogen-atoms ²³And R ²⁴Form the aliphatics heterocycle of nitrogen atom with nitrogen-atoms.

Work as R ²¹～R ²⁴During for these groups, the photosensitive composition that contains compound (2a) can form the color filter of excellent heat resistance.

Above-mentioned aliphatics heterocycle can be enumerated, and is for example as follows.

Represent R ²⁶And R ²⁷1 valency saturated hydrocarbyl of carbon number 1～20 can enumerate and R ⁸～R ¹¹In the identical group of saturated hydrocarbyl enumerated.

R ²¹～R ²⁴In-R ²⁶Preferably be hydrogen atom, methyl or ethyl independently of one another.In addition ,-SO ₃R ²⁶And-SO ₂NHR ²⁶In R ²⁶The branched-chain alkyl of preferred carbon number 3～20, the more preferably branched-chain alkyl of carbon number 6～12, further preferred 2-ethylhexyl.Work as R ²⁶During for these groups, the photosensitive composition that contains compound (2a) can form foreign matter and produce few color filter.

Z1 ⁺For ⁺N (R ²⁷) ₄, Na ⁺Or K ⁺, preferred ⁺N (R ²⁷) ₄

As above-mentioned ⁺N (R ²⁷) ₄, preferred 4 R ²⁷Among have at least 2 to be 1 valency saturated hydrocarbyl of carbon number 5～20.In addition, 4 R ²⁷Total carbon atom number preferred 20～80, more preferably 20～60.Contain and work as R ²⁷The photosensitive composition of the compound (2a) during for these groups can form foreign matter and produce few color filter.

M1 is preferred 1～4, and more preferably 1 or 2.

Compound (2a) can be enumerated, for example the compound shown in formula (1-1)～formula (1-25).In addition, in the formula.R ²⁶1 valency saturated hydrocarbyl of expression carbon number 1～20, the branched-chain alkyl of preferred carbon number 6～12, further preferred 2-ethylhexyl.Wherein, sulfonamide compounds, the quaternary ammonium salt of C.I. acid red 289, the sulfonamide compounds of C.I. acid violet 102 or the quaternary ammonium salt of C.I. acid violet 102 of preferred C.I. acid red 289.Such compound can be enumerated, the compound shown in formula (1-1)～formula (1-8), formula (1-11) and formula (1-12) etc.

In addition, xanthene dye (Aa) more preferably contains the dyestuff of compound shown in the formula (3a) (below be also referred to as " compound (3a) ").When using compound (3a), more than the preferred 50 quality % of the content of the compound (3a) in the xanthene dye (Aa), more preferably more than the 70 quality %, further more than the preferred 90 quality %.

[in the formula (3a), R ³¹And R ³²The alkyl that represents independently of one another carbon number 1～4.

R ³³And R ³⁴Represent independently of one another the alkyl of carbon number 1～4, the alkyl sulfenyl of carbon number 1～4 or the alkyl sulphonyl of carbon number 1～4.

R ³¹And R ³³Can form with nitrogen-atoms the ring of nitrogen atom, R ³²And R ³⁴Can form with nitrogen-atoms the ring of nitrogen atom.

P and q represent 0～5 integer independently of one another.When p is 2 when above, a plurality of R ³³Can be identical or different, when q is 2 when above, a plurality of R ³⁴Can be identical or different.]

Represent R ³¹, R ³², R ³³And R ³⁴The alkyl of carbon number 1～4 can enumerate methyl, ethyl, propyl group, butyl, isopropyl, isobutyl, sec-butyl, the tert-butyl group etc.

Represent R ³³And R ³⁴The alkyl sulfenyl of carbon number 1～4 can enumerate methyl mercapto, ethylmercapto group, rosickyite base, butylthio, isopropyl sulfenyl etc.

Represent R ³³And R ³⁴The alkyl sulphonyl of carbon number 1～4 can enumerate methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, butyl sulfonyl, isopropyl sulfonyl etc.

R ³¹And R ³²Preferably be methyl and ethyl independently of one another.R ³³And R ³⁴The alkyl of preferred carbon number 1～4, more preferably methyl.

The integer of m and n preferred 0～2, more preferably 0 or 1.

Compound (3a) can be enumerated, for example respectively by the compound shown in formula (1-26)～formula (1-32).Wherein, based on the point of the dissolubility excellence in organic solvent, the compound shown in the preferred formula (1-26).

Xanthene dye (Aa) can use commercially available xanthene dye (for example China and foreign countries change into " the Chugai AminolFast Pink R-H/C " of (strain) system, " the Rhodamin 6G " of ridge, field chemical industry (strain) system).In addition, also can take commercially available xanthene dye as initial feed, synthesize with reference to JP2010-32999-A.

The preferred phthalocyanine dye (Ab) of dyestuff (A1).Compound shown in phthalocyanine dye (Ab) preferred formula (4).

[in the formula (4), G ¹The alkylidene of expression carbon number 2～16, this alkylidene is contained-CH ₂-can be replaced by-O-.

J ¹The expression hydrogen atom ,-NR ^aR ^bOr-NR ^aR ^bH ⁺Q ^-

R ^aAnd R ^bThe alkyl that represents independently of one another hydrogen atom or carbon number 1～8.

Q ^-Expression halide ion, BF ₄ ^-, PF ₆ ^-, ClO ₄ ^-, X-CO ₂ ^-Or Y-SO ₃ ^-

X and Y represent 1 valency organic group independently of one another.

P represents 1～4 integer.]

P the hydrogen atom quilt-SO that compound shown in formula (4) expression (4-0) is contained ₂-NH-G ¹-J ¹Replace.When p is 2 when above, a plurality of-SO ₂-NH-G ¹-J ¹Each other can be identical or different.

The alkylidene of carbon number 2～12 can be enumerated, methylene, ethylidene, propylidene, butylidene etc.

-CH ₂The alkylidene of the carbon number 2～12 that-quilt-O-replaces can be enumerated the group shown in the group shown in the formula (G-1) and the formula (G-2).

[in formula (G-1) and the formula (G-2), G ²～G ⁵The alkylidene that represents independently of one another carbon number 1～8.

N1 represents 1～3 integer.

N2 represents 0～3 integer.

Wherein, the carbon atom that the group shown in the formula (G-1) is contained and oxygen atom add up to 3～12, the carbon atom that the group shown in the formula (G-2) is contained and oxygen atom add up to 2～12.

* the bonding position of expression and-NH-.]

The alkyl of carbon number 1～4 can be enumerated, methyl, ethyl, propyl group, butyl etc.

-SO ₂-NH-G ¹-J ¹Can enumerate for example group shown in the following formula.

Work as G ¹During for the group shown in the formula (G-1) ,-SO ₂-NH-G ¹-J ¹Can enumerate for example group shown in the following formula.

Work as G ¹During for the group shown in the formula (G-2) ,-SO ₂-NH-G ¹-J ¹Can enumerate for example group shown in the following formula.

Work as J ¹For-NR ^aR ^bThe time ,-SO ₂-NH-G ¹-J ¹Can enumerate for example group shown in the following formula.

Work as J ¹For-NR ^aR ^bH ⁺Q ^-The time ,-SO ₂-NH-G ¹-NR ^aR ^bH ⁺Can enumerate for example group shown in the following formula.

X and Y represent 1 valency organic group.1 valency organic group can be enumerated, the naphthenic base of the alkyl of carbon number 1～20, carbon number 3～20, the aryl of carbon number 6～20 and their combination group etc.

The alkyl of carbon number 1～20 can be enumerated, methyl, ethyl, propyl group, butyl, hexyl, decyl etc.

The naphthenic base of carbon number 3～20 can be enumerated, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ring decyl etc.

The aryl of carbon number 6～20 can be enumerated, phenyl, naphthyl, anthryl etc.

X-CO ₂ ^-To contain CO ₂ ^-The organism negative ion of base, Y-SO ₃ ^-To contain SO ₃ ^-The organism negative ion of base can be enumerated for example negative ion shown in formula (Q-1)～formula (Q-4).

[R ^yThe alkyl of expression carbon number 1～20.

N3 represents 0～5 integer.]

Q ^-Preferred X-CO ₂ ^-And Y-SO ₃ ^-, the more preferably negative ion shown in the formula (Q-4).When being these negative ion, has the tendency that the dissolubility of compound in solvent shown in the formula (2) uprises.

Compound shown in the formula (4) can be enumerated the compound of putting down in writing among the JP2011-28236-A for example.Wherein, the compound shown in preferred formula (4-1)～formula (4-5), the more preferably compound shown in the compound shown in the formula (4-2) and the formula (4-5).

Pigment (A2) can be enumerated, and for example classifies as the compound of pigment in the Colour Index (Colour Index) (Britain dyeing association of man (The Societyof Dyers and Colourists) publishes).

Pigment can be enumerated, such as, C.I. pigment yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,137,138,139,147,148,150,153,154,166,173,180,185,194,214, the yellow uitramarines such as 219;

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

C.I. Pigment Red 9,97,105,122,123,144,149,166,168,175,176,177,180,192,209,215,216,224,242,254,255,264, the red pigments such as 265;

C.I. pigment blue 15,15:3,15:4,15:6,60, the blue pigments such as 80; C.I.

pigment violet

1,19,23,29,32,36, the violet pigments such as 38;

C.I. pigment Green 7,36, the viridine greens such as 58;

C.I. bistre 23, the brown pigments such as 25;

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

When photosensitive composition of the present invention is mixed with blue-colored photosensitive polymer combination, the preferred C.I. pigment blue 15 of pigment, 15:3,15:4,15:6, the blue pigments such as 60 and C.I.

pigment violet

1,19,23,29,32,36, the violet pigments such as 38, more preferably C.I. pigment blue 15: 3,15:6 and C.I. pigment Violet 23, further preferred C.I. pigment blue 15: 6.

When photosensitive composition of the present invention is mixed with the green coloring photosensitive polymer combination, the preferred C.I. pigment Green 7 of pigment, the viridine greens such as 36,58 and C.I. pigment yellow 13 8,139, the yellow uitramarines such as 150.

