CN102629076A

CN102629076A - Colored photosensitive resin composition

Info

Publication number: CN102629076A
Application number: CN2012100176974A
Authority: CN
Inventors: 城内公之; 小山惠范
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2011-02-08
Filing date: 2012-01-19
Publication date: 2012-08-08
Also published as: TW201235784A; KR20120090840A; KR101910521B1; JP2012181506A; TWI578105B; JP5919830B2

Abstract

The invention provides a colored photosensitive resin composition, comprising colorants, resin, polymerized compounds, polymerization initiators and solvents. The colorants comprise xanthene dyes and pigments; the solvents comprise dipropylene glycol single methyl ether acetate. A substrate is coated with the colored photosensitive resin composition and is then performed drying under reduced pressure to manufacture a dried coating which has less defects of generating bocca shapes.

Description

Photosensitive composition

Technical field

The present invention relates to photosensitive composition.

Background technology

Photosensitive composition can be used in the manufacturing of employed color filter in the display device such as display panels, organic electroluminescence panel, plasma display device.

In Jap.P. Publication Laid-Open 2010-32999 communique, known have as colorant contain xanthene dye and pigment, and contain the photosensitive composition of propylene glycol monomethyl ether and 4-hydroxy-4-methyl-2 pentanone as solvent.

Summary of the invention

Behind coating photosensitive composition on the substrate, carry out drying under reduced pressure and make when filming after the drying, produce bocca (crater: the bowl-like depression) defective of shape sometimes.The object of the present invention is to provide and produce the few photosensitive composition of crateriform defective.

The method that is used to deal with problems

The present invention provides following [1]～[5].

[1] a kind of photosensitive composition, it contains colorant, resin, polymerizable compound, polymerization initiator and solvent,

Said colorant is the colorant that contains xanthene dye (xanthene dye) and pigment,

Said solvent is for containing the solvent of DPGME acetic acid esters (dipropylene-glycol monomethylether acetate).

[2] like [1] described photosensitive composition, wherein, the content of DPGME acetic acid esters is more than the 0.1 quality % below the 30 quality % in solvent.

[3] like [1] or [2] described photosensitive composition, wherein, solvent is for further containing the solvent of ethyl lactate.

[4] like [3] described photosensitive composition, wherein, solvent is for further containing the solvent of propylene glycol monomethyl ether and/or propylene glycol monomethyl ether.

[5] like each described photosensitive composition in [1]～[4], wherein, resin is an alkali soluble resin.

[6] like each described photosensitive composition in [1]～[5], wherein, polymerizable compound is (methyl) acrylic ester.

[7] a kind of color filter, it forms through each described photosensitive composition in [1]～[6].

[8] a kind of display device, it contains [7] described color filter.

Even if photosensitive composition of the present invention is coated on the substrate, and carries out drying under reduced pressure and its dry back is made film, also seldom produce crateriform defective.

Embodiment

Photosensitive composition of the present invention is for containing colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D) and solvent (E); And colorant (A) is for containing the colorant of pigment and xanthene dye, and solvent is the photosensitive composition that contains the solvent of DPGME acetic acid esters.

Colorant (A) used in the photosensitive composition of the present invention contains pigment and xanthene dye.

As pigment, can enumerate organic pigment and inorganic pigment, can enumerate the compound that in color index (Colour index) (The Society of Dyers and Colourists publication), is classified as pigment.Wherein, preferred organic pigment.

As organic pigment; Particularly, can enumerate for example yellow uitramarine such as C.I.pigment yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,137,138,139,147,148,150,153,154,166,173,194,214;

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

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

C.I.pigment blue 15,15:3,15:4,15:6,60, blue pigments such as 80; Violet pigments such as C.I.pigment Violet 1,19,23,29,32,36,38;

Viridine greens such as C.I.pigment green 7,36,58;

Dark brown pigment such as C.I.pigment brown 23,25; And

Black pigments such as C.I.pigment black 1,7.

Wherein, preferred C.I.pigment blue 15,15:3,15:4,15:6,60, blue pigments such as 80; Violet pigments such as C.I.pigment Violet 1,19,23,29,32,36,38.More preferably contain at least a pigment that is selected among C.I.pigment Violet 23, C.I.pigment blue15:3 and the C.I.pigment blue15:6, further preferably contain the pigment of C.I.pigment blue15:6.Through making up these pigment and xanthene dye, can obtain the color filter of thermotolerance and look excellent performance.These pigment can separately or mix use more than 2 kinds.

As required, can implement rosin to said pigment has handled, has used the surface treatment that imports pigment derivative that acidic groups or basic group are arranged or pigment dispersing agent etc., utilized macromolecular compound etc. that the grafting of surface of pigments is handled, handled or based on the clean of organic solvent that is used to remove impurity and water etc., remove processing etc. based on the ion exchange process of ionic impurity etc. based on the micronize of sulfuric acid micronize method etc.In addition, the pigment optimization particle diameter is even.Carry out dispersion treatment through containing pigment dispersing agent, can obtain the dispersible pigment dispersion of pigment homodisperse state in solution.

As said pigment dispersing agent, can use commercially available surfactant, can enumerate for example surfactants such as silicone-based, fluorine system, ester system, kation system, negative ion system, nonionic system, both sexes, polyester system, polyamine system, acrylic acid series etc.As said surfactant; Can enumerate except that polyethylene oxide alkyl ethers class, polyoxyethylene alkyl phenyl ethers, polyethylene glycol di class, D-sorbite fatty acid ester, fatty acid modified polyesters, tertiary amine modified polyurethane, polyethyleneimine: amine etc.; In addition; Also have trade name KP (Shin-Etsu Chemial Co., Ltd's system), Floren (Kyoeisha Chemical Co., Ltd.'s system), Solsperse (Zeneca Co., Ltd. system), EFKA (CIBA corporate system), AJISPER (Ajinomoto Fine-Techno Co., Inc. system), Disperbyk (BYK-Chemie corporate system) etc.These can be distinguished independent use or make up more than 2 kinds and use.

When using pigment dispersing agent, with respect to pigment 100 mass parts, its use amount is preferably below 100 mass parts, more preferably 5～50 mass parts.Then there is the tendency of the dispersible pigment dispersion that obtains uniform disperse state in the use amount of pigment dispersing agent if in above-mentioned scope.

Xanthene dye is the dyestuff that contains the compound with cluck ton skeleton.

As xanthene dye, can enumerate the xanthene dye of for example C.I. acid red 51,52,87,92,94,289,388, 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 record of TOHKEMY 2010-32999 communique and the xanthene dye of No. 4492760 record of Jap.P. etc.

Wherein, as xanthene dye, preferably contain the compound shown in the formula (1) (below be sometimes referred to as the dyestuff of " compound (1) ".Compound (1) can be its dynamic isomer.When using compound (1), with respect to the total amount of xanthene dye, the content of compound (1) is preferably more than the 50 quality %, more preferably more than the 70 quality %, further is preferably more than the 90 quality %.Particularly, in fact preferably only use compound (1) as xanthene dye.

[in the formula (1), R ¹～R ⁴Represent independently that respectively hydrogen atom, carbon number are the aromatic hydrocarbyl of 1 valency of saturated hydrocarbyl or the carbon number 6～10 of 1～20 1 valency, the contained hydrogen atom of this aromatic hydrocarbyl can by halogen atom ,-R ⁸,-OH ,-OR ⁸,-SO ₃ ^-,-SO ₃H ,-SO ₃ ^-M ⁺,-CO ₂H ,-CO ₂ ^-M ⁺,-CO ₂R ⁸,-SR ⁸,-SO ₂R ⁸,-SO ₃R ⁸Or-SO ₂NR ⁹R ¹⁰Replace.Hydrogen atom contained in the said saturated hydrocarbyl also can be replaced by the aromatic hydrocarbyl of carbon number 6～10 or halogen atom, and hydrogen atom contained in this aromatic hydrocarbyl can be replaced by the alkoxy of carbon number 1～3, and is contained in the said saturated hydrocarbyl-CH ₂-can by-O-,-CO-or-NR ¹¹-replace.R ¹And R ²Can form the ring that comprises nitrogen-atoms, R together ³And R ⁴Can form the ring that contains nitrogen-atoms together.

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

M representes 0～5 integer.M is 2 when above, a plurality of R ⁵Can be identical or different.

R ⁶And R ⁷The alkyl of representing hydrogen atom or carbon number 1～6 respectively independently.

M ⁺Expression ⁺N (R ¹¹) ₄, Na ⁺Or K ⁺

X representes halogen atom.

A representes 0 or 1 integer.

R ⁸The saturated hydrocarbyl of 1 valency of expression carbon number 1～20, the contained hydrogen atom of this saturated hydrocarbyl can be replaced by halogen atom.

R ¹¹Saturated hydrocarbyl or the aralkyl of carbon number 7～10 of representing 1 valency of hydrogen atom, carbon number 1～20 respectively independently.

R ⁹And R ¹⁰The saturated hydrocarbyl of representing 1 valency of hydrogen atom or carbon number 1～20 respectively independently, the contained hydrogen atom of this saturated hydrocarbyl can be replaced by hydroxyl or halogen atom, and this representative examples of saturated aliphatic alkyl is contained-CH ₂-can by-O-,-CO-,-NH--or-NR ⁸-replace R ⁹And R ¹⁰Bonding forms the heterocycle of 3～10 yuan of rings that contain nitrogen-atoms mutually.

As R ¹～R ⁴In the aromatic hydrocarbyl of 1 valency of carbon number 6～10, can enumerate for example phenyl, toluyl, xylyl, sym-trimethyl benzene base, propyl group phenyl and butyl phenyl etc.

