CN101154038B - Curing colouration composition, color filtering device and liquid crystal display using the color filtering device - Google Patents
Curing colouration composition, color filtering device and liquid crystal display using the color filtering device Download PDFInfo
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- CN101154038B CN101154038B CN2007101483945A CN200710148394A CN101154038B CN 101154038 B CN101154038 B CN 101154038B CN 2007101483945 A CN2007101483945 A CN 2007101483945A CN 200710148394 A CN200710148394 A CN 200710148394A CN 101154038 B CN101154038 B CN 101154038B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
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- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Optical Filters (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Liquid Crystal (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention provides a curing color composition, comprising: colouring agent, dispersion resin, polymerization initiator, polymerized compound and solvent, which is characterized in that the solvent comprises: (A) solvent whose boiling point is 180-280 DEG C under the atmospheric pressure and (B) solvent whose boiling point is 130-170 DEG C under the atmospheric pressure and the solubility parameter is 8.5-10.5. The dispersion resin contains the high molecule compound represented by the general formula (1).
Description
Technical field
The present invention relates to be applicable to through slot coated mode and ink-jetting style prepare color filter curing colouration composition, use the color filter of this curing colouration composition preparation and use the liquid crystal indicator of this color filter preparation.
Background technology
In recent years, be accompanied by the large-scale pictureization of TV etc., pixel unit also becomes greatly since on the viewpoint of production efficiency than photolithography excellence etc., therefore expectation will prepare color filter as new dyed layer forming method through ink-jet method, develop several different methods.
In addition, in the color filter of TV purposes, require the high color filters of color characteristics such as contrast, also need use finer material as organic pigment of colorant etc.
As said method, developed that to comprise boiling point be that the ink-jet color filter of solvent, adhesive resin and colorant more than 250 ℃ (is opened 2000-310706 number referring to for example spy with resin combination.)。
Yet because the boiling point of solvent for use is too high, though therefore can guarantee the flatness in the dry run, because the molecular weight of adhesive resin is higher, so viscosity uprises, and can't obtain the stable discharge performance of resin combination.
In addition, disclose comprise in 60 weight % above glycerine, diethylene glycol and the monoethylene glycol more than a kind and boiling point be that the water class ink for color filter of 150～250 ℃ solvent (is opened 2001-350012 number referring to for example spy.)。
Yet, be 150 ℃～250 ℃ as the boiling point of solvent, but actual illustrative material is PGMEA (146 ℃ of boiling points), EEP (170 ℃ of boiling points); In addition as wetting agent; Use hydrophilic glycerine etc., consider that for shortages such as drying loads the flatness of dyed layer is deterioration also.
In addition; Disclosing and having used the Thermocurable ink composite with the color filter that comprises bonding agent and the monomer that contains epoxy radicals is the 1st mode; In addition, having stipulated wellability, and solvent species specific combined thing is that the method for the 2nd mode (is opened the 2002-371216 communique referring to for example spy.)。
Yet, owing to being comprises in order to ensure the wellability to substrate to have ehter bond, the solvent of OH base etc., contain the ink composite of the solvent of diethylene glycol class ehter bond, therefore as reliability, the for example dispersing of pigments stability degradation of color filter.
In addition, disclose and comprise the pigment that contains R, G and B, the active energy ray-curable printing ink of simple function and polyfunctional monomer is ink for color filter cover box (inkset) (referring to for example patent documentation 4).
Yet not enough as the dispersing of pigments property of colorant, the performance the when color filter that uses above-mentioned printing ink cover box to obtain is used for panel (for example contrast etc.) deterioration, in addition exists inkjet nozzle to be easy to generate and stops up such problem.
Even expectation is being used under the situation of molecule as this colorant like this, do not stop up in the nozzle tip of ink-jet, and when drop sticked on the substrate, the levelability of printing ink coating fluid was good, can form the method for the excellent color filter of flatness with pixel.
Summary of the invention
Considered the objective of the invention is of above-mentioned existing issue point: even provide a kind of under the situation that contains the high concentration colorant; The dispersiveness of colorant is also excellent; Be suitable for slot coated; Inkjet nozzle can not stop up, and the levelability of printing ink and coating fluid is good, can form the curing colouration composition of the excellent colored pixels portion of flatness.
Other purposes of the present invention provide a kind of color filter and the liquid crystal indicator that uses it that passes through the high-contrast of slot coated mode or ink-jetting style formation.
< 1>a kind of curing colouration composition; It is the curing colouration composition that contains colorant, dispersion resin, polymerization initiator, polymerizable compound and solvent; It is characterized in that, this solvent comprises boiling point under (A) normal pressure be 180 ℃～280 ℃ solvent with (B) solubility parameter be 8.5～10.5 and normal pressure under boiling point be 130～170 ℃ solvent; This dispersion resin contain be selected from by the macromolecular compound of formula (1) expression, comprise to come free formula (I) expression monomer copolymerization units polymkeric substance and contain by among the polymkeric substance of the structural unit of formula (a) expression more than a kind.
General formula (1)
In general formula (1), R
1Organic connection base of expression (m+n) valency, R
2Organic connection base of expression singly-bound or divalent.A
1Expression contains 1 valency organic group of organic pigment structure or heterocycle or contains the 1 valency organic group that the group, urea groups, urethane groups, the group with coordination property oxygen atom, the carbon number that are selected from acidic-group, have basic nitrogen atom are the group among alkyl, alkoxysilyl, epoxy radicals, NCO and the hydroxyl more than 4.N A
1Can be identical, also can be different.M representes 1～8, and n representes 2～9, and m+n satisfies 3～10.P
1The expression macromolecular scaffold.
General formula (I)
In general formula (I), R
01The expression hydrogen atom, or replace or unsubstituted alkyl.R
02The expression alkylidene.W representes-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.X representes to be selected from-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-,-among the NHCO-any.Y representes to be selected from NR
03, among the O, S any; R
03Expression hydrogen atom, alkyl or aryl.In the formula, N and the Y formation ring texture that is connected to each other.M, n are 0 or 1 independently of one another.
General formula (a)
In general formula (a), R
1aExpression hydrogen or methyl, R
2aThe expression alkylidene, Z
1Expression nitrogen heterocyclic ring structure.
< 2>curing colouration composition described in < 1 >; It is characterized in that; With respect to the all-mass of solvent contained in the above-mentioned curing colouration composition, containing being selected from of 5 quality %～80 quality % among the compound of (ii) (iii) being represented with general formula by formula (i), general formula more than a kind is 180 ℃～280 ℃ solvent as boiling point under above-mentioned (A) normal pressure.
R
1-O-(C
2H
4O)
n-R
2General formula (i)
R
1-O-(C
3H
6O)
n-R
2General formula (ii)
R
1-O-(C
4H
8O)
n-R
2General formula (iii)
Above-mentioned general formula (i), general formula (ii) with general formula (iii) in, R
1, R
2Represent that independently of one another hydrogen atom, carbon number are 1～8 straight or branched alkyl, aralkyl, carbonyl.R
1, R
2Do not represent hydrogen atom simultaneously.N representes 1～4 integer.
< 3>curing colouration composition described in < 1>or < 2 >; It is characterized in that, be selected from contain be selected from (methyl) acrylic acid, maleic acid, maleic anhydride, the crotonic acid more than a kind and the alkali soluble resins more than a kind that is selected among the multipolymer more than a kind in (methyl) butyl acrylate, (methyl) phenyl acrylate, (methyl) benzyl acrylate, the styrene be 5 quality %～50 quality % with respect to the all-mass of the resinous principle that comprises above-mentioned dispersion resin.
< 4>like each described curing colouration composition of < 1 >～< 3 >; It is characterized in that; Contained polymerization initiator is a Photoepolymerizationinitiater initiater in the above-mentioned curing colouration composition; The quality of all solids composition of this curing colouration composition is 10 quality %～16 quality % with respect to the total amount of this curing colouration composition, and is suitable for through the slot coated mode.
< 5>like each described curing colouration composition of < 1 >～< 3 >; It is characterized in that; Contained polymerization initiator is a thermal polymerization in the above-mentioned curing colouration composition; The quality of all solids composition of this curing colouration composition is 25 quality %～60 quality % with respect to the total amount of this curing colouration composition, and is suitable for through ink-jetting style.
Like each described curing colouration composition of < 1 >～< 3 >, it is characterized in that < 6>contained solvent (A) comprises the solvent that is selected among following (1)～(15) in the above-mentioned curing colouration composition.
(1) diethylene glycol diethyl ether (188 ℃ of boiling points)
(2) diethylene glycol monoethyl ether acetic acid esters (217 ℃ of boiling points)
(3) diethylene glycol monobutyl ether (231 ℃ of boiling points)
(4) butyl carbitol acetate (247 ℃ of boiling points)
(5) propylene glycol n-propyl ether acetic acid esters (187 ℃ of boiling points)
(6) propylene-glycol diacetate (190 ℃ of boiling points)
(7) propylene glycol n-butyl ether acetic acid esters (211 ℃ of boiling points)
(8) propylene glycol phenyl ether (243 ℃ of boiling points)
(9) propylene glycol phenyl ether acetic acid ester (258 ℃ of boiling points)
(10) dipropylene glycol monomethyl ether acetic acid esters (209 ℃ of boiling points)
(11) DPG n-propyl ether acetic acid esters (232 ℃ of boiling points)
(12) DPG n-butyl ether acetic acid esters (250 ℃ of boiling points)
(13) tripropylene glycol list n-butyl ether (274 ℃ of boiling points)
(1 4) tripropylene glycol methyl ether acetate (263 ℃ of boiling points)
(15) 1,3 butylene glycol diacetate esters (232 ℃ of boiling points)
Like each described curing colouration composition of < 1 >～< 3 >, it is characterized in that < 7>under the situation of slot coated mode, the content of contained solvent (A) is 5～30 quality % in the above-mentioned curing colouration composition.
Like each described curing colouration composition of < 1 >～< 3 >, it is characterized in that < 8>under the situation of ink-jetting style, the content of contained solvent (A) is 20～80 quality % in the above-mentioned curing colouration composition.
Like each described curing colouration composition of < 1 >～< 3 >, it is characterized in that < 9>contained solvent (B) comprises the solvent that is selected among following (1)～(12) in the above-mentioned curing type coloured composition.
(1) ethyl lactate (154 ℃ of SP value 10.0, boiling points)
(2) 3-methoxy propyl acetoacetic ester (158 ℃ of SP value 10.1, boiling points)
(3) 3-ethoxyl ethyl propionate (169 ℃ of SP value 8.8, boiling points)
(4) 3-ethoxy-propionic acid methyl esters (165 ℃ of SP value 9.3, boiling points)
(5) 3-methoxypropionic acid methyl esters (145 ℃ of SP value 9.5, boiling points)
(6) 2-ethoxy-propionic acid methyl esters (162 ℃ of SP value 9.2, boiling points)
(7) acetate ethyl cellosolve (156 ℃ of SP value 9.4, boiling points)
(8) isoamyl propionate (160 ℃ of SP value 8.5, boiling points)
(9) 2-heptanone (152 ℃ of SP value 8.8, boiling points)
(10) cyclohexanone (156 ℃ of SP value 9.9, boiling points)
(1 1) propylene glycol methyl ether acetate (146 ℃ of SP value 9.2, boiling points)
(1 2) propylene-glycol ethyl ether acetic acid esters (156 ℃ of SP value 9.1, boiling points)
Like each described curing colouration composition of < 1 >～< 3 >, it is characterized in that < 10>under the situation of slot coated mode, the content of contained solvent (B) is 5～30 quality % in the above-mentioned curing colouration composition.
Like each described curing colouration composition of < 1 >～< 3 >, it is characterized in that < 11>under the situation of ink-jetting style, the content of contained solvent (B) is 20～80 quality % in the above-mentioned curing colouration composition.
< 12>like each described curing colouration composition of < 1 >～< 3 >; It is characterized in that; Combination as solvent contained in the above-mentioned curing colouration composition (A) and solvent (B); Be solvent (A) for being selected from least a kind among propylene glycol n-butyl ether acetic acid esters, dipropylene glycol monomethyl ether acetic acid esters, the 1,3 butylene glycol diacetate esters, solvent (B) is the combination of ethyl lactate, propylene glycol methyl ether acetate.
< 13>a kind of color filter, it contains the dyed layer that use obtains like each described curing colouration composition preparation of < 1 >～< 12 >.
< 14>a kind of liquid crystal indicator, it has the color filter described in < 13 >.
Effect of the present invention is still indeterminate, infers as follows.
Can think, curing type coloured composition of the present invention through and with boiling point in the scope of stipulating and above-mentioned (A) solvent and above-mentioned (B) solvent with specific rerum natura, thereby make the dispersion resin among the present invention can fully be dissolved in the curing colouration composition of the present invention; In curing colouration composition, the strand lengthening is to the adsorbability enhancing of granules of pigments; And be adsorbed on the strand of the dispersion resin on the granules of pigments through growth; Can improve protecting colloid property, dispersing of pigments has good stability, so keeping quality is excellent; And the levelability of coating fluid is good, can form the excellent colored pixels portion of flatness.
According to the present invention, even can provide a kind of under the situation that contains the high concentration colorant, the dispersiveness of colorant is also excellent; Be suitable for slot coated; Inkjet nozzle can not stop up, and the levelability of printing ink and coating fluid is good, can form the curing colouration composition of the excellent colored pixels portion of flatness.
In addition, according to the present invention, the color filter and the liquid crystal indicator that uses it of the high-contrast that forms through slot coated mode or ink-jetting style can be provided.
Embodiment
Below, to curing colouration composition of the present invention, use the color filter of this curing colouration composition preparation and the liquid crystal indicator that uses this color filter preparation to carry out detailed explanation.
