CN102314089A

CN102314089A - Color filter is with light solidification pigmentation composition, color filter, manufacturing method of color filter and liquid crystal indicator

Info

Publication number: CN102314089A
Application number: CN2011101846818A
Authority: CN
Inventors: 藤本进二; 中村秀之
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2010-07-02
Filing date: 2011-07-01
Publication date: 2012-01-11
Also published as: TW201205194A; KR20120003384A; JP2012014053A

Abstract

The development property of pattern is excellent even the present invention provides, the residue on the substrate is few, the color filter that opening diameter is also big and survival rate is high of pattern baking back contact hole in the back is with manufacturing method of color filter, color filter and the liquid crystal indicator of light solidification pigmentation composition and colorrendering quality excellence.Color filter of the present invention contains (A) organic solvent, (B) pigment, (C) Photoepolymerizationinitiater initiater, (D) polymerizable compound and (E) bonding agent with light solidification pigmentation composition, said (D) polymerizable compound contain be selected from following (I) and (II) in the compound more than a kind: (I): 1～6 hydroxyl that have 2～6 (methyl) acryloyl groups, obtains by glycidyl and the polymerizable compound of the ring structure except that aromatic rings; (II): 1～12 hydroxyl that have 3～12 (methyl) acryloyl groups, obtains by glycidyl and the polymerizable compound of branched structure.

Description

Color filter is with light solidification pigmentation composition, color filter, manufacturing method of color filter and liquid crystal indicator

Technical field

The present invention relates to color filter with light solidification pigmentation composition, the color filter that has used said composition and manufacturing approach thereof and the liquid crystal indicator that used this color filter.

Background technology

Color filter is a component parts indispensable in the LCD.It is compact that LCD is compared with CRT as display device; Can seek power saving, and along with technical progress, be the degree more than equal at aspect of performance; Therefore, TV set image, computer picture and other display device change LCD into by CRT gradually.

In recent years, the exploitation of LCD is to be large-scale and to require the TV purposes of high image quality to develop towards picture than the PC of small size and the purposes of monitor from picture.Therefore, for use therein color filter,, also studying the size that increases substrate in order to improve its throughput rate always.In addition, employed mask in the pattern exposure for this color filter also uses large-area mask as requested, and the price of mask own is very expensive, thereby the cost that how to reduce mask becomes important problem.

A kind of method (for example with reference to patent documentation 1) of utilizing the Butut that adopts laser to form color filter is disclosed thus.But in this method that adopts semiconductor laser, the output of laser is little, and exposure expends time in, and can't boost productivity.

In addition, aspect the manufacturing color filter,, proposed when exposure, not use the color filter manufacturing method (for example with reference to patent documentation 2,3) of big photomask from reducing the aspect of total price.But, in order to obtain high productivity during with the laser explosure combination of height output, can the disappearance of pattern take place in pixel or peel off, fold, the pixel of therefore seeking to take into account the raising of throughput rate and forming excellent in shape.

In addition, for the liquid crystal indicator of color filter array (Color-filter On Array, below be designated as COA sometimes) mode, be to go up at thin film transistor (TFT) (the following TFT that is designated as sometimes) to form the color-filter layer that has the layer insulation membrane interaction concurrently.For this reason; As the characteristic that requires to color-filter layer; Except above-mentioned common requiring the characteristic; Also need the characteristic that requires as interlayer dielectric such as contact hole (contact hole) formation property, low-k, stripper patience, require characteristic, the resin coating as protective seam also is set on color-filter layer in order to satisfy these.

On the other hand, in blue pixel, from reasons such as thermotolerance, photostability, using phthalocyanine is blue pigment.But phthalocyanine is that blue pigment is high in the absorbance of ultraviolet range, is difficult to see through ultraviolet light, therefore in the Butut that uses ultraviolet laser, exists the fully problem of photocuring, primitive shape variation of pixel.Particularly under the situation of COA mode; For the driving that makes the ITO electrode that disposes on the dyed layer and dyed layer below terminal conducting with substrate; The contact hole that is shaped as rectangle～taper (guiding path) that the length of side is quadrilateral or diameter about 1～40 μ the m circular or pixel cross sections such as oval or コ font that are 1～40 μ m φ need formed on the colored pixels; But when the absorbance under the ultraviolet light zone is high; Have following problems: utilize the curing of exposure can not carry out, formed the pixel generation heat flow of pattern under the high temperature during back baking after pattern forms, formed contact hole is destroyed.

In addition, also proposed to use polymerizable compound (for example with reference to patent documentation 4) with triazine skeleton at the negative photosensitive composition of the color filter manufacturing that is used for the COA mode, but abundant not enough from the aspect that pattern becomes second nature.Also proposed in curing colouration composition to use epoxy acrylate as polymerizable compound (for example with reference to patent documentation 5～7), but that pattern become second nature is all insufficient with aromatic rings.

The prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2007-114602 communique

Patent documentation 2: TOHKEMY 2008-76709 communique

Patent documentation 3: TOHKEMY 2008-51866 communique

Patent documentation 4: TOHKEMY 2006-28455 communique

Patent documentation 5: japanese kokai publication hei 11-133599 communique

Patent documentation 6: No. 2894155 instructions of Jap.P.

Patent documentation 7: No. 3901807 instructions of Jap.P.

Summary of the invention

Invent problem to be solved

The object of the present invention is to provide the development property of formed pattern excellent, the color filter that opening diameter is big and survival rate contact hole is high of few, the formed pattern of the residue baking back contact hole in the back on the substrate of unexposed of the back of developing is with light solidification pigmentation composition and use this light solidification pigmentation composition and tone is good, colorrendering quality is excellent manufacturing method of color filter, color filter and liquid crystal indicator.

Be used to solve the means of problem

The means that are used to solve above-mentioned problem are described below.

< 1>a kind of color filter is used light solidification pigmentation composition; It contains (A) organic solvent, (B) pigment, (C) Photoepolymerizationinitiater initiater, (D) polymerizable compound and (E) bonding agent, said (D) polymerizable compound contain be selected from following (I) and (II) in the compound more than a kind.

(I): 1～6 hydroxyl that have 2～6 (methyl) acryloyl groups, obtains by glycidyl and the polymerizable compound of the ring structure except that aromatic rings

(II): 1～12 hydroxyl that have 3～12 (methyl) acryloyl groups, obtains by glycidyl and the polymerizable compound of branched structure

< 2>above-mentioned < 1>described color filter is used light solidification pigmentation composition; Wherein, the ring structure except that aromatic rings in said (I) is for being selected from a kind in hexahydrophthalic acid skeleton, tetrahydrophthalic acid skeleton, hydrogenated bisphenol A skeleton, cyclohexanedimethanol skeleton, isocyanuric acid ring (isocyanuric ring) and the tristane dimethanol skeleton.

< 3>above-mentioned < 1>described color filter is used light solidification pigmentation composition, and wherein, the branched structure in above-mentioned (II) is a kind that is selected from trimethylolpropane skeleton, pentaerythrite skeleton, dipentaerythritol skeleton, D-sorbite skeleton and the glycerol backbone.

< 4>wantonly 1 described color filter is used light solidification pigmentation composition in above-mentioned < 1 >～< 3 >, and wherein, above-mentioned (D) polymerizable compound further has following (HI) compound:

(III): the unsaturated group density of have 3～12 (methyl) acryloyl groups, the number of above-mentioned (methyl) acryloyl group being represented divided by the molecular weight of this polymerizable compound be 0.0067～0.0114 and with above-mentioned (I), the different polymerizable compound of (II) structure.

< 5>wantonly 1 described color filter is used light solidification pigmentation composition in above-mentioned < 1 >～< 4 >; Wherein, When using above-mentioned color filter to use light solidification pigmentation composition to form dried thickness to be the dyed layer of 2 μ m, the transmissivity of this dyed layer under wavelength 355nm is below 2%.

< 6>wantonly 1 described color filter is used light solidification pigmentation composition in above-mentioned < 1 >～< 5 >, and wherein, above-mentioned (B) pigment is the C.I. pigment blue 15: 6.

< 7>a kind of manufacturing method of color filter, it contains following operation: on substrate, bestow < 1 >～< 6>in wantonly 1 described color filter with light solidification pigmentation composition with the dyed layer that forms the dyed layer that constitutes by this coloured composition form operation, exposure process that this dyed layer is made public with pattern-like and will make public after dyed layer develop to form the developing procedure of colored pattern.

< 8>above-mentioned < 7>described manufacturing method of color filter, wherein, the exposure process that above-mentioned exposure process is to use the laser of 355nm to make public with pattern-like.

< 9>above-mentioned < 7>or < 8>described manufacturing method of color filter, it is the manufacturing method of color filter of color filter array mode.

< 10>a kind of color filter, it is made through wantonly 1 described manufacturing method of color filter in < 7 >～< 9 >.

< 11>a kind of liquid crystal indicator, it possesses < 10>described color filter.

The invention effect

According to the present invention; Can provide the development property of formed pattern excellent, the opening diameter of few, the formed pattern of the residue baking back contact hole in the back on the substrate of unexposed of the back of developing is big and the high color filter of survival rate contact hole use light solidification pigmentation composition, and this light solidification pigmentation composition of use and tone is good, colorrendering quality is excellent manufacturing method of color filter, color filter and liquid crystal indicator can be provided.

Embodiment

Below specify the present invention.

Color filter of the present invention is characterised in that with light solidification pigmentation composition; It contains (A) organic solvent, (B) pigment, (C) Photoepolymerizationinitiater initiater, (D) polymerizable compound and (E) bonding agent, above-mentioned (D) polymerizable compound contain be selected from following (I) and (II) in the compound more than a kind (following suitably be called " specific aggregation property compound ").

Light solidification pigmentation composition of the present invention is used for the formation of the colored pattern of color filter.

Below each constituent of light solidification pigmentation composition of the present invention is detailed.

In addition, in this instructions acryloyl group and methacryl are designated as (methyl) acryloyl group in the lump.

(D) polymerizable compound

Light solidification pigmentation composition of the present invention contain comprise be selected from following (I) and (II) in (D) polymerizable compound of compound more than a kind.

(I): 1～6 hydroxyl that have 2～6 (methyl) acryloyl groups, obtains by glycidyl and the polymerizable compound (following suitably be called " polymerizable compound (I) ") of the ring structure except that aromatic rings.

(II): 1～12 hydroxyl that have 3～12 (methyl) acryloyl groups, obtains by glycidyl and the polymerizable compound (following suitably be called " polymerizable compound (II) ") of branched structure.

Polymerizable compound (I) so long as in molecule, have 2～6 acryloyl groups or methacryl one or both and in molecule, have 1～6 hydroxyl that obtains by glycidyl but also have the compound of the ring structure except that aromatic rings, then can be the compound of arbitrary structures.

At this; As the ring structure except that aromatic rings, can enumerate out volution skeletons such as crosslinked ring skeletons such as heterocycle skeletons such as cycloolefin ring skeletons such as naphthenic hydrocarbon ring skeleton, cyclobutane, cyclopentene, cyclohexene such as cyclopropane ring skeleton, cyclo-butane ring skeleton, cyclopentane ring skeleton, cyclohexane ring skeleton, furan nucleus skeleton, tetrahydrofuran ring skeleton, pyrrole ring skeleton, pyrrolidine ring skeleton, pyridine ring skeleton, piperidine ring skeleton, triazine ring skeleton, isocyanuric acid ring skeleton, tristane ring skeleton, dicyclo undecane ring skeleton, spiral shell octane ring skeleton etc.Wherein, Non-staining property during from heating and the viewpoint of synthesizing; More preferably hexahydrophthalic acid skeleton, tetrahydrophthalic acid skeleton, hydrogenated bisphenol A skeleton, cyclohexanedimethanol skeleton, isocyanuric acid ring, tristane dimethanol skeleton, further preferred tetrahydrophthalic acid skeleton, hydrogenated bisphenol A skeleton.

Below show the skeleton of these preferred ring structures.In the following structural formula, * representes and structural unit that contains (methyl) acryloyl group and the binding site that contains the structural unit of the hydroxyl that is obtained by glycidyl.

Hexahydrophthalic acid skeleton tetrahydrophthalic acid skeleton

Hydrogenated bisphenol A skeleton cyclohexanedimethanol skeleton

Isocyanuric acid ring skeleton tristane dimethanol skeleton

Hydroxyl to being obtained by glycidyl in the specific aggregation property compound describes.If have ring structure and have acidic group or the compound of hydroxyl and have side chain and have acidic group or the compound of hydroxyl on addition (methyl) glycidyl acrylate for example; Then can obtain the addition product of (methyl) acryloyl group, make the glycidyl open loop simultaneously and generate hydroxyl.The hydroxyl that obtains thus comes from glycidyl, becomes secondary hydroxyl usually.Among the present invention, the hydroxyl that is obtained by glycidyl is meant the hydroxyl that the reaction through the compound with glycidyl generates.

This secondary hydroxyl makes light solidification pigmentation composition be easy to dissolving in alkali develops, but can not demonstrate dissolubility strong as the carboxylic acid group, alkali is developed moderately carry out, and through using such polymerizable compound, embodies effect of the present invention.

Preferred especially polymerizable compound (I) is following compound: in molecule, have 2～4 acryloyl groups or methacryl one or both; And in molecule, have 2～4 hydroxyls that obtain by glycidyl, but also have hexahydrophthalic acid skeleton or the ring structure of hydrogenated bisphenol A skeleton conduct except that aromatic rings.

As these polymerizable compounds (I); Structure preferably: with the ring structure except that aromatic rings is division center; Have acryloyl group or methacryl more than 2 endways, and at the hydroxyl that obtains by glycidyl that has on the side chain more than 1.

As the object lesson of polymerizable compound (I), can enumerate out following compound.

Polymerizable compound (II) so long as in molecule, have 3～12 acryloyl groups or methacryl one or both; And in molecule, has 1～12 hydroxyl that obtains by glycidyl; But also have the compound of branched structure, then can be the compound of arbitrary structures.