For R ¹～R ⁴In the aromatic hydrocarbyl of 1 valency of carbon number 6～10, as substituting group, preferably have and be selected from-SO ₃ ^-,-SO ₃H ,-SO ₃ ^-M ⁺And-SO ₂NR ⁹R ¹⁰In at least a kind, more preferably have and be selected from-SO ₃ ^-M ⁺And-SO ₂NR ⁹R ¹⁰In at least a kind.As this moment-SO ₃ ^-M ⁺, preferred-SO ₃ ^-+N (R ¹¹) ₄If R ¹～R ⁴Be these groups, then can form foreign matter and produce less and the color filter of excellent heat resistance by the photosensitive composition of the present invention that contains compound (1).

As R ¹And R ²The ring and the R that form together ³And R ⁴The ring that forms together can be enumerated for example following group.

As R ⁸～R ¹¹In the saturated hydrocarbyl of 1 valency of carbon number 1～20, can enumerate the alkyl of carbon numbers 1～20 such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, amyl group, isopentyl, neopentyl, hexyl, heptyl, octyl group, 2-ethylhexyl, nonyl, decyl, dodecyl, cetyl, eicosyl; The ester ring type saturated hydrocarbyl of carbon numbers 3～20 such as cyclopropyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, three ring decyls.

As-OR ⁸, can enumerate for example methoxyl, ethoxy, propoxyl group, butoxy, amoxy, hexyl oxygen base, heptyl oxygen base, octyl group oxygen base, 2-ethylhexyl oxygen base and eicosyl oxygen base etc.

As-CO ₂R ⁸, can enumerate for example methoxycarbonyl group, carbethoxyl group, the third oxygen carbonyl, tertbutyloxycarbonyl, own oxygen carbonyl and eicosyl oxygen carbonyl etc.

As-SR ⁸, can enumerate for example methyl sulfane base, ethyl sulfane base, butyl sulfane base, hexyl sulfane base, decyl sulfane base and eicosyl sulfane base etc.

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

As-SO ₃R ⁸, can enumerate for example methoxyl sulfonyl, ethoxy sulfonyl, propoxyl group sulfonyl, tert-butoxy sulfonyl, hexyl oxygen base sulfonyl and eicosyl oxygen sulfonyl etc.

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

N-methyl sulfamoyl, N-ethyl sulfamoyl, N-propyl group sulfamoyl, N-isopropyl sulfamoyl, normal-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) the substituted sulfamoyl of N-1 such as sulfamoyl; And

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-normal-butyl ethyl sulfamoyl, N, two (1-methyl-propyl) sulfamoyls of N-, N; N such as N-heptyl methyl sulfamoyl, the substituted sulfamoyl of N-2 etc.

In addition, for expression R ⁹And R ¹⁰The saturated hydrocarbyl of 1 valency 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 ¹⁰Bonding forms the heterocycle of 3～10 yuan of rings that contain nitrogen-atoms mutually.As this heterocycle, can enumerate for example following group.

R ⁵Preferably-CO ₂H ,-CO ₂R ⁸,-SO ₃ ^-,-SO ₃ ^-M ⁺,-SO ₃H or SO ₂NHR ⁹, more preferably SO ₃ ^-,-SO ₃ ^-M ⁺,-SO ₃H or SO ₂NHR ⁹

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

As R ⁶And R ⁷In the alkyl of carbon number 1～6, can enumerate the alkyl of the carbon number 1～6 in the above-mentioned alkyl of enumerating.

As R ¹¹In the aralkyl of carbon number 7～10, can enumerate benzyl, phenylethyl, phenyl butyl etc.

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

As ⁺N (R ¹¹) ₄, preferred 4 R ¹¹In at least 2 be the saturated hydrocarbyl of 1 valency of carbon number 5～20.In addition, 4 R ¹¹Total carbon atom number preferred 20～80, more preferably 20～60.Exist in the compound (1) ⁺N (R ¹¹) ₄The time, if R ¹¹Be these groups, then can form the color filter of few foreign by the photosensitive composition of the present invention that contains compound (1).

Compound shown in compound (1) preferred formula (2) (below be sometimes referred to as " compound (2) ") as xanthene dye, more preferably contains the dyestuff of compound (2).Compound (2) can be its dynamic isomer.When using compound (2), more than the preferred 50 quality % of the content of the compound in the xanthene dye (2), more preferably more than the 70 quality %, further more than the preferred 90 quality %.Particularly, preferably only use compound (2) as xanthene dye.

[in the formula (2), R ²¹～R ²⁴Represent independently respectively hydrogen atom ,-R ²⁶Or the aromatic hydrocarbyl of 1 valency of carbon number 6～10, the contained hydrogen atom of this aromatic hydrocarbyl can be by-SO ₃ ^-,-SO ₃ ^-M ^A+,-SO ₃H ,-SO ₃R ²⁶Or-SO ₂NHR ²⁶Replace.

X ^aThe expression halogen atom.

A1 representes 0 or 1 integer.

M1 representes 0～5 integer.When m1 is the integer more than 2, a plurality of R ²⁵Can be identical or different.

M ^A+Expression ⁺N (R ²⁷) ₄, Na ⁺Or K ⁺

R ²⁵Expression-SO ₃ ^-,-SO ₃ ^-M ^A+,-SO ₃H or SO ₂NHR ²⁶

R ²⁶The saturated hydrocarbyl of 1 valency of expression carbon number 1～20.

R ²⁷Saturated hydrocarbyl or the benzyl of representing 1 valency of carbon number 1～20 respectively independently.

As R ²¹～R ²⁴In the aromatic hydrocarbyl of 1 valency of carbon number 6～10, can enumerate with as R ¹～R ⁴In the same group of group enumerated of aromatic hydrocarbyl.

Wherein, as R ²¹～R ²⁴Combination, preferred R ²¹And R ²³Be hydrogen atom, and R ²²And R ²⁴Be the aromatic hydrocarbyl of 1 valency of carbon number 6～10, the contained hydrogen atom of this aromatic hydrocarbyl can be by-SO ₃ ^-,-SO ₃ ^-M ⁺,-SO ₃H ,-SO ₃R ²⁶Or-SO ₂NHR ²⁶Replace.More preferably R ²¹And R ²³Be hydrogen atom, and R ²²And R ²⁴Be the aromatic hydrocarbyl of 1 valency of carbon number 6～10, the contained hydrogen atom of this aromatic hydrocarbyl can be by-SO ₃ ^-M ⁺Or-SO ₂NHR ²⁶Replace.R ²¹～R ²⁴If these groups then can be formed the color filter of excellent heat resistance by the photosensitive composition of the present invention that contains compound (2).

As R ²⁶And R ²⁷In the saturated hydrocarbyl of 1 valency of carbon number 1～20, can enumerate with as R ⁸～R ¹¹In the identical group of group enumerated of saturated hydrocarbyl.

R ²¹～R ²⁴For-R ²⁶The time ,-R ²⁶Preferred independently respectively hydrogen atom, methyl or ethyl.

As-SO ₃R ²⁶And-SO ₂NHR ²⁶In R ²⁶, the branched-chain alkyl of preferred carbon number 3～20, the more preferably branched-chain alkyl of carbon number 6～12, further preferred 2-ethylhexyl.If R ²⁶Be these groups, the photosensitive composition that then contains compound (2) can form foreign matter and produce few color filter.

M ^A+For ⁺N (R ²⁷) ₄, Na ⁺Or K ⁺, preferred ⁺N (R ²⁷) ₄

As ⁺N (R ²⁷) ₄, preferred 4 R ²⁷In at least 2 be the saturated hydrocarbyl of 1 valency of carbon number 5～20.In addition, 4 R ²⁷The total carbon number preferred 20～80, more preferably 20～60.Exist in the compound (2) ⁺N (R ²⁷) ₄The time, can be by containing R ²⁷For forming foreign matter, the photosensitive composition of the present invention of the compound (2) of these groups produces few color filter.

As compound (1), can enumerate the for example compound shown in formula (1-1)～formula (1-30).In addition, in the following formula, Ra representes that carbon number is the saturated hydrocarbyl of 1～20 1 valency, and preferred carbon number is 6～12 branched-chain alkyl, more preferably representes the 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.As above-claimed cpd, can enumerate the for example compound shown in formula (1-1)～formula (1-8), formula (1-11) or the formula (1-12).

In addition, as xanthene dye, more preferably contain the dyestuff of the compound shown in the formula (3) (below be sometimes referred to as " compound (3) ").Compound (3) can be its dynamic isomer.When using compound (3), more than the preferred 50 quality % of the content of the compound in the xanthene dye (3), more preferably more than the 70 quality %, further more than the preferred 90 quality %.

[in the formula (3), R ³¹And R ³²The alkyl of representing carbon number 1～10 independently of one another.R ³³And R ³⁴Represent the alkyl of carbon number 1～4, the alkyl alkylthio base of carbon number 1～4 or the alkyl sulphonyl of carbon number 1～4 independently of one another.R ³¹And R ³³Can form the ring that contains nitrogen-atoms, R together ³²And R ³⁴Can form the ring that contains nitrogen-atoms together.

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

As expression R ³¹And R ³²The alkyl of carbon number 1～10, can enumerate methyl, ethyl, propyl group, butyl, isopropyl, isobutyl, sec-butyl, the tert-butyl group, hexyl, 2-ethylhexyl, nonyl, decyl etc.As expression R ³³And R ³⁴The alkyl of carbon number 1～4, wherein, can enumerate carbon number and be 4 group.