[curing colouration composition]
Curing colouration composition of the present invention is the curing colouration composition that contains colorant, dispersion resin, polymerization initiator, polymerizable compound and solvent; It is characterized in that; It is 180 ℃～280 ℃ solvent that this solvent comprises (A) boiling point under normal pressure and (B) solubility parameter is 8.5～10.5, and the boiling point under the normal pressure is 130～170 ℃ a solvent; This dispersion resin contain be selected from by the macromolecular compound of formula (1) expression, comprise to come free formula (I) expression monomer copolymerization units polymkeric substance and contain by among the polymkeric substance of the structural unit of formula (a) expression more than a kind.
General formula (1)
In general formula (1), R
1Organic connection base of expression (m+n) valency, R
2Organic connection base of expression singly-bound or divalent.A
1Expression contains 1 valency organic group of organic pigment structure or heterocycle or contains the 1 valency organic group that the group, urea groups, urethane groups, the group with coordination property oxygen atom, the carbon number that are selected from acidic-group, have basic nitrogen atom are the group among alkyl, alkoxysilyl, epoxy radicals, NCO and the hydroxyl more than 4.N A
1Can be identical, also can be different.M representes 1～8, and n representes 2～9, and m+n satisfies 3～10.P
1The expression macromolecular scaffold.
General formula (I)
In general formula (I), R
01The expression hydrogen atom, or replace or unsubstituted alkyl.R
02The expression alkylidene.W representes-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.X representes to be selected from-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-,-among the NHCO-any.Y representes to be selected from NR
03, among the O, S any, R
03Expression hydrogen atom, alkyl or aryl.In the formula, N and the Y formation ring texture that is connected to each other.M, n are 0 or 1 independently of one another.
General formula (a)
In general formula (a), R
1aExpression hydrogen or methyl, R
2aThe expression alkylidene, Z
1Expression nitrogen heterocyclic ring structure.
Below, solvent, dispersion resin, colorant, polymerizable compound and polymerization initiator as the necessary composition of curing colouration composition of the present invention are described.
< solvent >
It is 180 ℃～280 ℃ solvent that solvent contained in the curing colouration composition of the present invention comprises (A) boiling point under normal pressure and (B) solubility parameter is 8.5～10.5, and the boiling point under the normal pressure is 130～170 ℃ a solvent.
Below, solvent is described respectively.
((A) boiling point under normal pressure is 180 ℃～280 ℃ a solvent)
It is 180 ℃～280 ℃ solvent (below, suitably be called " high boiling solvent ") that curing colouration composition of the present invention contains (A) boiling point under normal pressure.
The boiling point of higher-boiling compound among the present invention under normal pressure is necessary for 180 ℃～280 ℃, is preferably 190 ℃～270 ℃, most preferably is 210 ℃～250 ℃.Through containing above-mentioned high boiling solvent, the drying of the slit in the time of preventing slot coated embodies levelability after coating, and what can prevent to be coated with is inhomogeneous, coating striped etc.In addition, in ink-jetting style, can prevent the drying of nozzle, the liquid planarization after droplet (shot droplet) is played in promotion.
As boiling point under the normal pressure is 180 ℃～280 ℃ solvent, can enumerate ester class, ethers, ketone equal solvent, from the viewpoint of dispersion stabilization, is preferably the strong polar group that does not have carboxylic acid residues such.
In addition; In these solvents; As the high boiling solvent among the present invention; Preferably with respect to the all-mass of solvent contained in the above-mentioned curing colouration composition, contain 5 quality %～80 quality % be selected among the compound of (ii) (iii) representing with general formula by formula (i), general formula more than a kind.
R
1-O-(C
2H
4O)
n-R
2General formula (i)
R
1-O-(C
3H
6O)
n-R
2General formula (ii)
R
1-O-(C
4H
8O)
n-R
2General formula (iii)
Above-mentioned general formula (i), general formula (ii) with general formula (iii) in, R
1, R
2Represent that independently of one another hydrogen atom, carbon number are 1～8 straight or branched alkyl, aralkyl, carbonyl.R
1, R
2Do not represent hydrogen atom simultaneously.N representes 1～4 integer.
Above-mentioned general formula (i)～general formula (iii) in, at R
1, R
2The expression carbon number is under the situation of 1～8 straight or branched alkyl; Can enumerate out saturated, unsaturated amyl group, hexyl, heptyl, octyl group, pentenyl, hexenyl, octenyl of for example methyl, ethyl, n-pro-pyl, isopropyl, propenyl, normal-butyl, sec-butyl, the tert-butyl group, other straight chains, side chain etc., preferable methyl, ethyl, isopropyl, normal-butyl etc.
Above-mentioned general formula (i)～general formula (iii) in, at R
1, R
2Under the situation of expression aralkyl, for example can enumerate out benzyl, adjacent methyl-benzyl, a methyl-benzyl, to methyl-benzyl, phenethyl etc., be preferably phenyl, benzyl.
Above-mentioned general formula (i)～general formula (iii) in, at R
1, R
2Under the situation of expression aryl, can enumerate out phenyl, o-tolyl, a tolyl, p-methylphenyl.
Above-mentioned general formula (i)～general formula (iii) in, at R
1, R
2Under the situation of expression carbonyl, can enumerate out acetyl group, propiono, propyl group carbonyl etc.
In these groups, at R
1, R
2All not being under the situation of hydrogen atom, as preferred combination, can enumerating out methyl, ethyl, propyl group or phenyl and acetyl group, perhaps all is combinations of acetyl group.In addition, at R
1, R
2Any be under the situation of hydrogen atom, as another the represented substituting group that is not hydrogen atom, can enumerate out methyl, ethyl, propyl group, phenyl or acetyl group.
The object lesson of high boiling solvent is represented in following (1)～(15) among the present invention.
(1) diethylene glycol diethyl ether (188 ℃ of boiling points)
(2) diethylene glycol monoethyl ether acetic acid esters (217 ℃ of boiling points)
(3) diethylene glycol monobutyl ether (231 ℃ of boiling points)
(4) butyl carbitol acetate (247 ℃ of boiling points)
(5) propylene glycol n-propyl ether acetic acid esters (187 ℃ of boiling points)
(6) propylene-glycol diacetate (190 ℃ of boiling points)
(7) propylene glycol n-butyl ether acetic acid esters (211 ℃ of boiling points)
(8) propylene glycol phenyl ether (243 ℃ of boiling points)
(9) propylene glycol phenyl ether acetic acid ester (258 ℃ of boiling points)
(10) dipropylene glycol monomethyl ether acetic acid esters (209 ℃ of boiling points)
(11) DPG n-propyl ether acetic acid esters (232 ℃ of boiling points)
(12) DPG n-butyl ether acetic acid esters (250 ℃ of boiling points)
(13) tripropylene glycol list n-butyl ether (274 ℃ of boiling points)
(14) tripropylene glycol methyl ether acetate (263 ℃ of boiling points)
(15) 1,3 butylene glycol diacetate esters (232 ℃ of boiling points)
In above-mentioned (1)～(15), be preferably above-mentioned (6), (7), (10), (11), (12) and (15) especially.
The content of high boiling solvent is under the situation of slot coated among the present invention; Gross mass with respect to solvent in the curing colouration composition of the present invention; Preferably contain 5 quality %～80 quality %, more preferably contain 5 quality %～60 quality %, especially preferably contain 5 quality %～30 quality %.In addition, under the situation that is ink-jetting style, preferably contain 5 quality %～80 quality %, especially preferably contain 20 quality %～80 quality %.If the content of high boiling solvent is more than the 5 quality %, then can bring into play the effect that suppresses obstructions such as nozzle.If the content of high boiling solvent is below the 80 quality %, the drying property of filming that then on substrate, forms is good, can shorten the quiescent interval in the painting process.
High boiling solvent among the present invention can use separately, also can combination more than 2 kinds be used.
((B) solubility parameter be 8.5～10.5 and normal pressure under boiling point be 130～170 ℃ solvent)
It is 8.5～10.5 that curing colouration composition of the present invention contains (B) solubility parameter, and the boiling point under the normal pressure is 130～170 ℃ a solvent (below, suitably be called " dispersion resin dissolving use solvent ").
So-called solubility parameter is the solubility parameter calculated through the Fedors method (below, suitably be called " SP value "), and the SP value that the dispersion resin among the present invention dissolves with solvent is preferably 8.5～10.5, further is preferably 9.0～10.0.
In addition, the SP value among the present invention is represented through following formula.
SP value (δ)=(Δ H/V) 1/2
Wherein, in formula, Δ H representes mole vaporization heat (cal), and V representes molar volume (cm
3).In addition; Δ H and V can use the total (Δ H) and molar volume (the Δ total amount (V) vi) of the mole vaporization heat (Δ ei) of the atomic group described in " POLYMER ENGINEERING AND SCIENCE, 1974, Vol.14; No.2, ROBERT F.FEDORS. (151～153 pages) ".
In addition, dispersion resin dissolves with solvent except the SP value has above-mentioned scope among the present invention, and the boiling point under normal pressure is necessary for 130 ℃～170 ℃.As the boiling point under normal pressure, more preferably 140 ℃～160 ℃.Dispersion resin dissolving be worth with the SP of solvent with the normal pressure situation of boiling point in these scopes down under, can suppress the shower nozzle obstruction, dispersion stabilization is good, keeping quality is excellence also.
Solvent is used in dissolving as the dispersion resin among the present invention, can enumerate the solvent of ester output class, ketone, ethers, and an end that most preferably is glycolss such as monoethylene glycol, propylene glycol is an ehter bond, and the other end is the compound of the structure of ester bond.
Dispersion resin dissolves the object lesson with solvent among expression the present invention in following (1)～(12).
(1) ethyl lactate (154 ℃ of SP value 10.0, boiling points)
(2) 3-methoxy propyl acetoacetic ester (158 ℃ of SP value 10.1, boiling points)
(3) 3-ethoxyl ethyl propionate (169 ℃ of SP value 8.8, boiling points)
(4) 3-ethoxy-propionic acid methyl esters (165 ℃ of SP value 9.3, boiling points)
(5) 3-methoxypropionic acid methyl esters (145 ℃ of SP value 9.5, boiling points)
(6) 2-ethoxy-propionic acid methyl esters (162 ℃ of SP value 9.2, boiling points)
(7) acetate ethyl cellosolve (156 ℃ of SP value 9.4, boiling points)
(8) isoamyl propionate (160 ℃ of SP value 8.5, boiling points)
(9) 2-heptanone (152 ℃ of SP value 8.8, boiling points)
(10) cyclohexanone (156 ℃ of SP value 9.9, boiling points)
(11) propylene glycol methyl ether acetate (146 ℃ of SP value 9.2, boiling points)
(12) propylene-glycol ethyl ether acetic acid esters (156 ℃ of SP value 9.1, boiling points)
In above-mentioned (1)～(12), more preferably above-mentioned (1), (2), (3), (7), (10), (11) and (12) are preferably above-mentioned (1), (2), (3), (10), (11) and (12) especially.
As (A) high boiling solvent among the present invention and the preferred compositions of (B) dispersion resin dissolving with solvent; Be: (A) high boiling solvent is propylene-glycol diacetate, propylene glycol n-butyl ether acetic acid esters, dipropylene glycol monomethyl ether acetic acid esters, DPG n-propyl ether acetic acid esters, DPG n-butyl ether acetic acid esters, 1,3 butylene glycol diacetate esters; (B) the dispersion resin dissolving uses solvent to be ethyl lactate, 3-methoxy propyl acetoacetic ester, 3-ethoxyl ethyl propionate, acetate ethyl cellosolve, propylene glycol methyl ether acetate.
As especially preferably combination; Be: (A) high boiling solvent is for being selected from propylene glycol n-butyl ether acetic acid esters, dipropylene glycol monomethyl ether acetic acid esters, 1; Among the 3-butylene glycol diacetate esters at least a kind, (B) combination of solvent as ethyl lactate, propylene glycol methyl ether acetate used in the dispersion resin dissolving.
Under the situation of slot coated; Dispersion resin dissolving is with the content of the solvent gross mass with respect to solvent in the curing colouration composition of the present invention among the present invention; Preferably contain 5 quality %～80 quality %; More preferably contain 5 quality %～60 quality %, especially preferably contain 5 quality %～30 quality %.In addition, under the situation that is ink-jetting style, preferably contain 5 quality %～80 quality %, especially preferably contain 20 quality %～80 quality %.If the content of high boiling solvent is more than the 5 quality %, then can bring into play the effect that suppresses obstructions such as nozzle.If the content of high boiling solvent is below the 80 quality %, the drying property of filming that then on substrate, forms is good, can shorten the quiescent interval in the painting process.
High boiling solvent among the present invention can use separately, also can combination more than 2 kinds be used.
(A) high boiling solvent and the dissolving of (B) dispersion resin have preferred range respectively with the content of the solid constituent of the mass ratio of solvent and curing colouration composition of the present invention among the present invention in slot coated mode and ink-jetting style.
Under the situation of slot coated, if (A) high boiling solvent with (B) dispersion resin dissolving to use the mass ratio of solvent be (A)/(B)=more than 5/100, then can suppress gap nozzle drying, be coated with striped, production of foreign matters.If (A) high boiling solvent with (B) dispersion resin dissolving to use the mass ratio of solvent be (A)/(B)=below 40/100; Then the drying of coated substrates can be accomplished at short notice; During substrate after conveyance coating; Substrate can be crooked, suppress since coating fluid flow cause in uneven thickness, the levelability of assurance thickness.In addition, the content of contained solid constituent is preferably 10 quality %～16 quality % with respect to the quality of curing colouration composition of the present invention in the curing colouration composition of the present invention, more preferably 12 quality %～16 quality %.If the content of above-mentioned solid constituent more than 10 quality %, then can prevent to hang from the liquid of the curing colouration composition of slit mouth, and can reduce dry load.If the content of above-mentioned solid constituent is below the 16 quality %, then can suppress the viscosity of curing colouration composition of the present invention, improve coating speed, can improve the quiescent interval.In addition, form in mode under the situation of dyed layer,, be fit to use Photoepolymerizationinitiater initiater as polymerization initiator contained in the curing colouration composition of the present invention through slot coated.It is detailed in the back.