At this; Branched structure is meant following structures: in molecule, have the tertiary carbon atom or the quaternary carbon atom that have been replaced by element beyond the dehydrogenations such as carbon atom, oxygen atom, sulphur atom, nitrogen-atoms; And with this branched structure is division center, has acryloyl group or methacryl more than 3 endways.Be trimethylolpropane skeleton, pentaerythrite skeleton, dipentaerythritol skeleton, D-sorbite skeleton, glycerol backbone etc. specifically; From polymerism, viscosity and synthetic on viewpoint; More preferably trimethylolpropane skeleton, pentaerythrite skeleton, dipentaerythritol skeleton, D-sorbite skeleton or glycerol backbone are preferably pentaerythrite skeleton, dipentaerythritol skeleton, D-sorbite skeleton especially.

These preferred branched structures below are shown.In the following structural formula, * representes and structural unit that contains (methyl) acryloyl group and the binding site that contains the structural unit of the hydroxyl that is obtained by glycidyl.

Trimethylolpropane skeleton pentaerythrite skeleton

Dipentaerythritol skeleton D-sorbite skeleton

Glycerol backbone

Preferred especially polymerizable compound (II) is following compound: in molecule, have 4～6 acryloyl groups or methacryl one or both; And in molecule, have 4～6 hydroxyls that obtain by glycidyl, but also have pentaerythrite skeleton, dipentaerythritol skeleton or D-sorbite skeleton as branched structure.

As these polymerizable compounds (II), the structure below preferably: with the branched structure is division center, has acryloyl group or methacryl more than 3 endways, and has the hydroxyl that is obtained by glycidyl more than 1 at side chain.

As the object lesson of polymerizable compound (II), can enumerate out following compound.

(D) polymerizable compound is preferably except that the polymerizable compound of above-mentioned (I), (II), contain also that (III) has 3～12 (methyl) acryloyl groups, unsaturated group density that the number of (methyl) acryloyl group is represented divided by the molecular weight of this polymerizable compound be 0.0067～0.0114 and with above-mentioned (I), polymerizable compound (following suitably be called " polymerizable compound (III) ") that (II) structure is different.Owing to also contain polymerizable compound (III), the color filter that the photo-thermal bridging property is high, development property is excellent, primitive shape is excellent, reliability is high can be provided.

As the object lesson of polymerizable compound (III), can enumerate out following compound.Wherein, numeral is a unsaturated group density.

Among the present invention, specific aggregation property compound can only contain a kind, also can be also with more than 2 kinds.

Promptly; As specific aggregation property compound; Can contain above-mentioned polymerizable compound (I) or any of above-mentioned polymerizable compound (II) more than a kind, in addition, also can and with polymerizable compound (I) more than a kind and more than a kind of polymerizable compound (II); Can use more than 2 kinds of polymerizable compound (I), also can use more than 2 kinds of polymerizable compound (II).

And, as polymerizable compound of the present invention, not only can use a kind that is selected from polymerizable compound (I) and the polymerizable compound (II), can also and use the polymerizable compound different with these polymerizable compound structures.

As can and the polymerizable compound different of usefulness with specific aggregation property compound structure, get final product so long as have the polymerizable compound of at least one ethylenic unsaturated double-bond.For example be to have at least 1, the polymerizable compound different of preferred terminal olefinic link formula unsaturated link more than 2 with specific aggregation property compound structure.

Such polymerizable compound is to be widely known by the people in this area, can limit ground not especially to them in the present invention and use.They for example have, and monomer, prepolymer are dipolymer, trimer and oligomer or their potpourri and their chemical forms such as multipolymer.

As the polymerizable compound different, be preferably above-mentioned polymerizable compound (III) with specific aggregation property compound structure.Can use the polymerizable compound different more than 2 kinds with specific aggregation property compound structure.

Example as monomer and multipolymer thereof; Can enumerate out unsaturated carboxylic acid (for example acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid etc.) and ester class thereof, amide-type, the amide-type that ester, unsaturated carboxylic acid and the aliphatic polyamine compound that preferably uses unsaturated carboxylic acid and aliphatic polyol compound to form forms.In addition, can also preferably use addition reaction product with the substituent esters of unsaturated carboxylic acids of nucleophilicities such as hydroxyl or amino, sulfydryl or amide-type and simple function or polyfunctional isocyanate's class or epoxies and with dehydration condensation product of simple function or polyfunctional carboxylic acid etc.In addition, has the addition reaction of substituent esters of unsaturated carboxylic acids of electrophilicitys such as NCO or epoxy radicals or amide-type and simple function or polyfunctional alcohols, amine, thio-alcohol and have halogen radical or the substituted reactant of the esters of unsaturated carboxylic acids of disengaging substituent such as tolysulfonyl oxygen base or amide-type and simple function or polyfunctional alcohols, amine, thio-alcohol also is preferred.In addition, as other example, also can use the compound group that above-mentioned unsaturated carboxylic acid is replaced to unsaturated phosphonic acids, styrene, vinyl ether etc.

The object lesson of the monomer of the ester that forms for aliphatic polyol compound and unsaturated carboxylic acid; As acrylic ester; Glycol diacrylate, triethylene glycol diacrylate, 1 are arranged; 3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris (acryloxy propyl group) ether, trimethylolethane trimethacrylate acrylic ester, hexanediyl ester, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol acrylate, D-sorbite triacrylate, D-sorbite tetraacrylate, D-sorbite five acrylic ester, D-sorbite six acrylic ester, three (acryloxy ethyl) isocyanuric acid ester, polyester acrylic ester oligomer, isocyanuric acid EO modification triacrylate etc.

As methacrylate; Tetramethylene glycol two (methacrylic acid) ester, triethylene glycol two (methacrylic acid) ester, neopentyl glycol two (methacrylic acid) ester, trimethylolpropane tris (methacrylic acid) ester, trimethylolethane trimethacrylate (methacrylic acid) ester, ethylene glycol bisthioglycolate (methacrylic acid) ester, 1,3 butylene glycol two (methacrylic acid) ester, hexanediol two (methacrylic acid) ester, pentaerythrite two (methacrylic acid) ester, pentaerythrite three (methacrylic acid) ester, pentaerythrite four (methacrylic acid) ester, dipentaerythritol two (methacrylic acid) ester, dipentaerythritol six (methacrylic acid) ester, D-sorbite three (methacrylic acid) ester, D-sorbite four (methacrylic acid) ester, two [to (3-methacryloxy-2-hydroxyl propoxyl group) phenyl] dimethylmethane, two-[to (methacryloxy ethoxy) phenyl] dimethylmethane etc. are arranged.

As itaconate, ethylene glycol bisthioglycolate itaconate, propylene glycol diitaconate, 1,3 butylene glycol diitaconate, 1 are arranged, 4-butylene glycol diitaconate, tetramethylene glycol diitaconate, pentaerythrite diitaconate, D-sorbite four itaconates etc.As crotonates, ethylene glycol bisthioglycolate crotonates, tetramethylene glycol two crotonatess, pentaerythrite two crotonatess, D-sorbite four crotonatess etc. are arranged.

As the iso-crotonic acid ester, ethylene glycol bisthioglycolate iso-crotonic acid ester, pentaerythrite two iso-crotonic acid esters, D-sorbite four iso-crotonic acid esters etc. are arranged.As maleate, ethylene glycol bisthioglycolate maleate, triethylene glycol dimaleate, pentaerythrite dimaleate, D-sorbite four maleates etc. are arranged.

As other the example of ester, the also preferred aliphatic alcohol that uses the for example special public clear 51-47334 communique of Japan, japanese kokai publication sho 57-196231 communique to put down in writing be the ester with aromatic series pastern bone frame, japanese kokai publication hei 1-165613 communique that ester class, japanese kokai publication sho 59-5240 communique, japanese kokai publication sho 59-5241 communique, japanese kokai publication hei 2-226149 communique are put down in writing put down in writing contain amino ester etc.

In addition, aforesaid ester monomer also can be processed potpourri and uses.

In addition; The object lesson of the amide monomer that forms as aliphatic polyamine compound and unsaturated carboxylic acid; Di-2-ethylhexylphosphine oxide-acrylic amide, di-2-ethylhexylphosphine oxide-Methacrylamide, 1 are arranged; The 6-hexa-methylene is two-acrylic amide, 1, and the 6-hexa-methylene is two-Methacrylamide, diethylene triamine three acrylic amides, xylylene bisacrylamide, the two Methacrylamides of xylylene etc.

As the example that other preferred acid amides is a monomer, can enumerate out the monomer that the special public clear 54-21726 communique of Japan is put down in writing with cyclohexylidene structure.

In addition; The carbamate that utilizes the addition reaction manufacturing of isocyanates and hydroxyl is that addition polymerization property compound also is preferred; As such object lesson, for example can enumerate out the polyisocyanate compounds that in 1 molecule, has the NCO more than 2 put down in writing in the special public clear 48-41708 communique of Japan and the vinyl monomer addition that contains hydroxyl shown in the formula (V) and the vinyl carbamate compound that in 1 molecule, contains the polymerism vinyl more than 2 that obtains etc.

General formula (IV)

CH ₂＝C(R ⁴)COOCH ₂CH(R ⁵)OH(IV) (IV)

(wherein, R ⁴And R ⁵Represent H or CH independently of one another ₃).

In addition, the carbamate compounds class of putting down in writing in the special public clear 58-49860 communique of putting down in writing in japanese kokai publication sho 51-37193 communique, the special fair 2-32293 communique of Japan, the special fair 2-16765 communique of Japan of urethane acrylate class, Japan, the special public clear 56-17654 communique of Japan, the special public clear 62-39417 communique of Japan, the special public clear 62-39418 communique of Japan with oxirane pastern bone frame also is preferred.And then; If use the addition polymerization property compounds of putting down in writing in japanese kokai publication sho 63-277653 communique, japanese kokai publication sho 63-260909 communique, the japanese kokai publication hei 1-105238 communique that in molecule, has amino structure or sulfide based structural, can obtain the very excellent light solidification pigmentation composition of film speed.

As other example, can enumerate out polyester acrylate class, epoxy resin and (methyl) acrylic acid of putting down in writing in each communique of japanese kokai publication sho 48-64183 communique, the special public clear 49-43191 communique of Japan, the special public clear 52-30490 communique of Japan and react polyfunctional acrylic ester or the methacrylates such as epoxy acrylate class that obtains.In addition, can enumerate out the vinyl phosphonate based compound put down in writing in the specific unsaturated compound put down in writing in the special public clear 46-43946 communique of Japan, special fair 1-40337 communique, the special fair 1-40336 communique, the japanese kokai publication hei 2-25493 communique etc.In addition, in the structure that contains perfluoroalkyl that can preferably use japanese kokai publication sho 61-22048 communique to be put down in writing in some cases.In addition, the compound that can also use Japan then to introduce as photo-curable monomer and oligomer in the will vol.20 of association, No.7,300～308 pages (1984).

From above viewpoint; As preferably; Can enumerate out bisphenol a diacrylate, bisphenol a diacrylate EO modification body, trimethylolpropane triacrylate, trimethylolpropane tris (acryloxy propyl group) ether, trimethylolethane trimethacrylate acrylic ester, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol five acrylic ester, dipentaerythritol acrylate, D-sorbite triacrylate, D-sorbite tetraacrylate, D-sorbite five acrylic ester, D-sorbite six acrylic ester, three (acryloxy ethyl) isocyanuric acid ester, tetramethylol methane tetraacrylate EO modification body, dipentaerythritol acrylate EO modification body etc.; In addition; As commercially available article, preferred oligourethane UAS-10, UAB-140 (Nippon Paper Chemicals corporate system), DPHA (Japanese chemical drug corporate system), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (common prosperity corporate system).

Wherein, Bisphenol a diacrylate EO modification body, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol five acrylic ester, dipentaerythritol acrylate, three (acryloxy ethyl) isocyanuric acid ester, tetramethylol methane tetraacrylate EO modification body, dipentaerythritol acrylate EO modification body etc. are as commercially available article, more preferably DPHA (Japanese chemical drug corporate system), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (chemistry Industrial Co., Ltd of common prosperity company system).

(D) be preferably 5 quality %～55 quality % in whole nonvolatile component of the content of polymerizable compound in light solidification pigmentation composition of the present invention, more preferably 10 quality %～50 quality % further are preferably 15 quality %～45 quality %.

If the use amount of polymerizable compound is this scope, then becoming obtains desired colourity, brightness, thickness easily, and it is good that the shape of pixel and contact hole also becomes.

In addition, (D) total content of polymerizable compound in the polymerizable compound (I) and polymerizable compound (II) can be 5 quality %～95 quality % in mass conversion, is preferably 30 quality %～70 quality %.

Wherein, Whole nonvolatile component of the light solidification pigmentation composition among the present invention are the total content of whole compositions of the light solidification pigmentation composition except that (A) solvent of formation light solidification pigmentation composition; Under the situation that forms color filter, typically refer to the content of the composition that constitutes dried light solidification pigmentation composition layer.

And polymerizable compound (III) preferably contains in (D) polymerizable compound in mass conversion and for example is 5 quality %～80 quality %, is preferably 20 quality %～60 quality %.Through contain polymerizable compound (III) in this scope, can form photo-thermal bridging property height, excellent, the excellent light solidification pigmentation composition of primitive shape of development property.

(B) pigment

Light solidification pigmentation composition of the present invention contains at least a kind of (B) pigment.

(B) pigment can be that inorganic pigment also can be an organic pigment, from reaching the viewpoint of high-transmission rate, preferably uses the as far as possible little person of particle size.The mean value of primary particle size is preferably 0.01 μ m～0.1 μ m, the scope of 0.01 μ m～0.05 μ m more preferably.

In the light solidification pigmentation composition of the present invention; Through (E) bonding agent of stating after using; Even the particle size of pigment hour dispersedly also can become well with dispersion stabilization, so can form colour purity excellence, tone is good, colorrendering quality is excellent colored pixels.

In addition; Among the present invention; In the contained pigment of light solidification pigmentation composition, preferred primary particle size less than the ratio of the pigment of 0.02 μ m in the total amount of pigment less than 10%, and primary particle size surpass 0.08 μ m the ratio of pigment in the total amount of pigment less than 5%.

Through primary particle size less than the ratio of the pigment of 0.02 μ m less than 10%, good heat resistance can prevent that colourity from changing; The ratio of pigment that surpasses 0.08 μ m through primary particle size is less than 5%, good contrast, and the ageing stability of light solidification pigmentation composition is good, and can prevent the foreign matter fault.