When photosensitive composition of the present invention is mixed with red colored photosensitive polymer combination, the preferred C.I. paratonere 177 of pigment, the red pigments such as 209,242,254,255, C.I. pigment orange 38,43, the orange pigments such as 71 and C.I. pigment yellow 13 8,139, the yellow uitramarines such as 150.

By containing above-mentioned pigment, see through spectrum and be easy to optimization, the photostability of color filter and chemical proofing are good.

Pigment (A2) can be as required; implement rosin and process, use the pigment derivative that imported acidic groups or basic group etc. to carry out surface treatment, by macromolecular compound etc. surface of pigments carried out grafting and process, carry out micronize by sulfuric acid micronize method etc. and process, perhaps implement to remove impurity, remove the processing of ionic impurity etc. by ion exchange process etc. by the cleaning treatment of organic solvent or water etc.

Pigment (A2) preferable particle size homogeneous.Carry out dispersion treatment by making it to contain pigment dispersing agent, can obtain pigment and be scattered in dispersible pigment dispersion in the solution with the homogeneous state.

Above-mentioned pigment dispersing agent can be enumerated, pigment dispersing agents such as kation system, negative ion system, nonionic system, both sexes, polyester system, polyamines system, acrylic acid series etc.These pigment dispersing agents can be used singly or two or more kinds in combination.Pigment dispersing agent can be enumerated with trade name, KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system), Off ロ one レ Application (common prosperity society chemistry (strain) system), ソ Le スパ one ス (ゼネカ (strain) system), EFKA (CIBA society system), アジスパ one (monosodium glutamate Off アイ Application テ Network ノ (strain) system), Disperbyk (PVC Star Network ケミ one society's system) etc.

When using pigment dispersing agent, its use amount is preferably below the above 100 quality % of 1 quality % with respect to pigment (A2), more preferably below the above 50 quality % of 5 quality %.If the use amount of pigment dispersing agent in above-mentioned scope, then has the tendency of the dispersible pigment dispersion that obtains the homogeneous disperse state.

Colorant (A) preferably contains dyestuff (A1).By containing dyestuff (A1), see through spectrum and be easy to optimization.

In addition, colorant (A) more preferably contains dyestuff (A1) and pigment (A2).At this moment, the content ratio of dyestuff (A1) and pigment (A2) is in quality criteria, and preferred 1: 99～99: 1, more preferably 3: 97～90: 10.By making it to contain such ratio, see through spectrum and be easy to optimization, the color filter of acquisition has the tendency of contrast, brightness, thermotolerance and chemical proofing excellence.

Dyestuff (A1) preferably contains the dyestuff of xanthene dye (Aa), more preferably contains the dyestuff of xanthene dye (Aa) and phthalocyanine dye (Ab).At this moment, the content ratio of xanthene dye (Aa) and phthalocyanine dye (Ab) is in quality criteria, and preferred 5: 95～95: 5, more preferably 20: 80～80: 20, further preferred 40: 60～65: 35.

Especially, colorant (A) is preferably the colorant that contains xanthene dye (Aa) and blue pigment, more preferably contains xanthene dye (Aa) and C.I. pigment blue 15: 6 colorant.The content ratio of xanthene dye (Aa) and blue pigment is in quality criteria, and preferred 1: 99～90: 10, more preferably 2: 98～70: 30, further preferred 2 _:98～50: 50.

The content of colorant (A) is with respect to the total amount of solid constituent, preferred 5～60 quality %, more preferably 8～50 quality %, further preferred 10～40 quality %.When the content of colorant (A) was in above-mentioned scope, the colour saturation when making color filter was abundant, and can contain in the composition must amount resin or polymerizable compound (C), so can form the enough color filters of physical strength.

Herein, " total amount of solid constituent " in this instructions refers to amount behind the desolventizing content from the total amount of photosensitive composition of the present invention.The total amount of solid constituent and with respect to its content of each composition can be measured by known analysis means such as, liquid phase chromatography, vapor-phase chromatography.

＜resin (B1) 〉

Resin (B1) is the resin that contains following structural unit: derive from the structural unit of at least a kind of being selected among the group that unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides consist of (below be also referred to as " (a) "), and derive from the structural unit of the monomer (below be also referred to as " (b) ") of cyclic ether structure with carbon number 2～4 and ethene unsaturated link.Resin (B1) further also can have to derive from and is different from (a) and (b), and can with the structural unit of the monomer of their copolymerization (below be also referred to as " (c) ").

Resin (B1) can be enumerated following resin [K1] and resin [K2].

Resin [K1]: (a) with (b) multipolymer;

Resin [K2]: (a) with (b) with (c) multipolymer.

(a) can enumerate particularly, such as, acrylic acid, methacrylic acid, butenoic acid, neighbour,, to unsaturated monocarboxylic acid classes such as vinyl benzoic acids;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-ethene phthalandione, 4-ethene phthalandione, 3,4,5,6-tetrahydrochysene phthalandione, 1,2,3,6-tetrahydrochysene phthalandione, dimethyl tetrahydro phthalandione, the Isosorbide-5-Nitrae-unsaturated dicarboxylic acid classes such as cyclohexene dioctyl phthalate;

Methyl-5-norborene-2,3-dioctyl phthalate, 5-carboxyl dicyclo [2.2.1]-2-heptene, 5,6-dicarboxyl dicyclo [2.2.1]-2-heptene, 5-carboxyl-5-methyl bicycle [2.2.1]-2-heptene, 5-carboxyl-5-ethyl dicyclo [2.2.1]-2-heptene, 5-carboxyl-6-methyl bicycle [2.2.1]-2-heptene, 5-carboxyl-6-ethyl dicyclo [2.2.1]-2-heptene etc. contain the dicyclo unsaturated compound class of carboxyl;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-ethene anhydride phthalic acid, 4-ethene anhydride phthalic acid, 3,4,5,6-tetrahydrochysene anhydride phthalic acid, 1,2,3,6-tetrahydrochysene anhydride phthalic acid, dimethyl tetrahydro anhydride phthalic acid, 5,6-dicarboxyl dicyclo [the 2.2.1]-unsaturated dicarboxylic acid class acid anhydrides such as 2-heptene acid anhydrides;

Unsaturated list ((methyl) acryloyloxyalkyl) the ester class of the polybasic carboxylic acids more than 2 yuan such as mono succinate (2-(methyl) acrylyl oxy-ethyl) ester, phthalandione list (2-(methyl) acrylyl oxy-ethyl) ester;

_α-(hydroxymethyl) unsaturated esters of acrylic acid acrylic compounds, that in a part, contain hydroxyl and carboxyl etc.

Wherein, based on the point of copolyreaction or the deliquescent point in aqueous alkali, preferred (methyl) acrylic acid and maleic anhydride etc., more preferably (methyl) acrylic acid.

In addition, in this instructions, " (methyl) acryloyl group " expression is selected from least a kind among the group that acryloyl group and methacryl consist of.The narration that " (methyl) acrylic acid " reaches " (methyl) acrylate " etc. also has same meaning.

(b) refer to have the polymerizable compound of the cyclic ether structure of carbon number 2～4 for example (for example, be selected among the group that oxirane ring, oxetanes ring and tetrahydrofuran ring consist of at least a kind) and ethene unsaturated link.(b) be preferably the monomer of cyclic ether with carbon number 2～4 and (methyl) acryloxy.

(b) can enumerate, such as the monomer (b1) with epoxy ethyl and ethene unsaturated link (below be also referred to as " (b1) "), have oxa-cyclobutyl and ethene unsaturated link monomer (b2) (below be also referred to as " (b2) "), have monomer (b3) (below be also referred to as " (b3) ") of tetrahydrofuran base and ethene unsaturated link etc.

(b1) can enumerate, for example have the monomer (b1-1) of the structure behind straight chain shape or the chain unsaturated fatty hydrocarbons epoxidation (below be also referred to as " (b1-1) "), have the monomer (b1-2) of the structure behind the unsaturated lipid ring type hydrocarbon epoxidation (below be also referred to as " (b1-2) ").

(b1-1) can enumerate, (methyl) acrylic acid glycidyl esters, (methyl) acrylic acid Beta-methyl glycidyl esters, (methyl) propenoic acid beta-ethyl glycidyl esters, the glycidyl vinyl ether, adjacent vinyl benzyl glycidyl ether, between the vinyl benzyl glycidyl ether, to the vinyl benzyl glycidyl ether, Alpha-Methyl-adjacent vinyl benzyl glycidyl ether, an Alpha-Methyl-vinyl benzyl glycidyl ether, Alpha-Methyl-to the vinyl benzyl glycidyl ether, 2,3-two (glycidyl oxygen ylmethyl) styrene, 2,4-two (glycidyl oxygen ylmethyl) styrene, 2,5-two (glycidyl oxygen ylmethyl) styrene, 2,6-two (glycidyl oxygen ylmethyl) styrene, 2,3,4-three (glycidyl oxygen ylmethyl) styrene, 2,3,5-three (glycidyl oxygen ylmethyl) styrene, 2,3,6-three (glycidyl oxygen ylmethyl) styrene, 3,4,5-three (glycidyl oxygen ylmethyl) styrene and 2,4,6-three (glycidyl oxygen ylmethyl) styrene etc.

(b1-2) can enumerate, an oxyethylene group cyclohexene, 1, (for example, セロキサイ De 2000 for 2-epoxy-4-vinyl cyclohexane; ダイセ Le chemical industry (strain) system), (methyl) acrylic acid 3,4-epoxycyclohexyl methyl ester (for example, サイ Network ロマ one A400; ダイセ Le chemical industry (strain) system), (methyl) acrylic acid 3,4-epoxycyclohexyl methyl ester (for example, サイ Network ロマ one M100; ダイセ Le chemical industry (strain) system), the compound shown in the formula (I), the compound shown in the formula (II) etc.