Under the situation of ink-jetting style, if (A) high boiling solvent with (B) dispersion resin dissolving to use the mass ratio of solvent be that (A)/(B)=more than 50/100, the levelability of then beating after dripping is good, can suppress the film thickness difference in the pixel, can prevent the nozzle drying, spray nozzle clogging.If (A) high boiling solvent with (B) dispersion resin dissolving to use the mass ratio of solvent be that (A)/(B)=below 300/100, then the favorable solubility of dispersion resin, spreading agent etc. can keep dispersiveness.In addition, the content of contained solid constituent is preferably 25 quality %～60 quality % with respect to the quality of curing colouration composition of the present invention in the curing colouration composition of the present invention, more preferably 30 quality %～50 quality %.If the content of above-mentioned solid constituent is more than the 25 quality %, then can prevent owing to curing colouration composition dividing plate of (BM) at the bottom of the fast black base overflows the colour mixture that produces.If the content of above-mentioned solid constituent is that then pigment can fully disperse below the 60 quality %, can suppress the obstruction in inkjet nozzle or the ink-jet conduit.In addition, forming through ink-jetting style under the situation of dyed layer,, be fit to use thermal polymerization as polymerization initiator contained in the curing colouration composition of the present invention.It is detailed in the back.
Curing colouration composition of the present invention as required, can also and be used except above-mentioned (A) to have the high boiling solvent of ad hoc structure and the dissolving of (B) dispersion resin with the solvent the solvent in the scope of not damaging effect of the present invention.
As such high boiling solvent, can enumerate out diethylene glycol monoethyl ether, 3,5,5-trimethyl-2-cyclohexene-1-ketone, butyl lactate, acetate 2-Octyl Nitrite, acetate 3-methoxyl-3-methyl butyl ester, gamma-butyrolacton.
In addition; As in, low boiling point solvent; Can enumerate out ethers, for example 3-oxo alkyl propionates classes 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, oxo methyl acetate, oxo ethyl acetate, oxo butyl acetate, methoxy menthyl acetate, methoxyacetic acid ethyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3-oxo methyl propionate, 3-oxo ethyl propionate; 2-oxo methyl propionate; Ethyl 2-oxopropanoate; 2-oxo propyl propionate; 2-methoxypropionic acid methyl esters; 2-methoxy propyl acetoacetic ester; 2-methoxy propyl propyl propionate; The 2-ethoxyl ethyl propionate; 2-oxo-2 Methylpropionic acid methyl esters; 2-oxo-2 Methylpropionic acid ethyl ester; 2-methoxyl-2 Methylpropionic acid methyl esters; 2-ethoxy-2 Methylpropionic acid ethyl ester; Methyl pyruvate; Ethyl pyruvate; Propyl pyruvate; Methyl acetoacetate; Ethyl acetoacetate; 2-ketobutyric acid methyl esters; 2-ketobutyric acid ethyl ester etc.; Ethers, for example diethylene glycol dimethyl ether, tetrahydrofuran, glycol monoethyl ether, ethylene glycol monoethyl ether, methylcellosolve acetate, acetate ethyl cellosolve, diethylene glycol monomethyl ether, propylene glycol methyl ether acetate etc.; Ketone, for example MEK, cyclohexanone, 2-heptanone, propione etc.; Aromatic hydrocarbon based, for example toluene, xylene etc.
< dispersion resin >
For curing colouration composition of the present invention; From the viewpoint of dispersion stabilization and storage stability, this dispersion resin contain be selected from by the macromolecular compound of formula (1) expression, comprise to come free formula (I) expression monomer copolymerization units polymkeric substance and contain by among the polymkeric substance of the structural unit of formula (a) expression more than a kind.
General formula (1)
In general formula (1), R
1Organic connection base of expression (m+n) valency, R
2Organic connection base of expression singly-bound or divalent.A
1Expression contains 1 valency organic group of organic pigment structure or heterocycle or contains the 1 valency organic group that the group, urea groups, urethane groups, the group with coordination property oxygen atom, the carbon number that are selected from acidic-group, have basic nitrogen atom are the group among alkyl, alkoxysilyl, epoxy radicals, NCO and the hydroxyl more than 4.N A
1Can be identical, also can be different.M representes 1～8, and n representes 2～9, and m+n satisfies 3～10.P
1The expression macromolecular scaffold.
General formula (I)
In the formula, R
01The expression hydrogen atom, or replace or unsubstituted alkyl.R
02The expression alkylidene.W representes-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.X representes to be selected from-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-,-among the NHCO-any.Y representes to be selected from NR
03, among the O, S any, R
03Expression hydrogen atom, alkyl or aryl.In the formula, N and the Y formation ring texture that is connected to each other.M, n are 0 or 1 independently of one another.
General formula (a)
In general formula (a), R
1aExpression hydrogen or methyl, R
2aThe expression alkylidene, Z
1Expression nitrogen heterocyclic ring structure.
Below, (B-1) that be fit to as dispersion resin among the present invention contained to come polymkeric substance and the polymkeric substance that (B-3) contains of copolymerization units of the monomer of free general formula (I) expression describe by the structural unit of general formula (a) expression by macromolecular compound, (B-2) of general formula (1) expression.
[macromolecular compound of (B-1) representing: (B-1) specific dispersion resin] by general formula (1)
At first, following macromolecular compound by general formula (1) expression (below, suitably be called " (B-1) specific dispersion resin ") is described.
General formula (1)
In above-mentioned general formula (1), A
1Expression contains 1 valency organic group of organic pigment structure or heterocycle or contains the 1 valency organic group that the group, urea groups, urethane groups, the group with coordination property oxygen atom, the carbon number that are selected from acidic-group, have basic nitrogen atom are the group among alkyl, alkoxysilyl, epoxy radicals, NCO and the hydroxyl more than 4.N A
1Can be identical, also can be different.
Though there is not special qualification; But more particularly; As above-mentioned " organic group that contains 1 valency of organic pigment structure "; Can enumerate out for example have phthalocyanines, the organic group of 1 valency of the pigment structure of insoluble azo class, azo lake class, anthraquinone class, quinacridine ketone, dioxazines, diketopyrrolo-pyrrole class, anthracene pyridines, anthanthrone class, indanthrone class, flavanthrones, purple perilla ketone, perylene class, thioindigo class etc. is as preferred example; The organic group that more preferably has 1 valency of phthalocyanines, azo lake class, anthraquinone class 、 dioxazines, diketopyrrolo-pyrrole class pigment structure etc., be preferably especially have phthalocyanines, the organic group of 1 valency of anthraquinone class, diketopyrrolo-pyrrole class pigment structure etc.
In addition; As above-mentioned " organic group that contains 1 valency of heterocycle "; Can enumerate out for example have thiophene, the organic group of 1 valency of furans, xanthene, pyrroles, pyrrolin, pyrrolidine, dioxolanes, pyrazoles, pyrazoline, pyrazolidine, imidazoles 、 oxazole, thiazole 、 oxadiazole, triazole, thiadiazoles, pyrans, pyridine, piperidines, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, Benzimidazolinone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoins, indoles, quinoline, carbazole, acridine, acridone, anthraquinone etc. is as preferred example, more preferably has the organic group of 1 valency of pyrrolin, pyrrolidine, pyrazoles, pyrazoline, pyrazolidine, imidazoles, triazole, pyridine, piperidines, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindoline, isoindolinone, Benzimidazolinone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoins, carbazole, acridine, acridone, anthraquinone etc.
In addition, above-mentioned organic pigment structure or heterocycle also can have substituting group, as this substituting group, can enumerate out carbon number such as methyl, ethyl for example and be 1～20 alkyl; Carbon number such as phenyl, naphthyl is 6～16 aryl; Hydroxyl; Amino; Carboxyl; Sulfoamido, N-sulfoamido; Carbon numbers such as acetoxyl group are 1～6 acyloxy; Carbon number such as methoxyl, ethoxy is 1～20 alkoxy; Halogen atom such as chlorine, bromine; Carbon numbers such as methoxycarbonyl, ethoxy carbonyl, cyclohexyloxy carbonyl are 2～7 alkoxy carbonyl; Cyanic acid; Carbonate groups such as tert-butyl group carbonic ester etc.Wherein, these substituting groups can also maybe make up linking group and organic pigment structure or the heterocycle bonding that constitutes with this structural unit through the following structures unit.
-O-?-S-
As above-mentioned " organic group that contains 1 valency of acidic-group "; Can enumerate out for example have the carboxylic acid group, the organic group of 1 valency of sulfonic group, sulfate mono ester group, phosphate, phosplate base, boronate etc. is as preferred example; The organic group that more preferably has 1 valency of carboxylic acid group, sulfonic group, sulfate mono ester group, phosphate, phosplate base etc. is preferably the organic group of 1 valency with carboxylic acid group, sulfonic group, phosphate etc. especially.
In addition, as above-mentioned " organic group that contains 1 valency of group ", can enumerate out and for example have amino (NH with basic nitrogen atom
2) 1 valency organic group, have substituted imido (NHR
8,-NR
9R
10) organic group (wherein, the R of 1 valency
8, R
9, R
10Be that carbon number is that 1～20 alkyl, carbon number are that aryl, carbon number more than 6 is the aralkyl more than 7 independently of one another.), have by the organic group of 1 valency of the guanidine radicals of following formula (a1) expression, have by the organic group of 1 valency of the amidino groups of following formula (a2) expression etc. as preferred example.
In formula (a1), R
11And R
12Represent that independently of one another carbon number is that 1～20 alkyl, carbon number are that aryl, carbon number more than 6 is the aralkyl more than 7.
In formula (a2), R
13And R
14Represent that independently of one another carbon number is that 1～20 alkyl, carbon number are that aryl, carbon number more than 6 is the aralkyl more than 7.
In these groups, more preferably amino (NH
2), substituted imido (NHR
8,-NR
9R
10, wherein, R
8, R
9And R
10Represent that independently of one another carbon number is 1～10 alkyl, phenyl, benzyl.), by the guanidine radicals of following formula (a1) expression [in formula (a1), R
11And R
12Represent that independently of one another carbon number is 1～10 alkyl, phenyl, benzyl.], by the amidino groups of following formula (a2) expression [in formula (a2), R
13And R
14Represent that independently of one another carbon number is 1～10 alkyl, phenyl, benzyl.] etc.
The preferred especially amino (NH that uses
2), substituted imido (NHR
8,-NR
9R
10, wherein, R
8, R
9And R
10Represent that independently of one another carbon number is 1～5 alkyl, phenyl, benzyl.), by the guanidine radicals of following formula (a1) expression [in formula (a1), R
11And R
12Represent that independently of one another carbon number is 1～5 alkyl, phenyl, benzyl.], by the amidino groups of following formula (a2) expression [in formula (a2), R
13And R
14Represent that independently of one another carbon number is 1～5 alkyl, phenyl, benzyl.] etc.
As above-mentioned " urea groups ", for example can enumerate out-NR
15CONR
16R
17(wherein, R
15, R
16And R
17Represent that independently of one another hydrogen atom or carbon number are that 1～20 alkyl, carbon number are that aryl, carbon number more than 6 is the aralkyl more than 7.) as preferred example, more preferably-NR
15CONHR
17(wherein, R
15And R
17Represent that independently of one another hydrogen atom or carbon number are that 1～10 alkyl, carbon number are that aryl, carbon number more than 6 is the aralkyl more than 7.), be preferably especially-NHCONHR
17(wherein, R
17Expression hydrogen atom or carbon number are that 1～10 alkyl, carbon number are that aryl, carbon number more than 6 is the aralkyl more than 7.)。
As above-mentioned " urethane groups ", for example can enumerate out-NHCOOR
18,-NR
19COOR
20,-OCONHR
21,-OCONR
22R
23(wherein, R
18, R
19, R
20, R
21, R
22And R
23Represent that independently of one another carbon number is that 1～20 alkyl, carbon number are that aryl, carbon number more than 6 is the aralkyl more than 7.) wait as preferred example, more preferably-NHCOOR
18,-OCONHR
21(wherein, R
18, R
21Represent that independently of one another carbon number is that 1～20 alkyl, carbon number are that aryl, carbon number more than 6 is the aralkyl more than 7.) wait, be preferably especially-NHCOOR
18,-OCONHR
21(wherein, R
18, R
21Represent that independently of one another carbon number is that 1～10 alkyl, carbon number are that aryl, carbon number more than 6 is the aralkyl more than 7.) etc.
As above-mentioned " group ", can enumerate out for example acetylacetone based, crown ether etc. with coordination property oxygen atom.
As above-mentioned " carbon number is the alkyl more than 4 "; Can enumerate out carbon number and be alkyl, carbon number more than 4 and be aryl, carbon number more than 6 and be aralkyl more than 7 etc. as preferred example; More preferably carbon number is that 4～20 alkyl, carbon number are that 6～20 aryl, carbon number are aralkyl of 7～20 etc., and being preferably carbon number especially and being 4～15 alkyl (for example octyl group, dodecyl etc.), carbon number and be 6～15 aryl (for example phenyl, naphthyl etc.), carbon number is aralkyl (for example benzyl etc.) of 7～15 etc.
As above-mentioned " alkoxysilyl ", can enumerate out trimethoxysilyl, triethoxysilyl etc.
As with organic base that is connected of above-mentioned adsorption site bonding; The organic base that is connected that is preferably singly-bound or constitutes by 1～100 carbon atom, 0～10 nitrogen-atoms, 0～50 oxygen atom, 1～200 hydrogen atom and 0～20 sulphur atom; This organic connection base can be no substituted, also can be have substituted.
As the object lesson of this organic connection base, can enumerate out the group that the following structures unit maybe constitutes this structural unit combination.