Primary particle size from thermotolerance and the viewpoint that prevents that colourity from changing, is more preferably less than 5% less than the ratio of the pigment of 0.02 μ m.

Primary particle size surpasses the ratio of pigment of 0.08 μ m from the viewpoint of optimized contrast, preferably less than 3%.

The primary particle size of pigment can use TEM (transmission electron microscope) to measure.In this case, can study size distribution through the TEM photo is carried out graphical analysis.For example can be through measuring the total population in the observation sample under 3～100,000 times and grasping size-grade distribution less than 0.02 μ m and the population that surpasses the pigment of 0.08 μ m.More specifically, utilize transmission electron microscope to observe down the pigment powder, take pictures, measure the major diameter of 1000 primary particles, calculate less than 0.02 μ m and surpass the ratio of the primary particle of 0.08 μ m at 3～100,000 times.Change the position of pigment powder, carry out this operation adding up to 3 positions, then that the result is average.

As can be used as the inorganic pigment that (B) pigment uses; Can enumerate out metallic compounds such as metal oxide, metal complex, particularly can enumerate tap a blast furnace, the metal oxide of cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony etc. and composite oxides of above-mentioned metal etc.

In addition, as can be used as the above-mentioned organic pigment that (B) pigment uses, for example can enumerate out:

C.I. paratonere 1; 2; 3; 4; 5; 6; 7; 9; 10; 14; 17; 22; 23; 31; 38; 41; 48:1; 48:2; 48:3; 48:4; 49; 49:1; 49:2; 52:1; 52:2; 53:1; 57:1; 60:1; 63:1; 66; 67; 81:1; 81:2; 81:3; 83; 88; 90; 105; 112; 119; 122; 123; 144; 146; 149; 150; 155; 166; 168; 169; 170; 171; 172; 175; 176; 177; 178; 179; 184; 185; 187; 188; 190; 200; 202; 206; 207; 208; 209; 210; 216; 220; 224; 226; 242; 246; 254; 255; 264; 270; 272; 279:

C.I. pigment yellow 1; 2; 3; 4; 5; 6; 10; 11; 12; 13; 14; 15; 16; 17; 18; 20; 24; 31; 32; 34; 35; 35:1; 36; 36:1; 37; 37:1; 40; 42; 43; 53; 55; 60; 61; 62; 63; 65; 73; 74; 77; 81; 83; 86; 93; 94; 95; 97; 98; 100; 101; 104; 106; 108; 109; 110; 113; 114; 115; 116; 117; 118; 119; 120; 123; 125; 126; 127; 128; 129; 137; 138; 139; 147; 148; 150; 151; 152; 153; 154; 155; 156; 161; 162; 164; 166; 167; 168; 169; 170; 171; 172; 173; 174; 175; 176; 177; 179; 180; 181; 182; 185; 187; 188; 193; 194; 199; 213; 214;

C.I. pigment orange 2,5,13,16,17:1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73;

C.I. pigment Green 7,10,36,37,58;

C.I. pigment blue 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,60,64,66,79, the Cl substituting group with 79 become the material, 80 that OH obtains;

C.I. pigment violet 1,19,23,27,32,37,42;

C.I. pigment brown 25,28 etc.

Wherein, as the pigment that can preferably use, can enumerate out following material.But the present invention is not limited to these.

C.I. pigment yellow 11,24,108,109,110,138,139,150,151,154,167,180,185;

C.I. pigment orange 36,71;

C.I. pigment red 122,150,171,175,177,209,224,242,254,255,264;

C.I. pigment violet 19,23,32;

C.I. pigment blue 15: 1,15:3,15:6,16,22,60,66;

C.I. pigment Green 7,36,37,58.

Light solidification pigmentation composition of the present invention is owing to be used for the formation of blue colored pixels, thereby can bring into play effect of the present invention well, so preferably.Owing to be used for blue phthalocyanine is that the absorbance of blue pigment in the ultraviolet range is high, ultraviolet light is difficult to see through; So exist in the pattern that uses ultraviolet light as exposure light source forms and to make pixel photocuring fully, thereby problem of primitive shape variation.If the present invention is used for blue light solidification pigmentation composition, then can brings into play effect of the present invention fully.

As being used for blue phthalocyanine is blue pigment, can enumerate out C.I. pigment blue 15, C.I. pigment blue 15: 1, C.I. pigment blue 15: 2, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6, C.I. pigment blue 16, C.I. pigment blue 1 7:1, C.I. alizarol saphirol 75 and C.I. alizarol saphirol 79 etc.Wherein, C.I. pigment blue 15: 6 is excellent aspect thermotolerance, photostability, contrast, so can more preferably use.

Preferred phthalocyanine is a blue pigment with respect to the ratio that contains of the total amount of (B) pigment that uses in the light solidification pigmentation composition of the present invention is more than the 50 quality %.Be blue pigment with respect to the ratio of whole pigment through phthalocyanine be more than the 50 quality %, can obtain high thermotolerance, photostability, contrast value.

In addition, in the light solidification pigmentation composition of the present invention, be also to contain violet pigment the blue pigment preferably as the pigment that is used for the colourity adjustment except above-mentioned phthalocyanine.Through containing violet pigment, the mazarine that can reach high NTSC ratio can be provided.

As violet pigment, can use C.I. pigment violet 19, C.I. pigment Violet 23 and C.I. pigment violet 32 etc.Wherein, the C.I. pigment Violet 23 is from the aspect of brightness, photostability, thermotolerance, high-contrast and further preferred.

Can come suitably to select the addition of (B) pigment in light solidification pigmentation composition according to desired colourity, brightness, thickness, be the scope of 5 quality %～50 quality % with respect to whole nonvolatile component (all solids composition outside desolventizing) preferably.More preferably 10 quality %～40 quality % further are preferably 15 quality %～30 quality %.

If (B) addition of pigment is this scope, then become and obtain desired colourity, brightness, thickness easily, it is good that the shape of pixel and contact hole also becomes.

Whole nonvolatile component of the light solidification pigmentation composition among the present invention are meant the total content of whole compositions of the light solidification pigmentation composition except that (A) solvent that constitutes light solidification pigmentation composition; Under the situation that forms color filter, typically refer to the content of the composition that constitutes dried light solidification pigmentation composition layer.

(coated pigment)

Especially preferably use organic pigment as (B) pigment among the present invention, and the preferred pigment that uses miniaturization operation or dispersion step through pigment with macromolecular compound (B) pigment to be covered and to obtain.More preferably use through with macromolecular compound with pigment lining and to the formation that also can suppress 2 aggregations through the pigment of miniaturization, can make coated pigment that its dispersiveness of disperseing with the state of 1 particle is improved, or the excellent coated pigment of dispersion stabilization kept through 1 time of disperseing particle-stabilisedly.

(E) bonding agent of stating after also can using is as the macromolecular compound that is used to be covered.

Through pigment being covered, thereby, its state with 1 particle is disperseed to also can suppress the formation of 2 aggregations through the pigment of miniaturization with macromolecular compound.That is, the dispersiveness of coated pigment is improved, and is also excellent through the dispersion stabilization that 1 time of disperseing is kept particle-stabilisedly.

About the macromolecular compound that is used for coated pigment or the coating method of pigment, more preferably use the disposal route and the macromolecular compound of record in paragraph [0025]～[0078] of TOHKEMY 2009-1441269 communique.

In addition, among the present invention, at least a kind of spreading agent of preferred use uses pigment dispersing to process pigment dispensing composition.Use under the situation of above-mentioned coated pigment too.Through the use of this spreading agent, can improve dispersing of pigments property.

As spreading agent, for example can suitably select known pigment dispersing agent or surfactant to use.

As spreading agent; Particularly; Can use the compound of a plurality of kinds, for example can enumerate out: organic siloxane polymer KP341 (Shin-Etsu Chemial Co., Ltd's system), (methyl) acrylic acid series (being total to) polymer P OLYFLOW No.75, No.90, No.95 (chemistry Industrial Co., Ltd of common prosperity company system), W001 kations such as (Yu Business Co., Ltd's corporate systems) are surfactant; Nonionics such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether, NONIN HS 240, polyoxyethylene nonylplenyl ether, polyethylene glycol dilaurate, polyglycol distearate, sorbitan fatty acid esters are surfactant; W004, W005, W017 negative ion such as (Yu Business Co., Ltd's corporate systems) are surfactant; EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (being Ciba Specialty Chemicals corporate system), DISPERSE AID6, DISPERSE AID 8, DISPERSE AID 15, DISPERSE AID 9100 macromolecule dispersing agents such as (being SAN NOPCO corporate system); Various SOLSPERSE spreading agents such as SOLSPERSE 3000,5000,9000,12000,13240,13940,17000,24000,26000,28000 (Japanese Lubrizol Co., Ltd. corporate system); ADEKA PLURONICL31; F38; L42; L44; L61; L64; F68; L72; P95; F77; P84; F87; P94; L101; P103; F108; L121; P-123 (rising sun electrification Co., Ltd. system) and IONET S-20 (Sanyo Chemical Industries Co., Ltd.'s system); Disperbyk 101; 103; 106; 108; 109; 111; 112; 116; 130; 140; 142; 162; 163; 164; 166; 167; 170; 171; 174; 176; 180; 182; 2000; 2001; 2050; 2150 (BYK-CHEMIE corporate systems).

In addition, also can enumerate out oligomer or the polymkeric substance that acrylic acid series copolymer equimolecular end or side chain have polar group.

As the content of spreading agent, be 1 quality %～100 quality % with respect to the quality optimization of (B) pigment, 3 quality %～70 quality % more preferably.

In addition, when in light solidification pigmentation composition, adding (B) pigment, from the viewpoint of pigment-dispersing; Preferred preparation in advance contains the pigment dispensing composition of pigment and spreading agent; Then said composition is cooperated, as required, can in this pigment dispensing composition, add pigment derivative.

There are the part of compatibility or the pigment derivative of polar group to be adsorbed in surface of pigments and, pigment to be scattered in the pigment dispensing composition as fine particle through making to import to have with its adsorption site use as spreading agent with spreading agent.Because the light solidification pigmentation composition that contains this pigment dispensing composition can prevent the aggegation again of pigment, so when forming the color filter that contrast is high, the transparency is excellent, be effective.

Particularly, pigment derivative be with the organic pigment be precursor skeleton and import at this precursor skeleton acidic-group or basic group are arranged, aromatic group is as substituent compound.

As the organic pigment that forms precursor skeleton, can enumerate out quinoline a word used for translation ketone series pigments, phthualocyanine pigment, azo pigment, quinophthalone series pigments, isoindoline series pigments, isoindolone series pigments, quinoline pigment, diketopyrrolo-pyrrole pigment, benzimidazolone pigment etc. particularly.In addition, also can use flaxen aromatic series polycyclic compunds such as the naphthalene system that generally is not known as pigment, anthraquinone system, triazine system, quinoline system as precursor skeleton.

As pigment derivative, can use the pigment derivative of record in japanese kokai publication hei 11-49974 communique, japanese kokai publication hei 11-189732 communique, japanese kokai publication hei 10-245501 communique, TOHKEMY 2006-265528 communique, japanese kokai publication hei 8-295810 communique, japanese kokai publication hei 11-199796 communique, TOHKEMY 2005-234478 communique, TOHKEMY 2003-240938 communique, the TOHKEMY 2001-356210 communique etc.

As the content of pigment derivative in pigment dispensing composition, be 1 quality %～30 quality % with respect to the quality optimization of pigment, 3 quality %～20 quality % more preferably.This content is in above-mentioned scope the time, can viscosity suppressed to such an extent that disperse well in low and improve the dispersion stabilization after disperseing.The result is, the transmissivity of light solidification pigmentation composition that contains this pigment dispensing composition is high, can obtain excellent color characteristics, is suitable for making the color filter of the high-contrast with good color characteristics.

The bead dispersion machine etc. that the dispersing of pigments method for example can have been used zirconia bead etc. through utilization carries out differential to the potpourri that obtains with dispersion pigment such as homogenizer and spreading agent in advance and looses and carry out.

[dyestuff]

In the scope of not damaging effect of the present invention, light solidification pigmentation composition of the present invention except pigment can also and with dyestuff as colorant.

As not having special restriction, can use the known dyestuff that in the past was used for the color filter purposes as the dyestuff of colorant.For example japanese kokai publication sho 64-90403 communique, japanese kokai publication sho 64-91102 communique, japanese kokai publication hei 1-94301 communique, japanese kokai publication hei 6-11614 communique, Japanese spy step on No. 2592207, United States Patent (USP) the 4th; 808; No. 501 instructionss, United States Patent (USP) the 5th; 667; No. 920 instructionss, United States Patent (USP) the 5th; The pigment of record in 059, No. 500 instructions, japanese kokai publication hei 5-333207 communique, japanese kokai publication hei 6-35183 communique, japanese kokai publication hei 6-51115 communique, japanese kokai publication hei 6-194828 communique, japanese kokai publication hei 8-211599 communique, japanese kokai publication hei 4-249549 communique, japanese kokai publication hei 10-123316 communique, japanese kokai publication hei 11-302283 communique, japanese kokai publication hei 7-286107 communique, TOHKEMY 2001-4823 communique, japanese kokai publication hei 8-15522 communique, japanese kokai publication hei 8-29771 communique, japanese kokai publication hei 8-146215 communique, japanese kokai publication hei 11-343437 communique, japanese kokai publication hei 8-62416 communique, TOHKEMY 2002-14220 communique, TOHKEMY 2002-14221 communique, TOHKEMY 2002-14222 communique, TOHKEMY 2002-14223 communique, japanese kokai publication hei 8-302224 communique, japanese kokai publication hei 8-73758 communique, japanese kokai publication hei 8-179120 communique, the japanese kokai publication hei 8-151531 communique etc.

As chemical constitution, can use dyestuffs such as pyrazoles azo system, aniline azo system, triphenyl methane system, anthraquinone system, Anthrapyridone system, benzylidene system, oxonols (oxonol) are, Pyrazolotriazole azo system, pyridone azo system, cyanines system, phenothiazine system, pyrrolo-pyrazoles azomethine system, xanthene system, phthalocyanine system, chromene system, indigo system.