As expression Russia R ³³And R ³⁴The alkyl alkylthio base of carbon number 1～4, can enumerate methyl sulfane base, ethyl sulfane base, propylthio alkyl, butyl sulfane base and isopropyl sulfane base etc.

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

R ³¹And R ³²Preferable methyl, ethyl, propyl group or isopropyl independently of one another.R ³³And R ³⁴The alkyl of preferred carbon number 1～4, more preferably methyl.

The integer of p and q preferred independently of one another 0～2, more preferably 1 or 2.

As compound (3), for example can enumerate the compound shown in formula (1-31)～formula (1-43) respectively.Wherein, to the excellent viewpoint of the dissolubility of organic solvent, the compound shown in preferred formula (1-31)～formula (1-40).

As xanthene dye, also can use commercially available xanthene dye (for example China and foreign countries change into " the Chugai Aminol Fast Pink R-H/C " of Co., Ltd.'s system, " the Rhodamin 6G " of Taoka Chemical Industries Co. Ltd.'s system etc.).In addition, also can synthesize with reference to TOHKEMY 2010-32999 communique with commercially available xanthene dye as initial feed.

Colorant (A) can contain the dyestuff different with xanthene dye.As these dyestuffs, can enumerate for example azo dyes, metal complex azo dyes, anthraquinone dye, triphenhlmethane dye, anthocyanin dye, naphthoquinone dyestuff, quinoneimine dye, methine dyes, squarylium cyanine dyes and phthalocyanine dye.

Colorant (A) can be selected according to the color of desirable color filter, also can make up multiple dye well pigment and use.

In the colorant (A), with respect to the total amount of colorant (A), preferred 1～80 quality % of the content of xanthene dye, more preferably 3～50 quality %, further preferred 3～35 quality %.With respect to colorant (A), preferred 20～99 quality % of the content of pigment, more preferably 50～97 quality %, further preferred 65～97 quality %.The content of xanthene dye and pigment is in the described scope time, can obtain the color filter of thermotolerance and look excellent performance.

With respect to the solid constituent in the photosensitive composition of the present invention, preferred 5～60 quality % of the content of colorant (A), more preferably 8～55 quality %, further preferred 10～50 quality %.The content of colorant (A) is in the described scope time, and the colour saturation when processing color filter is abundant, and can in composition, contain the resin of necessary amount, therefore, have can form the sufficient pattern of physical strength tendency, so preferably.At this, solid constituent is meant by the total amount of photosensitive composition of the present invention and removes the amount after desolvating.The total amount of solid constituent reaches with respect to the content of this each composition and can measure through known analysis means such as for example liquid chromatography or gas chromatography etc.

Photosensitive composition of the present invention contains resin (B).As resin (B), not special restriction, preferred bases soluble resin.

As resin (B), can enumerate for example following resin [K1]～[K4] etc.

[K1] have the cyclic ether structure of carbon number 2～4 and the monomer (a) of ethylenic unsaturated bond (below be sometimes referred to as " (a) "), with the multipolymer that is selected from least a kind (b) in unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides (below be sometimes referred to as " (b) ").

[K2] (a) and (b) and can with the monomer (c) of (a) copolymerization (wherein, with (a) and (b) different.) multipolymer of (below be sometimes referred to as " (c) ")

[K3] (b) with (c) multipolymer

The resin that [K4] obtains (b) and multipolymer (c) and (a) reaction.

The resin that [K5] obtains (a) and multipolymer (c) and (b) reaction.

[K6] makes (a) and multipolymer (c) and (b) reaction, reacts the resin that obtains with carboxylic acid anhydrides again.

(a) be meant the polymerizable compound of the cyclic ether structure that for example has carbon number 2～4 (for example being selected from least a kind in the group that oxirane ring, oxetanes ring and tetrahydrofuran ring constitute) and ethylenic unsaturated bond.(a) preferably have the cyclic ether of carbon number 2～4 and the monomer of (methyl) acryloxy.

Need to prove that in this instructions, " (methyl) acrylic acid " expression is selected from least a kind in acrylic acid and the methacrylic acid.The statement that reaches " (methyl) acryloyl group ", " (methyl) acrylic ester " etc. also has same implication.

As (a), can enumerate the monomer (a1) that for example has Oxyranyle and ethylenic unsaturated bond (below be sometimes referred to as " (a1) "), have oxetanyl and ethylenic unsaturated bond monomer (a2) (below be sometimes referred to as " (a2) "), have monomer (a3) (below be sometimes referred to as " (a3) ") of tetrahydrofuran base and ethylenic unsaturated bond etc.

About (a1), can enumerate and for example have straight chain shape or the branched unsaturated aliphatic hydrocarbon structure after by epoxidation and the monomer (a1-1) of ethylenic unsaturated bond (below be sometimes referred to as " (a1-1) ") and have the structure of ester ring type unsaturated hydrocarbon after and the monomer (a1-2) of ethylenic unsaturated bond (below be sometimes referred to as " (a1-2) ") by epoxidation.

As (a1-1); Can enumerate (methyl) acrylic acid glycidyl esters, (methyl) acrylic acid Beta-methyl glycidyl esters, (methyl) propenoic acid beta-ethyl glycidyl esters, glycidyl vinyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, Alpha-Methyl-o-vinyl benzyl glycidyl ether, Alpha-Methyl-m-vinyl benzyl glycidyl ether, Alpha-Methyl-p-vinyl benzyl glycidyl ether, 2, two (the glycidyl oxygen ylmethyl) styrene, 2 of 3-, two (the glycidyl oxygen ylmethyl) styrene, 2 of 4-; Two (the glycidyl oxygen ylmethyl) styrene, 2 of 5-; Two (the glycidyl oxygen ylmethyl) styrene, 2,3 of 6-, 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, 2,4,6-three (glycidyl oxygen ylmethyl) styrene etc.

As (a1-2), can enumerate single oxyethylene group cyclohexene, 1, (for example, CELLOXIDE 2000 for 2-epoxy radicals-4-vinyl cyclohexane; Daicel chemical industry Co., Ltd. system), 3,4-epoxycyclohexyl methyl (methyl) acrylic ester (for example, Cyclomer A400; Daicel chemical industry Co., Ltd. system), 3,4-epoxycyclohexyl methyl (methyl) acrylic ester is (for example: CyclomerMlOO; Daicel chemical industry Co., Ltd. system), reach compound shown in the formula (I) and the compound shown in the formula (II) etc.

[in formula (I) and the formula (II), R ^aAnd R ^bThe alkyl of representing hydrogen atom or carbon number 1～4 independently of one another, the contained hydrogen atom of this alkyl can be replaced by hydroxyl.

X ¹And X ²Represent independently of one another singly-bound ,-R ^c-, *-R ^c-O-, *-R ^c-S-, *-R ^c-NH-.

R ^cThe alkane 2 basis of expression carbon number 1～6.

* represent bonding point with O.

As the alkyl of carbon number 1～4, can enumerate methyl, ethyl, n-propyl group, isopropyl, normal-butyl, sec-butyl, the tert-butyl group etc.

By the alkyl that hydroxyl has replaced, can enumerate 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. as hydrogen atom.

As R ^aAnd R ^b, can preferably enumerate hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, more preferably enumerate hydrogen atom, methyl.

As alkane 2 basis, can enumerate methylene, ethylidene, propane-1,2-two bases, propane-1,3-two bases, butane-1,4-two bases, pentane-1,5-two bases, hexane-1,6-two bases etc.

As X ¹And X ², can preferably enumerate singly-bound, methylene, ethylidene, *-CH ₂-O-(* representes the bonding point with O) base, *-CH ₂CH ₂-O-base more can preferably be enumerated singly-bound, *-CH ₂CH ₂-O-base.

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

As the compound shown in the formula (II), can enumerate the compound shown in formula (II-1)～formula (II-15) etc.Can preferably enumerate the compound shown in formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11)～formula (II-15).Can more preferably enumerate the 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 independent use.In addition, these can be with ratio mixed arbitrarily.During mixing, its mixture ratio is with molar ratio computing, and preferred formula (I): formula (II) is 5: 95～95: 5, and more preferably 10: 90～90: 10, preferred especially 20: 80～80: 20.

As the monomer with oxetanyl and ethylenic unsaturated bond (a2), more preferably has the monomer of oxetanyl and (methyl) acryloyl group oxygen base.As (a2), can enumerate 3-methyl-3-methacryloxy methyl oxetanes, 3-methyl-3-acryloyl-oxy ylmethyl oxetanes, 3-ethyl-3-methacryloxy methyl oxetanes, 3-ethyl-3-acryloyl-oxy ylmethyl oxetanes, 3-methyl-3-methacryloxyethyl oxetanes, 3-methyl-3-acryloxy ethyl oxetanes, 3-ethyl-3-methacryloxyethyl oxetanes, 3-ethyl-3-acryloxy ethyl oxetanes etc.

As the monomer with tetrahydrofuran base and ethylenic unsaturated bond (a3), more preferably has the monomer of tetrahydrofuran base and (methyl) acryloyl group oxygen base.

As (a3), particularly, can enumerate acrylic acid tetrahydrofuran ester (for example, Viscoat V#150, Osaka Organic Chemical Industry Co., Ltd.'s system), reach methacrylic acid tetrahydrofuran ester etc.

As (a), from can so that to the higher aspect of reliability of thermotolerance, chemical proofing etc. of color filter consider, be preferably (a1).And then, consider more preferably (a1-2) from the aspect of the excellent storage stability of photosensitive composition.