Have under the substituent situation at above-mentioned organic connection base; As this substituting group, can enumerate out carbon number such as methyl, ethyl for example and be carbon numbers such as 1～20 alkyl, phenyl, naphthyl and be carbon numbers such as 6～16 aryl, hydroxyl, amino, carboxyl, sulfoamido, N-sulfoamido, acetoxyl group and be carbon numbers such as 1～6 acyloxy, methoxyl, ethoxy and be carbon numbers such as halogen atom, methoxycarbonyl, ethoxy carbonyl, cyclohexyloxy carbonyl such as 1～6 alkoxy, chlorine, bromine and be carbonate groups such as 2～7 alkoxy carbonyl, cyanic acid, tert-butyl group carbonic ester etc.
In above-mentioned, as above-mentioned A
1, be preferably and comprise at least a kind and be selected from the organic group of 1 valency that organic pigment structure, heterocycle structure, acidic-group, the group with basic nitrogen atom, urea groups and carbon number are the position of the alkyl more than 4.
As above-mentioned A
1, more preferably by the organic group of 1 valency of formula (4) expression.
General formula (4)
In above-mentioned general formula (4), B
1Be above-mentioned adsorption site (promptly; Being selected from organic pigment structure, heterocycle structure, acidic-group, the group with basic nitrogen atom, urea groups, urethane groups, the group with coordination property oxygen atom, carbon number is the position of alkyl, alkoxysilyl, epoxy radicals, NCO and hydroxyl more than 4), R
24Expression singly-bound or (a+1) organic connection base of valency.A representes 1～10 integer, a B
1Can be identical, also can be different.
As above-mentioned by B
1The adsorption site of expression can be enumerated out and the A that constitutes above-mentioned general formula (1)
1The same group of adsorption site, preference is also identical.
Wherein, be preferably that to be selected from organic pigment structure, heterocycle structure, acidic-group, the group with basic nitrogen atom, urea groups and carbon number be the position of the alkyl more than 4.
R
24Expression singly-bound or (a+1) organic connection base of valency, a represent 1～10.Preferred a is 1～7, and more preferably a is 1～5, and preferred especially a is 1～3.
Organic connection base as (a+1) valency; Comprise the group that constitutes by 1～100 carbon atom, 0～10 nitrogen-atoms, 0～50 oxygen atom, 1～200 hydrogen atom and 0～20 s' sulphur atom; Can be no substituted, also can have substituting group.
As the object lesson of organic connection base of above-mentioned (a+1) valency, can enumerate out the group (also can form ring structure) that following structural unit maybe constitutes this structural unit combination.
As R
24Organic base that is connected of (a+1) valency that is preferably singly-bound or constitutes by 1～50 carbon atom, 0～8 nitrogen-atoms, 0～25 oxygen atom, 1～100 hydrogen atom and 0～10 sulphur atom; Organic base that is connected of singly-bound or (a+1) valency of being made up of 1～30 carbon atom, 0～6 nitrogen-atoms, 0～15 oxygen atom, 1～50 hydrogen atom and 0～7 sulphur atom more preferably is preferably singly-bound or organic base that is connected of (a+1) valency of being made up of 1～10 carbon atom, 0～5 nitrogen-atoms, 0～10 oxygen atom, 1～30 hydrogen atom and 0～5 sulphur atom especially.
In above-mentioned group; Organic connection base at (a+1) valency has under the substituent situation; As this substituting group, can enumerate out carbon number such as methyl, ethyl for example and be carbon numbers such as 1～20 alkyl, phenyl, naphthyl and be carbon numbers such as 6～16 aryl, hydroxyl, amino, carboxyl, sulfoamido, N-sulfoamido, acetoxyl group and be carbon numbers such as 1～6 acyloxy, methoxyl, ethoxy and be carbon numbers such as halogen atom, methoxycarbonyl, ethoxy carbonyl, cyclohexyloxy carbonyl such as 1～6 alkoxy, chlorine, bromine and be carbonate groups such as 2～7 alkoxy carbonyl, cyanic acid, tert-butyl group carbonic ester etc.
In above-mentioned general formula (1), R
2Organic connection base of expression singly-bound or divalent.N R
2Can be identical, also can be different.
Organic connection base as divalent; Comprise the group that constitutes by 1～100 carbon atom, 0～10 nitrogen-atoms, 0～50 oxygen atom, 1～200 hydrogen atom and 0～20 s' sulphur atom; Can be no substituted, also can have substituting group.
As the object lesson of organic connection base of above-mentioned divalent, can enumerate out the group that the following structures unit maybe constitutes this structural unit combination.
-O-?-S-
As R
2Organic base that is connected of the divalent that is preferably singly-bound or constitutes by 1～50 carbon atom, 0～8 nitrogen-atoms, 0～25 oxygen atom, 1～100 hydrogen atom and 0～10 sulphur atom; Organic base that is connected of singly-bound or the divalent that is made up of 1～30 carbon atom, 0～6 nitrogen-atoms, 0～15 oxygen atom, 1～50 hydrogen atom and 0～7 sulphur atom more preferably is preferably singly-bound or organic base that is connected of the divalent that is made up of 1～10 carbon atom, 0～5 nitrogen-atoms, 0～10 oxygen atom, 1～30 hydrogen atom and 0～5 sulphur atom especially.
In above-mentioned group; Organic connection base at divalent has under the substituent situation; As this substituting group, can enumerate out carbon number such as methyl, ethyl for example and be carbon numbers such as 1～20 alkyl, phenyl, naphthyl and be carbon numbers such as 6～16 aryl, hydroxyl, amino, carboxyl, sulfoamido, N-sulfoamido, acetoxyl group and be carbon numbers such as 1～6 acyloxy, methoxyl, ethoxy and be carbon numbers such as halogen atom, methoxycarbonyl, ethoxy carbonyl, cyclohexyloxy carbonyl such as 1～6 alkoxy, chlorine, bromine and be carbonate groups such as 2～7 alkoxy carbonyl, cyanic acid, tert-butyl group carbonic ester etc.
In above-mentioned general formula (1), R
1Organic connection base of expression (m+n) valency.M+n satisfies 3～10.
As above-mentioned by R
1Organic connection base of (m+n) valency of expression; Contain the group that constitutes by 1～100 carbon atom, 0～10 nitrogen-atoms, 0～50 oxygen atom, 1～200 hydrogen atom and 0～20 s' sulphur atom; Can be no substituted, also can have substituting group.
As the object lesson of organic connection base of above-mentioned (m+n) valency, can enumerate out the group (also can form ring structure) that the following structures unit maybe constitutes this structural unit combination.
Organic connection base as (m+n) valency; Be preferably the group that constitutes by 1～60 carbon atom, 0～10 nitrogen-atoms, 0～40 oxygen atom, 1～120 hydrogen atom and 0～10 s' sulphur atom; Organic base that is connected of (m+n) valency that more preferably is made up of 1～50 carbon atom, 0～10 nitrogen-atoms, 0～30 oxygen atom, 1～100 hydrogen atom and 0～7 sulphur atom is preferably the group that is made up of 1～40 carbon atom, 0～8 nitrogen-atoms, 0～20 oxygen atom, 1～80 hydrogen atom and 0～5 s' sulphur atom especially.
In above-mentioned group; Organic connection base at (m+n) valency has under the substituent situation; As this substituting group, can enumerate out carbon number such as methyl, ethyl for example and be carbon numbers such as 1～20 alkyl, phenyl, naphthyl and be carbon numbers such as 6～16 aryl, hydroxyl, amino, carboxyl, sulfoamido, N-sulfoamido, acetoxyl group and be carbon numbers such as 1～6 acyloxy, methoxyl, ethoxy and be carbon numbers such as halogen atom, methoxycarbonyl, ethoxy carbonyl, cyclohexyloxy carbonyl such as 1～6 alkoxy, chlorine, bromine and be carbonate groups such as 2～7 alkoxy carbonyl, cyanic acid, tert-butyl group carbonic ester etc.
Following illustrate above-mentioned by R
1The object lesson (concrete example (1)～(17)) of organic connection base of (m+n) valency of expression.But in the present invention, be not limited to these.
In above-mentioned object lesson, from acquired, the synthetic easy property of raw material, to the deliquescent viewpoint of all kinds of solvents, organic connection base of most preferred (m+n) valency is following group.
In above-mentioned general formula (1), m representes 1～8.As m, be preferably 1～5, more preferably 1～4, be preferably 1～3 especially.
In addition, in above-mentioned general formula (1), n representes 2～9.As n, be preferably 2～8, more preferably 2～7, be preferably 3～6 especially.
In above-mentioned general formula (1), P
1The expression macromolecular scaffold can be according to selection from known polymkeric substance etc. such as purpose.M P
1Can be identical, also can be different.
In polymkeric substance; In order to constitute macromolecular scaffold; [for example be preferably the modifier that is selected from polymer of vinyl monomer or multipolymer, esters polymer, ether polymer, polyurethane polymer, acylamide polymer, epoxide polymer, polysiloxane base polymer and these materials or multipolymer; Comprise multipolymer of polyethers/polyurethane copolymer, polyethers/polymer of vinyl monomer etc. (can be in random copolymers, segmented copolymer, the graft copolymer any)] among at least a; More preferably be selected from least a among modifier or the multipolymer of polymer of vinyl monomer or multipolymer, esters polymer, ether polymer, polyurethane polymer and these materials, be preferably polymer of vinyl monomer or multipolymer especially.
In addition, being preferably above-mentioned polymkeric substance is soluble in organic solvent.If lower with the compatibility of organic solvent, then for example as under the situation of pigment dispersing agent, die down with the compatibility of dispersion medium, can't guarantee the sufficient adsorbed layer of decentralized stabilization.
As above-mentioned vinyl monomer; Have no particular limits, for example be preferably (methyl) esters of acrylic acid, crotonates class, vinyl ester, maleic acid diester class, dimethyl ester class, itaconic acid diester class, (methyl) acrylic amide, phenylethylene, vinyl ethers, vinyl ketones, olefines, maleimide, (methyl) vinyl cyanide, have the vinyl monomer of acidic-group etc.
Below, the preference of these vinyl monomers is described.
As (methyl) esters of acrylic acid; Can enumerate out (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid pentyl ester, the just own ester of (methyl) acrylic acid, (methyl) cyclohexyl acrylate, (methyl) acrylic acid tert-butyl group cyclohexyl, (methyl) 2-EHA, (methyl) acrylic acid uncle monooctyl ester, (methyl) dodecylacrylate, (methyl) acrylic acid stearyl, (methyl) acrylic acid acetoxyl group ethyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 3-hydroxypropyl acrylate, (methyl) acrylic acid 4-hydroxy butyl ester, (methyl) acrylic acid 2-methoxyl methyl esters, (methyl) acrylic acid 2-ethoxy ethyl ester, (methyl) acrylic acid 2-(2-methoxy ethoxy) ethyl ester, (methyl) acrylic acid 3-phenoxy group-2-hydroxy propyl ester, (methyl) acrylic acid 2-chloro ethyl ester, (methyl) glycidyl acrylate, (methyl) acrylic acid-3,4-epoxy radicals cyclohexyl methyl esters, (methyl) acrylic acid vinyl esters, (methyl) acrylic acid 2-phenyl vinyl ester, (methyl) acrylic acid-1-amylene ester, (methyl) acrylic acid allyl ester, (methyl) acrylic acid 2-aryloxy group ethyl ester, (methyl) acrylic acid propargyl ester, (methyl) acrylic acid benzyl ester, (methyl) acrylic acid diethylene glycol monomethyl ether, (methyl) acrylic acid diethylene glycol monoethyl ether, (methyl) acrylic acid triethylene glycol monomethyl ether, (methyl) acrylic acid Triethylene glycol ethyl ether, (methyl) polyalkylene glycol acrylate monomethyl ether, (methyl) polyalkylene glycol acrylate list ether, (methyl) acrylic acid beta-phenoxy ethoxy ethyl ester, (methyl) acrylic acid Nonylphenoxy polyglycol, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentenyl oxygen base ethyl ester, (methyl) acrylic acid trifluoro ethyl ester, (methyl) acrylic acid octafluoro pentyl ester, (methyl) acrylic acid perfluoro capryl ethyl ester, (methyl) acrylic acid two ring pentyl esters, (methyl) acrylic acid tribromophenyl, (methyl) acrylic acid tribromophenoxy ethyl ester, (methyl) acrylic acid-gamma-butyrolacton etc.
As the example of crotonates class, can enumerate out butyl crotonate and the own ester of crotonic acid etc.
As the example of vinyl ester, vinyl-acetic ester, chloracetic acid vinyl esters, vinyl propionate base ester, butyric acid vinyl esters, methoxyacetic acid vinyl esters and benzoic acid vinyl esters etc.
As the example of maleic acid diester class, can enumerate out dimethyl maleate, diethyl maleate and dibutyl maleate etc.
As the example of dimethyl ester class, can enumerate out dimethyl fumarate, DEF and dibutyl fumarate etc.
As the example of itaconic acid diester class, can enumerate out dimethyl itaconate, diethyl itaconate and dibutyl itaconate etc.
As (methyl) acrylic amide; Can enumerate out (methyl) acrylic amide, N-methyl (methyl) acrylic amide, N-ethyl (methyl) acrylic amide, N-propyl group (methyl) acrylic amide, N-isopropyl (methyl) acrylic amide, N-normal-butyl (methyl) acrylic amide, the N-tert-butyl group (methyl) acrylic amide, N-cyclohexyl (methyl) acrylic amide, N-(2-methoxy ethyl) (methyl) acrylic amide, N; N-dimethyl (methyl) acrylic amide, N; N-diethyl (methyl) acrylic amide, N-phenyl (methyl) acrylic amide, N-nitrobenzophenone acrylic amide, N-ethyl-N phenyl acrylamide, N-benzyl (methyl) acrylic amide, (methyl) acryloyl morpholine, diacetone acrylamide, N hydroxymethyl acrylamide, N-hydroxyethyl acrylic amide, vinyl (methyl) acrylic amide, N, N-diallyl (methyl) acrylic amide, N-allyl (methyl) acrylic amide etc.