[in formula (I) and the formula (II), R ^B1And R ^B2The alkyl of expression hydrogen atom or carbon number 1～4, the contained hydrogen atom of this alkyl can be replaced by hydroxyl.

X ^B1And X ^B2The expression singly-bound ,-R ^B3-, *-R ^B3-O-, *-R ^B3-S-or *-R ^B3-NH-.

R ^B3The alkylidene of expression carbon number 1～6.

* represent the bonding position with O.]

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

Alkyl after hydrogen atom is replaced by hydroxyl can be enumerated, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyl-1-Methylethyl, 2-hydroxyl-1-Methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl etc.

R ^B1And R ^B2Preferably can enumerate hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl and 2-hydroxyethyl, more preferably hydrogen atom and methyl.

Alkylidene can be enumerated, methylene, ethylidene, 1,2-propylidene, 1,3-propylidene, Isosorbide-5-Nitrae-butylidene, 1,5-pentylidene, 1,6-hexylidene etc.

X ^B1And X ^B2Preferably can enumerate singly-bound, methylene, ethylidene, *-CH ₂-O-and *-CH ₂CH ₂-O-, more preferably singly-bound, *-CH ₂CH ₂-O-(* represents the bonding position with O).

Compound shown in the formula (I) can be enumerated, formula (I-1)～formula (I-15) arbitrarily shown in compound etc.Wherein, preferred formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) and formula (I-11)～formula (I-15) arbitrarily shown in compound, the more preferably compound shown in formula (I-1), formula (I-7), formula (I-9) or the formula (I-15).

Compound shown in the formula (II) can be enumerated, formula (II-1)～formula (II-15) arbitrarily shown in compound etc.Wherein, preferred formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) and formula (II-11)～formula (II-15) arbitrarily shown in compound, the more preferably compound shown in formula (II-1), formula (II-7), formula (II-9) or the formula (II-15).

Compound shown in compound shown in the formula (I) and the formula (II) can be distinguished separately use, also can mix with arbitrary ratio and use.When mix using, the compound shown in the compound shown in the formula (I) and the formula (II) contain ratio in molar basis, preferred 5: 95～95: 5, more preferably 10: 90～90: 10, further preferred 20: 80～80: 20.

As the monomer (b2) with oxa-cyclobutyl and ethene unsaturated link, more preferably has the monomer of oxa-cyclobutyl and (methyl) acryloxy.(b2) can enumerate 3-methyl-3-methacryloxy methyl oxetanes, 3-methyl-3-acryloyl-oxy ylmethyl oxetanes, 3-ethyl-3-methacryloxy methyl oxetanes, 3-ethyl-3-acryloyl-oxy ylmethyl oxetanes, 3-methyl-3-methacryloxyethyl oxetanes, 3-methyl-3-acryloxy Ethyloxetane, 3-ethyl-3-methacryloxyethyl oxetanes, 3-ethyl-3-acryloxy Ethyloxetane etc.

As the monomer (b3) with tetrahydrofuran base and ethene unsaturated link, more preferably has the monomer of tetrahydrofuran base and (methyl) acryloxy.(b3) can enumerate particularly acrylic acid tetrahydro furfuryl ester (such as, PVC スコ one ト V#150, Osaka organic chemistry industry (strain) system) and methacrylic acid tetrahydro furfuryl ester etc.

As (b), the point based on reliabilities such as the thermotolerance that can further improve the color filter of acquisition, chemical proofings is preferably (b1).Further, based on the point of the excellent storage stability of photosensitive composition, more preferably (b1-2).

(c) can enumerate, for example, (methyl) methyl acrylate, (methyl) acrylic acid ethyl ester, (methyl) n-butylacrylate, (methyl) acrylic acid sec-butyl ester, (methyl) acrylic acid tertiary butyl ester, (methyl) 2-ethylhexyl acrylate, (methyl) dodecylacrylate, (methyl) acrylic acid Lauryl Ester, (methyl) acrylic acid stearyl, (methyl) acrylic acid cyclopentyl ester, (methyl) acrylic acid cyclohexyl ester, (methyl) acrylic acid 2-methylcyclohexyl ester, (methyl) acrylic acid three ring [5.2.1.0 ^2,6] decane-(in this technical field, popular name is called " (methyl) acrylic acid dicyclo pentyl ester " to 8-base ester.In addition, be also referred to as " (methyl) acrylic acid three ring decyl ester "), (methyl) acrylic acid three ring [5.2.1.0 ^2,6] decene-(in this technical field, popular name is called " (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate " to 8-base ester.), (methyl) esters of acrylic acid such as (methyl) acrylic acid dicyclo amoxy ethyl ester, (methyl) isobornyl acrylate, (methyl) acrylic acid adamantane esters, (methyl) acrylic acid allyl ester, (methyl) acrylic acid propargyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid naphthyl ester, (methyl) acrylic acid benzyl ester;

(methyl) esters of acrylic acid of the hydroxyls such as (methyl) acrylic acid 2-hydroxyethyl ester, (methyl) acrylic acid 2-hydroxy-propyl ester;

The dicarboxylic diesters such as diethyl maleate, DEF, diethyl itaconate;

Dicyclo [2.2.1]-2-heptene, 5-methyl bicycle [2.2.1]-2-heptene, 5-ethyl dicyclo [2.2.1]-2-heptene, 5-hydroxyl dicyclo [2.2.1]-2-heptene, 5-hydroxymethyl dicyclo [2.2.1]-2-heptene, 5-(2 '-hydroxyethyl) dicyclo [2.2.1]-2-heptene, 5-methoxyl dicyclo [2.2.1]-2-heptene, 5-ethoxy dicyclo [2.2.1]-2-heptene, 5,6-dihydroxy dicyclo [2.2.1]-2-heptene, 5,6-two (hydroxymethyl) dicyclo [2.2.1]-2-heptene, 5,6-two (2 '-hydroxyethyl) dicyclo [2.2.1]-2-heptene, 5,6-dimethoxy dicyclo [2.2.1]-2-heptene, 5,6-diethoxy dicyclo [2.2.1]-2-heptene, 5-hydroxy-5-methyl base dicyclo [2.2.1]-2-heptene, 5-hydroxyl-5-ethyl dicyclo [2.2.1]-2-heptene, 5-hydroxymethyl-5-methyl bicycle [2.2.1]-2-heptene, 5-tert-butoxycarbonyl dicyclo [2.2.1]-2-heptene, 5-cyclohexyl oxygen base carbonyl dicyclo [2.2.1]-2-heptene, 5-phenyloxycarbonyl dicyclo [2.2.1]-2-heptene, 5,6-two (tert-butoxycarbonyl) dicyclo [2.2.1]-2-heptene, 5,6-two (cyclohexyl oxygen base carbonyl) dicyclo [the 2.2.1]-dicyclo unsaturated compound classes such as 2-heptene;

The dicarbapentaborane imide derivative classes such as N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, 3-maleimide yl benzoic acid N-succinimide ester, 4-dimaleoyl imino butyric acid N-succinimide ester, 6-dimaleoyl imino caproic acid N-succinimide ester, 3-dimaleoyl imino propionic acid N-succinimide ester, N-(9-acridinyl) maleimide;

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

Wherein, based on copolyreaction and stable on heating point, optimization styrene, vinyltoluene, N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide and dicyclo [2.2.1]-2-heptene.

In the resin [K1], derive from the ratio of structural unit of each monomer with respect to all structural units that consist of resin [K1], be preferably following value:

Derive from the structural unit of (a): 2～60 % by mole

Derive from the structural unit of (b): 40～98 % by mole

More preferably

Derive from the structural unit of (a): 10～50 % by mole

Derive from the structural unit of (b): 50～90 % by mole.

When the ratio of the structural unit that consists of resin [K1] is in above-mentioned scope, has the tendency of solvent resistance excellence of colored pattern of storage stability, the development when forming colored pattern and the acquisition of photosensitive composition.

Resin [K1] but the citing document put down in writing in the method for record and the document in reference example such as the document " experimental method of Polymer Synthesizing " (the grand row work publishing house in large Tianjin (strain) chemistry is with the 1st edition the 1st printing distribution on March 1st, 1972 of people) make.

Particularly, can enumerate (a) of ormal weight and (b), in the reaction vessels of packing into such as polymerization initiator and solvent, by the nitrogen replace oxygen, make the deoxidation environment by for example, the method that when stirring, heats and be incubated.In addition, polymerization initiator as used herein and solvent etc. are not particularly limited, and can use normally used compound in this field.For example, as polymerization initiator, can enumerate azo-compound (2,2 '-azoisobutyronitrile, 2,2 '-azo two (2,4-methyl pentane nitrile) etc.) or organic peroxide (benzoyl peroxide etc.), as solvent, get final product so long as can dissolve each monomer, can enumerate solvent described later (E) as the solvent of photosensitive composition etc.

In addition, the resin for obtaining can directly use reacted solution, also can use the solution after concentrated or the dilution, also can use the solid (powder) by method taking-ups such as precipitations again.Especially, the solvent during as its polymerization by using solvent described later (E), can be directly used in reacted solution the manufacturing of photosensitive composition, and then simplifies the manufacturing process of photosensitive composition.

In the resin [K2], the ratio of the structural unit in each source is preferably following value with respect to all structural units that consist of resin [K2]:

Derive from the structural unit of (a): 2～45 % by mole

Derive from the structural unit of (b): 2～95 % by mole

Derive from the structural unit of (c): 1～65 % by mole

More preferably

Derive from the structural unit of (a): 5～40 % by mole

Derive from the structural unit of (b): 5～80 % by mole

Derive from the structural unit of (c): 5～60 % by mole.

The ratio of the structural unit of resin [K2] is in above-mentioned scope the time, has the tendency of solvent resistance, thermotolerance and physical strength excellence of colored pattern of storage stability, the development when forming colored pattern and the acquisition of photosensitive composition.