(A) organic solvent

Light solidification pigmentation composition of the present invention can use general solvent to prepare.In addition, above-mentioned pigment dispersing combination also can use solvent to prepare.As being used for organic solvent of the present invention, from coating, the spray nozzle clogging when suppressing coating, the viewpoint of removing property of solvent when dyed layer forms, preferred boiling point is 110 ℃～200 ℃ a organic solvent.

As can be used for organic solvent of the present invention, can enumerate out:

The ester class; For example 2-oxygen base alkyl propionates class (for example 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-oxygen base-2 Methylpropionic acid methyl esters, 2-oxygen base-2 Methylpropionic acid ethyl ester, 2-methoxyl-2 Methylpropionic acid methyl, 2-ethoxy-2 Methylpropionic acid ethyl ester etc.) such as 3-oxygen base alkyl propionates such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, ethoxyacetic acid methyl esters, ethoxyacetic acid ethyl ester, ethoxyacetic acid butyl ester, methoxy menthyl acetate, methoxyacetic acid ethyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate and 3-oxygen base methyl propionate, 3-oxygen base propionic acid ethyl class (for example 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate etc.), 2-oxygen base methyl propionate, 2-oxygen base ethyl propionate, 2-oxygen base propyl propionate and methyl pyruvate, ethyl pyruvate, Propyl pyruvate, acetoacetate methyl, ethyl acetoacetate, 2-ketobutyric acid methyl esters, 2-ketobutyric acid ethyl ester, 1,3 butylene glycol diacetate esters etc.;

Ethers, for example diethylene glycol dimethyl ether, tetrahydrofuran, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol single-butyl ether, methyl proxitol acetate, propylene glycol ethylether acetic acid esters, propylene glycol propyl ether acetic acid esters, diethylene glycol diethyl ether, TC acetic acid esters, diethylene glycol single-butyl ether, diethylene glycol single-butyl ether acetic acid esters, propylene glycol n-propyl ether acetic acid esters, propylene-glycol diacetate, propylene glycol n-butyl ether acetic acid esters, propylene glycol phenyl ether, propylene glycol phenyl ether acetic acid ester, DPGME acetic acid esters, DPG n-propyl ether acetic acid esters, DPG n-butyl ether acetic acid esters, tripropylene glycol list n-butyl ether, tripropylene glycol methyl ether acetic acid esters etc.;

Ketone, for example acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone etc.;

Alcohols, for example ethanol, isopropyl alcohol, methyl proxitol, propylene glycol list n-propyl ether, propylene glycol list n-butyl ether;

Aromatic hydrocarbon based, for example toluene, xylene etc.

Wherein, preferred 3-ethoxy-c acid methyl, 3-ethoxy-propionic acid ethyl, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid methyl esters, 2-heptanone, cyclohexanone, ethyl carbitol acetic acid esters, acetate of butyl carbitol, methyl proxitol, methyl proxitol acetate, propylene glycol ethylether acetic acid esters etc.

Solvent except can using separately, can also make up 2 kinds with on use.

Can come suitably to select the content of (A) organic solvent in the light solidification pigmentation composition of the present invention as required; But from the viewpoint of coating, the mode that preferably reaches 10 quality %～30 quality % according to the concentration of the nonvolatile component of light solidification pigmentation composition prepares.

(C) Photoepolymerizationinitiater initiater

Light solidification pigmentation composition of the present invention contains (C) Photoepolymerizationinitiater initiater.

Photoepolymerizationinitiater initiater is for to decompose through light, thus the polymeric compounds of initiation, promotion (D) polymerizable compound.

As Photoepolymerizationinitiater initiater, preferably ultraviolet exposure wavelength there is the Photoepolymerizationinitiater initiater of absorption, even when ultraviolet wavelength is not absorbed, also can have sensitivity to ultraviolet wavelength through the sensitizing coloring matter of stating after also using.In addition, Photoepolymerizationinitiater initiater can use separately or and with 2 kinds with on use.

As spendable Photoepolymerizationinitiater initiater among the present invention, can enumerate out for example organic halogenation compound 、 oxadiazole compound, carbonyls, ketal compound, benzoin compound, acridine compound, organic peroxy compound, azo-compound, coumarin compound, triazo-compound, Metallocenic compound, six aryl united imidazoles, organic boronic compound, disulfonic acid compound, oxime ester compound, salt compound, acylphosphanes (oxide) compound.

As the organic halogenation compound; Can enumerate out particularly if " Bull Chem.SocJapan " 42,2924 (1969), United States Patent (USP)s the 3rd such as woodss; 905; No. 815 instructionss, the special public clear 46-4605 communique of Japan, japanese kokai publication sho 48-36281 communique, japanese kokai publication sho 55-32070 communique, japanese kokai publication sho 60-239736 communique, japanese kokai publication sho 61-169835 communique, japanese kokai publication sho 61-169837 communique, japanese kokai publication sho 62-58241 communique, japanese kokai publication sho 62-212401 communique, japanese kokai publication sho 63-70243 communique, japanese kokai publication sho 63-298339 communique, M.P.Hutt " Journal of Heterocyclic Chemistry " 1 (No.3); (1970) etc. the compound of record can enumerate out being substituted with trihalomethyl De oxazole compound, s-triaizine compounds especially in.

As carbonyls; Can enumerate out benzophenone derivates, 2 such as benzophenone, michaelis ketone (Michler ' s ketone), 2 methyl benzophenone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, 2-chlorobenzophenone, 4-bromine benzophenone, 2-carboxyl benzophenone; 2-dimethoxy-2-phenyl acetophenone, 2; 2-diethoxy acetophenone, 1-hydroxycyclohexylphenylketone, alpha-hydroxy-2-aminomethyl phenyl acetone, 1-hydroxyl-1-Methylethyl-(p-isopropyl phenyl) ketone, 1-hydroxyl-1-(to dodecylphenyl) ketone, 2-methyl isophthalic acid-(4 '-(methyl mercapto) phenyl)-2-morpholinyl-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1,2; 4; 6-trimethylbenzoyl-diphenyl-phosphine oxide, 1; 1; 1-trichloromethyl-(to butyl phenyl) ketone, 2-benzyl-2-dimethylamino-acetophenone derivs, thioxanthones, 2-ethyl thioxanthones, 2-isopropyl thioxanthone, 2-clopenthixal ketones, 2 such as 4-morpholinyl phenyl propyl ketone; 4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2, thioxanthone derivates such as 4-diisopropyl thioxanthones, ESCAROL 507 ethyl ester, to benzoate derivatives such as diethylamino ethyl benzoate etc.

As six aryl united imidazoles, can enumerate out for example Japanese special fair 6-29285 communique, No. the 3rd, 479,185, United States Patent (USP), No. the 4th, 311,783, United States Patent (USP), United States Patent (USP) the 4th, 622; Wait all cpds of putting down in writing in each instructions No. 286, can enumerate out 2,2 '-two (Chloro-O-Phenyl)-4 particularly, 4 ', 5,5 '-tetraphenyl bisglyoxaline, 2; 2 '-two (o-bromophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (neighbours, right-dichlorophenyl)-4; 4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5; 5 '-four (m-methoxyphenyl) bisglyoxaline, 2,2 '-two (neighbour, neighbour '-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2; 2 '-two (ortho-nitrophenyl base)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (o-methyl-phenyl-)-4,4 '; 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (adjacent trifluorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline etc.

As oxime ester compound, can enumerate out the compound put down in writing in the compound put down in writing in J.C.S.Perkin II (1979) 1653-1660, J.C.S.Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, the TOHKEMY 2000-66385 communique, TOHKEMY 2000-80068 communique, the Japan special table 2004-534797 communique etc.As object lesson, be preferably IRGACURE OXE-01, OXE-02 of Ciba Specialty Chemicals corporate system etc.

Wherein, As Photoepolymerizationinitiater initiater; Viewpoint from the exposure sensitivity is preferably selected from the compound in trihalomethyl triazine based compound, benzyl dimethyl ketal compound, alpha-hydroxyacetone compounds, alpha-amido ketonic compound, acylphosphanes based compound, phosphine oxide based compound, Metallocenic compound, oxime ester compound, triarylimidazoles dipolymer, based compound, benzothiazole based compound, benzophenone based compound, acetophenone based compound and derivant thereof, cyclopentadiene-benzene-iron complex and salt thereof, halogen first oxadiazole compound, the 3-aryl substituted cumarin compound.

More preferably trihalomethyl triazine based compound, alpha-amido ketonic compound, acylphosphanes based compound, phosphine oxide based compound, oxime ester compound, triarylimidazoles dipolymer, based compound, benzophenone based compound, acetophenone based compound most preferably are at least a compound that is selected from trihalomethyl triazine based compound, alpha-amido ketonic compound, oxime compound, triarylimidazoles dipolymer, the benzophenone based compound.

Can enumerate out the oxime ester compound shown in the following general formula (5) as the preferred oxime ester compound of Photoepolymerizationinitiater initiater among the present invention.

In the above-mentioned general formula (5), R ⁸Represent the substituting group of monovalence, Q independently of one another with P ¹And Q ²Represent the organic group of divalence independently of one another, Ar representes aryl.N is 0～5 integer.P exists when a plurality of, and a plurality of P represent the substituting group of monovalence independently of one another.

The Photoepolymerizationinitiater initiater that can be preferred for light solidification pigmentation composition of the present invention is the compound of record in TOHKEMY 2010-72633 communique paragraph [0089]～[0173].

Be used for the compound of the compound shown in the above-mentioned general formula of the present invention (5) for having absorbing wavelength in the wavelength coverage of 250nm～500nm.More preferably can enumerate out the compound that has absorbing wavelength in the wavelength coverage of 300nm～380nm.The high compound of absorbance of preferred especially 308nm and 355nm.

(C) content of Photoepolymerizationinitiater initiater is preferably 0.1 quality %～20 quality % with respect to the whole nonvolatile component in the light solidification pigmentation composition, and more preferably 0.5 quality %～15 quality % are preferably 3 quality %～15 quality % especially.Can obtain good sensitivity in the time of in this scope and pattern becomes second nature.

[sensitizing coloring matter]

From improving the viewpoint of sensitivity, preferably in light solidification pigmentation composition of the present invention, add sensitizing coloring matter.The polyreaction of the free-radical generating reaction of this sensitizing coloring matter exposure through absorbable wavelength promotion Photoepolymerizationinitiater initiater composition or the polymerizable compound that is caused thus.

As this sensitizing coloring matter, can enumerate out known beam split sensitizing coloring matter or dyestuff or absorbing light and with interactional dyestuff of Photoepolymerizationinitiater initiater or pigment.

Preferred beam split sensitizing coloring matter or dyestuff as can be used for sensitizing coloring matter of the present invention can be enumerated out the polynuclear aromatic same clan (for example Bi 、 perylene, benzophenanthrene), xanthene class (for example luciferin, eosin, erythrosine, rhodamine B, rose-red), cyanines class (for example thia carbon cyanines, oxa-carbon cyanines), part cyanines class (for example part cyanines, carbon part cyanines), thiazide (for example thionine, methylene blue, toluidine blue), acridine (for example acridine orange, chloroflavin, acridine yellow), phthalocyanines (for example phthalocyanine, metal phthalocyanine), porphyrin class (for example tetraphenylporphyrin, central metal displacement porphyrin), chlorophyll class (for example chlorophyll, chlorophyllin, central metal displacement chlorophyll), metal complex, anthraquinone class (for example anthraquinone), side's acid interior type (for example in side's acid (squarylium)) etc.

Following illustration the example of preferred beam split sensitizing coloring matter or dyestuff.

Can enumerate out the polystyrene pigment of putting down in writing in the special public clear 37-13034 communique of Japan; The dye of positive ion of putting down in writing in the japanese kokai publication sho 62-143044 communique; The special public clear 59-24147 communique record De quinoxaline salt of Japan; The new methylene blue compound of japanese kokai publication sho 64-33104 communique record; The anthraquinone class of japanese kokai publication sho 64-56767 communique record; The benzoxanthene dye of japanese kokai publication hei 2-1714 communique record; The acridine of japanese kokai publication hei 2-226148 communique and the record of japanese kokai publication hei 2-226149 communique; The pyrans salt of the special public clear 40-28499 communique record of Japan; The cyanine class of the special public clear 46-42363 communique record of Japan; The coumarone pigment of japanese kokai publication hei 2-63053 number record; The conjugation ketone pigment of japanese kokai publication hei 2-85858 communique, japanese kokai publication hei 2-216154 communique; The pigment of japanese kokai publication sho 57-10605 communique record; Azo Chinese cassia tree fork (azo cinnamylidene) derivant of the special fair 2-30321 communique record of Japan; The cyanine of japanese kokai publication hei 1-287105 communique record is a pigment; The xanthene of japanese kokai publication sho 62-31844 communique, japanese kokai publication sho 62-31848 communique, the record of japanese kokai publication sho 62-143043 communique is a pigment; The aminobenzene ketenes of the special public clear 59-28325 communique record of Japan; The pigment of japanese kokai publication hei 2-179643 communique record; Part cyanines pigment of japanese kokai publication hei 2-244050 communique record; Part cyanines pigment of the special public clear 59-28326 communique record of Japan; Part cyanines pigment of japanese kokai publication sho 59-89303 communique record; Part cyanines pigment of japanese kokai publication hei 8-129257 communique record; The benzopyrene of japanese kokai publication hei 8-334897 communique record is a pigment.

As other preferred configuration of sensitizing coloring matter, can enumerate out the compound group that belongs to following and have the pigment of maximum absorption wavelength at 350～450nm.

For example can enumerate out in the polynuclear aromatic same clan (for example pyrene, perylene, benzophenanthrene), xanthene class (for example luciferin, eosin, erythrosine, rhodamine B, rose-red), cyanine class (for example sulphur carbon cyanines, oxygen carbon v cyanines), part cyanines class (for example part cyanines, carbon part cyanines), thiazide (for example thionine, methylene blue, toluidine blueness), acridine (for example acridine orange, chloroflavin, acriflavine), anthraquinone class (for example anthraquinone), the side's acid type (in the for example square acid).

The content of sensitizing coloring matter is preferably 0.1 quality %～20 quality % with respect to the whole nonvolatile component in the light solidification pigmentation composition, more preferably 0.5 quality %～15 quality %.