As the example of phenylethylene, can enumerate out styrene, methyl styrene, dimethyl styrene, trimethylbenzene ethene, ethyl styrene, cumene ethene, butylstyrene, hydroxy styrenes, methoxy styrene, butyl phenyl ether ethene, acetoxy-styrene, chlorostyrene, dichlorobenzene ethene, bromostyrene, chloro methyl styrene, through can be by hydroxy styrenes, vinyl benzoic acid methyl esters and the AMS etc. of the group of acidic materials deprotection (for example t-Boc etc.) protection.
As the example of vinyl ethers, can enumerate out methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl group vinyl ether, methoxy ethyl vinyl ether and Vinyl phenyl ether etc.
As the example of vinyl ketones, can enumerate out methyl vinyl ketone, ethyl vinyl ketone, propyl ethylene base ketone, phenyl vinyl ketone etc.
As the example of olefines, can enumerate out ethene, propylene, isobutylene, butadiene, isoprene etc.
As the example of maleimide, can enumerate out maleimide, butyl maleimide, cyclohexyl maleimide, phenyl maleimide etc.
Can also use by (methyl) vinyl cyanide, vinyl substituted heterocyclic group (for example, vinylpyridine, N-vinyl pyrrolidone, VCz etc.), N-vinyl formamide, N-vinyl acetamide, N-acetyl imidazole, vinyl caprolactone etc.
Except above-claimed cpd, can also use to have the for example vinyl monomer of functional groups such as urethane groups, urea groups, sulfoamido, phenylol, imide.Have the monomer of urethane groups or urea groups as this, for example can utilize NCO and hydroxyl or amino addition reaction suitably to synthesize.Specifically, monomer that can be through containing NCO with contain the compound of 1 hydroxyl or contain the compound of 1 uncle or secondary amino group addition reaction, or contain the monomer of hydroxyl or contain the monomer of 1 uncle or secondary amino group and the addition reaction of isocyanates etc. and suitably synthesize.
As above-mentioned example, can enumerate out vinyl monomer or have sulfonic vinyl monomer with carboxylic acid group with vinyl monomer of acidic-group.
As vinyl monomer, can enumerate out (methyl) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid mono alkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer etc. with carboxylic acid group.In addition, can also use (methyl) acrylic acid 2-hydroxyl ethyl ester etc. to have addition reaction, ω-carboxyl-polycaprolactone list (methyl) acrylic ester of the such cyclic acid anhydride of monomer and maleic anhydride or phthalic anhydride, the cyclohexane dicarboxylic acid acid anhydride of hydroxyl etc.In addition, as the precursor of carboxyl, can also use the monomer of acid anhydrides such as containing maleic anhydride, itaconic anhydride, citraconic anhydride.In addition, in these materials,, be preferably (methyl) acrylic acid especially from viewpoints such as copolymerization property or cost, dissolubilities.
In addition; As having sulfonic vinyl monomer; 2-acrylic amide-2-methyl propane sulfonic acid etc. can be enumerated out,, mono phosphoric acid ester (2-acryloxy ethyl ester), mono phosphoric acid ester (1-methyl-2-acryloxy ethyl ester) etc. can be enumerated out as vinyl monomer with phosphate.
In addition, as vinyl monomer, can also use the vinyl monomer that contains phenol property hydroxyl or contain vinyl monomer of sulfoamido etc. with acidic-group.
Secondary at above-mentioned macromolecular compound by general formula (1) expression, be preferably macromolecular compound by formula (2) expression.
General formula (2)
In above-mentioned general formula (2), A
2Expression contains at least a kind, and to be selected from organic pigment structure, heterocycle, acidic-group, the group with basic nitrogen atom, urea groups, urethane groups, the group with coordination property oxygen atom, carbon number be the 1 valency organic group at the position of alkyl, alkoxysilyl, epoxy radicals, NCO and hydroxyl more than 4.N A
2Can be identical, also can be different.
In addition, above-mentioned A
2With the above-mentioned A in the above-mentioned general formula (1)
1Definition identical, preferred mode is also identical.
In above-mentioned general formula (2), R
4, R
5Organic connection base of representing singly-bound or divalent independently of one another.N R
4Can be identical, also can be different.In addition, m R
5Can be identical, also can be different.
As by R
4, R
5Organic connection base of divalent of expression, can use with as above-mentioned general formula (1) by R
2The listed identical group of enumerating of the organic connection base of divalent of expression, preferred mode is also identical.
In above-mentioned general formula (2), R
3Organic connection base of expression (m+n) valency.M+n satisfies 3～10.
As above-mentioned by R
3Organic connection base of (m+n) valency of expression; Comprise the group that constitutes by 1～60 carbon atom, 0～10 nitrogen-atoms, 0～50 oxygen atom, 1～100 hydrogen atom and 0～20 s' sulphur atom; Can be no substituted, also can have substituting group.
As above-mentioned by R
3Organic connection base of (m+n) valency of expression, specifically, can enumerate out with as above-mentioned general formula (1) by R
1The listed identical group of enumerating of the organic connection base of (m+n) valency of expression, preferred mode is also identical.
In above-mentioned general formula (2), m representes 1～8.As m, be preferably 1～5, more preferably 1～4, be preferably 1～3 especially.
In addition, in above-mentioned general formula (2), n representes 2～9.As n, be preferably 2～8, more preferably 2～7, be preferably 3～6 especially.
P in the above-mentioned general formula (2)
2The expression macromolecular scaffold can be according to selection from known polymkeric substance etc. such as purpose.M P
2Can be identical, also can be different.For the optimal way of polymkeric substance, with the P in the above-mentioned general formula (1)
1Identical.
In macromolecular compound by above-mentioned general formula (2) expression, the R shown in most preferably being below all satisfying
3, R
4, R
5, P
2, m and n material.
R
3: above-mentioned object lesson (1), (2), (10), (11), (16) or (17)
R
4: organic base that is connected of the divalent that is made up of " 1～10 carbon atom, 0～5 nitrogen-atoms, 0～10 oxygen atom, 1～30 hydrogen atom and 0～5 sulphur atom " that singly-bound, following structural unit maybe constitute the combination of this structural unit (also can have substituting group; As this substituting group, can enumerate out carbon number such as methyl, ethyl for example and be carbon numbers such as 1～20 alkyl, phenyl, naphthyl and be carbon numbers such as 6～16 aryl, hydroxyl, amino, carboxyl, sulfoamido, N-sulfoamido, acetoxyl group and be carbon numbers such as 1～6 acyloxy, methoxyl, ethoxy and be carbon numbers such as halogen atom, methoxycarbonyl, ethoxy carbonyl, cyclohexyloxy carbonyl such as 1～6 alkoxy, chlorine, bromine and be carbonate groups such as 2～7 alkoxy carbonyl, cyanic acid, tert-butyl group carbonic ester etc.)
-O-S-
-C≡C-
R
5: singly-bound, vinyl, propenyl, following radicals (a) or following radicals (b) in addition, in following radicals, R
25Expression hydrogen atom or methyl, 1 expression 1 or 2.
P
2: the modifier of polymer of vinyl monomer or multipolymer, esters polymer, ether polymer, polyurethane polymer or these materials
m：1～3
n：3～6
The acid number of (B-1) the specific dispersion resin among the present invention is preferably below 200 (mgKOH/g), more preferably below 160 (mgKOH/g), is preferably especially below 120 (mgKOH/g).If acid number surpasses 200 (mgKOH/g), then dispersing of pigments property, dispersion stabilization worsen sometimes.
Molecular weight as (B-1) the specific dispersion resin among the present invention in weight-average molecular weight, is preferably 3000～100000, and more preferably 5000～80000, be preferably 7000～60000 especially.If weight-average molecular weight in above-mentioned scope, then can realize good dispersiveness and dispersion stabilization.
(synthetic method)
Above-mentioned macromolecular compound by general formula (1) expression (comprising the compound by general formula (2) expression) is had no particular limits, can synthesize through following method etc.
1. the isocyanates etc. that makes the polymkeric substance that has imported the functional group that is selected from carboxyl, hydroxyl, amino etc. endways and the carboxylic acid halides with a plurality of above-mentioned adsorption sites, has the alkyl halide of a plurality of above-mentioned adsorption sites or have a plurality of above-mentioned adsorption sites carries out the method for high molecular weight reactive.
2. make the polymkeric substance that imported carbon-to-carbon double bond endways with have a plurality of above-mentioned adsorption sites the mercaptan method of carrying out the Michael addition reaction.
3. make the polymkeric substance that imported carbon-to-carbon double bond endways with have a plurality of above-mentioned adsorption sites the mercaptan method of in the presence of free-radical generating agent, reacting.
4. the method that polymkeric substance that has imported a plurality of mercaptan endways and the compound with carbon-to-carbon double bond and above-mentioned adsorption site are reacted in the presence of free-radical generating agent.
Have a plurality of above-mentioned adsorption sites mercaptan compound in the presence of, make the method for vinyl monomer generation free radical polymerization.
In said method, the easy property angle on synthetic, macromolecular compound of the present invention preferably uses 2,3,4,5 synthetic method synthetic, more preferably uses 3,4,5 synthetic method synthetic.Especially have under the situation by the structure of general formula (2) expression at macromolecular compound of the present invention, the easy property angle on synthetic most preferably uses 5 synthetic method synthetic.
Synthetic method as above-mentioned 5 more particularly, is preferably in the presence of the compound by formula (3) expression, makes the method for vinyl monomer generation free radical polymerization.
General formula (3)
In above-mentioned general formula (3), R
6, R
7, A
3, m and n respectively with above-mentioned general formula (2) in R
3, R
4, A
2, m and n definition identical, its optimal way is also identical.
Can be synthetic by the compound of above-mentioned general formula (3) expression through following method etc., the easy property angle from synthesizing is preferably following 7 method.
6. the method that is converted to mercaptan compound from the halogenide with a plurality of above-mentioned adsorption sites (can be enumerated out and thiocarbamide reaction the method for hydrolysis, the method and the CH that directly react with NaSH
3COSNa reaction also makes the method etc. of its hydrolysis)
7. make the compound that has 3～10 sulfydryls in a part and have above-mentioned adsorption site and have the method that to carry out addition reaction with the compound of the functional group of sulfydryl reaction
As " can with the functional group of sulfydryl reaction " in the above-mentioned synthetic method 7, be preferably and enumerate carboxylic acid halides, alkyl halide, isocyanates, carbon-to-carbon double bond etc.
Preferred especially " can with the functional group of sulfydryl reaction " be carbon-to-carbon double bond, and addition reaction is the free radical addition reaction.In addition, as carbon-to-carbon double bond, from reactive viewpoint of sulfydryl, more preferably 1 replaces or 2 substituted vinyl.
As the object lesson (object lesson (18)～(34)) of the compound that in a part, has 3～10 sulfydryls, can enumerate out following compound.
In above-mentioned group, from acquired, the synthetic easy property of raw material, to all kinds of solvents
Deliquescent viewpoint is set out, and preferred especially compound is following compound.
To have above-mentioned adsorption site and have can with the compound of the functional group of sulfydryl reaction (specifically; Be to contain at least 1 to be selected from organic pigment structure, heterocycle structure, acidic-group, the group with basic nitrogen atom, urea groups, urethane groups, the group with coordination property oxygen atom, carbon number be the position of alkyl, alkoxysilyl, epoxy radicals, NCO and hydroxyl more than 4 and the compound with carbon-to-carbon double bond) there is not special qualification, can enumerate out following material.
Above-mentioned " compound that has 3～10 sulfydryls in a part " with " have above-mentioned adsorption site and have can with the compound of the functional group of sulfydryl reaction " the free radical addition reaction product for example through utilization make above-mentioned " compound that has 3～10 sulfydryls in a part " with " have above-mentioned adsorption site; and have can with the compound of the functional group of sulfydryl reaction " in appropriate solvent, dissolve; To wherein adding free-radical generating agent, obtain about 50 ℃～100 ℃ methods (mercaptan-alkene reaction method) that addition takes place down.
As the appropriate solvent that in above-mentioned mercaptan-alkene reaction method, uses; Can according to used " compound that has 3～10 sulfydryls in a part ", " have above-mentioned adsorption site, and have can with the compound of the functional group of sulfydryl reaction " and the dissolubility of " the free radical addition reaction product of generation " select arbitrarily.
Can enumerate out for example methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, 1-methoxyl-2-propyl alcohol, 1-methoxyl-2-propyl-acetic acid ester, acetone, MEK, methyl isobutyl ketone, methoxy propyl yl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethyl formamide, chloroform, toluene.These solvents can use mixing more than two kinds.
In addition; As free-radical generating agent; Can utilize 2,2 '-azo two (isobutyronotrile) (AIBN), 2,2 '-azo two (2; 4 '-methyl pentane nitrile), 2, persulfate that superoxide that such azo-compound, the benzoyl peroxide of 2 '-azo-bis-iso-dimethyl is such and potassium persulfate, ammonium persulfate are such etc.
Vinyl monomer as using in above-mentioned 5 the synthetic method has no particular limits, for example can use with obtain above-mentioned general formula (1) by P
1The identical material of vinyl monomer that the uses during macromolecular scaffold of expression.
Above-mentioned vinyl monomer can be only with a kind of polymerization, also can and with making its copolymerization more than two kinds.
In addition, under the situation that is applicable to the curing colouration composition that must carry out the alkaline development processing, macromolecular compound of the present invention preferably makes vinyl monomer with acidic-group more than a kind and the vinyl monomer copolymerization that does not have acidic-group more than a kind.
As macromolecular compound of the present invention, preferably use these vinyl monomers and by the compound of above-mentioned general formula (3) expression, through known method, polymerization and obtaining according to conventional methods.In addition, the compound by above-mentioned general formula (3) expression among the present invention has the function as chain-transferring agent, below, only be called " chain-transferring agent " sometimes.
For example; Can obtain through following method, said method is: these vinyl monomers and above-mentioned chain-transferring agent are dissolved in the appropriate solvent, to wherein adding radical polymerization initiator; Under about 50 ℃～220 ℃, in solution, make the method (solution polymerization process) of its polymerization.