Resin (B1) can be enumerated particularly, (methyl) acrylic acid 3,4-epoxycyclohexyl methyl ester/(methyl) acrylic copolymer, acrylic acid 3,4-epoxy three ring [5.2.1.0 ^2.6] decyl ester/resins [K1] such as (methyl) acrylic copolymer; (methyl) acrylic acid glycidyl esters/(methyl) acrylic acid benzyl ester/(methyl) acrylic copolymer, (methyl) acrylic acid glycidyl esters/styrene/(methyl) acrylic copolymer, acrylic acid 3,4-epoxy three ring [5.2.1.0 ^2.6] decyl ester/(methyl) acrylic acid/N-N-cyclohexylmaleimide multipolymer, acrylic acid 3,4-epoxy three ring [5.2.1.0 ^2.6] decyl ester/(methyl) acrylic acid/vinyl toluene copolymer, 3-methyl-3-(methyl) acrylic acid acyloxy methyl oxetanes/(methyl) acrylic acid/resins [K2] such as N-N-cyclohexylmaleimide multipolymer.

Resin [K2] can adopt for example identical with the manufacture method of resin [K1] method to make.

The polystyrene conversion weight-average molecular weight of resin (B1) is preferred 3,000～100,000, and more preferably 5,000～50,000, further preferred 5,000～30,000.When molecular weight was in above-mentioned scope, the hardness with color filter improved, residual film ratio is high, unexposed portion is for the favorable solubility of developer solution, the tendency that the exploring degree improves.

The molecular weight distribution of resin (B1) [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] is preferred 1.1～6, and more preferably 1.2～4.

Preferred 50～the 170mg-KOH/g of acid number of resin (B1), more preferably 60～150mg-KOH/g, further preferred 70～135mg-KOH/g.Acid number herein be as in and the amount (mg) of the required potassium hydroxide of 1g resin measure and value, can try to achieve by for example carrying out titration with potassium hydroxide aqueous solution.

The content of resin (B1) is with respect to the total amount of resin (B1) and resin (B2), preferred 10～90 quality %, more preferably 25～85 quality %, further preferred 50～80 quality %.

＜resin (B2) 〉

Resin (B2) is the resin that contains (a) and derive from the structural unit (below be also referred to as " (x) ") of the monomer with ester ring type hydrocarbon structure.Wherein, resin (B2) does not contain the structural unit (b) of the monomer that derives from cyclic ether structure with carbon number 2～4 and ethene unsaturated link.Resin (B2) further also can contain to derive from and is different from (a), (b) and (x), and can with the structural unit of the monomer of their copolymerization (below be also referred to as " (d) ").

Resin (B2) can be enumerated following resin [K3] and resin [K4].

Resin [K3]: (a) with (x) multipolymer;

Resin [K4]: (a) with (x) with (d) multipolymer.

(a) can enumerate the compound identical with (a) of resin (B1).Wherein, based on the point of copolyreaction or the deliquescent point in aqueous alkali, preferred (methyl) acrylic acid and maleic anhydride, more preferably (methyl) acrylic acid.

(x) can enumerate, have (methyl) esters of acrylic acid of monocycle ester ring type hydrocarbon structure such as, (methyl) acrylic acid cyclopentyl ester, (methyl) acrylic acid cyclohexyl ester, (methyl) acrylic acid 2-methylcyclohexyl ester etc.;

(methyl) acrylic acid three ring [5.2.1.0 ^2,6] decane-8-base ester, (methyl) acrylic acid three ring [5.2.1.0 ^2,6] decene-8-base ester, (methyl) acrylic acid dicyclo n-pentyl oxygen base ethyl ester, (methyl) isobornyl acrylate, (methyl) acrylic acid adamantane esters etc. have (methyl) esters of acrylic acid of many ring greases ring type hydrocarbon structure;

Dicyclo [2.2.1]-2-heptene, 5-methyl bicycle [2.2.1]-2-heptene, 5-ethyl dicyclo [2.2.1]-2-heptene, 5-hydroxyl dicyclo [2.2.1]-2-heptene, 5-hydroxymethyl dicyclo [2.2.1]-2-heptene, 5-(2 '-hydroxyethyl) dicyclo [2.2.1]-2-heptene, 5-methoxyl dicyclo [2.2.1]-2-heptene, 5-ethoxy dicyclo [2.2.1]-2-heptene, 5,6-dihydroxy dicyclo [2.2.1]-2-heptene, 5,6-two (hydroxymethyl) dicyclo [2.2.1]-2-heptene, 5,6-two (2 '-hydroxyethyl) dicyclo [2.2.1]-2-heptene, 5,6-dimethoxy dicyclo [2.2.1]-2-heptene, 5,6-diethoxy dicyclo [2.2.1]-2-heptene, 5-hydroxy-5-methyl base dicyclo [2.2.1]-2-heptene, 5-hydroxyl-5-ethyl dicyclo [2.2.1]-2-heptene, 5-hydroxymethyl-5-methyl bicycle [2.2.1]-2-heptene, 5-tert-butoxycarbonyl dicyclo [2.2.1]-2-heptene, 5-cyclohexyl oxygen base carbonyl dicyclo [2.2.1]-2-heptene, 5-phenyloxycarbonyl dicyclo [2.2.1]-2-heptene, 5,6-two (tert-butoxycarbonyl) dicyclo [2.2.1]-2-heptene, the dicyclo unsaturated compound class of 5,6-two (cyclohexyl oxygen base carbonyl) dicyclo [2.2.1]-2-heptene etc.; N-N-cyclohexylmaleimide etc. has the N-substituted maleimide of ester ring type hydrocarbon structure; Deng.

Wherein, (x) be preferably at least a kind that is selected among the group that (methyl) esters of acrylic acid with ester ring type hydrocarbon structure and dicyclo unsaturated compound class consist of, (methyl) esters of acrylic acid that more preferably has the ester ring type hydrocarbon structure further preferably has (methyl) esters of acrylic acid of many ring greases ring type hydrocarbon structure.When (x) was these monomers, when making colored pattern by the photosensitive composition of the present invention that contains resin (B2), the origin that produces in the developer solution after the development can tail off in the stripping film of photosensitive composition.In addition, suppressed also that these stripping films are attached on the colored pattern and the foreign matter that produces.

(d) can enumerate, for example from (c) of resin (B1), remove the compound that is equivalent to (x).

(d) can enumerate, for example (methyl) methyl acrylate, (methyl) acrylic acid ethyl ester, (methyl) n-butylacrylate, (methyl) acrylic acid sec-butyl ester, (methyl) acrylic acid tertiary butyl ester, (methyl) 2-ethylhexyl acrylate, (methyl) dodecylacrylate, (methyl) acrylic acid Lauryl Ester, (methyl) acrylic acid stearyl, (methyl) acrylic acid allyl ester, (methyl) acrylic acid propargyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid naphthyl ester, (methyl) esters of acrylic acids such as (methyl) acrylic acid benzyl ester;

(methyl) acrylic acid 2-hydroxyethyl ester, (methyl) acrylic acid 2-hydroxy-propyl ester etc. contain (methyl) esters of acrylic acid of hydroxyl;

The dicarboxylic diesters such as diethyl maleate, DEF, diethyl itaconate;

The dicarbapentaborane imide derivative classes such as N-phenylmaleimide, N-benzyl maleimide, 3-maleimide yl benzoic acid N-succinimide ester, 4-dimaleoyl imino butyric acid N-succinimide ester, 6-dimaleoyl imino caproic acid N-succinimide ester, 3-dimaleoyl imino propionic acid N-succinimide ester and N-(9-acridinyl) maleimide;

Styrene, α-methyl styrene, adjacent vinyltoluene, a vinyltoluene, to vinyltoluene, to methoxy styrene, vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl-acetic ester, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc.

Wherein, optimization styrene, vinyltoluene, N-phenylmaleimide, N-benzyl maleimide, (methyl) acrylic acid benzyl ester etc. have the monomer of aromatic hydrocarbon structure, more preferably styrene, vinyltoluene and (methyl) acrylic acid benzyl ester.When (d) was these monomers, the viscosity with resin (B2) solution in the polymerization or after the polymerization can not become too high, and the tendency of easy operating.In addition, by in photosensitive composition, using the resin (B2) that contains the structural unit that derives from these monomers, the generation of the stripping film in the time of then can further suppressing to develop.

In the resin [K3], the ratio of the structural unit in each monomer source is preferably following value with respect to all structural units that consist of resin [K3]:

Derive from the structural unit of (a): 2～60 % by mole

Derive from the structural unit of (x): 40～98 % by mole

More preferably

Derive from the structural unit of (a): 10～50 % by mole

Derive from the structural unit of (x): 50～90 % by mole.

When the ratio of the structural unit of resin [K3] is in above-mentioned scope, has the tendency that obtains the good colored pattern of shape.

Resin [K3] can adopt for example identical with the manufacture method of resin [K1] method to make.

In the resin [K4], the ratio of the structural unit in each monomer source is preferably following value with respect to all structural units that consist of resin [K4]:

Derive from the structural unit of (a): 2～45 % by mole

Derive from the structural unit of (x): 2～95 % by mole

Derive from the structural unit of (d): 1～65 % by mole

More preferably

Derive from the structural unit of (a): 5～40 % by mole

Derive from the structural unit of (x): 5～80 % by mole

Derive from the structural unit of (d): 5～60 % by mole.

When the ratio of the structural unit of resin [K4] is in above-mentioned scope, has the tendency that obtains the good colored pattern of shape.

When containing the structural unit that derives from the monomer with aromatic hydrocarbon structure (below be also referred to as " (d ') ") as (d) of resin [K4], preferred

Derive from the structural unit of (a): 5～45 % by mole

Derive from the structural unit of (x): 5～80 % by mole

Derive from the structural unit of (d '): 30～65 % by mole

More preferably

Derive from the structural unit of (a): 10～40 % by mole

Derive from the structural unit of (x): 5～40 % by mole

Derive from the structural unit of (d '): 40～65 % by mole.

When resin [K4] is these resins, have the stripping film that further minimizing causes by development generation, obtain the tendency of the good colored pattern of shape.