[mercaptan compound]

Light solidification pigmentation composition among the present invention preferably contains mercaptan compound.

Mercaptan compound among the present invention plays a role as being total to sensitizer, perhaps shows the effect of the adaptation that improves formed colored pixels and substrate.Altogether sensitizer have further raising sensitizing coloring matter or Photoepolymerizationinitiater initiater to the sensitivity of active radioactive ray, or suppress the effects such as polymerization obstruction that cause because of oxygen of polymerizable compound.

As mercaptan compound, can example go out the mercaptopropionic acid derivants such as THEIC-BMPA shown in ethylene glycol bis thiopropionate (EGTP), the two thiopropionates (BDTP) of butylene glycol, trimethylolpropane tris thiopropionate (TMTP), pentaerythrite tetrathio propionic ester (PETP), the following formula particularly; Ethylene glycol bis thioglycolic acid ester (EGTG), the two thioglycolic acid esters (BDTG) of butylene glycol, the two thioglycolic acid esters (HDTG) of hexanediol, trimethylolpropane tris thioglycolic acid ester (TMTG), pentaerythrite tetrathio ethyl glycolate thioglycolic acid derivants such as (PETG); 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1; 2-ethane two mercaptan, 1,3-propane two mercaptan, 1,6-hexa-methylene two mercaptan, 2; 2 '-(methylene two sulfo-s) diethyl alkanethiol, internal compensation-2, thio-alcohols such as 3-dimercaptosuccinic acid, P-xylene two mercaptan, m-xylene two mercaptan; Sulfydryl ethers such as two (mercaptoethyl) ether.

These compounds can use separately or make up 2 kinds with on use.

As the mercaptan compound that uses among the present invention, the more preferably compound shown in the formula (I).

General formula (I)

In the general formula (I), R representes hydrogen atom, alkyl or aryl, and A representes to form with N=C-N the atomic group of heterocycle.

In the general formula (I), R representes hydrogen atom, alkyl or aryl.

As the alkyl shown in the R; Can enumerate out carbon number and be the alkyl of 1～20 straight chain shape, branched or ring-type, more preferably carbon number is that alkyl, the carbon number of 1～12 straight chain shape are that alkyl and the carbon number of 3～12 branched is the alkyl of 5～10 ring-type.

As its object lesson, can enumerate out methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, cetyl, octadecyl, eicosyl, isopropyl, isobutyl, isobutyl, the tert-butyl group, isopentyl, neopentyl, 1-methyl butyl, isohesyl, 2-ethylhexyl, 2-methyl hexyl, cyclohexyl, cyclopentyl, 2-norborny etc.

As the aryl shown in the R; Except that the aryl of single ring architecture; Can also enumerate out the aryl of aryl that 1～3 phenyl ring forms fused rings, phenyl ring and 5 yuan of unsaturated ring formation fused rings etc.; As concrete example, can enumerate out phenyl, naphthyl, anthryl, phenanthryl, indenyl, acenaphthenyl, fluorenyl etc., wherein more preferably phenyl, naphthyl.

These alkyl and aryl can also further have substituting group; As the substituting group that can import, alkyl, the carbon number that can enumerate out carbon number and be 1～20 straight chain shape, branched or ring-type is that alkenyl, the carbon number of 2～20 straight chain shape, branched or ring-type is that 2～20 alkynyl, carbon number are that 6～20 aryl, carbon number are that 1～20 acyloxy, carbon number are that 2～20 alkoxy-carbonyl oxy, carbon number are that 7～20 aryloxycarbonyl oxygen base, carbon number are that 1～20 carbamyl oxygen base, carbon number are that 1～20 carboxamide groups, carbon number are that 1～20 sulfoamido, carbon number are that 1～20 carbamyl, sulfamoyl, carbon number are that 1～20 replacement sulfamoyl, carbon number are that 1～20 alkoxy, carbon number are that 6～20 aryloxy group, carbon number are that 7～20 aryloxycarbonyl, carbon number are that 2～20 alkoxy carbonyl, carbon number are that 1～20 N-acyl group sulfamoyl, carbon number are that 1～20 N-sulfamoyl carbamyl, carbon number are that 1～20 alkyl sulphonyl, carbon number are that 6～20 aryl sulfonyl, carbon number are that 2～20 alkoxycarbonyl amino, carbon number are that 7～20 aryloxycarbonyl is amino, amino, carbon number is that 1～20 substituted-amino, carbon number are that 1～20 imino group, carbon number are that 3～20 ammonium, carboxyl, sulfo group, oxygen base, sulfydryl, carbon number are that 1～20 alkyl sulphinyl, carbon number are that 6～20 aryl sulfonyl kia, carbon number are that 1～20 alkyl sulfenyl, carbon number are that 6～20 artyl sulfo, carbon number are that 1～20 urea groups, carbon number are that 2～20 heterocyclic radical, carbon number are that 1～20 acyl group, sulfamoyl are importing, carbon number is that 1～2 replacement sulfamoyl is An Ji, carbon number is 2～20 silicyl, NCO, isocyanide base, halogen atom (for example fluorine atom, chlorine atom, bromine atoms etc.), cyanic acid, nitro, base etc.

In addition, in the general formula (I), A representes to form with N=C-N the atomic group of heterocycle.

As the atom that constitutes this atomic group, can enumerate out carbon atom, nitrogen-atoms, hydrogen atom, sulphur atom, selenium atom etc.

In addition, the heterocycle that A and N=C-N form can also further have substituting group, as the substituting group that can import, can enumerate out with abovementioned alkyl and aryl in the identical substituting group of substituting group that can import.

In addition, as mercaptan compound, the more preferably compound shown in formula (II) or the general formula (III).

General formula (II) general formula (III)

In the general formula (II), R ¹The expression aryl, X representes hydrogen atom, halogen atom, alkoxy, aryloxy group, alkyl or aryl.

In the general formula (III), R ²Expression alkyl or aryl, X representes hydrogen atom, halogen atom, alkoxy, aryloxy group, alkyl or aryl.

In general formula (II) and the general formula (III), as the halogen atom shown in the X, preferred fluorine atom, chlorine atom, bromine atoms, iodine atom.

In general formula (II) and the general formula (III); As alkoxy shown in the X and aryloxy group; Can enumerate out methoxyl, ethoxy, propoxyl group, isopropoxy, butoxy, amoxy, own oxygen base, dodecyl oxygen base, benzyloxy, allyloxy, benzene ethoxy, carboxyl ethoxy, methoxycarbonyl ethoxy, ethoxy carbonyl ethoxy, methoxy ethoxy, phenoxy group ethoxy, methoxy ethoxy ethoxy, ethoxy ethoxy ethoxy, morpholinyl ethoxy, morpholinyl propyl oxygen base, allyloxy ethoxy ethoxy, phenoxy group, toloxyl, xylyloxy, 2; 4,6-triple phenoxyl, isopropyl benzene oxygen base, methoxyl phenoxy group, ethoxy phenoxy, chlorophenoxy, bromine phenoxy group, acetyl group oxygen base, benzoyl oxygen base, naphthoxy etc.

In general formula (II) and the general formula (III), R ²Perhaps the alkyl implication shown in the R of the alkyl shown in the X and general formula (I) is identical, and its preferred range is also identical.

In addition, in general formula (II) and the general formula (III), R ¹, R ²Perhaps the aryl shown in the X is identical with the aryl implication shown in the R of general formula (I) independently of one another, and its preferred range is also identical.

In general formula (II) and the general formula (III), R ¹, R ², or X shown in each group can also further have substituting group, as this substituting group, with identical as the listed group of enumerating of the substituting group that can import in the alkyl or aryl shown in the R of general formula (I).

In general formula (II) and the general formula (III), from the deliquescent viewpoint of propylene glycol monomethyl ether (the following PGMEA that suitably is called), more preferably X is a hydrogen atom.

In the general formula (II), from sensitivity and the deliquescent viewpoint of PGMEA, most preferably R ¹Be phenyl.

In the general formula (III), from sensitivity and the deliquescent viewpoint of PPGMEA, more preferably R ²Be methyl, ethyl, phenyl, benzyl.

In the compound shown in compound shown in the general formula (II) and the general formula (III), from the deliquescent viewpoint of PGMEA, the compound shown in the general formula (III) most preferably.

These mercaptan compounds can be used J.Appl.Chem., and 34, the method for record among the 2203-2207 (1961) is synthetic.

In the light solidification pigmentation composition of the present invention; Compound shown in the general formula (I) can use a kind separately; Also can in addition, can also the compound that be selected from the compound shown in the general formula (II) also be used with the compound that is selected from the compound shown in the general formula (III) also with more than 2 kinds.

The content of the mercaptan compound in the light solidification pigmentation composition is preferably 0.1 quality %～5.0 quality % with respect to the solid constituent of light solidification pigmentation composition, more preferably 0.2 quality %～4 quality %.In the time of in this scope, can not damage the polymerism of light solidification pigmentation composition, therefore preferred.

(E) bonding agent

The light solidification pigmentation composition that uses among the present invention contains (E) bonding agent from improving the epithelium characteristic, giving purpose such as developing property.At this,, can use the macromolecular compounds such as resin, macromolecule dispersing agent of alkali soluble resin, epoxy resin, pigment lining usefulness as (E) bonding agent.When considering the development of carrying out with alkali, preferably contain alkali soluble resin at least.

Below alkali soluble resin, the epoxy resin of these bonding agents is detailed.

As the alkali soluble resin that uses in the light solidification pigmentation composition of the present invention, can from alkali soluble resin, suitably select as the group (for example carboxyl, phosphate, sulfonic group, hydroxyl etc.) that has at least 1 promotion alkali-soluble wire organic high molecular polymer and the molecule (being the molecule of main chain preferably) with acrylic acid series copolymer, styrene based copolymer.

As above-mentioned alkali soluble resin, more preferably can enumerate out acid cellulose derivant that the methacrylic acid copolymer put down in writing in each communique of the special public clear 54-34327 communique of polymkeric substance, for example japanese kokai publication sho 59-44615 communique, Japan that side chain has the carboxylic acid group, the special public clear 58-12577 communique of Japan, the special public clear 54-25957 communique of Japan, japanese kokai publication sho 59-53836 communique, japanese kokai publication sho 59-71048 communique, acrylic copolymer, itaconic acid copolymer, crotonic acid multipolymer, maleic acid, partial esterification maleic acid etc. and side chain have the carboxylic acid group, have the acrylic acid series copolymers such as compound that the addition acid anhydrides forms on the polymkeric substance of hydroxyl.

As acid number, be preferably 20mgKOH/g～200mgKOH/g, more preferably 30mgKOH/g～180mgKOH/g, further be preferably the scope of 50mgKOH/g～150mgKOH/g.

As the alkali soluble resin that uses among the present invention, preferred especially (methyl) acrylic acid and the multipolymer that can form with other monomer of its copolymerization.

As other monomer that ability and (methyl) acrylic acid copolymer close, can enumerate out (methyl) alkyl acrylate, (methyl) acrylic acid aryl ester, vinyl compound etc.Wherein, the hydrogen atom of alkyl and aryl can also be substituted the base replacement.

As above-mentioned (methyl) alkyl acrylate and (methyl) acrylic acid aryl ester, can enumerate out CH ₂=C (R) (COOR ') [wherein; R representes hydrogen atom or methyl; R ' expression carbon number is that 1～8 alkyl or carbon number are 6～12 aryl], can enumerate out (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) CA, (methyl) acrylic acid naphthalene ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid hydroxyalkyl acrylate (alkyl is that carbon number is 1～8 alkyl), methacrylic acid hydroxyl ethylene oxidic ester, tetrahydrofurfuryl methacrylate etc. particularly.

As vinyl compound, can enumerate out CH ₂=CR ¹R ²[wherein, R ¹Expression hydrogen atom or carbon number are 1～5 alkyl, R ²The expression carbon number is 6～10 aromatic hydrocarbon ring], can enumerate out styrene, AMS, vinyltoluene, vinyl cyanide, vinylacetate, N-vinyl pyrrolidone, polystyrene macromolecular monomer, polymethylmethacrylate macromonomer etc. particularly.

Other monomer of above-mentioned ability copolymerization can use a kind separately, or makes up more than 2 kinds and use.

In above-mentioned, preferred especially (methyl) benzyl acrylate/(methyl) acrylic copolymer, by multiple copolymer that (methyl) benzyl acrylate/(methyl) acrylic acid/other monomer constitutes.

In addition, the resin that has the polyalkylene oxide chain at molecular side chain is also preferably as alkali soluble resin.

As the polyalkylene oxide chain, for polyethylene oxide chain, polypropyleneoxide chain, gather tetramethylene glycol chain or they and usefulness, the end of these chains is the alkyl of hydrogen atom or straight or branched.

The number of repeat unit of polyethylene oxide chain, polypropyleneoxide chain is preferably 1～20, more preferably 2～12.

As the acrylic acid series copolymer that has the polyalkylene oxide chain at side chain, preference is as containing polyethyleneglycol (methyl) acrylic ester, polypropylene glycol list (methyl) acrylic ester, gathering (ethylene glycol and 1,2-propylene glycol) single (methyl) acrylic ester etc. and these terminal OH bases and gathered the acrylic acid series copolymer as copolymer composition such as (ethylene glycol and 1,2-propylene glycol) single (methyl) acrylic ester by alkyl-blocked compound, for example methoxy poly (ethylene glycol) list (methyl) acrylic ester, ethoxy polypropylene glycol list (methyl) acrylic ester, methoxyl.

Acrylic acid series copolymer preferably has the acid number of the scope of 20mgKOH/g～200mgKOH/g as previously mentioned.Acid number is when 200mgKOH/g is following, and acrylic resin can not become excessive to the dissolubility of alkali, and the appropriate scope (development tolerance) that can prevent to develop narrows down.On the other hand, be 20mgKOH/g when above, the dissolubility of alkali is difficult to diminish, can prevent that therefore development time from prolonging.

In addition; In order to embody the range of viscosities of the operations such as coating that are easy for light solidification pigmentation composition; And guarantee film strength, the weight-average molecular weight Mw of acrylic resin (the polystyrene conversion value of measuring through the GPC method) is preferably 2000～100000, more preferably 3000～50000.