As the appropriate solvent that in solution polymerization process, uses, can suitably select according to the dissolubility of employed monomer and the multipolymer that is generated.Can enumerate out for example methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, 1-methoxyl-2-propyl alcohol, 1-methoxyl-2-propyl-acetic acid ester, acetone, MEK, methyl isobutyl ketone, methoxy propyl yl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethyl formamide, chloroform, toluene.These solvents can use mixing more than two kinds.
In addition; As radical polymerization initiator; Can use 2,2 '-azo two (isobutyronotrile) (AIBN), 2,2 '-azo two (2; 4 '-methyl pentane nitrile), 2, persulfate that superoxide that such azo-compound, the benzoyl peroxide of 2 '-azo-bis-iso-dimethyl is such and potassium persulfate, ammonium persulfate are such etc.
[(B-2) comprising the polymkeric substance of the copolymerization units of the monomer that comes free general formula (I) expression: (B-2) specific dispersion resin]
Below, the polymkeric substance of the copolymerization units that comprises the monomer that comes free general formula (I) expression (below, suitably be called " (B-2) specific dispersion resin ") is described.
General formula (I)
In the polymkeric substance of the copolymerization units that comprises the monomer that comes free general formula (I) expression, R
01Expression hydrogen atom, replacement or unsubstituted alkyl.R
02The expression alkylidene.W representes-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.X representes-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-or-NHCO-.Y representes-NR
03-,-O-,-S-or-N=, being connected with the N atom through the atomic group that is adjacent forms ring texture.R
03Expression hydrogen atom, alkyl or aryl.M, n are 0 or 1 independently of one another.
Below, the monomer by general formula (I) expression as the copolymerization units of necessity of (B-2) specific dispersion resin among the present invention is elaborated.
In general formula (I), R
01Expression hydrogen atom or replacement or unsubstituted alkyl.
As by R
01The alkyl of expression is preferably carbon number and is 1～12 alkyl, and more preferably carbon number is 1～8 alkyl, is preferably carbon number especially and is 1～4 alkyl.
By R
01The alkyl of expression is under the situation of substituted alkyl, as the substituting group that can import, can enumerate out for example hydroxyl, alkoxy, aryloxy group, acyloxy, halogen group etc.
As by R
01The preferred alkyl of expression specifically, can be enumerated out methyl, ethyl, propyl group, normal-butyl, isobutyl, the tert-butyl group, n-hexyl, cyclohexyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-methoxy ethyl etc.
R
02The expression alkylidene.
As by R
02The alkylidene of expression is preferably carbon number and is 1～12 alkylidene, and more preferably carbon number is 1～8 alkylidene, is preferably carbon number especially and is 1～4 alkylidene.
By R
02The alkylidene of expression can have substituting group under the situation that can import, as this substituting group, can enumerate out for example hydroxyl, alkoxy, aryloxy group, acyloxy etc.
As by R
02The preferred alkylidene of expression specifically, can be enumerated out methylene, ethylidene, propylidene, trimethylene, tetramethylene etc.
W representes-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene, be preferably-C (=O) O-or-CONH-.
Y representes-NR
03-,-O-,-S-or-N=, being connected with the N atom through the atomic group that is adjacent forms ring texture.
R
03Expression hydrogen atom, alkyl or aryl are preferably hydrogen atom or methyl.
As Y, be preferably especially-S-,-NH-or-N=.
The ring texture that is connected and forms with the N atom through the atomic group that is adjacent as Y; Can enumerate out single ring architectures such as imidazole ring, pyrimidine ring, triazole ring, tetrazole ring, thiazole ring 、 oxazole ring; And condensed ring structure such as benzimidazole ring, benzothiazole ring, benzoxazole ring, purine ring, quinazoline ring, perimidine ring; From with the viewpoint of the compatibility of pigment, be preferably the condensed ring structure.In addition, in the condensed ring structure, particularly preferably enumerate out benzimidazole ring, benzothiazole ring, benzoxazole ring.
X representes-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-or-NHCO-.
As X, be preferably especially-O-,-S-,-CONH-,-NHCONH-and-NHC (=O) S-.
M, n represent 0 or 1 independently of one another, and m and n all are preferably 1 especially.
Below enumerate out preferred object lesson (monomer M-1～monomer M-18), but the present invention is not limited to these by the monomer of general formula (I) expression.
From giving the viewpoint of dispersing of pigments stability, (B-2) the specific dispersion resin among the present invention especially preferably comprises from the copolymerization units of the monomer of above-mentioned general formula (I) expression with from the graft copolymer of the copolymerization units of the polyreactive oligomers that has ethylenic unsaturated bond endways.
This has the polyreactive oligomers of ethylenic unsaturated bond endways owing to be the compound with regulation molecular weight, therefore is also referred to as " macromonomer ".In following explanation, also " polyreactive oligomers that has ethylenic unsaturated bond endways " among the present invention suitably is called " polyreactive oligomers " or " macromonomer " sometimes.
The polyreactive oligomers that uses according to expectation among the present invention is made up of the part of polymeric chain part and its terminal polymerizable functional group with ethylenical unsaturated double bonds.From obtaining the viewpoint of graft polymer of expectation, this group with ethylenical unsaturated double bonds is preferably in the end that only is included in polymer chain.Group as having ethylenical unsaturated double bonds is preferably (methyl) acryloyl group, vinyl, is preferably (methyl) acryloyl group especially.
In addition, the number-average molecular weight in polystyrene conversion of this macromonomer (Mn) is preferably in 1000～10000 scope, in 2000～9000 scope.
Homopolymer that the part of above-mentioned polymer chain is normally formed by at least a monomer that is selected among (methyl) alkyl acrylate, styrene and derivant, vinyl cyanide, vinyl acetate and the butadiene or multipolymer or polyethylene oxide, polypropyleneoxide, polycaprolactone.
The oligomer that above-mentioned polyreactive oligomers is preferably represented by formula (II).
General formula (II)
In above-mentioned general formula (II), R
11And R
13Represent hydrogen atom or methyl independently of one another.
R
12Expression comprises the linking group that carbon number is 1～12 alkylidene, and this linking group can be that carbon number is 1～12 alkylidene, can also be the linking group that a plurality of these alkylidenes are formed by connecting through ester bond, ehter bond, amido link etc.As R
12, preferably carbon number is that 1～4 alkylidene or carbon number are the group that 1～4 alkylidene connects through ester bond.By R
12The alkylidene of expression can also further have substituting group (for example hydroxyl).
Y
11Expression do not have substituent phenyl, have phenyl that 1 carbon number is 1～4 alkyl or-COOR
14Wherein, R
14The expression carbon number is that 1～6 alkyl, phenyl or carbon number are 7～10 aralkyl.Y be preferably phenyl or-COOR
14, wherein, R
14The expression carbon number is 1～12 alkyl.
Q representes 20～200 integer.
As the preference of the polyreactive oligomers (macromonomer) that uses in (B-2) the specific dispersion resin among the present invention synthetic, can enumerate out gather (methyl) methyl acrylate, gather (methyl) n-butyl acrylate and gather (methyl) isobutyl acrylate, bonding gathers the polymkeric substance of (methyl) acryloyl group in an end of the molecule of polystyrene.As this polyreactive oligomers that can in market, obtain, can enumerate out single end carried out the metering system acidylate polystyrene oligomer (Mn=6000, trade name: AS-6, East Asia synthetic chemical industry (strain) make), carried out gathering (methyl) methyl acrylate (Mn=6000, trade name: AA-6, East Asia synthetic chemical industry (strain) are made) and gathering (methyl) n-butyl acrylate (Mn=6000, trade name: AB-6, East Asia synthetic chemical industry (strain) are made) of metering system acidylate at single end what single end had carried out the metering system acidylate.
In order to obtain specific acid number, (B-2) of the present invention specific dispersion resin preferably also contains the copolymerization units from the monomer with acidic group.
As monomer, can enumerate out unsaturated monocarboxylic classes such as acrylic acid, methacrylic acid, crotonic acid, α-Lv Daibingxisuan, cinnamic acid with acidic group; Unsaturated dicarboxylic or its anhydrides such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid; Unsaturated multi-anhydride more than 3 yuan or its anhydrides; List [(methyl) acryloxyalkyl] the ester class of mono succinate (2-acryloxy ethyl ester), mono succinate (2-methacryloxy ethyl ester), phthalic acid list (2-acryloxy ethyl ester), the phthalic acid list polybasic carboxylic acids more than 2 yuan such as (2-methacryloxy ethyl esters); List (methyl) esters of acrylic acid of two terminal carboxyl group polymkeric substance such as ω-carboxyl-polycaprolactone single-acrylate, ω-carboxyl-polycaprolactone monomethacrylates etc.
(B-2) of the present invention specific dispersion resin is in the scope of not damaging its effect, but the vinyl monomer that can also contain copolymerization is as copolymer composition.
As the vinyl monomer that can use therein; Do not have special qualification, for example be preferably ester class, phenylethylene, (methyl) vinyl cyanide of (methyl) esters of acrylic acid, crotonates class, vinyl ester, maleic acid diester class, dimethyl ester class, itaconic acid diester class, (methyl) acrylic amide, vinyl ethers, vinyl alcohol etc.As the object lesson of this vinyl monomer, can enumerate out following compound.
Promptly; As (methyl) esters of acrylic acid, can enumerate out (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, the just own ester of (methyl) acrylic acid, (methyl) cyclohexyl acrylate, (methyl) acrylic acid tert-butyl group cyclohexyl, (methyl) 2-EHA, (methyl) acrylic acid uncle monooctyl ester, (methyl) dodecylacrylate, (methyl) acrylic acid stearyl, (methyl) acrylic acid acetoxyl group ethyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-methoxyl ethyl ester, (methyl) acrylic acid 2-ethoxy ethyl ester, (methyl) acrylic acid 2-(2-methoxy ethoxy) ethyl ester, (methyl) acrylic acid 3-phenoxy group-2-hydroxy propyl ester, (methyl) acrylic acid benzyl ester, (methyl) acrylic acid diethylene glycol monomethyl ether, (methyl) acrylic acid diethylene glycol monoethyl ether, (methyl) acrylic acid triethylene glycol monomethyl ether, (methyl) acrylic acid Triethylene glycol ethyl ether, (methyl) polyalkylene glycol acrylate monomethyl ether, (methyl) polyalkylene glycol acrylate list ether, (methyl) acrylic acid beta-phenoxy ethoxy ethyl ester, (methyl) acrylic acid Nonylphenoxy macrogol ester, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentenyl oxygen base ethyl ester, (methyl) acrylic acid trifluoro ethyl ester, (methyl) acrylic acid octafluoro pentyl ester, (methyl) acrylic acid perfluoro capryl ethyl ester, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid tribromophenyl, (methyl) acrylic acid tribromophenoxy ethyl ester etc.
In addition, in this manual, when any or both of expression in " acrylic acid, methacrylic acid ", note is made " (methyl) acrylic acid " sometimes.
As the example of crotonates class, can enumerate out butyl crotonate and the own ester of crotonic acid etc.
As the example of vinyl ester, can enumerate out vinylacetate, vinyl propionic ester, vinyl butyrate, vinyl methoxyacetic acid ester and benzoic acid vinyl esters etc.
As the example of maleic acid diester class, can enumerate out dimethyl maleate, diethyl maleate and dibutyl maleate etc.
As the example of dimethyl ester class, can enumerate out dimethyl fumarate, DEF and dibutyl fumarate etc.
As the example of itaconic acid diester class, can enumerate out dimethyl itaconate, diethyl itaconate and dibutyl itaconate etc.
As (methyl) acrylic amide; Can enumerate out (methyl) acrylic amide, N-methyl (methyl) acrylic amide, N-ethyl (methyl) acrylic amide, N-propyl group (methyl) acrylic amide, N-isopropyl (methyl) acrylic amide, N-normal-butyl (methyl) acrylic amide, the N-tert-butyl group (methyl) acrylic amide, N-cyclohexyl (methyl) acrylic amide, N-(2-methoxy ethyl) (methyl) acrylic amide, N; N-dimethyl (methyl) acrylic amide, N, N-diethyl (methyl) acrylic amide, N-phenyl (methyl) acrylic amide, N-benzyl (methyl) acrylic amide, (methyl) acryloyl morpholine, diacetone acrylamide, etc.
As the example of phenylethylene, can enumerate out styrene, methyl styrene, dimethyl styrene, trimethylbenzene ethene, ethyl styrene, cumene ethene, butylstyrene, hydroxy styrenes, methoxy styrene, butyl phenyl ether ethene, acetoxy-styrene, chlorostyrene, dichlorobenzene ethene, bromostyrene, chloro methyl styrene, through can be by hydroxy styrenes, vinyl benzoic acid methyl esters and the AMS etc. of the group of acidic materials deprotection (for example t-Boc etc.) protection.
As the example of vinyl ethers, can enumerate out methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether and methoxy ethyl vinyl ether etc.
Optimal way as (B-2) of the present invention specific dispersion resin; Preferably can enumerate out the copolymerization units from the monomer of above-mentioned general formula (I) expression that contains 2～50 quality %, the copolymerization units from the polyreactive oligomers that has ethylenic unsaturated bond endways of 10～90 quality %, 1～30 quality % are from the multipolymer from the copolymerization units of vinyl monomer of the copolymerization units of the monomer with acidic-group, 0～20 quality %.
Below, enumerate object lesson [exemplary compounds 1～exemplary compounds 16] and its weight-average molecular weight of (B-2) the specific dispersion resin that can in curing colouration composition of the present invention, be suitable for, but the present invention is not limited to these.