Resin [K4] can adopt for example identical with the manufacture method of resin [K1] method to make.

Resin (B2) can be enumerated particularly, (methyl) acrylic acid cyclohexyl ester/(methyl) acrylic copolymer, (methyl) acrylic acid three ring decyl ester/(methyl) acrylic copolymers, dicyclo [the 2.2.1]-2-heptene/resins [K3] such as (methyl) acrylic copolymer; (methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid benzyl ester/(methyl) acrylic copolymer, (methyl) acrylic acid three ring decyl ester/(methyl) acrylic acid benzyl ester/(methyl) acrylic copolymers, (methyl) acrylic acid three ring decyl ester/styrene/(methyl) acrylic copolymers, (methyl) acrylic acid three ring decyl ester/vinyltoluene/(methyl) acrylic copolymers, dicyclo [the 2.2.1]-2-heptene/styrene/resins [K4] such as (methyl) acrylic copolymer.

Wherein, resin (B2) preferred resin [K4].

The polystyrene conversion weight-average molecular weight of resin (B2) is preferred 3,000～100,000, and more preferably 3,000～30,00O, further preferred 4,000～15,000.When molecular weight was in above-mentioned scope, the hardness with color filter was improved, and residual film ratio is high, unexposed portion is for the favorable solubility of developer solution, the tendency that the exploring degree improves.

The molecular weight distribution of resin (B2) [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] is preferred 1.1～6, and more preferably 1.2～4.

Preferred 50～the 170mg-KOH/g of acid number of resin (B2), more preferably 60～150mg-KOH/g, further preferred 70～135mg-KOH/g.When acid number is in above-mentioned scope, has the tendency that obtains the good colored pattern of shape.When acid number was higher than above-mentioned range limit, colored pattern produced undercutting (Undercut) easily, and then caused that pattern peels off.In addition, prescribe a time limit when acid number is lower than under the above-mentioned scope, have the situation that produces the development residue.Acid number herein be as in and the amount (mg) of the required potassium hydroxide of 1g resin measure and value, can try to achieve by for example carrying out titration with potassium hydroxide aqueous solution.

The content of resin (B2) is with respect to the total amount of resin (B1) and resin (B2), preferred 10～90 quality %, more preferably 15～75 quality %, further preferred 50～80 quality %.

The total amount of resin (B1) and resin (B2) is with respect to the total amount of solid constituent, preferred 7～65 quality %, more preferably 13～60 quality %, further preferred 17～55 quality %.When above-mentioned total amount is in above-mentioned scope, have the exploring degree of colored pattern and the tendency that residual film ratio improves.

＜polymerizable compound (C) 〉

Polymerizable compound (C) is can be by living radical and/or the sour compound that carries out polymerization that is produced by heat or polymerization initiator (D), such as enumerating compound with polymerism ethene unsaturated link etc., preferred (methyl) acrylate compounds.

Wherein, polymerizable compound (C) is preferably the polymerizable compound with 3 above ethene unsaturated links.Such polymerizable compound can be enumerated, for example, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, tripentaerythritol eight (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, the four seasons penta tetrol ten (methyl) acrylate, the four seasons penta tetrol nine (methyl) acrylate, three (2-(methyl) acrylyl oxy-ethyl) isocyanuric acid ester, glycol-modified pentaerythrite four (methyl) acrylate, glycol-modified dipentaerythritol six (methyl) acrylate, propylene glycol modified pentaerythrite four (methyl) acrylate, propylene glycol modified dipentaerythritol six (methyl) acrylate, caprolactone modification pentaerythrite four (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate etc.

Wherein, preferred dipentaerythritol five (methyl) acrylate and dipentaerythritol six (methyl) acrylate.

The weight-average molecular weight of polymerizable compound (C) is preferred more than 150 below 2,900, and more preferably 250～1, below 500.

The content of polymerizable compound (C) is with respect to the total amount of solid constituent, preferred 7～65 quality %, more preferably 13～60 quality %, further preferred 17～55 quality %.When the content of polymerizable compound (C) is in above-mentioned scope, have the residual film ratio of colored pattern and the tendency that chemical proofing improves.

＜polymerization initiator (D) 〉

Polymerization initiator (D) produces living radical, acid etc. so long as can pass through the effect of light or heat, and the compound that polymerization is begun namely is not particularly limited, and can use known polymerization initiator.

Polymerization initiator (D) can be enumerated, benzene alkyl ketone compound, triaizine compounds, acylphosphine oxide compound, O-acyl group oxime compound and united imidazole etc.Wherein, preferably contain the polymerization initiator of O-acyl group oxime compound, more preferably contain the polymerization initiator of O-acyl group oxime compound and benzene alkyl ketone compound.

O-acyl group oxime compound is the compound with part-structure shown in the formula (d1).

Below, * represents bonding position.

O-acyl group oxime compound can be enumerated; N-benzoyloxy-1-(4-thiophenyl phenyl)-1-butanone-2-imines for example; N-benzoyloxy-1-(4-thiophenyl phenyl)-1-octanone-2-imines; N-benzoyloxy-1-(4-thiophenyl phenyl)-3-cyclopentyl-1-acetone-2-imines; N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] ethane-1-imines; N-acetoxyl group-1-[9-ethyl-6-{2-methyl-4-(3; 3-dimethyl-2,4-dioxa cyclopentyl-methyl oxygen base) benzoyl }-9H-carbazole-3-yl] ethane-1-imines; N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-3-cyclopentyl propane-1-imines; N-benzoyloxy-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-3-cyclopentyl-1-acetone-2-imines etc.Also can use the commercially available products such as イ Le ガキユア (registered trademark) OXE01, OXE02 (above BASF society system), N-1919 (ADEKA society system).

Benzene alkyl ketone compound is the compound with part-structure shown in part-structure shown in the formula (d2) or the formula (d3).In these part-structures, phenyl ring can have substituting group.

Compound with part-structure shown in the formula (d2) can be enumerated, such as, 2-methyl-2-morpholino-1-(4-methyl mercapto phenyl)-1-acetone, 2-dimethylamino-1-(4-morpholinyl phenyl)-2-benzyl-1-butanone, 2-dimethylamino-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-the 1-butanone etc.Also can use the commercially available products such as イ Le ガキユア (registered trademark) 369,907 and 379 (above BASF society system).

Compound with part-structure shown in the formula (d3) can be enumerated, for example, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2-hydroxy-2-methyl-1-(4-(2-hydroxyl-oxethyl) phenyl)-1-acetone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenyl the phenyl)-oligomer of 1-acetone, α, α-diethoxy acetophenone, benzyl dimethyl ketal etc.

Based on the point of sensitivity, benzene alkyl ketone compound preferably has the compound of part-structure shown in the formula (d2).

Triaizine compounds can be enumerated, for example, 2,4-two (trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazines, 2,4-two (trichloromethyl)-6-(4-methoxyl naphthyl)-1,3,5-triazine, 2,4-two (trichloromethyl)-6-piperonyl-1,3, the 5-triazine, 2,4-two (trichloromethyl)-6-(4-methoxyl-styrene)-1,3, the 5-triazine, 2,4-two (trichloromethyl)-6-(2-(5-methylfuran-2-yl) vinyl)-1,3,5-triazines, 2,4-two (trichloromethyl)-6-(2-(furans-2-yl) vinyl)-1,3,5-triazine, 2,4-two (trichloromethyl)-6-(2-(4-diethylamino-2-aminomethyl phenyl) vinyl)-1,3, the 5-triazine, 2,4-two (trichloromethyl)-6-(2-(3,4-Dimethoxyphenyl) vinyl)-1,3,5-triazine etc.

The acylphosphine oxide compound can be enumerated, TMDPO etc.Can use the commercially available products such as イ Le ガキユア (registered trademark) 819 (BASF society system).

United imidazole can be enumerated, for example; 2,2 '-two (2-chlorphenyls)-4; 4 '; 5,5 '-tetraphenyl bisglyoxaline; 2,2 '-two (2; the 3-dichlorophenyl)-4; 4 ', 5,5 '-tetraphenyl bisglyoxaline (reference example such as JPH06-75372-A; JPH06-75373-A etc.); 2; 2 '-two (2-chlorphenyls)-4; 4 ', 5,5 '-tetraphenyl bisglyoxaline; 2; 2 '-two (2-chlorphenyls)-4; 4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxaline; 2; 2 '-two (2-chlorphenyls)-4; 4 ', 5,5 '-four (dialkoxy phenyl) bisglyoxaline; 2; 2 '-two (2-chlorphenyls)-4; 4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxaline (reference example such as JPS48-38403-B; JPS62-174204-A etc.); 4; the imidazolium compounds (reference example such as JPH07-10913-A etc.) that the phenyl alkoxy carbonic acyl radical of 4 ' 5,5 '-position replaces etc.

Further polymerization initiator (D) can be enumerated the benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether, benzoin isobutyl ether; Benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl thioether, 3,3 ', 4,4 '-four (t-butylperoxy carbonyl) benzophenone, 2, the benzophenone cpds such as 4,6-tri-methyl benzophenone; The naphtoquinone compounds such as 9,10-phenanthrenequione, 2-EAQ, camphorquinone; 10-butyl-2-chloro-acridine ketone, benzil, phenyl glyoxalic acid methylester, two cyclopentadiene titanium compounds etc.Preferably they and polymerization described later initiation auxiliary agent (D1) (especially amine) are used in combination.

Acid agent can be enumerated, salts such as 4-hydroxy phenyl dimethyl sulfonium tosilate, 4-hydroxy phenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl dimethyl sulfonium tosilate, 4-acetoxyl group phenyl methyl benzyl sulfonium hexafluoro antimonate, triphenylsulfonium tosilate, triphenylsulfonium hexafluoro antimonate, diphenyl iodine tosilate, diphenyl iodine hexafluoro antimonate, or nitrobenzyl toluenesulfonic acid salt, benzoin toluenesulfonic acid salt etc.