As (b), particularly, for example can enumerate: acrylic acid, methacrylic acid, crotonic acid, neighbour,, to unsaturated monocarboxylic classes such as vinyl benzoic acids;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3; 4,5,6-tetrahydrophthalic acid, 1; 2; 3, unsaturated dicarboxylic classes such as 6-tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid, 1,4 one cyclohexene dicarboxylic acid;

Methyl-b-ENB-2; 3-dicarboxylic acid, 5-carboxyl dicyclo [2.2.1] hept-2-ene", 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-6-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-carboxylic dicyclo unsaturated compound classes such as 6-ethyl dicyclo [2.2.1] hept-2-ene";

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

Unsaturated list [(methyl) acryloxyalkyl] the ester class of the polybasic carboxylic acid that divalents such as mono succinate [2-(methyl) acryloxy ethyl] ester, phthalic acid list [2-(methyl) acryloxy ethyl] ester are above; And

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

Wherein, from the viewpoint of copolyreaction property, the resin that obtains deliquescent viewpoint, preferred acrylic acid, methacrylic acid, maleic anhydride etc. to aqueous alkali.

As (c), for example can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butylacrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) dodecylacrylate, (methyl) acrylic acid Lauryl Ester, (methyl) stearyl acrylate base ester, (methyl) acrylic acid cyclopentyl ester, (methyl) acrylic acid cyclohexyl ester, (methyl) acrylic acid 2-methylcyclohexyl ester, three ring [5.2.1.0 ^2,6] decane-8-base (methyl) acrylic ester (in this technical field, as trivial name, is called as dicyclopentenyl (methyl) acrylic ester.), dicyclopentenyl oxygen base ethyl (methyl) acrylic ester, three the ring [5.2.1.0 ^2,6] decene-8-base (methyl) acrylic ester is (in this technical field.As trivial name, be called as dicyclopentenyl (methyl) acrylic ester.), (methyl) esters of acrylic acid such as (methyl) isobornyl acrylate, (methyl) acrylic acid adamantane esters, (methyl) acrylic acid allyl ester, (methyl) acrylic acid alkynes propyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid naphthalene ester, (methyl) benzyl acrylate;

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

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

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

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

Styrene, AMS, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxy styrene, vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylic amide, Methacrylamide, vinyl acetate, 1; 3-butadiene, isoprene, and 2; 3-dimethyl-1,3-butadiene etc.

Wherein, from copolyreaction property and stable on heating viewpoint, optimization styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, dicyclo [2.2.1] hept-2-ene" etc.

In the resin [K1], be derived from separately the ratio of structural unit in the entire infrastructure unit that constitutes resin [K1], preferably in following scope.

Be derived from the structural unit of (a): 50～98 moles of % (more preferably 60～90 moles of %).

Be derived from the structural unit of (b): 2～50 moles of % (more preferably 10～40 moles of %).

If the ratio of the structural unit of resin [K1] is in the above-mentioned scope, then have photosensitive composition storage stability, development property, and the solvent resistance of color filter become good tendency.

Resin [K1] can reference example such as document " experimental method of Polymer Synthesizing " (" the high son that divides closes into the experiment method ") (big Tianjin grand row work sale room Co., Ltd. chemistry is with the 1st edition the 1st printing distribution on March 1st, 1972 of the people) method of record and the citing document of document record make.

Particularly, can enumerate following method: in reaction vessel, add (a) of ormal weight and (b), polymerization initiator and solvent etc., for example form the deoxidation atmosphere through the nitrogen replace oxygen, the method for limit heating and insulation is stirred on the limit.In addition, at this, employed polymerization initiator and solvent etc. are not special to be limited, and also can use any one in the normally used material in this field.For example, can enumerate as polymerization initiator: azo-compound [2,2 '-azoisobutyronitrile, 2; 2 '-azo two (2; The 4-methyl pentane nitrile) etc.) or organic peroxide (benzoyl peroxide etc.), as solvent, for the material of each monomer of solubilized gets final product; As the solvent (E) of photosensitive composition of the present invention, the solvent of stating after can using etc.

Need to prove that the multipolymer that obtains can directly use reacted solution, also can use concentrate or dilution after solution, can also use through the material of methods such as deposition again with the form taking-up of solid (powder).Particularly when carrying out this polymerization; As solvent; Contained solvent in the photosensitive composition of the application of the invention; Can reacted solution directly be used for the preparation of photosensitive composition of the present invention, therefore, can the manufacturing process of photosensitive composition of the present invention be simplified.

In the resin [K2], in the entire infrastructure unit that constitutes resin [K2], the ratio that is derived from structural unit separately is preferably following scope.

Be derived from the structural unit of (a): 2～95 moles of % (more preferably 5～80 moles of %);

Be derived from the structural unit of (b): 4～45 moles of % (more preferably 10～30 moles of %);

Be derived from the structural unit of (c): 1～65 mole of % (more preferably 5～60 moles of %);

If the ratio of the structural unit of resin [K2] is in the above-mentioned scope, then to have solvent resistance, thermotolerance and the physical strength of storage stability, development property and the color filter of photosensitive composition to become good tendency.

Resin [K2] can be made with the same method of method that the manufacturing approach of for example resin [K1] is put down in writing.

Particularly, can enumerate following method: in reaction vessel, add the (a) and (b) of ormal weight and (c), polymerization initiator and solvent, for example form the deoxidation atmosphere through the nitrogen replace oxygen, the method for limit heating and insulation is stirred on the limit.The polymkeric substance that obtains can directly use, and also can use to concentrate or the solution of dilution, can also use through the material of methods such as deposition again with the form taking-up of solid (powder).

In the resin [K3], be derived from the ratio of structural unit separately, in the entire infrastructure unit that constitutes resin [K3], be preferably following scope.

(b) 2～50 moles of %, more preferably 5～40 moles of %;

(c) 50～98 moles of %, more preferably 60～95 moles of %;

Resin [K3] can be made with the same method of for example putting down in writing as the manufacturing approach of resin [K1] of method.

Resin [K4] can be through obtaining (b) and (c) multipolymer, and the cyclic ether that makes the carbon number 2～4 that (a) have and the carboxyl that (b) is had or carboxylic acid anhydrides addition and obtain.

At first, to (b) and (c) multipolymer to make with the same method of putting down in writing as the manufacturing approach of [K1] of method.At this moment, be derived from the ratio of structural unit separately, in the entire infrastructure unit that constitutes (b) and multipolymer (c), be preferably following scope.

(b) 5～50 moles of %, more preferably 10～45 moles of %

(c) 50～95 moles of %, more preferably 55～90 moles of %

Then, make the contained carboxyl of cyclic ether and the structural unit that is derived from (b) in the said multipolymer of the carbon number 2～4 that (a) had and/or the part reaction of carboxylic acid anhydrides.

Then the manufacturing of (b) and multipolymer (c) is replaced into air with atmosphere in the beaker by nitrogen, in beaker, adds the catalysts of (a), carboxyl and cyclic ether, for example reacts 1～10 hour down at 60～130 ℃, thus, can obtain resin [K4].As said catalysts, can enumerate for example three (dimethylaminomethyl) phenol etc.With respect to total metering of (a)～(c), the use amount of said catalysts is preferably 0.001～5 quality %.As said polymerization inhibitor, can enumerate for example quinhydrones etc.With respect to (a)～(c) total metering, preferred 0.001～5 quality % of the use amount of said polymerization inhibitor.The thermal discharge that reaction conditionss such as feeding method, temperature of reaction and time can consider manufacturing equipment, produced by polymerization etc. is suitably adjusted.Need to prove that same with polymerizing condition, the thermal discharge that can consider manufacturing equipment, is produced by polymerization etc. are suitably adjusted feeding method, temperature of reaction.

With respect to (b) 100 moles, preferred 5～80 moles of the use amount of this moment (a), more preferably 10～75 moles, more preferably 15～70 moles.If in this scope, there is the balance of solvent resistance, thermotolerance and physical strength of storage stability, development property and sensitivity and the color filter of photosensitive composition to become good tendency.

About resin [K5], in the phase one, with the same method of manufacturing approach of above-mentioned resin [K1], obtain (a) and (c) multipolymer.With above-mentioned same, the multipolymer that obtains can directly use reacted solution, also can use to concentrate or the solution of dilution, can also use through the material of methods such as deposition again with the form taking-up of solid (powder).

With respect to the total molal quantity of the entire infrastructure unit that constitutes described multipolymer, be derived from the ratio of (a) and structural unit (c), be preferably following scope separately.

Be derived from the structural unit of (a): 5～95 moles of % (more preferably 10～90 moles of %)

Be derived from the structural unit of (c): 5～95 moles of % (more preferably 10～90 moles of %)

And then, with the same condition of manufacturing approach of resin [K4], make carboxylic acid that (b) had or carboxylic acid anhydrides and (a) and the cyclic ether reaction that is derived from (a) that multipolymer had (c), obtain resin [K5].

With respect to (a) 100 moles, be preferably 5～80 moles with the use amount of (b) of described copolymer reaction.Because cyclic ether is reactive high, is difficult to remaining unreacted (a), so as (a) that be used for resin [K5], preferred (a1), and then preferred (a1-1).

The resin of resin [K6] for carboxylic acid anhydrides and resin [K5] reaction is formed.The hydroxyl reaction that carboxylic acid anhydrides and reaction through cyclic ether and carboxylic acid or carboxylic acid anhydrides are produced.

As carboxylic acid anhydrides, can enumerate maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4; 5; 6-tetrabydrophthalic anhydride, 1,2,3; 6-tetrabydrophthalic anhydride, dimethyl tetrahydro phthalic anhydride, 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene" acid anhydride etc.