Exemplary compounds (1): above-mentioned monomer M-2/ end has carried out the polymethyl methacrylate copolymer (10/90 quality %, weight-average molecular weight 50000) of metering system acidylate
Exemplary compounds (2): above-mentioned monomer M-2/ methacrylic acid/end has carried out the polymethyl methacrylate copolymer (10/15/75 quality %, weight-average molecular weight 25000) of metering system acidylate
Exemplary compounds (3): above-mentioned monomer M-3/ methacrylic acid 2-hydroxyl ethyl ester/end has carried out the polymethyl methacrylate copolymer (5/10/85 quality %, weight-average molecular weight 40000) of metering system acidylate
Exemplary compounds (4): above-mentioned monomer M-3/ methacrylic acid/methacrylic acid benzyl ester multipolymer/end has carried out the polymethyl methacrylate copolymer (15/5/10/65 quality %, weight-average molecular weight 60000) of metering system acidylate
Exemplary compounds (5): above-mentioned monomer M-4/ end has carried out the polymethyl methacrylate copolymer (10/90 quality %, weight-average molecular weight 80000) of metering system acidylate
Exemplary compounds (6): above-mentioned monomer M-4/ methacrylic acid/end has carried out the polymethyl methacrylate copolymer (10/15/75 quality %, weight-average molecular weight 30000) of metering system acidylate
Exemplary compounds (7): above-mentioned monomer M-5/ acrylic acid/end has carried out the polymethyl methacrylate copolymer (25/15/60 quality %, weight-average molecular weight 60000) of metering system acidylate
Exemplary compounds (8): above-mentioned monomer M-5/ end has carried out the butyl polyacrylate multipolymer (15/85 quality %, weight-average molecular weight 40000) of metering system acidylate
Exemplary compounds (9): above-mentioned monomer M-6/ methacrylic acid 2-hydroxyl ethyl ester/end has carried out the polymethyl methacrylate copolymer (15/10/75 quality %, weight-average molecular weight 80000) of metering system acidylate
Exemplary compounds (10): above-mentioned monomer M-6/ end has carried out the polymethyl methacrylate copolymer (12/88 quality %, weight-average molecular weight 50000) of metering system acidylate
Exemplary compounds (11): above-mentioned monomer M-7/ methacrylic acid/end has carried out the polymethyl methacrylate copolymer (10/15/75 quality %, weight-average molecular weight 25000) of metering system acidylate
Exemplary compounds (12): above-mentioned monomer M-7/ methacrylic acid/methacrylic acid benzyl ester/methoxy polyethylene glycol methacrylate-styrene polymer multipolymer (10/10/50/30 quality %, weight-average molecular weight 40000)
Exemplary compounds (13): above-mentioned monomer M-10/ methacrylic acid 2-hydroxyl ethyl ester/end has carried out the polystyrene copolymer (5/10/85 quality %, weight-average molecular weight 20000) of metering system acidylate
Exemplary compounds (14): above-mentioned monomer M-10/ methacrylic acid/end has carried out the polymethyl methacrylate copolymer (10/15/75 quality %, weight-average molecular weight 25000) of metering system acidylate
Exemplary compounds (15): above-mentioned monomer M-10/ methoxy polyethylene glycol methacrylate-styrene polymer multipolymer (15: 85 quality %, weight-average molecular weight 15000)
Exemplary compounds (16): above-mentioned monomer M-13/ methacrylic acid/end has carried out the polymethyl methacrylate copolymer (10/15/75 quality %, weight-average molecular weight 20000) of metering system acidylate
As (B-2) specific dispersion resin among the present invention can be like above-mentioned multipolymer through making by the monomer of above-mentioned general formula (I) expression, according to the polyreactive oligomers of expectation and usefulness or other monomers free radical polymerization taking place in solvent and obtain.As radical polymerization initiator; Can use known compound; Preferred azo-initiator (the dimethyl-2 for example that uses; 2 '-azo two (2 Methylpropionic acid ester), azoisobutyronitrile, 2,2 '-azo two (2-amidine propane), 2 hydrochlorides etc.), superoxide (benzoyl peroxide, potassium persulfate etc.).Except initiating agent, can also add chain-transferring agent (for example 2 mercapto ethanol, 3-mercaptopropionic acid, 2-TGA, lauryl mercaptan) and synthesize.
(B-2) content of specific dispersion resin with respect to after state the quality of colorant, be preferably 0.5～100 quality %, more preferably 3～70 quality %.If (B-2) content of specific dispersion resin is in this scope, then can obtain enough pigment dispersing effects.In addition, surpass 100 quality %, can't expect that also pigment dispersing agent has better effect even pigment dispersing agent adds.
[(B-3) comprising polymkeric substance: (B-3) specific dispersion resin] by the structural unit of general formula (a) expression
Then, describe comprising by the polymkeric substance of the structural unit of general formula (a) expression (below, suitably be called " (B-3) specific dispersion resin ").
General formula (a)
In general formula (a), R
1aExpression hydrogen or methyl, R
2aThe expression alkylidene, Z
1Expression nitrogen heterocyclic ring structure.
As by R
2aThe alkylidene of expression; Can enumerate out methylene, ethylidene, trimethylene, tetramethylene, hexa-methylene, 2-hydroxy propylidene, methylene oxygen base, ethyleneoxy group, methylene oxygen base carbonyl, methylene sulfenyl etc.; Wherein, be preferably methylene, methylene oxygen base, methylene oxygen base carbonyl, methylene sulfenyl.
In above-mentioned general formula (a), Z
1Expression nitrogen heterocyclic ring structure; Specifically, can enumerate out for example have pyridine ring, the heterocycle structure of pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, quinoline ring, acridine ring, phenothiazine ring 、 Fen oxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benzotriazole structure, benzothiazole structure, cyclic amide structure, ring-type urethane structure and cyclic imide structure.
In these heterocycle structures, as by Z
1The nitrogen heterocyclic ring structure of expression is preferably the structure by formula (b) or general formula (c) expression.
General formula (b) general formula (c)
In above-mentioned general formula (b), X
1Be be selected from singly-bound, alkylidene (for example, methylene, ethylidene, propylidene, trimethylene, tetramethylene etc.) ,-O-,-S-,-NR-and-C (=O)-among any.In addition, wherein, R representes hydrogen atom or alkyl, representes the alkyl under the alkyl situation as R, can enumerate out for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl, n-octyl, 2-ethylhexyl, n-octadecane base etc.
In these groups, X
1Be preferably singly-bound, methylene ,-O-,-C (=O)-, be preferably especially-C (=O)-.
In above-mentioned general formula (b) and general formula (c), ring A, ring B and ring C represent aromatic rings independently of one another.As this aromatic rings; Can enumerate out phenyl ring, naphthalene nucleus, indenes ring, azulenes, fluorenes ring, anthracene nucleus, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, phenothiazine ring 、 Fen oxazine ring, acridone ring, anthraquinone ring etc.; Wherein, Be preferably phenyl ring, naphthalene nucleus, anthracene nucleus, pyridine ring 、 Fen oxazine ring, acridine ring, phenothiazine ring 、 Fen oxazine ring, acridone ring, anthraquinone ring, be preferably phenyl ring, naphthalene nucleus, pyridine ring especially.
Below enumerate out preferred object lesson [illustration monomer (M-1)～(M-7)], but the present invention is not limited to these by the structural unit of general formula (a) expression.
Be preferably by the structural unit of above-mentioned general formula (a) expression and in (B-3) specific dispersion resin, contain 2 quality %～50 quality %, more preferably contain 4 quality %～30 quality %, be preferably especially and contain 5 quality %～20 quality %.
(B-3) specific dispersion resin among the present invention is except containing the structural unit by above-mentioned general formula (a) expression, also contains the polyreactive oligomers that the has ethylenical unsaturated double bonds endways graft copolymer as copolymerization units.
The such a polyreactive oligomers that has ethylenical unsaturated double bonds endways can enumerate out with above-mentioned (B-2) specific dispersion resin in be used as the identical material of polyreactive oligomers of copolymer composition, its optimal way (oligomer of being represented by general formula (II)) or preference (object lesson) are also identical.
In order to obtain specific acid number, (B-3) the specific dispersion resin among the present invention preferably also contain have acidic-group monomer (structural unit) as copolymer composition.
As monomer, can enumerate out (methyl) acrylic acid, to the succinic anhydride addition product of vinyl benzoic acid, maleic acid, fumaric acid, itaconic acid, (methyl) acrylic acid 2-hydroxyl ethyl ester, the fumaric acid anhydride addition product of (methyl) acrylic acid 2-hydroxyl ethyl ester etc. with acidic-group.
(B-3) specific dispersion resin among the present invention is in the scope of not damaging its effect, but the vinyl monomer that can also contain copolymerization is as copolymer composition.
As the vinyl monomer that can use therein, can enumerate out with above-mentioned (B-2) specific dispersion resin in be used as the identical material of vinyl monomer of copolymer composition, its preference is also identical.
In addition; As the optimal way of (B-3) specific dispersion resin among the present invention, preferably can enumerate out the multipolymer of vinyl monomer of the structural unit with acidic-group, the 0 quality %～20 quality % of the polyreactive oligomers that has ethylenical unsaturated double bonds endways that contains 2 quality %～50 quality %, 1 quality %～30 quality % by the structural unit of above-mentioned general formula (a) expression and 10 quality %～90 quality %.
Below, enumerate out object lesson [exemplary compounds (I)～exemplary compounds (XV)] and its weight-average molecular weight of (B-3) the specific dispersion resin that can in curing colouration composition of the present invention, be suitable for, but the present invention is not limited to these.
Exemplary compounds (I): above-mentioned illustration monomer (M-1)/end has carried out the polymethyl methacrylate copolymer (copolymerization ratio=10/90 quality %, weight-average molecular weight 50000) of metering system acidylate
Exemplary compounds (II): above-mentioned illustration monomer (M-1)/methacrylic acid/end has carried out the polymethyl methacrylate copolymer (10/15/75 quality %, weight-average molecular weight 25000) of metering system acidylate
Exemplary compounds (III): above-mentioned illustration monomer (M-1)/methacrylic acid 2-hydroxyl ethyl ester/end has carried out the polymethyl methacrylate copolymer (5/10/85 quality %, weight-average molecular weight 40000) of metering system acidylate
Exemplary compounds (IV): above-mentioned illustration monomer (M-1)/methacrylic acid/benzyl methacrylate multipolymer/end has carried out the polymethyl methacrylate copolymer (15/5/10/65 quality %, weight-average molecular weight 60000) of metering system acidylate
Exemplary compounds (V): above-mentioned illustration monomer (M-5)/end has carried out the polymethyl methacrylate copolymer (20/80 quality %, weight-average molecular weight 80000) of metering system acidylate
Exemplary compounds (VI): above-mentioned illustration monomer (M-5)/methacrylic acid/end has carried out the polymethyl methacrylate copolymer (10/15/75 quality %, weight-average molecular weight 30000) of metering system acidylate
Exemplary compounds (VII): above-mentioned illustration monomer (M-5)/acrylic acid/end has carried out the polymethyl methacrylate copolymer (25/15/60 quality %, weight-average molecular weight 60000) of metering system acidylate
Exemplary compounds (VIII): above-mentioned illustration monomer (M-5)/end has carried out the butyl polyacrylate multipolymer (15/85 quality %, weight-average molecular weight 40000) of metering system acidylate
Exemplary compounds (IX): above-mentioned illustration monomer (M-5)/methacrylic acid 2-hydroxyl ethyl ester/end has carried out the polymethyl methacrylate copolymer (15/10/75 quality %, weight-average molecular weight 80000) of metering system acidylate
Exemplary compounds (X): above-mentioned illustration monomer (M-6)/end has carried out the polymethyl methacrylate copolymer (12/88 quality %, weight-average molecular weight 50000) of metering system acidylate
Exemplary compounds (XI): above-mentioned illustration monomer (M-6)/methacrylic acid/end has carried out the polymethyl methacrylate copolymer (10/15/75 quality %, weight-average molecular weight 25000) of metering system acidylate
Exemplary compounds (XII): above-mentioned illustration monomer (M-6)/methacrylic acid/benzyl methacrylate/methoxy polyethylene glycol methacrylate-styrene polymer multipolymer (10/10/50/30 quality %, weight-average molecular weight 40000)
Exemplary compounds (XIII): above-mentioned illustration monomer (M-6)/methacrylic acid 2-hydroxyl ethyl ester/end has carried out the polystyrene copolymer (5/10/85 quality %, weight-average molecular weight 20000) of metering system acidylate
Exemplary compounds (XIV): above-mentioned illustration monomer (M-6)/methacrylic acid/methyl methacrylate/end has carried out the polymethyl methacrylate copolymer (8/12/10/70 quality %, weight-average molecular weight 60000) of metering system acidylate
Exemplary compounds (XV): above-mentioned illustration monomer (M-6)/methoxy polyethylene glycol methacrylate-styrene polymer multipolymer (15: 85 quality %, weight-average molecular weight 15000)
As (B-3) the specific dispersion resin among the present invention as above-mentioned multipolymer can be through will constituting by the structural unit of above-mentioned general formula (a) expression monomer, obtain according to the polyreactive oligomers or the free radical polymerization in solvent of other monomers of expectation and usefulness.In this free radical polymerization, use and identical radical polymerization initiator and the chain-transferring agent of material that when synthesizing (B-2) specific dispersion resin, uses.
(B-3) content of specific dispersion resin with respect to after the quality of the colorant stated, be preferably 0.5～100 quality %, more preferably 3～70 quality %.If (B-2) content of specific dispersion resin is in this scope, then can obtain enough pigment dispersing effects.In addition, surpass 100 quality %, can't expect that also pigment dispersing agent has the effect of further raising even pigment dispersing agent adds.
In order to state colorant after disperseing with above-mentioned (B-1) specific dispersion resin, dispersion resin; Can in colorant, add above-mentioned dispersion resin and above-mentioned solvent prepares millbase, it is carried out dispersion treatment through methods such as flash distillation processing or kneading, bowl mill, sand mill, ball mill, 2 or 3 beaming roller grinding machines, extruder, coating wobbler, ultrasonic dispersing machine, homogenizers.These disposal routes can make up more than 2 kinds.For even carbon blacks, as required, the spreading agent of stating after can using.