The content of polymerization initiator (D) is with respect to total amount 100 mass parts of resin (B1), resin (B2) and polymerizable compound (C), preferred 0.1～30 mass parts, more preferably 1～20 mass parts.When the content of polymerization initiator (D) was in above-mentioned scope, because high-sensitivity is so that have the tendency that the time shutter shortens, and then throughput rate was improved.

When containing polymerization initiator (D), can further contain polymerization and cause auxiliary agent (D1).It is for the compound of promotion by the polymerization of the optical polymerism compound of polymerization initiator initiated polymerization, perhaps sensitizer that polymerization causes auxiliary agent (D1).

Polymerization causes auxiliary agent (D1) can be enumerated, amines, alkoxy anthracene compound, thioxanthones compound and carboxylic acid compound etc., preferred thioxanthones compound.

Amines can be enumerated, triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl esters, EDMAB, 4-dimethylaminobenzoic acid isopentyl ester, benzoic acid 2-dimethylamino ethyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, N, the N-dimethyl-p-toluidine, 4,4 '-two (dimethylamino) benzophenone (common name Michler's keton), 4,4 '-two (diethylamino) benzophenone, 4,4 '-two (ethylmethylamino) benzophenone etc., wherein, preferred 4,4 '-two (diethylamino) benzophenone.Can use the commercially available products such as EAB-F (hodogaya chemical industry (strain) system).

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

The thioxanthones compound can be enumerated, ITX, ITX, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones etc.

Carboxylic acid compound can be enumerated, thiophenyl acetic acid, methylbenzene ethyl thioglycollic acid, ethylbenzene ethyl thioglycollic acid, ethyl methyl benzene ethyl thioglycollic acid, dimethyl benzene ethyl thioglycollic acid, methoxybenzene ethyl thioglycollic acid, dimethoxy benzene ethyl thioglycollic acid, chlorobenzene ethyl thioglycollic acid, dichloro-benzenes ethyl thioglycollic acid, N-phenylglycine, phenoxyacetic acid, naphthyl thioacetic acid, N-naphthyl glycocoll, naphthoxy acetic acid etc.

When using these polymerizations to cause auxiliary agent (D1), its use amount is with respect to total amount 100 mass parts of resin (B1), resin (B2) and polymerizable compound (C), preferred 0.1～30 mass parts, more preferably 1～20 mass parts.The amount that causes auxiliary agent (D1) when polymerization can further form colored pattern with high sensitivity in this scope the time, have the tendency that the throughput rate of color filter improves.

＜solvent (E) 〉

Solvent (E) is not particularly limited, and can use normally used solvent in this field.Such as can from ester solvent (molecule contains-COO-, do not contain-O-solvent), ether solvents (molecule contains-O-, do not contain-COO-solvent), ether-ether solvent (molecule contains-COO-and-solvent of O-), choice for use the ketone solvent (molecule contains-CO-, do not contain-COO-solvent), alcoholic solvent, aromatic hydrocarbon solvents, amide solvent, dimethyl sulfoxide (DMSO) etc.

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

Ether solvents can be enumerated, the glycol monomethyl methyl ether, ethylene glycol monomethyl ether, the glycol monomethyl propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, TC, the diethylene glycol single-butyl ether, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list propyl ether, the propylene glycol single-butyl ether, 3-methoxyl-n-butyl alcohol, 3-methoxyl-3-methyl butanol, tetrahydrofuran, oxinane, Isosorbide-5-Nitrae-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, the diethylene glycol dipropyl ether, the diethylene glycol dibutyl ethers, anisole, phenetol, methyl anisole etc.

The ether-ether solvent can be enumerated, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, the 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, the 2-methoxy methyl propionate, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester, 3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butylacetic acid ester, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, propylene glycol list propyl ether acetic acid esters, the DPGME acetic acid esters, the ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, the TC acetic acid esters, diethylene glycol single-butyl ether acetic acid esters etc.

Ketone solvent can be enumerated, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-HEPTANONE, 3-heptanone, 4-heptanone, 4-methyl-2 pentanone, cyclopentanone, cyclohexanone, isophorone etc.

Alcoholic solvent can be enumerated, methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerine etc.

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

Amide solvent can be enumerated, DMF, DMA, 1-METHYLPYRROLIDONE etc.

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

Among the above-mentioned solvent, based on the point of coating, drying property, the boiling point under the preferred 1atm (standard atmospheric pressure) is at the organic solvent below 180 ℃ more than 120 ℃.Solvent (E) is preferred, propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxyl ethyl propionate, glycol monomethyl methyl ether, diethylene glycol monomethyl ether, TC and 4-hydroxy-4-methyl-2-pentanone, more preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether, ethyl lactate and 3-ethoxyl ethyl propionate.

The content of solvent (E) is with respect to the total amount of photosensitive composition, preferred 70～95 quality %, more preferably 75～92 quality %.In other words, preferred 5～30 quality % of the solid constituent of photosensitive composition, more preferably 8～25 quality %.When the content of solvent (E) was in above-mentioned scope, it is good that the flatness when having coating becomes, and colour saturation fully makes display characteristic become good tendency when forming color filter in addition.

＜surfactant (F) 〉

Surfactant (F) can be enumerated, and silicone-based surfactant, fluorine are surfactant and the silicone-based surfactant with fluorine atom etc.They can have polymerizable group at side chain.

The silicone-based surfactant can be enumerated, and has the surfactant of siloxane bond etc. in the molecule.Can enumerate particularly TORAY SILICONE (ト one レシリコ one Application) DC3PA, same SH7PA, same DC11PA, same SH21PA, same SH28PA, same SH29PA, same SH30PA, same SH8400 (trade name: Dong Li Dow Corning Corporation (eastern レダウコ one ニ Application グ (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 Application テイ Block パ Off オ one マ Application スマテリア Le ズジヤパ Application contract commercial firm system) etc.

Above-mentioned fluorine is that surfactant can be enumerated, and has the surfactant of fluoro carbochain etc. in the molecule.Can enumerate particularly Off ロラ one De (registered trademark) FC430, same FC431 (Sumitomo スリ one エ system (strain) system), メガ Off ア Star Network (registered trademark) F142D, same F171, same F172, same F173, same F177, same F183, same F554, same R30, same RS-718-K (DIC (strain) system), エ Off ト Star プ (registered trademark) EF301, same EF303, same EF351, same EF352 (the マテリア of Mitsubishi Le electronics changes into (strain) system), サ one Off ロ Application (registered trademark) S381, same S382, same SC101, same SC105 (Asahi Glass (strain) system), E5844 ((strain) ダイキ Application Off アイ Application ケミカ Le institute system) etc.

Above-mentioned silicone-based surfactant with fluorine atom can be enumerated, and has the surfactant of siloxane bond and fluoro carbochain etc. in the molecule.Can enumerate particularly メガ Off ア Star Network (registered trademark) R08, same BL20, same F475, same F477, same F443 (DIC (strain) system) etc.

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

The content of surfactant (F) is with respect to the total amount of photosensitive composition, below the above 0.2 quality % of preferred 0.001 quality %, more preferably below the above 0.1 quality % of 0.002 quality %, further below the above 0.05 quality % of preferred 0.01 quality %.In addition, this content does not comprise the content of above-mentioned pigment dispersing agent.When the content of surfactant (F) is in above-mentioned scope, can make the flatness of color filter become good.

＜other composition 〉

Photosensitive composition of the present invention also can contain known adjuvant in these technical fields such as filling agent, other macromolecular compound, adhesion promotor, antioxidant, light stabilizer, chain-transferring agent as required.

The manufacture method of＜photosensitive composition 〉

Photosensitive composition of the present invention can be by for example, colorant (A), resin (B1), resin (B2), polymerizable compound (C) and polymerization initiator (D) and the polymerization used as required caused auxiliary agent (D1), solvent (E), surfactant (F) and other composition mix to prepare.

As colorant (A), when containing pigment (A2), preferably in advance pigment (A2) is mixed with solvent (E), use ball mill etc. makes it to disperse, until the mean grain size of pigment becomes the following degree of 0.2 μ m.At this moment, as required, can mix above-mentioned pigment dispersing agent, part or all resin (B1) or the resin of part or all (B2).In the dispersible pigment dispersion that obtains, with dyestuff (A1), polymerization initiator (D), remaining solvent (E), surfactant (F) and other composition etc. that the concentration of regulation is mixed remaining resin (B1), remaining resin (B2) and polymerizable compound (C) and used as required, can prepare the target photosensitive composition thus.

When containing dyestuff (A1), can in advance dyestuff (A1) be dissolved in respectively in the solvent (E).Preferably the filtrator of this solution with aperture 0.01～1 μ m degree filtered.

Mixed photosensitive composition preferably filters with the filtrator of aperture 0.1～10 μ m degree.

The manufacture method of＜color filter and liquid crystal indicator 〉

As the film method of (sometimes also with " colored pattern is filmed " referred to as " colored pattern ") of the colored pattern of being made color filter by photosensitive composition of the present invention, can enumerate photoetching process, ink-jet method, print process etc.Preferred photoetching process wherein.Photoetching process is that photosensitive composition of the present invention is coated substrate, forms composition layer by volatile ingredients such as dry desolventizings.Then, the method that is situated between and by photomask the said composition layer is exposed, develops.After the development, can heat to form as required colored pattern.In the formation method of above-mentioned colored pattern, by the time not using photomask in exposure, and/or do not develop, can form as the painted of solidfied material of above-mentioned composition layer and film.Thus obtained colored pattern is filmed and painted filming can be used as color filter.

The thickness of making color filter is not particularly limited, and can suitably adjust according to purpose or purposes etc. 0.1～30 μ m for example, preferred 0.1～20 μ m, further preferred 0.5～6 μ m.