In addition, in order to improve the cross-linking efficiency of the light solidification pigmentation composition that can use in the present invention, the preferred alkali soluble resin that uses with polymerizable group.This alkali soluble resin with polymerizable group can use separately, can also and use with the alkali soluble resin that does not have polymerizable group.

As the alkali soluble resin with polymerizable group, polymkeric substance that contains allyl, (methyl) acryloyl group, allyloxy alkyl etc. at side chain etc. is useful.This alkali soluble resin with the two keys of polymerism can carry out the development in the alkaline developer, and has photo-curable and Thermocurable, thereby preferred.Wherein, has allyl as the resin of side chain polymerizable group high being more preferably of high, the heat-resisting decomposability of curable owing to resist.

The preference of the alkali soluble resin that contains polymerizable group below is shown, but so long as contain the resin of alkali-soluble group such as COOH base, OH base and the two keys (unsaturated link between carbon-to-carbon) of polymerism at 1 molecule, then is not limited to the compound shown in following.

Promptly can enumerate out:

(1) reaction of acryl resin through containing carboxyl and following compound obtain through the urethane-modified acryl resin that contains the two keys of polymerism, said compound contain at least 1 through making NCO and OH radical reaction in advance residual (methyl) acryloyl group of 1 unreacted NCO;

(2) has the acryl resin that contains unsaturated group that the reaction of the compound of epoxy radicals and the two keys of polymerism obtains in acryl resin through containing carboxyl and the molecule simultaneously

(3) sour side group (acid pendant group) type Epocryl

(4) acryl resin that contains the two keys of polymerism that obtains through the acryl resin that contains the OH base and 2 yuan of anhydride reactions with the two keys of polymerism.

The resin of preferred especially (1) and (2) in above-mentioned.

As concrete example, can use through making for example acrylic acid 2-hydroxy methacrylate and the monomer that contains the COOH base compound that obtains of methacrylic acid and can reacting etc. for example of the compound that has the epoxide ring of responding property of OH base and the two keys of polymerism compounds such as (for example) glycidyl acrylates and monomer with the multipolymer that monomers such as the acrylic acid series of their copolymerization or vinyl based compound form with OH base.In the reaction of OH base, except epoxide ring, can also use compound with anhydride group, NCO, acryloyl group.

In addition; The reactant that can also use the reaction of saturated or unsaturated multi-anhydride and following compound and obtain, said compound are through making the compound of putting down in writing in unsaturated carboxylic acid such as acrylic acid and japanese kokai publication hei 6-102669 communique, the japanese kokai publication hei 6-1938 communique with epoxide ring react the compound that obtains.

Can dissolve the compound of the two keys of group and polymerism as alkali such as having the COOH base simultaneously, for example can enumerate out DIANAL NR series (Rayon Co., Ltd. of Mitsubishi system); Photomer 6173 (the polyurethane acroleic acid oligomer (Polyurethane acrylic oligomer), the Diamond Shamrock Co.Ltd that contain the COOH base, system); PVC スコ one ト R-264, KS RESIST 106 (being Osaka Organic Chemical Industry Co., Ltd.'s system); CYCLOMER P series, PLACCEL CF200 series (being Daicel chemical industry Co., Ltd. system); Ebecryl 3800 (Daicel-cytec Co., Ltd. system) etc.

Addition when using alkali soluble resin as (E) bonding agent is preferably the scope of 3 quality %～50 quality %, more preferably 5 quality %～30 quality % in whole nonvolatile component of light solidification pigmentation composition.

When the preparation light solidification pigmentation composition, except above-mentioned alkali soluble resin, the following epoxy resin of also preferred interpolation.As epoxy resin, can enumerate out bisphenol A-type, cresols phenolic varnish type, biphenyl type, alicyclic epoxy compound etc. have 2 above epoxide rings in molecule compound.

For example as bisphenol A-type; Can enumerate out EPOTOHTO YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 etc. (above is Toto Kasei KK's system), DENACOL EX-1101, EX-1102, EX-1103 etc. (above is Nagase Chemtex Co., Ltd. system), PLACCEL GL-61, GL-62, G101, G102 (above is Daicel chemical industry Co., Ltd. system) etc.; In addition; As spendable compound, can also enumerate out Bisphenol F type similar, bisphenol-s epoxy resin with it.

In addition, can also use epoxy acrylates such as Ebecryl 3700,3701,600 (above be Daicel-cytec Co., Ltd. system).

As the cresols phenolic varnish type, can enumerate out EPOTOHTO YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704 etc. (above is Toto Kasei KK's system), DENACOL EM-125 etc. (above is Nagase Chemtex system); As biphenyl type, can enumerate out 3,5,3 ', 5 '-tetramethyl-4,4 '-diglycidyl biphenyl etc.; As the alicyclic epoxy compound, can enumerate out CELLOXIDE 2021,2081,2083,2085, EPOLEAD GT-301, GT-302, GT-401, GT-403, EHPE-3150 (above the Daicel of being chemical industry Co., Ltd. system), サ Application ト one ト ST-3000, ST-4000, ST-5080, ST-5100 etc. (above be Toto Kasei KK's system), Epiclon 430, Epiclon 673, Epiclon 695, Epiclon850S, Epiclon 4032 (above be Dainippon Ink Chemicals's system) etc.

In addition; Can also use 1; 1; 2,2-four (to the glycidoxypropyl phenyl) ethane, three (to the glycidoxypropyl phenyl) methane, triglycidyl group three (hydroxyethyl) isocyanuric acid ester, o-phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, ethylene oxidic ester that the skeleton of amine type epoxy resin OTOHTO YH-434, YH-434L, bisphenol A type epoxy resin is obtained with dipolymer acid modification etc.

Wherein, preferred " number of molecular weight/epoxide ring " is more than 100, more preferably 130～500.If " number of molecular weight/epoxide ring " is little, then curable contraction high, when solidifying is big, and if " number of molecular weight/epoxide ring " is excessive, then curable is not enough, lacks reliability, perhaps flatness variation, thereby not preferred.

As the concrete preferred compound that satisfies this condition; Can enumerate out EPOTOHTO YD-115,118T, 127, YDF-170, YDPN-638, YDPN-701, PLACCEL GL-61, GL-62,3; 5; 3 ', 5 '-tetramethyl-4,4 ' diglycidyl biphenyl, CELLOXIDE2021,2081, EPOLEAD GT-302, GT-403, EHPE-3150 etc.

Addition when using epoxy resin as (E) bonding agent is preferably the scope of 0.1 quality %～30 quality % in whole nonvolatile component of light solidification pigmentation composition; More preferably 0.5 quality %～20 quality % most preferably are 1 quality %～10 quality %.If be the addition of this scope; Then can under the situation that does not hinder optical polymerism, obtain the sensitivity of making public fully; And can have thermal polymerization property simultaneously, can give highly heat-resistant, resistance to chemical reagents thus, but also can guarantee the storage stability of resist solution.

< other additive >

In addition, except that mentioned component, can also use various known adjuvants in the light solidification pigmentation composition that the present invention uses according to purpose.

Below such adjuvant is described.

(surfactant)

When increasing pigment concentration, because the thixotropy of coating fluid generally can increase, the thickness that therefore is easy to when light solidification pigmentation composition coating or transfer printing are on substrate to take place to form behind the light solidification pigmentation composition layer (dyed layer is filmed) is uneven.In addition, particularly when utilizing the slot coated method to form light solidification pigmentation composition layer (dyed layer is filmed), importantly the coating fluid levelling of light solidification pigmentation composition layer formation usefulness forms filming of uniform thickness before drying.Therefore, preferably in above-mentioned light solidification pigmentation composition, contain suitable surfactant.As above-mentioned surfactant, can enumerate out in TOHKEMY 2003-337424 communique, the japanese kokai publication hei 11-133600 communique disclosed surfactant as preferred surfactants.

As the surfactant that is used to improve coating, can add nonionic is that surfactant, fluorine are surfactant, polysiloxane series surfactant etc.

As nonionic is surfactant, and nonionics such as preference such as polyoxyethylene glycol class, polyoxy propandiols, polyoxyethylene alkyl ether class, polyoxyethylene alkylaryl ether class, polyxyethylated ester class, polyoxypropylene alkyl ether, polyoxypropylene alkylaryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters, single glycerine alkyl esters are surfactant.

Polyether polyols classes such as polyoxyethylene glycol, polyoxy propylene glycol are arranged particularly; Polyoxyalkylene alkyl classes such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as NONIN HS 240, polystyrene-basedization of polyoxyethylene ether, polyoxyethylene tribenzyl phenyl ether, polystyrene-basedization of polyoxyethylene-propylene ether, polyoxyethylene nonylplenyl ether; Nonionics such as polyoxyalkylene dialkyls such as polyoxyethylene dilaurate, polyoxyethylene distearate, sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters class are surfactant.

Their object lesson for example is an ADEKA PLURONIC series; ADEKANOL series; TETRONIC series (above is ADEKA Co., Ltd. system); EMULGEN series; RHEODOL series (above is Kao Corp's system); ELEMINOL series; NONIPOL series; OCTAPOL series; DODEKAPOL series; NEWPOL series (above is Sanyo Chemical Industries Co., Ltd.'s system); PIONIN series (above is Zhu Ben's Oil Corporation's system); NISSANNONION series (above is NOF Corp's system) etc.Can suitably use these commercially available article.Preferred HLB value is 8～20, more preferably 10～17.

As fluorine is surfactant, the compound that can preferably use endways, any position at least in main chain and the side chain has fluoroalkyl or fluorine alkylidene.

As concrete commercially available article, MEGAFAC F142D, MEGAFAC F172, MEGAFAC F173, MEGAFAC F176, MEGAFAC F177, MEGAFAC F183, MEGAFAC F780, MEGAFAC F781, MEGAFAC R30, MEGAFAC R08 (above is Dainippon Ink Chemicals's system), FLUORAD FC-135, FLUORAD FC-170C, FLUORAD FC-430, FLUORAD FC-431 (above is Sumitomo 3M Co., Ltd. system), SURFLON S-112, SURFLON S-113, SURFLON S-131, SURFLON S-141, SURFLON S-145, SURFLON S-382, SURFLON SC-101, SURFLON SC-102, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC-106 (above is Asahi Glass Co., Ltd's system), EFTOP EF351, EFTOP 352, EFTOP 801, EFTOP 802 (above is JEMCO Co., Ltd. system) etc. are for example arranged.

As the polysiloxane series surfactant, for example can enumerate out TORAY SILICONE DC3PA, TORAY SILICONE DC7PA, TORAY SILICONE SH11PA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAYSILICONE SH29PA, TORAY SILICONE SH30PA, TORAY SILICONE SH-190, TORAY SILICONE SH-193, TORAY SILICONE SZ-6032, TORAY SILICONE SF-8428, TORAY SILICONE DC-57, TORAY SILICONE DC-190 (above the Dow of being Corning Toray Silicone Co., Ltd. system), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above be Momentive Performance Materials Japan corporate system) etc.

These surfactants be preferably below 5 mass parts with respect to coating fluid 100 mass parts that form the light solidification pigmentation composition layer, more preferably the amount below 2 mass parts is used.When the amount of surfactant surpasses 5 mass parts, when coating is dry, be easy to generate rough surface sometimes, flatness is easy to variation.

In addition, seeking to promote uncured alkali dissolution property, when further improving the development property of light solidification pigmentation composition, can add organic carboxyl acid, preferred molecular weight is the low-molecular-weight organic carboxyl acid below 1000.For example can enumerate out formic acid, acetate, propionic acid, butyric acid, valeric acid, trimethylace tonitric, caproic acid, diethacetic acid, enanthic acid, aliphatics monocarboxylic acid such as sad particularly; Aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, methylmalonic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl succinic acid, citraconic acid; Aliphatic tricarboxylic acids such as the third three acid, aconitic acid, camphoronic acid; Benzoic acid, methyl benzoic acid, cumfrey, 2,3-mesitylenic acid, 3, aromatic series monocarboxylic acids such as 5-mesitylenic acid; Aromatic series poly carboxylic acid such as phthalic acid, m-phthalic acid, terephthalic acid (TPA), trimellitic acid, trimesic acid, mellophanic acid, PMA; Other carboxylic acids such as phenylacetic acid, phenoxyacetic acid, methoxybenzene ethoxyacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, Chinese cassia tree fork acetate, coumaric acid, umbellic acid.

(alkoxysilane compound containing trialkylsilyl group in molecular structure)

From the viewpoint of raising, can use alkoxysilane compound containing trialkylsilyl group in molecular structure, particularly silane coupling agent in the light solidification pigmentation composition that uses among the present invention with the adaptation of substrate.

As silane coupling agent; Preferably have as can with the silane coupling agent of the alkoxysilyl of the hydrolization group of inorganic material chemical bonding; Be preferably and organic resin between interact or form key to show (methyl) acryloyl group, phenyl, sulfydryl or the epoxy silane of compatibility, wherein more preferably (methyl) acryloyl group propyl trimethoxy silicane.

Be preferably the scope of 0.2 quality %～5.0 quality % in all solids composition in the light solidification pigmentation composition that addition when using silane coupling agent uses in the present invention, more preferably 0.5 quality %～3.0 quality %.

(sensitizer altogether)

The light solidification pigmentation composition that uses among the present invention also preferably contains common sensitizer as required.Common sensitizer among the present invention have further raising sensitizing coloring matter or initiating agent to the sensitivity of active radioactive ray, or suppress the effects such as polymerization obstruction of the polymerizable compound (polymerizable compound) that oxygen causes.

Example as so common sensitizer; " Journal of Polymer Society " the 10th volume 3173 pages of (1972), the special public clear 44-20189 communiques of Japan, japanese kokai publication sho 51-82102 communique, japanese kokai publication sho 52-134692 communique, japanese kokai publication sho 59-138205 communique, japanese kokai publication sho 60-84305 communique, japanese kokai publication sho 62-18537 communique, the japanese kokai publication sho 64-33104 communique of work such as amine, for example M.R.Sander, the compound of Research Disclosure33825 number record etc. can be enumerated out, triethanolamine, ESCAROL 507 ethyl ester can be enumerated out particularly, to the formoxyl xylidin, to the methyl mercapto xylidin etc.

As other example that is total to sensitizer; The disulfide compound of thioether class, for example japanese kokai publication sho 56-75643 communique etc. can be enumerated out, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-sulfydryl-4 (3H)-quinoline, β-mercaptonaphthalene etc. can be enumerated out particularly.