As resin (B), particularly, can enumerate 3,4-epoxy radicals cyclohexyl methyl (methyl) acrylic ester/(methyl) acrylic copolymer, 3,4-epoxy three ring [5.2.1.0 ^2.6] decyl acrylic ester/resins [K1] such as (methyl) acrylic copolymer; (methyl) glycidyl acrylate/(methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) glycidyl acrylate/styrene/(methyl) acrylic copolymer, 3,4-epoxy three ring [5.2.1.0 ^2.6] decyl acrylic ester/(methyl) acrylic acid/N-cyclohexyl maleimide copolymer, 3,4-epoxy three ring [5.2.1.0 ^2.6] decyl acrylic ester/(methyl) acrylic acid/vinyl toluene copolymer, 3-methyl-3-(methyl) acryloyl-oxy ylmethyl oxetanes/resins [K2] such as (methyl) acrylic acid/styrol copolymer; (methyl) benzyl acrylate/(methyl) acrylic copolymer, styrene/resins [K3] such as (methyl) acrylic copolymer; Make resin that (methyl) benzyl acrylate/(methyl) acrylic copolymer and the addition of (methyl) acrylic acid glycidyl form, make the resin that (methyl) acrylic acid three ring decyl ester/styrene/(methyl) acrylic copolymers and the addition of (methyl) glycidyl acrylate form, the resins such as resin [K4] that (methyl) acrylic acid three ring decyl ester/(methyl) benzyl acrylate/(methyl) acrylic copolymers and the addition of glycidyl (methyl) acrylic ester are formed; Make the multipolymer of dicyclopentenyl (methyl) acrylic ester/(methyl) glycidyl acrylate react the resins such as resin [K5] that form with resin, the multipolymer that makes (methyl) acrylic acid two cyclopentene ester/styrene/(methyl) glycidyl acrylate and (methyl) acrylic acid that the reaction of (methyl) acrylic acid forms; Make the multipolymer and the resin that the reaction of (methyl) acrylic acid forms of (methyl) acrylic acid two cyclopentene esters/(methyl) glycidyl acrylate, react and resins such as resin [K6] etc. with tetrabydrophthalic anhydride again.Wherein, preferred resin [K1] and resin [K2], more preferably resin [K1], further preferred 3,4-epoxy three ring [5.2.1.0 ^2.6] decyl acrylic ester/(methyl) acrylic copolymer.If resin (B) is derived from the resin of the structural unit of (a) for containing, then can improve the reliability such as thermotolerance, chemical proofing of the color filter that obtains more.

The weight-average molecular weight of the polystyrene conversion of resin (B) is preferred 3,000～100,000, and more preferably 5,000～50,000, further preferred 5,000～35,000, preferred especially 6,000～30,000, especially preferred 7,000～28,000.If molecular weight is said scope, then there is hardness of film to improve, residual film ratio also improves, unexposed the favorable solubility to developer solution, and the tendency of resolution raising.

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

Preferred 50～the 150mg-KOH/g of acid number of resin (B), more preferably 60～135mg-KOH/g, further preferred 70～135mg-KOH/g.At this, acid number for in the value measured with the form of the amount (mg) of the needed potassium hydroxide of 1g resin, for example can try to achieve through using potassium hydroxide aqueous solution carry out titration.

With respect to the solid constituent of photosensitive composition of the present invention, preferred 7～65 quality % of the content of resin (B), more preferably 13～60 quality %, further preferred 17～55 quality %.If the content of resin (B) is described scope, then has to form colored pattern, and improve the tendency of resolution and residual film ratio.

Photosensitive composition of the present invention contains polymerizable compound (C).Polymerizable compound (C) can preferably be enumerated (methyl) acrylate compounds for can for example enumerating the compound of the ethylenic unsaturated bond with polymerism etc. through carrying out polymeric compounds by the living radical of polymerization initiator (D) generation and acid etc.

Wherein, as polymerizable compound (C), preferably has the polymerizable compound of the ethylenic unsaturated bond more than 3.As such polymerizable compound, for example can enumerate pentaerythrite four (methyl) acrylic ester, dipentaerythritol five (methyl) acrylic ester, dipentaerythritol six (methyl) acrylic ester, tripentaerythritol eight (methyl) acrylic ester, tripentaerythritol seven (methyl) acrylic ester, the four seasons penta tetrol ten (methyl) acrylic ester, the four seasons penta tetrol nine (methyl) acrylic ester, three (2-(methyl) acryloyl group oxygen base ethyl) isocyanuric acid ester, glycol-modified pentaerythrite four (methyl) acrylic ester, glycol-modified dipentaerythritol six (methyl) acrylic ester, propylene glycol modified pentaerythrite four (methyl) acrylic ester, propylene glycol modified dipentaerythritol six (methyl) acrylic ester, caprolactone modification pentaerythrite four (methyl) acrylic ester, and caprolactone modification dipentaerythritol six (methyl) acrylic ester etc.Wherein, preferably can enumerate dipentaerythritol five (methyl) acrylic ester, dipentaerythritol six (methyl) acrylic ester etc.Polymerizable compound can use separately also can make up more than 2 kinds and use.

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

With respect to the solid constituent of photosensitive composition of the present invention, the content of polymerizable compound (C) is preferably 7～65 quality %, more preferably 13～60 quality %, further preferred 17～55 quality %.If the content of described polymerizable compound (C) is in the described scope, owing to have and can solidify fully, the residual film ratio during development improves, and is difficult for sneaking into undercutting in the colored pattern, and adherence becomes good tendency, so preferred.

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

As described polymerization initiator (D), so long as can the effect through light and heat produce living radical, acid etc., and compound that can initiated polymerization, then there is not special qualification, can use known polymerization initiator.

As polymerization initiator (D), preferably produce the compound of living radical through the effect of light, more preferably benzene alkyl ketone compound, triaizine compounds, acylphosphine oxideization contain thing, oxime compound and united imidazole, further preferred oxime compound.

Above-mentioned benzene alkyl ketone compound is for having the compound of the part-structure shown in part-structure shown in the formula (d2) or the formula (d3).In these part-structures, phenyl ring also can have substituting group.

As compound, for example can enumerate 2-methyl-2-morpholinyl-1-(4-methyl sulfane base phenyl) propane-1-ketone, 2-dimethylamino-1-(4-morpholino phenyl)-2-benzyl butane-1-ketone, and 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholino) phenyl] butane-1-ketone etc. with the part-structure shown in the formula (d2).Also can use the commercially available article of IRGACURE (registered trademark) 369,907 and 379 (above, BASF AG's system) etc.

As compound with the part-structure shown in the formula (d3); For example can enumerate 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-hydroxy-2-methyl-1-(4-(2-hydroxyl-oxethyl) phenyl) propane-1-ketone, 1-hydroxy-cyclohexyl benzophenone, 2-hydroxy-2-methyl-1-(the 4-isopropenyl phenyl) propane-oligomer of 1-ketone, α, α-diethoxy acetophenone, and benzyl dimethyl acetal etc.

Consider from the sensitivity aspect; As benzene alkyl ketone compound; The compound that preferably has the part-structure shown in the formula (d2), more preferably 2-methyl-2-morpholinyl-1-(4-methyl sulfane base phenyl) propane-1-ketone and 2-dimethylamino-1-(4-morpholino phenyl)-2-benzyl butane-1-ketone.

As said triaizine compounds, can enumerate 2, two (the trichloromethyl)-6-(4-methoxyphenyl) of 4--1,3,5-triazines, 2; Two (the trichloromethyl)-6-(4-methoxyl naphthyl) of 4--1,3,5-triazines, 2, two (the trichloromethyl)-6-piperonyls-1,3 of 4-; 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene) of 4--1,3,5-triazines, 2, two (the trichloromethyl)-6-(2-(5-methylfuran-2-yl) vinyl)-1 of 4-; 3,5-triazine, 2, two (the trichloromethyl)-6-(2-(furans-2-yl) vinyl)-1,3 of 4-; 5-triazine, 2, two (the trichloromethyl)-6-(2-(4-diethylester amino-2-methyl phenyl) vinyl) of 4--1,3,5-triazines, 2; Two (the trichloromethyl)-6-(2-(3, the 4-Dimethoxyphenyl) vinyl) of 4--1,3,5-triazines etc.

As said acylphosphine oxide compound, can enumerate 2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc.Can use IRGACURE (registered trademark) 819 commercially available article such as (BASF AG's systems).

Said oxime compound is for having the compound of the part-structure shown in the formula (d1).Following * representes bonding point.

As said oxime compound; Can enumerate N-benzoyl Oxy-1-(4-phenyl sulfane base phenyl) butane-1-ketone-2-imines, N-benzoyl Oxy-1-(4-phenyl sulfane base phenyl) octane-1-ketone-2-imines, N-benzoyl Oxy-1-(4-phenyl sulfane base phenyl)-3-cyclopentyl propane-1-ketone-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 cyclopentenyl 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-benzoyl Oxy-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-3-cyclopentyl propane-1-ketone-2-imines etc.Can use the commercially available article of IRGACURE (registered trademark) OXE01, OXE02 (more than, BASF AG's system), N-1919 (ADEKA corporate system) etc.Wherein, When photosensitive composition of the present invention is blue-colored photosensitive polymer combination; The brightness of the color filter that obtains is increased; So as said oxime compound, the preferred use is selected from least a kind in N-benzoyl Oxy-1-(4-phenyl sulfane base phenyl) butane-1-ketone-2-imines, N-benzoyl Oxy-1-(4-phenyl sulfane base phenyl) octane-1-ketone-2-imines and N-benzoyl Oxy-1-(4-phenyl sulfane base the phenyl)-3-cyclopentyl propane-1-ketone-2-imines.