Substrate can use the glass plates such as soda-lime glass of quartz glass, borosilicate glass, aluminosilicate glass, surface coating silicon dioxide, perhaps the resin plates such as polycarbonate, polymethylmethacrylate, polyethylene terephthalate, silicon, the substrate after aforesaid substrate forms aluminium, silver, silver/copper/palldium alloy film etc.Also can form other color-filter layer, resin bed, transistor, circuit etc. on these substrates.

Then, the method that forms pattern at the glass substrate that has formed thin film transistor (TFT) (hereinafter referred to as " TFT ") is described.

Specifically by known methods such as photoetching techniques, on glass substrate 21, take pixel as unit forms a plurality of TF

T22 (with reference to Fig. 1).TFT22 by grid (gate) electrode 22a, gate insulating film 22b, be formed on this gate insulating film 22b polysilicon film 22c and by for example oxide film (SiO ₂) and the film formed diaphragm 22d of the lamination of nitride film (SiNx) consist of; This gate electrode 22a for example is formed on the glass substrate 21 by molybdenum (Mo), consists of simultaneously the part of gate line; This gate insulating film 22b is by for example nitride film (SiN that is formed on the gate electrode 22a _x) and oxide film (SiO ₂) laminated film consist of.The zone relative with gate electrode 22a of polysilicon film 22c is raceway groove (channel) zone of TFT22, and the two side areas of this channel region is source electrode (source) zone or drain electrode (drain) zone.By the upper connecting hole (contact hole) that arranges of diaphragm 22d the source region of polysilicon film 22c is electrically connected with the signal wire 27 that is for example formed by aluminium (Al).In addition, by connecting hole described later (contact hole) 201 drain region of polysilicon film 22c is electrically connected with pixel electrode 24.

When on glass substrate 21, forming a plurality of TFT22 take pixel as unit, when forming TFT22, glass substrate 21 forms the alignment mark (not shown).This alignment mark is as the positioning datum in the formation operation of color-filter layer 23 described later.In addition, these alignment marks can dual-purpose be the mark that drives the applying benchmark of substrate and counter substrate also.When can forming the metal level such as distribution or polysilicon layer in the manufacturing process of TFT22, alignment mark utilize at least one deck wherein in same operation, to form.

Then, photosensitive composition of the present invention is coated on the glass substrate 21 that is formed with TFT22 and alignment mark, by volatile ingredients such as heat drying (preliminary drying) and/or drying under reduced pressure desolventizings, make it dry, form thickness 0.5～5.0 μ m, the composition layer of 1.0 μ m for example.

Coating process can be enumerated, spin-coating method, slot coated method, Xia Feng ﹠amp; Method of spin coating etc.

Preferred 30～120 ℃ of temperature when carrying out heat drying, more preferably 50～110 ℃.In addition, preferred 10 seconds～60 minutes of heat time heating time, more preferably 30 seconds～30 minutes.

When carrying out drying under reduced pressure, preferably under the pressure of 50～150Pa, carry out under 20～25 ℃ the temperature range.

Then, Jie by the photomask (not shown) to the composition layer irradiation ultraviolet radiation, optionally remove not part (being unexposed portion) by developer solution again, wash after obtaining thus to be configured as the composition layer of following pixel, this pixel is formed with the connecting hole (contact hole) 201 of the drain region that arrives polysilicon film 22c.

By developing, can make the unexposed portion of composition layer be dissolved in developer solution and remove.The aqueous solution of the alkali compounds such as developer solution preference such as potassium hydroxide, sodium bicarbonate, sodium carbonate, Tetramethylammonium hydroxide.Concentration in the aqueous solution of these alkali compounds, preferred 0.01～10 quality %, more preferably 0.03～5 quality %.Further, developer solution also can contain surfactant.

Developing method can use in paddling process, infusion process and the spray-on process etc. arbitrarily.Further, during development, substrate can be with arbitrarily angled inclination.

Then, for the composition layer reflow (reflow) that is formed with connecting hole (contact hole) 201 and/or make its curing, for example heating preferred 1～120 minute 10～60 minutes under 150～250 ℃ the temperature of scope, preferred 160～235 ℃ of scopes.Form thus photosensitive composition layer 23A.This photosensitive composition layer 23A is corresponding to color filter of the present invention.

Repeat this operation, form respectively photosensitive composition layer 23A by red colored photosensitive polymer combination, green coloring photosensitive polymer combination and blue-colored photosensitive polymer combination, thereby form the color-filter layer 23 (referring to Fig. 2) that contains Red lightscreening plate 23a, green color filter 23b and blue color filter 23c corresponding to each pixel column.Zone between each optical filter of color-filter layer 23 is the Mixed Zone in abutting connection with color, but these zones are lightproof areas relative with signal wire 27, so especially no problem on quality.In addition, the zone between these each optical filters can be not painted yet.

Then, for example form by for example spin-coating method that thickness is the photosensitive resin film 29 as diaphragm of 0.3～2.0 μ m, cover color-filter layer 23.Then, Jie by the photomask (not shown) to photosensitive resin film 29 irradiation ultraviolet radiations, optionally remove corresponding to the zone of connecting hole 201 and part not by developer solution again, form connecting hole (contact hole) 202 after washings of the drain region that arrives polysilicon film 22c.Then, for the reflow (reflow) of carrying out photosensitive resin film 29, for example heating under 200 ℃ under 100～300 ℃ the range temperature.Then, in order to remove residue and the organism such as dyestuff of connecting hole 202 interior accumulations, carry out etching with oxygen plasma, in order to remove the oxide film that forms owing to oxygen plasma, for example carry out etching with rare fluoric acid again.

Then, form transparent conductive material such as ITO (Indium-TinOxide: the oxide hybrid films of indium and tin) by for example sputtering method at photosensitive resin film 29, by photoetching technique and etching this ITO film is carried out pattern and form, form transparent pixel electrode 24 (referring to Fig. 3).In addition, this pixel electrode 24 also can be formed by aluminium (Al) or silver metals such as (Ag) according to the equipment difference of making.Then, after known method formation oriented film, bonding being somebody's turn to do drives substrate and counter substrate, can make liquid crystal indicator.

According to photosensitive composition of the present invention, but high finished product rate make the high-performance color filter that especially Superficial Foreign Body is few.This color filter is useful as the color filter that is used for display device (such as liquid crystal indicator, organic El device etc.), Electronic Paper, solid-state imager etc.

Embodiment

Then enumerate embodiment, the present invention is carried out further specific description.In the example, if the % of expression content or use amount and the special record of part nothing are quality criteria.

(synthesis example 1)

Potpourri (the trade name Chugai Aminol Fast Pink R of compound shown in compound shown in the throw-in type (A1-1a) and the formula (A1-1b) in the flask that possesses condenser pipe and stirring apparatus; China and foreign countries change into system) 8.9 parts of 15 parts, 150 parts of chloroforms and DMFs, stir when maintaining below 20 ℃ 10.9 parts of dropping thionyl chlorides.After drip finishing, be warming up to 50 ℃, keep making its reaction in 5 hours under synthermal, be cooled to thereafter 20 ℃.When under agitation maintaining cooled reaction solution below 20 ℃, drip the mixed liquor of 22.1 parts of 12.5 parts of 2-DEHAs and triethylamines.Thereafter, synthermal lower stirring made its reaction in 5 hours.After then the reaction mixture that obtains being heated up in a steamer desolventizing with rotary evaporator, add a small amount of methyl alcohol vigorous stirring.This potpourri is added in the mixed liquor of 375 parts of ion exchange waters while stirring, crystal is separated out.The crystal that filtration is separated out carefully cleans with ion exchange water, in 60 ℃ of lower drying under reduced pressure, obtains dyestuff (A1-1) (potpourri of compound shown in formula (A1-1-1)～formula (A1-1-8)) 11.3 parts.

(synthesis example 2)

Divide with 0.02L/ in the flask that possesses reflux condenser, tap funnel and stirring machine to pass into nitrogen and make the nitrogen environment atmosphere, drop into ethyl lactate 305 mass parts, be heated to 70 ℃ in the time of stirring.

Then, with acrylic acid 60 mass parts, acrylic acid 3,4-epoxy three ring [5.2.1.0 ^2.6] decyl ester (compound shown in the compound shown in the formula (I-1) and the formula (II-1) mixes with mol ratio at 50: 50) 240 mass parts are dissolved in ethyl lactate 140 mass parts and are mixed with solution, use tap funnel to last 4 hours this lysate is added drop-wise to insulation in 70 ℃ flask.

On the other hand, with polymerization initiator 2,2 '-azo two (2,4-methyl pentane nitrile), 30 mass parts are dissolved in the solution that obtains in ethyl lactate 225 mass parts, last 4 hours with another tap funnel and drip in flask.After the dropping of polymerization initiator solution finishes, remain on 70 ℃ lower 4 hours, be cooled to thereafter room temperature, obtaining weight-average molecular weight Mw is 9.1 * 10 ³, molecular weight distribution is 2.1, resin (B1-1) solution of solid constituent 26 quality %, solid constituent acid number 120mg-KOH/g.

Resin (B1-1) has following structural unit.

(synthesis example 3)

Divide with 0.02L/ in the flask that possesses stirring machine, thermometer, reflux condenser and tap funnel to pass into nitrogen and make the nitrogen environment atmosphere, drop into propylene glycol monomethyl ether 257 mass parts, be heated to 70 ℃ in the time of stirring.Then, with acrylic acid 57 mass parts, 83 parts of vinyltoluenes, acrylic acid 3,4-epoxy three ring [5.2.1.0 ^2.6] decyl ester (compound shown in the compound shown in the formula (I-1) and the formula (II-1) mixes with mol ratio at 50: 50) 238 mass parts are dissolved in propylene glycol monomethyl ether 140 mass parts and are mixed with solution, use tap funnel to last 4 hours this solution is added dropwise to insulation in 70 ℃ flask.On the other hand, with polymerization initiator 2,2 '-azo two (2,4-methyl pentane nitrile), 30 mass parts are dissolved in the solution that obtains in propylene glycol monomethyl ether 225 mass parts, last 4 hours with another tap funnel and drip in flask.After the dropping of polymerization initiator solution finishes, remain on 70 ℃ lower 4 hours, be cooled to thereafter room temperature, obtaining weight-average molecular weight Mw is 9.9 * 10 ³, solid constituent 37.5%, solid constituent acid number 112mg-KOH/g resin (B1-2) solution.Resin (B1-2) has following structural unit.