In addition; As other example of sensitizer altogether, can enumerate out the sulphur compound that hydrogen confession and body, the japanese kokai publication hei 6-308727 communique of organometallics (for example tributyl tin acetic acid esters etc.), the special public clear 55-34414 communique record of Japan of amino-acid compound (for example N-phenylglycine etc.), the special public clear 48-42965 communique record of Japan put down in writing (for example thioformaldehyde etc.) etc.

The viewpoint that the curing rate that brings from the balance of aggregation growth speed and chain transfer improves; The content of these common sensitizers is preferably the scope of 0.1 quality %～30 quality % with respect to all solids composition of light solidification pigmentation composition; The scope of 1 quality %～25 quality % more preferably further is preferably the scope of 1.5 quality %～20 quality %.

(polymerization inhibitor)

Among the present invention, for stop in the manufacturing of light solidification pigmentation composition or preserve in polymerisable polymerizable compound unwanted thermal polymerization takes place, preferably add a spot of hot polymerization inhibitor.

As spendable hot polymerization inhibitor among the present invention; Can enumerate out p-dihydroxy-benzene, p methoxy phenol, two-tert-butyl group-paracresol, pyrogallol, tert-butyl catechol, benzoquinones, 4; 4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-the inferior cerium salt of di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), N-nitroso-phenyl hydramine, phenoxazine, phenothiazine etc.

The addition that thermal resistance is gathered is preferably 0.01 quality %～5 quality % with respect to light solidification pigmentation composition.In addition, can also add advanced higher fatty acid derivatives such as being used for mountain Yu acid that the caused polymerization of anti-block suppresses or mountain Yu acid amides etc. as required, and it is distributed in the set of surfaces of photographic layer.The addition of advanced higher fatty acid derivative is preferably the 0.5 quality %～10 quality % of light solidification pigmentation composition.

(plastifier)

In addition, in order to improve the rerum natura of light solidification pigmentation composition, also can add inorganic filler or plastifier etc. among the present invention.

As plastifier; Phthalic acid dioctyl ester, phthalic acid two (dodecyl) ester, triethylene glycol dicaprylate, dimethyl EGP ethylene glycol phthalate, tricresyl alkaliine, dioctyl adipate, dibutyl sebacate, triacetyl glycerine etc. are for example arranged, and it can be the amount interpolation below the 10 quality % with the gross mass with respect to polymerizable compound and resin.

The light solidification pigmentation composition of the present invention that contains mentioned component to the exposure of ultraviolet laser with high sensitivity solidify, pattern becomes second nature excellence and the transmittance of the shape of the colored pattern that forms, visible light is all good, be suitable for the colored pattern that color filter uses and form.

< liquid crystal indicator is used manufacturing method of color filter >

Light solidification pigmentation composition of the present invention and manufacturing method of color filter are applicable to that liquid crystal indicator uses color filter.Below, light solidification pigmentation composition of the present invention and manufacturing method of color filter are described, but the present invention is not limited to the method.

Make color filter through using light solidification pigmentation composition on the transmitance substrate, to form colored pattern, also other operation can be set as required.

Manufacturing method of color filter of the present invention is characterised in that, comprises following operation: the color filter of on substrate, bestowing the invention described above forms operation with light solidification pigmentation composition with the dyed layer that forms the dyed layer that is made up of this light solidification pigmentation composition; The exposure process that this dyed layer is made public with pattern-like; Develop to form the developing procedure of pattern with the dyed layer after will making public.

In addition, operation (prebake conditions operation) that above-mentioned dyed layer is toasted and the operation (roasting procedure) that the above-mentioned dyed layer after developing is toasted also can be set as required.Sometimes these operations are called pattern in the lump and form operation.

[dyed layer formation operation]

It is that light solidification pigmentation composition of the present invention is applied on the substrate to form the operation of dyed layer that dyed layer of the present invention forms operation.As substrate, for example can enumerate out alkali-free glass, soda-lime glass, pyrex, the quartz glass that in liquid crystal indicator etc., uses and on them, adhere to nesa coating and the photo-electric conversion element substrate that uses in the substrate that obtains, solid-state imager etc.In addition, can also use plastic base.Preferred these substrates that use are with formation black matrix"s such as clathrates, at the blank parts formation colored pattern of grid.

For the driving fit of improvement as required and the layer on top, prevent the planarization of material diffusion or substrate surface also can on these substrates, undercoat be set.From the angle of further performance effect of the present invention, the substrate of preferably large-scale (about 1 length of side is more than the 1m).

As the method that on substrate, forms dyed layer, can use the method for bestowing of various coatings such as slot coated, ink-jet method, rotary coating, curtain coating coating, roller coat, silk screen print method etc.Wherein, from the viewpoint of precision and speed, preferred slot coated.

In addition, can also use and will be in advance bestowing the adhering molding transfer that the forms method to the substrate on the interim supporter through the above-mentioned method of bestowing.

About printing transferring method, also can preferably use the middle method for making of putting down in writing in paragraph [0096]～[0108] of paragraph [0023], [0036]～[0051] or the TOHKEMY 2006-47592 communique of TOHKEMY 2006-23696 communique among the present invention.

Bed thickness (for example coating thickness) about dyed layer among the present invention; In order to obtain sufficient color reproduction area and to obtain sufficient panel luminance; The mode that preferably reaches 0.5 μ m～3.0 μ m according to dried thickness forms film, more preferably reaches 1.5 μ m～2.5 μ m.

In addition, form dried thickness reach 2 μ m utilize the dyed layer that light solidification pigmentation composition obtains the time, the transmissivity of this dyed layer under wavelength 355nm is 2% when following, can bring into play effect of the present invention well, is preferred mode.That is, after the exposure light wavelength used in the exposure process stated be generally the scope of 300nm～380nm, light solidification pigmentation composition of the present invention has when forming pattern under the irradiation that the exposure light of this wavelength carries out in utilization; The shape of pattern is also good; And residue produces also few, and development property is excellent, and in the roasting procedure of back, also excessive heat flow can not take place; So can keep the pattern form after the development, for the special effect of destruction performance that prevents contact hole.

[exposure process]

Exposure process of the present invention is to utilize the ultraviolet laser of pattern-like to make public to above-mentioned dyed layer, perhaps makes public with ultraviolet ray etc. by means of the mask with pattern, thereby forms sub-image.Through exposure process of the present invention; In the pattern-like exposure area of light solidification pigmentation composition, utilize the initiation kind that produces by (C) Photoepolymerizationinitiater initiater, the polymerization curing reaction of (D) polymerizable compound is taken place and carry out; Cause thermal response through the heat that produces by the ultraviolet laser exposure simultaneously; Curing reaction is taken place and carry out, through the exposure area dual cure of light and heat takes place, thereby form the pattern that constitutes by consolidation zone and uncured zone.

One of characteristic of the ultraviolet laser that uses among the present invention is that illumination is high, in exposure process, in light solidification pigmentation composition, produces heat, causes in formed pixel inside sometimes and solidifies inequality.For this reason, in order to control the temperature that pixel forms the middle thing (light solidification pigmentation composition) that made public that uses, preferably exposure period is remained on constant temperature, and need consider the shape of exposure period.In addition, the depth of parallelism of the light of ultraviolet laser is high, therefore and the influence of the distance between the substrate little, make public while also preferably substrate is floated over carry in the air.

As the exciting media of laser, crystal, glass, liquid, pigment, gas etc. are arranged, can use the known laser that ultraviolet light had excitation wavelength such as the Solid State Laser of using these media, liquid laser, gas laser, semiconductor laser.Wherein, from the power of laser and the viewpoint of excitation wavelength, preferred Solid State Laser, gas laser.

Exposure wavelength as the ultraviolet laser that uses among the present invention; From angle consistent with the wavelength photoreceptor of photosensitive composition and that sensitivity is good, be preferably the scope of 300nm～380nm, more preferably 310nm～360nm scope, be preferably the laser explosure method of 355nm wavelength especially.

Particularly, can preferably use third harmonic (355nm), PRK XeCl (308nm), the XeF (353nm) of big, the less expensive Solid State Laser Nd:YAG laser of power especially.

In addition, as by the exposure of exposure thing (pattern), for example be 1mJ/cm ²～100mJ/cm ²Scope, 1mJ/cm more preferably ²～50mJ/cm ²Scope.When exposure during in this scope, the angle of the throughput rate that forms from pattern is preferred.

The ultraviolet laser that uses among the present invention is preferably the pulse laser that under the frequency of 20Hz～2000Hz, excites from the viewpoint of throughput rate.

Do not have special qualification as spendable exposure device among the present invention,, can use EGIS (V Technology Co., Ltd. system) or DF2200G (big Japanese Screen Co., Ltd. system) etc. as commercially available article.Also preferably use the device except that above-mentioned.

In addition, the also preferred active ray that uses with the wavelength below wavelength 300nm～450nm.In the exposure that utilizes active ray to carry out, can use low pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, chemical lamp etc.

When using mercury lamp, can preferably use have g line (436nm), i line (365nm), h line (405nm) equiwavelength's active ray.

[developing procedure]

Developing procedure of the present invention is that the dyed layer that has formed sub-image is developed to form pattern.The exposure area is solidified into pattern-like, through in development treatment, carrying out the alkali development treatment, illuminated portion (uncured portion) is dissolved in the aqueous alkali and removes, only the residual light part of having solidified forms pattern thus.

As developer solution, use organic base developer solution or inorganic base developer solution or its mixed liquor.

As the alkaline agent that uses in the developer solution; For example can enumerate out NaOH, potassium hydroxide, sodium carbonate, soda mint, sodium silicate, sodium metasilicate, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, TMAH, tetraethyl ammonium hydroxide, choline, pyrroles, piperidines, 1; 8-diazabicylo-organic basic compounds such as [5.4.0]-7-undecylene, preferred to use pure water that these alkali compounds are diluted to concentration is 0.001～10 quality %, be preferably alkaline aqueous solution that 0.01～1 quality % obtains as developer solution.In addition, when using the developer solution that constitutes by such alkaline aqueous solution, generally after development, wash (flushing) with pure water.

As development temperature, be preferably 20 ℃～35 ℃, more preferably 23 ℃～30 ℃.Development time is preferably 30 seconds～and 120 seconds, more preferably 40 seconds～90 seconds.Wherein, about the preferred compositions of development temperature and development time, for example can enumerate out under 25 ℃ of temperature, carry out 50 seconds～100 seconds, under 30 ℃ of temperature, carried out 40 seconds～80 seconds.

In addition, spray press be preferably 0.01MPa～0.5MPa, more preferably 0.05MPa～0.3MPa, further be preferably 0.1MPa～0.3MPa.Through selecting these conditions, can the shape of pattern at random be designed to rectangle or positive taper.

[roasting procedure]

Among the present invention,, the roasting procedure that the above-mentioned dyed layer after developing is toasted is set preferably in order to make the completion of cure of light solidification pigmentation composition.The method of toasting can be carried out through following manner: use heating plate or heating arrangements such as convection oven (heated air circulation type dryer), high frequency heating machine that the substrate with pattern after developing, washing is carried out continous way or step heating.

As the condition of baking, temperature is preferably 150 ℃～260 ℃, more preferably 180 ℃～260 ℃, most preferably is 200 ℃～240 ℃.Stoving time is preferably 10 minutes～and 150 minutes, more preferably 20 minutes～120 minutes, most preferably be 20 minutes～90 minutes.

In addition, when forming the colored pattern of a plurality of tones such as RGB 3 chromatographs, light shield layer, can repeat the circulation of formation, exposure, development and the baking of dyed layer according to required tone number; Also can of all kinds transfer in formation, exposure and the development of capable dyed layer after, last all tones part is toasted together.Thus, make the color filter that possesses the colored pixels that constitutes by required tone.

[other operation]

Among the present invention,, the operation of prebake conditions can be set before exposure process also for drying waits the dyed layer that forms through coating.The prebake conditions temperature of dyed layer is preferably 60 ℃～140 ℃, more preferably 80 ℃～120 ℃.The prebake conditions time is preferably 30 seconds～and 300 seconds, more preferably 80 seconds～200 seconds.

" liquid crystal indicator "

Color filter of the present invention is suitable for the making of liquid crystal indicator, has used the liquid crystal indicator of the color filter of making through pattern formation method of the present invention can show high-grade portrait.

Display device definition or each display device's example described in "Electron ィ su plastic Ritz ィ terrestrial Buses ィ su (Junior

Wood Akio book, (strain) Industrial Research Council 1990 issue) "," terrestrial ィ su plastic Ritz ィ terrestrial Buses ィ su (Ibuki cis chapter book, industrial Charts book (strain), Heisei issue), "and the like.In addition, the liquid crystal display device such as described in the "next generation LCD terrestrial plastic Ritz ィィ su Technology (Editorial Tatsuo Uchida, (strain) will be issued in 1994 Industrial Survey)" in the.The present invention's liquid crystal indicator applicatory is not particularly limited, for example applicable to the liquid crystal indicator of the variety of way of record in above-mentioned " inferior generation liquid crystal ディスプレィ technology ".

Color filter of the present invention is especially effective especially to the liquid crystal indicator of colored TFT mode.The liquid crystal indicator of colored TFT mode for example is recorded in " カラ one TFT liquid crystal ディスプレィ (upright publication (strain) altogether, distribution in 1996) ".Liquid crystal indicator or STN, TN, VA, OCS, FFS and R-OCB etc. that the present invention also enlarges applicable to the angle of visibility of pixel partitioning schemes such as transverse electric field type of drive, MVA such as IPS etc.

In addition, color filter of the present invention also especially preferably supplies in bright and high meticulous COA (Color-filter On Array) mode.For the liquid crystal indicator of COA mode, to color-filter layer require characteristic except above-mentioned common requiring the characteristic, also need to interlayer dielectric require characteristic, be low-k and stripper patience.Color filter of the present invention is except the exposure method that utilizes ultraviolet laser, and the tone or the thickness of the pixel through selecting the present invention's regulation can improve the projectiveness as the ultraviolet laser of exposure light.Thus, can improve colored pixels curable, form do not lack or peel off, the pixel of fold, therefore can improve the stripper patience of the dyed layer that directly or indirectly is located on the TFT substrate especially, be useful for the liquid crystal indicator of COA mode.In order to satisfy the characteristic that requires of low-k, resin coating can also be set on color-filter layer.