As united imidazole, can enumerate 2,2 '-two (2-chlorphenyl)-4,4 '; 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2, the 3-dichlorophenyl)-4; 4 ', 5,5 '-tetraphenyl bisglyoxaline is (for example with reference to japanese kokai publication hei 6-75372 communique, and japanese kokai publication hei 6-75373 communique etc.), 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2; 2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxaline, 2; 2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (dialkoxy phenyl) bisglyoxaline, 2; 2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxaline is (for example with reference to the special public clear 48-38403 communique of Japan, and japanese kokai publication sho 62-174204 communique etc.), the phenyl of 4,4 ' 5,5 '-position is by (the for example reference such as japanese kokai publication hei 7-10913 communique of the substituted imidazolium compounds of carbonylic alkoxy.) etc.Preferably can enumerate 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline.

And then, can enumerate benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether, benzoin isobutyl ether as polymerization initiator (D); Benzophenone, o-benzoyl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl thioether, 3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 2,4, benzophenone cpds such as 6-tri-methyl benzophenone; 9, naphtoquinone compounds such as 10-phenanthrenequione, 2-EAQ, camphorquinone; 10-butyl-2-chloro-acridine ketone, benzil, phenyl glyoxalic acid methylester, two cyclopentadiene titanium compounds etc.Preferred these with after the polymerization stated cause auxiliary agent (D1) (especially amine) combination and use.

As utilizing the acidic acid agent of light, for example can enumerate salt such as 4-hydroxy phenyl dimethyl disulfide tosilate, 4-hydroxy phenyl dimethyl disulfide hexafluoro antimonate, 4-acetoxyl group phenyl dimethyl disulfide tosilate, 4-acetoxyl group phenyl methyl dibenzylsulfide hexafluoro antimonate, triphenyl sulphur tosilate, triphenyl sulphur hexafluoro antimonate, diphenyl iodine tosilate, diphenyl iodine hexafluoro antimonate and nitrobenzyl toluenesulfonic acid salts, and benzoin toluenesulfonic acid salt etc.

With respect to total metering 100 mass parts of resin (B) and polymerizable compound (C), preferred 0.1～30 mass parts of the content of polymerization initiator (D), more preferably 1～20 mass parts.If the content of Photoepolymerizationinitiater initiater is in the above-mentioned scope, then can realizes highly sensitiveization and shorten the time shutter, thereby productivity is improved.

Photosensitive composition of the present invention also contains polymerization and causes auxiliary agent (D1).Polymerization causes compound or the sensitizer that auxiliary agent (D1) uses for the polymerization that is used to promote to utilize the polymerizable compound of polymerization initiator initiated polymerization, can use with polymerization initiator (D) combination usually.

Cause auxiliary agent (D1) as polymerization, can enumerate amines, alkoxy anthracene compound, thioxanthones compound, carboxylic acid compound etc.

As amines; Can enumerate triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylamino benzoic acid methyl esters, 4-dimethylamino ethyl benzoate, 4-dimethylamino benzoic acid isopentyl ester, benzoic acid 2-dimethylamino ethyl ester, 4-dimethylamino benzoic acid 2-Octyl Nitrite, N; N-dimethyl-p-toluidine, 4; 4 '-two (dimethylamino) benzophenone (common name Michler's keton), 4,4 '-two (diethylester is amino) benzophenone, 4,4 '-two (ethylmethylamino) benzophenone etc.; Wherein preferred 4,4 '-two (diethylester is amino) benzophenone.Also can use the commercially available article of EAB-F (Baotugu Chemical Industrial Co., Ltd's system) etc.

As the alkoxy anthracene compound, can enumerate 9,10-dimethoxy anthracene, 2-ethyl-9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene, 9,10-dibutoxy anthracene, 2-ethyl-9,10-dibutoxy anthracene etc.

As the thioxanthones compound, can enumerate 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones etc.

As carboxylic acid compound, can enumerate phenyl sulfane guanidine-acetic acid, aminomethyl phenyl sulfane guanidine-acetic acid, ethylphenyl sulfane guanidine-acetic acid, Methylethyl phenyl sulfane guanidine-acetic acid, 3,5-dimethylphenyl sulfane guanidine-acetic acid, methoxyphenyl sulfane guanidine-acetic acid, Dimethoxyphenyl sulfane guanidine-acetic acid, chlorphenyl sulfane guanidine-acetic acid, dichlorophenyl sulfane guanidine-acetic acid, N-phenylglycine, phenoxyacetic acid, naphthyl thioacetic acid, N-naphthyl glycocoll, naphthoxy acetic acid etc.

Polymerization initiation auxiliary agent can use separately also can make up more than 2 kinds and use.

When using polymerization to cause auxiliary agent (D1), with respect to total metering 100 mass parts of resin (B) and polymerizable compound (C), preferred 0.1～30 mass parts of its use amount, more preferably 1～20 mass parts.If it is in this scope that polymerization causes the amount of auxiliary agent (D1), then exists and further to form pattern, and improve the productive tendency of pattern with high sensitivity.

Photosensitive composition of the present invention contains solvent (E).Solvent (E) is for containing the solvent of DPGME acetic acid esters.

With respect to the total amount of solvent (E), below the above 30 quality % of the preferred 0.1 quality % of the content of DPGME acetic acid esters, more preferably below the above 20 quality % of 1 quality %, further below the above 15 quality % of preferred 2 quality %.

Solvent (E) can contain the solvent beyond the DPGME acetic acid esters.Do not limit as such solvent is special, can use normally used solvent in this field.For example can enumerating, ester solvent (comprises in the molecule-the COO-structure; Do not comprise-solvent of O-structure), ether solvents (comprises in the molecule-the O-structure; Do not comprise-solvent of COO-structure), the ether-ether solvent solvent of COO-structure and-O-structure (comprise in the molecule-), ketone solvent (comprise in the molecule-the CO-structure; Do not comprise-solvent of COO-structure), alcoholic solvent (comprise the OH base in the molecule, do not comprise-the O-structure ,-the CO-structure and-solvent of COO-structure), aromatic hydrocarbon solvents, amide solvent, and dimethyl sulfoxide etc.

As ester solvent, can enumerate 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.

As ether solvents; Can enumerate glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol single-butyl ether, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list propyl ether, propylene glycol single-butyl ether, 3-methoxyl-1-butanols, 3-methoxyl-3-methyl butanol, tetrahydrofuran, oxinane, 1,4-diox, diethylene glycol dimethyl ether, diethylene glycol diethylester ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ethers, methyl phenyl ethers anisole, phenetol, methylbenzene methyl ether etc.

As the ether-ether solvent, can enumerate methoxy menthyl acetate, methoxyacetic acid ethyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, 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, monoethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, TC acetic acid esters, diethylene glycol single-butyl ether acetic acid esters etc.

As ketone solvent, can enumerate 4-hydroxy-4-methyl-2 pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2 pentanone, cyclopentanone, cyclohexanone, different Fu Er ketone etc.

As alcoholic solvent, can enumerate methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, monoethylene glycol, propylene glycol, glycerine etc.

As aromatic hydrocarbon solvents, can enumerate benzene,toluene,xylene, sym-trimethyl benzene etc.

As amide solvent, can enumerate N, dinethylformamide, DMAC N,N, N-Methyl pyrrolidone etc.

These solvents can use separately also can make up more than 2 kinds and use.

In the above-mentioned solvent, from the viewpoint of coating, drying property, the boiling point among the preferred 1atm is the organic solvent below 180 ℃ more than 120 ℃.Wherein, Preferred propylene glycol monomethyl ether, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, 3-ethoxyl ethyl propionate, glycol monomethyl methyl ether, diethylene glycol monomethyl ether, TC, 4-hydroxy-4-methyl-2 pentanone, N; Dinethylformamide, N-Methyl pyrrolidone etc., more preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether, ethyl lactate, 3-ethoxyl ethyl propionate etc.

Solvent (E) preferably contains DPGME acetic acid esters and ethyl lactate.With respect to the total amount of solvent (E), below the above 90 quality % of the preferred 5 quality % of content of the ethyl lactate of this moment, more preferably below the above 80 quality % of 20 quality %, further below the above 70 quality % of preferred 40 quality %.

In addition, solvent (E) preferably comprises the DPGME acetic acid esters at the interior mixed solvent more than 3 kinds, the more preferably mixed solvent more than 4 kinds.

Solvent (E) is for comprising the DPGME acetic acid esters when the interior mixed solvent more than 3 kinds; Solvent (E) preferably comprises the solvent of DPGME acetic acid esters, ethyl lactate and propylene glycol monomethyl ether and/or propylene glycol monomethyl ether, more preferably comprises the solvent of DPGME acetic acid esters, ethyl lactate, propylene glycol monomethyl ether and propylene glycol monomethyl ether.And then, comprise the total amount of the total content of these and DPGME acetic acid esters, ethyl lactate, propylene glycol monomethyl ether and propylene glycol monomethyl ether with respect to solvent (E), be preferably more than the 90 quality %, more preferably more than the 95 quality %.

Solvent (E) is when comprising propylene glycol monomethyl ether, with respect to the total amount of solvent (E), below the above 40 quality % of the preferred 1 quality % of its content, more preferably below the above 30 quality % of 5 quality %.

If solvent (E) be above-mentioned solvent, it is few and also can suppress to produce inequality then to carry out producing in the film that drying under reduced pressure makes crateriform defective.