(synthesis example 4)

To possess in the flask of stirring machine, thermometer, reflux condensing tube, tap funnel and nitrogen ingress pipe and make the nitrogen environment atmosphere, drop into 210 parts of propylene glycol monomethyl ether, be warming up to 100 ℃ in the time of stirring.Then, to make 22 parts of 106 parts of methacrylic acid benzyl esters, 22 parts in acrylic acid and methacrylic acid dicyclo pentyl esters (Hitachi changes into (strain) FA-513M processed) be dissolved in 215 parts of propylene glycol monomethyl ether, further dissolving 2,3.6 parts of solution that are mixed with of 2 '-azoisobutyronitrile, be added drop-wise in the flask, 100 ℃ of lower continuing stirred 5 hours, obtained weight-average molecular weight Mw1.00 * 10 ⁴, solid constituent 34.1%, solid constituent acid number be resin (B2-1) solution of 109mgKOH/g.Resin (B2-1) has following structural unit.

(synthesis example 5)

Divide with 0.02L/ in the flask that possesses reflux condenser, tap funnel and stirring machine to pass into nitrogen and make the nitrogen environment atmosphere, drop into 220 parts of ethyl lactates, be heated to 70 ℃ in the time of stirring.Then, with 84 parts of methacrylic acids and acrylic acid 3,4-epoxy three ring [5.2.1.0 ^2.6] 336 parts of decyl ester (compound shown in the compound shown in the formula (I-1) and the formula (II-1) mixes with mol ratio at 50: 50), be dissolved in 140 parts of the ethyl lactates and be mixed with solution, use tap funnel to last 4 hours this solution is added drop-wise to insulation in 70 ℃ flask.On the other hand, with polymerization initiator 2,30 parts of 2 '-azos two (2,4-methyl pentane nitrile) are dissolved in the solution that obtains in 95 parts of the ethyl lactates, last 4 hours with another tap funnel and drip in flask.After the dropping of polymerization initiator solution finishes, remain on 70 ℃ lower 4 hours, be cooled to thereafter room temperature, obtaining weight-average molecular weight Mw is 8.0 * 10 ³, molecular weight distribution is 2.5, solid constituent is 48%, the solution acid number is resin (B1-3) solution of 50mg-KOH/g (acid number that solid constituent converts is 104mgKOH/g).Resin (B1-3) has following structural unit.

The mensuration of the weight-average molecular weight of the resin that obtains in the synthesis example (Mw) and number-average molecular weight (Mn) is used the GPC method, carries out according to following condition.

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

Chromatographic column: SHIMADZU Shim-pack GPC-80M

Chromatogram column temperature: 40 ℃

Solvent: THF (tetrahydrofuran)

Flow velocity: 1.0mL/min

Detecting device: RI

Proofread and correct and use standard substance: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (eastern ソ one (strain) system)

With the ratio (Mw/Mn) of the weight-average molecular weight of the polystyrene conversion of above-mentioned acquisition and number-average molecular weight as molecular weight distribution.

Embodiment 1～6 and comparative example 1

(preparation of photosensitive composition)

Each composition that mixes the amount of Table 1 obtains photosensitive composition.

[table 1]

¹⁾(A2-1) with pigment dispersing agent, (E-1) ⁵⁾The propylene glycol monomethyl ether of described amount reaches (E-2) ⁶⁾The propylene glycol monomethyl ether of described amount is mixed, and uses ball mill to make it pre-dispersed.

²⁾(E-1) ²⁾The summation of expression propylene glycol monomethyl ether content.

³⁾(E-2) ³⁾The summation of expression propylene glycol monomethyl ether content.

⁴⁾Resin (B1) ⁴⁾The content that the expression solid constituent converts.

In addition, in the table 1, each composition is as follows.

Colorant (A): (A1-1): dyestuff (A1-1)

The salt (オリヱ Application ト chemical industry (strain) system) (dyestuff) of colorant (A): (A1-2): C.I. direct blue 264 and dodecylbenzene sulfonic acid

Colorant (A): (A2-1): C.I. pigment blue 15: 6 (pigment)

Resin (B1): (B1-1): resin (B1-1)

Resin (B1): (B1-2): resin (B1-2)

Resin (B1): (B1-3): resin (B1-3)

Resin (B2): (B2-1): resin (B2-1)

Polymerizable compound (C): dipentaerythritol acrylate (KAYARAD (registered trademark) DPHA; Japan's chemical drug (strain) system)

Polymerization initiator (D): (D-1): N-benzoyloxy-1-(4-thiophenyl phenyl)-1-octanone-2-imines (イ Le ガキユア (registered trademark) OXE 01; BASF society system; O-acyl group oxime compound)

Polymerization initiator (D): (D-2): 2-methyl-2-morpholino-1-(4-methyl mercapto phenyl)-1-acetone (イ Le ガキユア (registered trademark) 907; BASF society system; Benzene alkyl ketone compound)

Polymerization causes auxiliary agent (D1): 2,4-diethyl thioxanthone (KAYACURE (registered trademark) DETX-S; Japan's chemical drug (strain) system; The thioxanthones compound)

Solvent (E): (E-1): propylene glycol monomethyl ether

Solvent (E): (E-2): propylene glycol monomethyl ether

Solvent (E): (E-3): ethyl lactate

Surfactant (F): (F-1): polyether modified silicone oil (TORAY SILICONE SH8400; The beautiful DOW CORNING in east (strain) system)

(development evaluation)

At 2 inches square glass substrates (イ one グ Le XG; Corning Incorporated (コ one ニ Application グ society) system) on, behind spin-coating method coating photosensitive composition, formed composition layer in 3 minutes at 100 ℃ of lower preliminary dryings.The substrate that will be formed with the above-mentioned composition layer under 25 ℃, impregnated in added 10ml to contain nonionic be surfactant 0.12% with the double dish of the water system developer solution of sodium carbonate 2% in 120 seconds, the developer solution behind the visualization dipping.Do not find origin in developer solution when the stripping film of photosensitive composition, development is judged as and well is designated as zero, be designated as when finding stripping film is arranged *.Finding in developer solution has origin in the stripping film of photosensitive composition, and then it can be attached on the color filter as foreign matter, and then produces harmful effect, so not preferred.The results are shown in Table 2.

(making of color filter)

At 2 inches square glass substrates (イ one グ Le XG; Corning Incorporated's system) on, behind spin-coating method coating photosensitive composition, formed composition layer in 3 minutes in 100 ℃ of lower preliminary dryings.After the cooling, will be formed with the substrate of said composition layer and the interval of the figuratum quartz glass of tool photomask processed and be made as 200 μ m, use exposure machine (TME-150RSK; トプコ Application (strain) system), under atmospheric atmosphere gas, with 40mJ/cm ²Exposure (365nm benchmark) carry out irradiation.In addition, the irradiation of this moment is that the radiating light that ultrahigh pressure mercury lamp is emitted sees through optical filter (UV-35: Korean and Japanese light splitting (strain) system) carry out.In addition, irradiation is situated between and (has the foursquare shading light part that the 1 limit length of side is 30 μ m by having formed at grade pattern, these foursquare 100 μ m that are spaced apart) photomask carry out (below, to carry out light-struck part corresponding to the light transmission part of photomask and be called " exposed portion ", will be corresponding to the shading of photomask part, do not carry out light-struck part and be called " unexposed portion ").Behind the irradiation, with above-mentioned film under 25 ℃, to be immersed in contain in the water system developer solution that nonionic is surfactant 0.12% and sodium carbonate 2% 60 seconds and develop, after the washing, in baking oven, carry out 20 minutes rear baking under 230 ℃, obtain thus to be formed with at unexposed portion the color filter in the square hole of 30 μ m.

(determining film thickness)

Use determining film thickness device (DEKTAK3; Japan's vacuum technique (strain) system)), the exposed portion of the color filter that obtains carried out determining film thickness.The results are shown in Table 2.

(chromaticity evaluation)

For the exposed portion of the color filter that obtains, use color measurement instrument (OSP-SP-200; Olympus (strain) system) measures spectrophotometric spectra, xy chromaticity coordinate (x, y) and tristimulus values Y in the XYZ color specification system of the isochrome function mensuration CIE of use illuminant-C.The larger expression brightness of Y value is higher.The results are shown in Table 2.

[table 2]

Confirm the photosensitive composition of embodiment when color filter forms, be not found to the generation of the stripping film that is caused by development.Thus, by the color filter that is made by photosensitive composition of the present invention, can make display device with high finished product rate.

According to photosensitive composition of the present invention, in the developer solution after development, origin is seldom arranged in the stripping film of photosensitive composition.

Claims

1. a photosensitive composition contains

(A) colorant;

(B1) contain the resin of following structural unit: derive from least a kind the structural unit that is selected among the group that unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides consist of, and derive from the structural unit of the monomer of cyclic ether structure with carbon number 2～4 and ethene unsaturated link;

(B2) contain the resin of following structural unit: derive from least a kind the structural unit that is selected among the group that unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides consist of, with the structural unit that derives from the monomer with ester ring type hydrocarbon structure, wherein, the structural unit that does not contain the monomer that derives from cyclic ether structure with carbon number 2～4 and ethene unsaturated link;

(C) polymerizable compound;

(D) polymerization initiator.

2. photosensitive composition according to claim 1 wherein, (B2) further contains the structural unit that derives from the monomer with aromatic hydrocarbyl.

3. photosensitive composition according to claim 1 and 2, wherein, content (B2) is 10～90 quality % with respect to (B1) and (B2) total amount.

4. a color filter is formed by the described photosensitive composition of any one of claim 1～3.

5. a display device possesses color filter claimed in claim 4.