And; On the dyed layer that forms through the COA mode; For the driving that makes the ITO electrode that is arranged on the dyed layer and dyed layer below terminal conducting with substrate; Need forming the length of side and be the circular or pixel cross sectional shapes such as oval or コ font that rectangle or diameter about 1～40 μ m be 1～40 μ m φ is the contact hole (guiding path) of rectangle～taper; Preferably the size (i.e. the length on one side) with guiding path is set at below the 5 μ m especially, but the application of the invention also can form the guiding path below the 5 μ m.When the shape in the pixel cross section of contact hole does not have rectangle～taper or opening when insufficient; Can cause the broken string or the poor flow of nesa coating; When such color filter is used to draw a portrait display device; Cause sometimes showing bad, but the coloured composition of the application of the invention, the shape that can suppress contact hole worsens or the generation of the problem that its destruction causes.

About backlight, be recorded in the 25th～30 page (Yagi spark gap is grand bright) etc. in the 18th～24 page (the island health is abundant), monthly magazine ディスプレィ in December, 2005 number in SID meeting Digest 1380 (2005) people such as () A.Konno, monthly magazine ディスプレィ in December, 2005 number.

To be used for liquid crystal indicator through the color filter that pattern formation method of the present invention is made; With the three-wavelength pipe combination of known cold-cathode tube in the past the time, can realize high-contrast; Led light source (RGB-LED) through making red, green, blue can provide the high color reproducibility of brightness height and colour purity good liquid crystal indicator as backlight in addition.

Embodiment

Below, through embodiment the present invention is described more specifically, but the present invention is only otherwise break away from its purport, is not limited to following examples.Wherein, short of special qualification, " part " and " % " is quality criteria.

Have on-the side chain heterocycle macromolecular compound synthetic-

(synthesizing of polymkeric substance 1)

M-6 (following structure) 27.0g, methyl methacrylate 126.0g, methacrylic acid 27.0g and 1-methoxyl-2-propyl alcohol 420.0g are imported in the there-necked flask that nitrogen has been replaced; With stirring machine (new eastern science Co., Ltd.: Three-One Motor) stir, while make nitrogen flow in the flask heat temperature raising to 90 ℃.To wherein adding 2,2-azo two (2, the 4-methyl pentane nitrile) (with the system V-65 of the pure medicine of light Co., Ltd.) 1.80g was 90 ℃ of heated and stirred 2 hours.After 2 hours, add V-651.80g again, heated and stirred obtained 30 quality % solution of polymkeric substance 1 after 3 hours.Utilization is the weight-average molecular weight that the gel permeation chromatography (GPC) of standard substance has been measured resulting polymkeric substance 1 with the polystyrene, and the result is 2.1 ten thousand.In addition, learn that the acid number of per unit solid constituent is 99mgKOH/g through the titration of having used NaOH.

(making of coated pigment 1)

With pigment (C.I. pigment blue 15: 6) the solution 20g of 50g, sodium chloride 500g, above-mentioned polymkeric substance 1 and the diglycol 100g kneader (aboveground making is made) of 1 gallon of stainless steel of packing into, mixing 9 hours.Then, this potpourri is dropped in about 3 liters water,, filter after 1 hour with the homo-mixer stir about, washing is to remove sodium chloride and solvent, drying, preparation coated pigment 1.

(making of coated pigment 2)

The pigment that in preparation, uses (C.I. pigment blue 15: 6) change into the pigment (C.I. pigment Violet 23), likewise prepare coated pigment 2 with coated pigment 1.

-light solidification pigmentation composition layer formation operation-

(preparation of pigment dispensing composition 1)

Pigment dispensing composition 1 is prepared as follows.

Promptly; Composition to following record utilizes homogenizer with rotating speed 3; Mixed in 3 hours 000r.p.m. stir, prepare mixed solution, carry out 8 hours dispersion treatment then through the bead dispersion machine ULTRA APEX MILL (longevity industrial group's system) that has used 0.1mm φ zirconia bead.Wherein, the organic solvent methyl proxitol acetate is designated as PGMEA.

Coated pigment 1 16.5%

Spreading agent: Disperbyk161BYK-CHEMIE corporate system [30% solution] 8%

Alkali soluble resin: benzyl methacrylate/methacrylic acid=75/25 [mass ratio] multipolymer (weight-average molecular weight Mw is 5000 PGMEA solution (solid constituent 50%)) 2%

·PGMEA 73.5％

(preparation of pigment dispensing composition 2)

Composition to following record carries out the operation same with the preparation of pigment dispensing composition 1, preparation pigment dispensing composition 2.

Coated pigment 1 11.55%

Coated pigment 2 4.95%

Spreading agent: Disperbyk161BYK-CHEMIE corporate system [30% solution] 8%

·PGMEA 73.5％

< embodiment 1 >

(preparation of light solidification pigmentation composition)

The composition of the composition 1 shown in following mixed prepare blue light solidification pigmentation composition.

1 9.08 parts of pigment dispensing compositions

2 5.59 parts of pigment dispensing compositions

Surfactant: 5.00 parts of F-554DIC corporate system 0.2%PGMEA solution

0.20 part of silane coupling agent (following structure)

0.68 part of Photoepolymerizationinitiater initiater (following structure)

Polymerizable compound (kind and the amount of the compound of record in the table 1)

Bonding agent: allyl methacrylate/methacrylic acid=80/20mol% multipolymer

Weight-average molecular weight is 30000,18.54 parts of 20%PGMEA solution

8.72 parts of solvent: PGMEA

Silane coupling agent

Polymerization initiator

(formation of light solidification pigmentation composition layer)

Resulting blueness is carried out slot coated with light solidification pigmentation composition on glass substrate.

Specifically, regulate interval and discharge-amount between slit and the glass substrate,, be coated with the coating speed of 120mm/ second so that the bed thickness of the light solidification pigmentation composition layer after the baking of back reaches 3.2 μ m.

-prebake conditions operation, exposure process-

Then, use heating plate under 100 ℃, to carry out 120 seconds heating (prebake conditions processing), utilize the exposure device that has used Nd:YAG laser (Pulseo, third harmonic 355nm, Spectra-Physics corporate system) then, reach about 1.0mJ/cm according to irradiation energy ²Mode regulate the optics system, use photomask (the mask bore is 25 μ m φ) that the light solidification pigmentation composition laminar surface is made public.Multiple-exposure through the light solidification pigmentation composition laminar surface being carried out 20 times carries out pattern exposure.

-developing procedure, the back roasting procedure-

Afterwards; Use developing apparatus (High-Technologies of Hitachi corporate system); Utilizing potassium hydroxide is 1.0% developer solution (solution that 1 part of CDK-1 is obtained with 99 parts of dilutions of pure water, 25 ℃) of developer solution CDK-1 (FUJIFILM Electronic Materials Co., Ltd. system); To spray to press and be set at 0.2MPa, and expose the time that time of glass added 20 seconds with unexposed light solidification pigmentation composition layer dissolving and develop, and wash with pure water.

Then, in 220 ℃ cleaning oven, carry out baking processing after 30 minutes, formation has the substrate of the blue pixel after the thermal treatment.Carry out following evaluation, the result is shown in Table 2.

(evaluation)

[the contact hole survival rate after contact hole opening diameter, the back baking]

Use has the mask of round type pattern (the mask bore is 25 μ m φ) that is used for forming in pixel portions the contact hole (below be sometimes referred to as CH) of 25 μ m φ; Utilize above-mentioned operation to form the blue pixel that color filter is used with exposure GAP=150 μ m, the CH opening diameter after measuring behind the roasting procedure.In addition, calculate the CH survival rate through the CH opening diameter behind CH opening diameter before the baking of back and the above-mentioned back roasting procedure with following formula.

CH survival rate (%)=[CH opening diameter (baking back, back)/CH opening diameter (before the baking of back)] * 100

[development property]

The glass substrate that will have the light solidification pigmentation composition layer that obtains through above-mentioned painting process, prebake conditions operation and exposure process develops under the condition of above-mentioned developing procedure, measures up to unexposed light solidification pigmentation composition layer dissolving and the time (second) till exposing glass.Little person is preferred for numerical value.

[live width sensitivity]

The glass substrate that will have the light solidification pigmentation composition layer that obtains through above-mentioned painting process and prebake conditions operation is the mask of 170 μ m across mask linewidths; Under the condition of above-mentioned exposure process, make public; And under the condition of above-mentioned developing procedure, develop, measure the live width of formed pixel then.Live width is big more, and sensitivity is high more.

[residue]

The glass of pixel peripheral part that will be used for the glass substrate that has the light solidification pigmentation composition layer of above-mentioned live width sensitometry is observed with scanning electron microscope (SEM), by following benchmark evaluation residue.

-metewand-

Zero: no residue produces.

*: there is residue to produce.

< embodiment 2～8, comparative example 1～3 >

Except with the preparation of light solidification pigmentation composition by changing the kind of polymerizable compound shown in the below table 1 and the content, operating equally with embodiment 1, form substrate with blue pixel.In addition, likewise estimate CH opening diameter, CH survival rate, development property, live width sensitivity and residue with embodiment 1.The result is shown in table 2 in the lump.

Table 1

Specific aggregation property compound 1～6 used in the table 1 is described below.Structure is as follows.

In addition, DPHA is the dipentaerythritol acrylate (trade name: DPHA), be equivalent to polymerizable compound of the present invention (III) of Nippon Kayaku K. K's system.In addition, use 2 kinds of polymerizable compounds in embodiment 1～6 and the comparative example 2～3.

Specific aggregation property compound 1:Nagase Chemtex corporate system trade name DA-722

Specific aggregation property compound 2: the system trade name EA-5420 of Xin Zhong village chemical industrial company

Specific aggregation property compound 3: the system trade name EA-5421 of Xin Zhong village chemical industrial company

Specific aggregation property compound 4: the system trade name EA-5323 of Xin Zhong village chemical industrial company

Specific aggregation property compound 5: the system trade name EA-5324 of Xin Zhong village chemical industrial company

Specific aggregation property compound 6: the system trade name EA-5721 of Xin Zhong village chemical industrial company

In addition, the comparative compound 1 that uses in the comparative example 2 is the trade name EA-6320 of the Xin Zhong village chemical industrial company system of following structure for having the polymerizable compound of aromatic rings.In addition, the comparative compound 2 that uses in the comparative example 3 is the polymerizable compounds with the OH base that is not to be obtained by glycidyl, is the trade name Alonix M-305 of Toagosei Co., Ltd's system of following structure.

Specific aggregation property compound 1 specific aggregation property compound 2

Specific aggregation property compound 3

Specific aggregation property compound 4

Specific aggregation property compound 5

Specific aggregation property compound 6

Comparative compound 1 comparative compound 2

Table 2

Result by table 2 can know that the CH opening diameter of the color filter of embodiment (color filter with the colored pixels that obtains through light solidification pigmentation composition of the present invention) is wide, and the CH survival rate is good.Hence one can see that, and the thermal deformation that is caused by the back baking of the colored pattern that forms through light solidification pigmentation composition of the present invention has obtained suitable inhibition, and the destruction of the contact hole that is caused by thermal treatment has obtained inhibition.Can know that in addition the development property of embodiment is good, the live width sensitivity of embodiment and comparative example are equal extent, and the residue of embodiment is good, compare excellent extraordinarily with comparative example.Known that by above light solidification pigmentation composition of the present invention is compared with existing product, excellent aspect the colored pattern formation purposes of color filter, particularly the shaping aspect of contact hole is excellent.

Claims

1. a color filter is used light solidification pigmentation composition; It contains (A) organic solvent, (B) pigment, (C) Photoepolymerizationinitiater initiater, (D) polymerizable compound and (E) bonding agent, said (D) polymerizable compound contain be selected from following (I) and (II) in the compound more than a kind:

(II): 1～12 hydroxyl that have 3～12 (methyl) acryloyl groups, obtains by glycidyl and the polymerizable compound of branched structure.

2. color filter as claimed in claim 1 is used light solidification pigmentation composition; Wherein, the ring structure except that aromatic rings in said (I) is a kind that is selected from hexahydrophthalic acid skeleton, tetrahydrophthalic acid skeleton, hydrogenated bisphenol A skeleton, cyclohexanedimethanol skeleton, isocyanuric acid ring and the tristane dimethanol skeleton.

3. color filter as claimed in claim 1 is used light solidification pigmentation composition; Wherein, the branched structure in said (II) is a kind that is selected from trimethylolpropane skeleton, pentaerythrite skeleton, dipentaerythritol skeleton, D-sorbite skeleton and the glycerol backbone.

4. color filter as claimed in claim 1 is used light solidification pigmentation composition, and wherein, said (D) polymerizable compound further has following (III) compound:

(III): the unsaturated group density of have 3～12 (methyl) acryloyl groups, the number of said (methyl) acryloyl group being represented divided by the molecular weight of this polymerizable compound be 0.0067～0.0114 and with the different polymerizable compound of structure of said (I), (II).

5. color filter as claimed in claim 1 is used light solidification pigmentation composition, and wherein, when using said color filter to use light solidification pigmentation composition to form dried thickness to be the dyed layer of 2 μ m, the transmissivity of this dyed layer under wavelength 355nm is below 2%.

6. color filter as claimed in claim 1 is used light solidification pigmentation composition, and wherein, said (B) pigment is the C.I. pigment blue 15: 6.

7. manufacturing method of color filter, it contains following operation:

On substrate, bestow each described color filter in the claim 1～6 and form operation with the dyed layer that forms the dyed layer that constitutes by this coloured composition with light solidification pigmentation composition;

The exposure process that this dyed layer is made public with pattern-like; With

Dyed layer after the exposure is developed to form the developing procedure of colored pattern.

8. manufacturing method of color filter as claimed in claim 7, wherein, the exposure process that said exposure process is to use the laser of 355nm to make public with pattern-like.

9. manufacturing method of color filter as claimed in claim 7, it is the manufacturing method of color filter of color filter array mode.

10. color filter, it is made through the described manufacturing method of color filter of claim 7.

11. a liquid crystal indicator, it possesses the described color filter of claim 10.