With respect to the total amount of photosensitive composition of the present invention, preferred 70～95 quality % of the content of solvent (E), more preferably 75～92 quality %.In other words, preferred 5～30 quality % of the solid constituent of photosensitive composition of the present invention, more preferably 8～25 quality %.If the content of solvent (E) is that it is good that the flatness when coating is arranged becomes in the above-mentioned scope, and since when forming color filter colour saturation abundant, so display characteristic becomes good tendency.

Photosensitive composition of the present invention can also contain surfactant (G).As surfactant (G), can enumerate the silicone-based surfactant, fluorine is surfactant and the silicone-based surfactant with fluorine atom etc.These can have polymerizable group at side chain.

As the silicone-based surfactant, can enumerate surfactant with siloxane bond etc.Particularly, can enumerate: Toray Silicone (trade name) DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone 8400 (Dong Li Dow Corning Corporation system), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemial Co., Ltd's system), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF41460 (MomentivePerformance MaterialJapan contract corporate system) etc.

As described fluorine is surfactant, can enumerate surfactant with fluorocarbon chain etc.Particularly, can enumerate Fluorad (registered trademark) FC430, Fluorad FC431 (Sumitomo 3M corporate system), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, MegafacF173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, MegafacRS-718-K (Dainippon Ink Chemicals's system), Ftop (registered trademark) EF301, Ftop EF303, FtopEF351, Ftop EF352 (the Mitsubishi Materials electronics changes into Co., Ltd.'s system), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass Co., Ltd's system), E5844 ((strain) (big aurin refinement institute system) etc.。

As silicone-based surfactant, can enumerate surfactant with siloxane bond and fluorine carbon etc. with described fluorine atom.Particularly, can enumerate Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, Megafac F443 (Dainippon Ink Chemicals's system) etc.

These surfactants can use separately also can make up more than 2 kinds and use.

Total amount with respect to photosensitive composition of the present invention; Below the above 0.2 quality % of the preferred 0.001 quality % of the content of surfactant (G); More preferably below the above 0.1 quality % of 0.002 quality %, further below the above 0.05 quality % of preferred 0.01 quality %.If the content of surfactant (F) is in the above-mentioned scope, then can make the flatness of filming good.

Photosensitive composition of the present invention can contain filling agent, other various adjuvants such as macromolecular compound, driving fit promoter, anti-oxidant, ultraviolet screener, light stabilizer, chain-transferring agent (below be sometimes referred to as " other composition ") as required.

Photosensitive composition of the present invention can cause auxiliary agent (D1), surfactant (G) and other composition through the polymerization that makes for example colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D) and solvent (E) and use as required to be mixed and prepares.

Pigment optimization mixes with a part or whole solvents (E) in advance, and use ball mill etc. to disperse the mean grain size until pigment be the degree below the 0.2 μ m.At this moment, also can cooperate a part of or whole of above-mentioned pigment dispersing agent, resin (B) as required.The remaining one-tenth of mixing grades so that it for concentration of regulation, can prepare the target photosensitive composition thus in the dispersible pigment dispersion that obtains.

Xanthene dye preferably dissolves and preparation solution in the part of solvent (E) or all in advance.Preferably the filtrator of this solution about through aperture 0.01～1 μ m filtered.

Preferably the photosensitive composition that is mixed with the as stated filtrator about through aperture 0.01～10 μ m is filtered.

As using photosensitive composition of the present invention to form the colored pattern method of color filter, can enumerate: the method for photoetching process and use ink-jet apparatus etc.Photoetching process is following method: photosensitive composition of the present invention is coated on substrate or other the resin bed (for example forming other photosensitive composition layer etc. in elder generation on the substrate); Remove, volatile ingredient such as dry solvent and form drying after film; Relending films after helping photomask to this drying makes public; Develop, form method of patterning thus.In above-mentioned photoetching process, through when making public, not using photomask and/or not developing, can form painted filming, also can process color filter.

The thickness of the color filter of making is not special to be limited, can suitably adjust according to the material that uses, purposes etc., and for example be 0.1～30 μ m, preferred 1～20 μ m, further preferred 1～6 μ m.

Through on substrate, being coated with photosensitive composition, and carrying out heat drying (preliminary drying) and/or carry out drying under reduced pressure, remove and desolvate, can obtain filming after the level and smooth drying.

As substrate, resin plate, silicon such as glass plate such as the soda-lime glass that can use quartz glass, pyrex, alumina silicate glass, the surface silica dioxide coating is formed or polycarbonate, polymethylmethacrylate, polyethylene terephthalate, on aforesaid substrate, formed the substrate of aluminium, silver, silver/copper/palldium alloy film etc.

As coating process, can enumerate spin-coating method, slot coated method, slit and spin-coating method etc.

Preferred 30～120 ℃ of heat drying, more preferably 40～100 ℃.In addition, as heat time heating time, preferred 10 second～60 minute, more preferably 30 second～30 minute.

Drying under reduced pressure preferably under the pressure of 50～150Pa, carries out in 20～25 ℃ temperature range.When photosensitive composition of the present invention carries out drying under reduced pressure under such condition, also realized the few effect of the crateriform defective of so-called generation.

The thickness of filming after the drying is not special to be limited, and can suitably adjust according to the material that uses, purposes etc.

Film after the drying and make public by the photomask that is used to form the purpose pattern.Pattern on the photomask of this moment is unqualified, can use the pattern that is suitable for the target purposes.

As the light source that is used to make public, preferably send the light source of light of the wavelength of 250～450nm.For example use the light of the wave filter intercepting of this wavelength region may of intercepting, perhaps also can use the BPF. that takes out these wavelength region may that near near near the light the 436nm, the 408nm, the 365nm is carried out selectivity and take out less than 350nm.Particularly, can enumerate mercury lamp, light emitting diode, metal halide lamp, Halogen lamp LED etc.

Owing to can shine parallel rays equably to the finish side of exposing to the sun, perhaps make mask and formed the substrate of filming after the drying and carry out position correspondence accurately, so preferably use devices such as mask aligner (maskaligner), stepping exposure device.

Can be through after the exposure, contact with developer solution and make the unexposed portion dissolving and remove (i.e. development), obtain colored pattern thus.As developer solution, the WS of the alkali compounds of preference such as potassium hydroxide, soda mint, tetramethyl ammonium hydroxide etc. and so on.Preferred 0.01～10 quality % of concentration in the WS of these alkali compounds, more preferably 0.03～5 quality %.And then developer solution also can contain surfactant.

Developing method can be paddling process, infusion process, spray process etc. any.And then can make substrate tilt to angle arbitrarily when developing.

Preferably wash after the development.

And then as required, also can carry out the back baking.Preferred 150～250 ℃ of back baking temperature, more preferably 160～220 ℃.Preferred 1～120 minute of back stoving time, more preferably 10～60 minutes.

According to photosensitive composition of the present invention, especially can make the few color filter of defective.This color filter is as display device (for example liquid crystal indicator, organic El device, and Electronic Paper) or to be used for the color filter of solid-state imager useful.

Embodiment

Below through embodiment photosensitive composition of the present invention is further specified." % " in the example reaches " part " short of special instruction, then is quality % and mass parts.

Synthetic example 1

15 parts in the potpourri of the compound shown in compound shown in the throw-in type in the flask that has condenser pipe and stirring apparatus (A0-1) and the formula (A0-2) (China and foreign countries' system of changing into), 150 parts of chloroforms and N; 8.9 parts of dinethylformamides under agitation keep 10.9 parts of 20 ℃ of following temperature thionyl chloride.After drip finishing, be warming up to 50 ℃, keep under synthermal and reacted in 5 hours, then, be cooled to 20 ℃.Cooled reaction solution is under agitation maintained below 20 ℃, drip the mixed liquor of 12.5 parts of 2-DEHAs and 22.1 parts of triethylamines simultaneously.Then, reacted in 5 hours synthermal the stirring down.Then, the reaction mixture that obtains is distilled except that after desolvating with Rotary Evaporators, add a spot of methyl alcohol and carry out strong agitation.This potpourri is joined while stirring in the mixed liquor of 375 parts of ion exchange waters, crystallization is separated out.Filter out the crystallization of separating out, fully clean, under 60 ℃, carry out drying under reduced pressure, obtain 11.3 ones of dyestuff A1 (potpourri of compound (1-1)～compound (1-8)) with ion exchange water.

Synthetic example 2

200 parts of 20 parts of compounds shown in hybrid under the shading condition (1x) and N-ethyl ortho-aminotoluenes (Wako Pure Chemical Industries, Ltd.'s system) stir the solution that obtains 6 hours down at 110 ℃.After the reactant liquor that obtains is cooled to room temperature, is added in the mixed liquor of 800 parts in water, 50 parts of 35% hydrochloric acid and at room temperature stirred 1 hour, the result, crystallization is separated out.After the crystallization that obtains to separate out with the form of the residue of suction strainer, carry out drying, obtain 24 parts of the compounds shown in the formula (1-31).Yield is 80%.

(1x) (1-31)

(quality analysis) ionization MODE=ESI+:m/z=[M+H] ⁺603.4

Exact mass (ExactMass): 602.2

Synthetic example 3

Except using N-propyl group-2, ethyl-beyond the o-toluidine, example 1 is same with synthesizing, and has obtained the compound shown in the formula (1-39) for 6-xylidin replacement N-.

The evaluation of the compound shown in the formula (1-39)

(quality analysis) ionization MODE=ESI+:m/z=[M+H] ⁺659.9

Exact mass (ExactMass): 658.9

Synthetic example 4

In beaker, form the nitrogen atmosphere, add ethyl lactate 305 mass parts, be heated to 70 ℃ while stirring with 0.02L/ minute mobile nitrogen with reflux condenser, titration funnel and stirring machine.Then, in methacrylic acid 60 mass parts, 3,4-epoxy three ring [5.2.1.0 ^2.6] (compound shown in compound shown in the formula (I-1) and the formula (II-1) is to mix at 50: 50 with mol ratio to the decyl acrylic ester.) dissolve in 240 mass parts and ethyl lactate 140 mass parts, prepare solution thus, use tap funnel with 4 hours to insulation this lysate of dropping in 70 ℃ beaker.

On the other hand, to making polymerization initiator 2, two (2, the 4-methyl pentane nitrile) 30 mass parts of 2 '-azo are dissolved in the solution in ethyl lactate 225 mass parts, use other tap funnel to be added drop-wise in the beaker with 4 hours.The solution of polymerization initiator drip finish after, kept 4 hours at 70 ℃, cool to room temperature then, having obtained weight-average molecular weight Mw is 9.1 * 10 ³, molecular weight distribution is 2.5, solid constituent is resin B 1 solution of 33 quality %, solution acid number 34mg-KOH/g.Calculate from above-mentioned solid constituent and solution acid number, the solid constituent acid number of resin B 1 is 100mg-KOH/g.Resin B 1 has the structural unit shown in following.

Synthetic example 4

In beaker with stirrer, thermometer, reflux condensing tube, tap funnel and nitrogen ingress pipe; Import propylene glycol monomethyl ether 182g; After making the interior atmosphere of beaker transfer nitrogen to by air; After being warmed up to 100 ℃; Dropping adds 2 in the potpourri that is made up of benzyl methacrylate 70.5g (0.40 mole), methacrylic acid 43.0g (0.5 mole), methacrylic acid dicyclopentenyl ester (Hitachi changes into the system FA-513M of Co., Ltd.) 22.0g (0.10 mole) and propylene glycol monomethyl ether 136g, the solution behind 2 '-azobis isobutyronitrile 3.6g, and then 100 ℃ of continuation stirrings.Then; Make the interior atmosphere of beaker become air from nitrogen; GMA 35.5g [0.25 mole, (carboxyl of the methacrylic acid that uses with respect to this reaction is 50 moles of %)], three (dimethyl) amino methyl phenol 0.9g and quinhydrones 0.145g are put in the beaker; Continue reaction at 110 ℃, having obtained solid constituent 32%, solid constituent acid number is resin B 2 solution of 79mgKOH/g.Utilizing the weight-average molecular weight of the polystyrene conversion that GPC measures is 30,000.

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

Device: K2479 (Shimadzu Scisakusho Ltd's system)

Post: SHIMADZU Shim-pack GPC-80M

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 (TOSOH Co., Ltd's system)

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

Embodiment 1～12 and comparative example 1

Mix each composition according to the composition shown in table 1 and the table 2, obtain photosensitive composition.

Table 1

Table 2

In table 1 and the table 2, (A-1) ¹⁾Mix with the total amount of acrylic acid series spreading agent and propylene glycol monomethyl ether, make its dispersion in advance and use.Wherein, (A-1) in the comparative example 1 mixes for 137 parts with acrylic acid series spreading agent and propylene glycol monomethyl ether, makes its dispersion in advance and uses.

Need to prove that in table 1 and the table 2, each composition is represented following material.

Colorant (A): (A-1): C.I.pigment blue15:6 (pigment)

Colorant (A): (A-2): dyestuff A1 (xanthene dye)

Colorant (A): (A-3): the compound (xanthene dye) shown in the formula (1-39)

Resin (B): (B-1): the mass parts that the expression solid constituent converts in resin B 1 table.

Resin (B): (B-2): the mass parts that the expression solid constituent converts in resin B 2 tables.

Polymerizable compound (C): (C-1): dipentaerythritol acrylate (KAYARAD DPHA: Nippon Kayaku K. K's system)

Polymerization initiator (D): (D-1): N-benzoyl Oxy-1-(4-phenyl sulfane base phenyl) octane-1-ketone-2-imines (IRGACURE OXE01:BASF NIPPON corporate system)

Solvent (E): (E-1): DPGME acetic acid esters

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

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

Solvent (E): (E-4): propylene glycol monomethyl ether

Solvent (E): (E-5): 4-hydroxy-4-methyl-2 pentanone

Surfactant (G): (G-1): polyether modified silicone oil (Toray Silicone SH8400: eastern beautiful DOW CORNING Co., Ltd. system)

< making of colored pattern >

(Eagle 2000 at 2 inches square glass substrates; The Corning corporate system) goes up with behind the spin-coating method coating photosensitive composition, after 100 ℃ of following preliminary dryings formed drying in 3 minutes, film.Put cold after, will be formed with the substrate of filming after this drying and be made as 100 μ m, use exposure machine (TME-150RSK with interval with quartz glass system photomask of pattern (100 μ m line and intermittent pattern); The Topcon corporate system), under air atmosphere, with 150mJ/cm ³Exposure (365nm benchmark) carry out rayed.After the rayed, film in comprising the water system developer solution that nonionic is surfactant 0.12% and potassium hydroxide 0.04% 23 ℃ of following immersion development 80 seconds above-mentioned, after the washing, in baking oven, baking obtains colored pattern after carrying out 20 minutes under 220 ℃.Put cold after, use determining film thickness device (DEKTAK3: ULVAC Corp's system)) that the thickness of the colored pattern that obtains is measured, the result is 2.2 μ m.

< chromaticity evaluation >

Use colour examining machine (OSP-SP-200; Olympus (strain) system) colored pattern that obtains is measured beam split, use the characteristic function of illuminant-C that xy chromaticity coordinate in the XYZ color specification system of CIE (Bx, By) and tristimulus values (tristimulus values) Y are measured.The big more expression brightness of the value of Y is high more.The result is shown in table 3 and table 4.

< flaw evaluation >

(Eagle 2000 at 3 inches square glass substrates; The Corning corporate system) utilizes spin-coating method coating photosensitive composition on, before the decompression degree arrives 0.5torr, carry out drying through drying under reduced pressure machine (VCD Microtech Co., Ltd. system).In transparent baking oven, carry out 3 minutes prebake conditions then, after having formed drying on the substrate, film thus at 100 ℃.(250 times of multiplying powers: VF-7510: the KEYENCE of Co., Ltd. system) observe filming after this drying, counting is removed the defective number of the crateriform shape that the whole base plate after the scope of 1cm exists from the substrate end with the surface configuration optical microscope.The result is shown in table 3 and table 4.

< thermotolerance evaluation >

Do not use the photomask during except exposure, to have made painted filming with the same method of the making of pattern.Should paintedly film and in baking oven, heat 2 hours, equally colourity and tristimulus values Y measured with above-mentioned at 230 ℃.Calculate aberration Δ Eab by colourity before and after the heating and tristimulus values Y ^*Aberration Δ Eab ^*More little, it is more little to be illustrated in the look variation of heating front and back, and thermotolerance is good more.With the aberration Δ Eab that tries to achieve ^*Value be shown in " thermotolerance " hurdle of table 3 and table 4.

Table 3

Embodiment 1

Embodiment 2

Embodiment 3

Embodiment 4

Embodiment 5

Embodiment 6

Comparative example 1

Bx

?0.150

By

?0.087

Y

?9.9

Defective (individual)

?8

?7

?5

?4

?2

?55

Thermotolerance

?3.2

?3.1

?3.3

?3.1

?3.2

?3.3

Table 4

Embodiment 7

Embodiment 8

Embodiment 9

Embodiment 10

Embodiment 11

Embodiment 12

Bx

?0.150

0.150

By

?0.087

0.087

Y

?10.2

10.2

Defective (individual)

?8

?5

5

3

Thermotolerance

?3.3

?3.1

?3.3

3.3

3.2

3.1

Embodiment 13～18

Except the compound shown in the use formula (1-31) replaces dyestuff A1, same with embodiment 1～6, obtain photosensitive composition separately.Carry out operation same as described above, obtain filming after the few drying of defective.And then, obtained the colored pattern of brightness, excellent heat resistance.

Can know by above-mentioned result,, film after can obtaining not reduce the few drying of brightness, thermotolerance and the defective of the color filter that obtains according to the photosensitive composition of embodiment 1～12.

So, after forming drying, film by photosensitive composition of the present invention, and with the colored pattern that obtains by filming after this drying as color filter, can yield rate make display device well.

Utilizability on the industry

Behind base plate coating photosensitive composition of the present invention, to carry out drying under reduced pressure again and film after the drying of making, the crateriform defective of generation is few.

Claims

1. photosensitive composition, it contains colorant, resin, polymerizable compound, polymerization initiator and solvent,

Said colorant is the colorant that contains xanthene dye and pigment,

Said solvent is the solvent that contains the DPGME acetic acid esters.

2. photosensitive composition as claimed in claim 1, wherein,

The content of said DPGME acetic acid esters in solvent is more than the 0.1 quality % below the 30 quality %.

3. according to claim 1 or claim 2 photosensitive composition, wherein,

Said solvent is for also containing the solvent of ethyl lactate.

4. photosensitive composition as claimed in claim 3, wherein,

Said solvent is for also containing the solvent of propylene glycol monomethyl ether and/or propylene glycol monomethyl ether.

5. photosensitive composition as claimed in claim 1, wherein,

Resin is an alkali soluble resin.

6. photosensitive composition as claimed in claim 1, wherein,

Polymerizable compound is (methyl) acrylic ester.

7. color filter, it utilizes the described photosensitive composition of claim 1 to form.

8. display device, it contains the described color filter of claim 7.