The dispersion of colorant can only use above-mentioned dispersion resin to carry out, and also can and use following spreading agent.For can and the spreading agent of usefulness, can enumerate out as after the spreading agent stated.Spreading agent can use separately, also can multiple combination be used.Can destroy the cohesion of colorant, carbon black granules simultaneously at colorant, black carbon surface polymeric adsorbent through dispersion treatment, make the particle diameter miniaturization.
As above-mentioned spreading agent, normally have being substituted of hydrophilic parts such as carboxyl, OH base, sulfonic group, phosphate, amino, carbonyl, polyoxyalkylene part and phenyl (comprising naphthalene nucleus etc.), alicyclic ring, alkyl and they simultaneously lipophilicities such as group part compound, comprise the hydrophilic segment with pigment similar structures and/or the compound of oleophilic moiety etc.Illustrative compound below can using.But be not limited to these compounds.
EFKA-1101,1120,1125,4008,4009,4046,4047,4520,4010,4015,4020; 4050,4055,4060; 4080,4300,4330; 4400; 4401,4402,4403; 4406; 4800,5010,5044,5244; 5054; 5055,5063,5064; 5065; (above is the manufacturing of AVECIA society), キ ヤ リ ボ Application B such as 5066,5070,5207 (above make for EFKAADDITIVES society), Anti-Terra-U, Anti-Terra-U100, Anti-Terra-204, Anti-Terra-205, Anti-Terra-P, Disperbyk-101,102,103,106,108,109,110,111,112,151, P-104, P-104S, P105,220S, 203,204,205,9075,9076,9077 (above make for BYK society), Disparlon 7301,325,374,234,1220,2100,2200, KS260, KS273N, 1210,2150, KS860, KS873N, 7004,1813,1860,1401,1200,550, EDAPLAN 470,472,480,482, K-SPERSE131,152,152MS (above make), ソ Le ス パ one ス 3000,5000,9000,12000,13240,13940,17000,22000,24000,26000,28000, キ ヤ リ ボ Application L 1, エ レ ミ ノ one Le MBN-1, サ Application ス パ one Le PS-2, サ Application ス パ one Le PS-8, イ オ ネ Star ト S-20 (Sanyo changes into manufacturing) デ イ ス パ one ス エ イ De 6, デ イ ス パ one ス エ イ De 8, デ イ ス パ one ス エ イ De 15, デ イ ス パ one ス エ イ De 9100 (サ Application ノ プ コ Zhi Zao) etc. for nanmu originally changes into society.These materials can use separately, also can be with also using more than 2 kinds.The content of spreading agent is 1 quality %～25 quality % with respect to the all-mass of colorant, is preferably 2 quality %～20 quality %.
In addition, if increase pigment concentration in order to form high colour purity, then the thixotropy of coating fluid becomes big usually; Therefore; After coating, be easy to generate the inhomogeneous of thickness, in addition, especially in the slot coated method; Importantly until drying, the liquid homomergic flow is flat and form filming of uniform thickness.Therefore, in this curing colouration composition, preferably contain suitable surfactant.
As above-mentioned surfactant, can enumerate out the spy and open 2003-337424 communique, spy and open in the flat 11-133600 communique disclosed surfactant as preferred material.
As the surfactant that is used to improve coating, can add nonionic class surfactant, fluorine class surfactant, polysiloxane-based surfactant etc.As nonionic class surfactants such as nonionic class surfactant, 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.Specifically, can be polyoxyalkylene diols classes such as polyoxyethylene glycol, polyoxy propylene glycol; Polyoxyalkylene alkyl classes such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as NONIN HS 240, polyoxyethylene polystyrene ether, polyoxyethylene tribenzyl phenyl ether, polystyrene-basedization of polyoxyethylene-propylene ether, polyoxyethylene nonylplenyl ether; Nonionic class surfactants such as polyoxyalkylene dialkyls such as polyoxyethylene dilaurate, polyoxyethylene distearate, dehydration sorbitol fatty acid ester, polyoxyalkylene dehydration sorbitol fatty acid ester class.These object lessons can be ア デ カ プ Le ロ ニ Star Network シ リ one ズ for example; ア デ カ ノ one Le シ リ one ズ イ; テ ト ロ ニ Star Network シ リ one ズ (above make for ADEKA); エ マ Le ゲ Application シ リ one ズ; レ オ De one Le シ リ one ズ (above) for spending king's (strain) to make; エ レ ミ ノ one Le シ リ one ズ; ノ ニ Port one Le シ リ one ズ; オ Network タ Port one Le シ リ one ズ; De デ カ Port one Le シ リ one ズ; ニ ユ one Port one Le シ リ one ズ (above make) for Sanyo changes into (strain); パ イ オ ニ Application シ リ one ズ (above this grease of bamboo (strain) manufacturing); ニ Star サ Application ノ ニ オ Application シ リ one ズ (above Japanese grease (strain) manufacturing) etc.Can suitably use these commercially available materials.Preferred HLB value is 8～20, more preferably 10～17.
As fluorine class surfactant, can suitably use endways, at least one position of main chain and side chain has the compound of fluoro-alkyl or fluoro alkylidene.As concrete commercially available article, can enumerate out for example メ ガ Off ア Star Network F142D, メ ガ Off ア Star Network F172, メ ガ Off ア Star Network F173, メ ガ Off ア Star Network F176, メ ガ Off ア Star Network F177, メ ガ Off ア Star Network F183, メ ガ Off ア Star Network 780, メ ガ Off ア Star Network 781, メ ガ Off ア Star Network R30, メ ガ Off ア Star Network R08 (big Japanese ink (strain) is made), Off ロ ヲ one De FC-135, Off ロ ヲ one De FC-170C, Off ロ ヲ one De FC-430, Off ロ ヲ one De FC-431 (manufacturing of Sumitomo ス リ one エ system (strain)), サ one Off ロ Application S-112, サ one Off ロ Application S-113, サ one Off ロ Application S-131, サ one Off ロ Application S-141, サ one Off ロ Application S-145, サ one Off ロ Application S-382, サ one Off ロ Application SC-101, サ one Off ロ Application SC-102, サ one Off ロ Application SC-103, サ one Off ロ Application SC-104, サ one Off ロ Application SC-105, サ one Off ロ Application SC-106 (Asahi Glass (strain) manufacturing), エ Off ト Star プ EF351, エ Off ト Star プ 352, エ Off ト Star プ 801, エ Off ト Application プ 802 (JEMCO (strain) conduct) etc.
As a silicone-based surfactant includes, for example strike a Toray Shin re co a nn DC3PA, strike a Ritz Shin re co a nn DC7PA, strike a Ritz Shin re co a nn SH11PA, strike a Ritz Shin re co a nn SH21PA, strike a Ritz Shin re co a nn SH28PA, coat a Ritz Shin re co a nn? SH29PA, strike a Ritz Shin re co a nn SH30PA, strike a Ritz Shin re co a nn SH-190, strike a Ritz Shin re co a nn SH-193, strike a Ritz Shin re co a nn SZ-6032, strike a Ritz Shin re co a nn SF-8428, Suites a Ritz Shin re co a nn DC-57, strike a Ritz Shin re co a nn DC-190 (above Toray · double ウ co a ni nn bag · Shin re co a nn (strain) manufactured), TSF-4440, TSF-4300, TSF-4445, TSF-4446 , TSF-4460, TSF-4452 (more of GE by Toshiba Silicone an nn (strain) manufacturing) and so on.
These surfactants preferably use below 5 weight portions with respect to 1 00 weight portions liquid against corrosion, more preferably use below 2 weight portions.Amount at surfactant surpasses under the situation of 5 weight portions, in the coating drying, is easy to generate check surface, and flatness worsens easily.
In addition, in curing colouration composition of the present invention, as required, can also contain alkali soluble resins.
As the alkali soluble resins that can in curing colouration composition of the present invention, contain; Be the wire organic high molecular polymer, can from the alkali soluble resins that molecule (being the molecule of main chain preferably), has at least 1 alkali-soluble group of promotion (for example carboxyl, phosphate, sulfonic group, hydroxyl etc.), suitably select with acrylic copolymer, styrene copolymer.
Preferred mode as above-mentioned alkali soluble resins; Can enumerate out the polymkeric substance that has carboxylic acid at side chain; For example be to open clear 59-44615 number, special public clear 54-34327 number, special public clear 58-12577 communique, special public clear 54-25957 number, spy like the spy to open clear 59-53836 communique, spy and open the methacrylic acid copolymer put down in writing in each communique of clear 59-71048 number, acrylic copolymer, itaconic acid copolymer, citraconic acid multipolymer, maleic acid, partial esterification maleic acid etc., and have the acid cellulose derivant of carboxylic acid, polymkeric substance and acid anhydrides addition and the acrylic copolymers such as material that obtain with hydroxyl at side chain.
The acid number of the polymkeric substance that has at side chain as above-mentioned alkali soluble resins is 20～200mgKOH/g, is preferably 30～180mgKOH/g, more preferably in the scope of 50～150mgKOH/g.
For the concrete component unit of alkali soluble resins, preferred especially (methyl) acrylic acid with can with the multipolymer of other monomer of its copolymerization.As above-mentioned can with other monomer of (methyl) acrylic acid copolymer, can enumerate out (methyl) alkyl acrylate, (methyl) acrylic acid aryl ester, vinyl compound etc.Wherein, the hydrogen atom of alkyl and aryl also can be substituted the base replacement.
As above-mentioned (methyl) alkyl acrylate and (methyl) acrylic acid aryl ester, be CH
2=C (R
1) (COOR
3) [wherein, R
1Expression hydrogen atom or carbon number are 1～5 alkyl,, R
2The expression carbon number is 6～10 aromatic hydrocarbon ring, R
3The expression carbon number is that 1～8 alkyl or carbon number are 6～12 aralkyl.]; Specifically, 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) acrylic acid benzyl ester, (methyl) acrylic acid tolyl ester, (methyl) acrylic acid naphthyl ester, (methyl) acrylic acid cyclohexyl ester, (methyl) acrylic acid hydroxyalkyl acrylate (alkyl is that carbon number is 1～8 alkyl), hydroxyl glycidyl methacrylate, tetrahydrofurfuryl methacrylate etc.
In addition, can also enumerate out the preferred mode of resin conduct that has the polyalkylene oxide chain at molecular side chain.As above-mentioned polyalkylene oxide chain, can also be polyethylene oxide chain, polypropyleneoxide chain, polytetramethylene glycol chain or and to use these materials, end be the alkyl of hydrogen atom or straight or branched.
The repetitive of polyethylene oxide chain, polypropyleneoxide chain is preferably 1～20, and more preferably 2～12.The acrylic acid esters co-polymer that on these side chains, has the polyalkylene oxide chain is with for example polyethyleneglycol (methyl) acrylic ester, polypropylene glycol list (methyl) acrylic ester, gathers (ethylene glycol and 1,2-propylene glycol) single (methyl) acrylic ester etc. and with the OH base of these materials compound with alkyl envelope chain, and for example methoxy poly (ethylene glycol) list (methyl) acrylic ester, ethoxy polypropylene glycol list (methyl) acrylic ester, methoxyl gather (ethylene glycol and 1,2-propylene glycol) single (methyl) acrylic ester etc. and be the acrylic acid esters co-polymer of copolymer composition.
In addition, as above-mentioned vinyl compound, can enumerate out the compound that is expressed from the next.
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, R
3The expression carbon number is that 1～8 alkyl or carbon number are 6～12 aralkyl.
Specifically, can enumerate out styrene, AMS, vinyltoluene, vinyl cyanide, vinylacetate, N-vinyl pyrrolidone, polyphenyl ethyl macromonomer, polymethylmethacrylate macromonomer etc.
But other monomer of copolymerization can use a kind separately, also can combination more than 2 kinds be used.Wherein, the multiple copolymer that is preferably (methyl) acrylic acid benzyl ester/(methyl) acrylic copolymer especially or constitutes by (methyl) acrylic acid benzyl ester/(methyl) acrylic acid/other monomer.
As stated, acrylic resin has the acid number of the scope of 20～200mgKOH/g.Surpass under 200 the situation at acid number, acrylic resin is excessive to the dissolubility of alkali, and development proper range (wide degree develops) narrows down.On the other hand, if less than 20 is then too small, the dissolubility of alkali being diminished, in development, need the excessive time of cost, is not preferred.
In addition; In order to realize on operations such as coating, easily to use the range of viscosities of colored resist; And in order to ensure film strength, the matter average molecular weight Mw of acrylic resin (the polystyrene conversion value of measuring according to the GPC method) is preferably 2000～100000, more preferably 3000～50000.
For the acid number that makes acrylic resin in above-mentioned specific scope, can be to the suitably adjustment and easily carrying out of the copolymerization ratio of each monomer.In addition, for the scope that makes the matter average molecular weight in above-mentioned scope, can be when monomer copolymerization, according to polymerization through use appropriate amount chain-transferring agent and easily carry out.
Acrylic resin for example can be with himself through known free radical polymerization manufactured.In radical polymerization, the kind and the polymerizing conditions such as amount, solvent types thereof of the temperature when making acrylic resin, pressure, radical initiator so long as those skilled in the art just can easily set, can carry out condition enactment.
In addition; In order to improve the cross-linking efficiency of curing colouration composition of the present invention; Can use separately the resin that in alkali soluble resins, has polymerizable group or and with the alkali soluble resins that does not have polymerizable group, can use the polymkeric substance etc. that contains aryl, (methyl) acrylic, aryloxy alkyl etc. at side chain.Alkali soluble resins with the two keys of polymerism can develop through alkaline developer, in addition, still has the material of photo-curable and Thermocurable.The example ((1)～(4)) that contains the polymkeric substance of these polymerizable groups illustrates following, as long as comprise unsaturated link between alkali solubility groups such as COOH base, OH base and carbon-to-carbon, just is not limited to following material.
The polyurethane-modified acryl resin that contains polymerism pair keys that (1) obtains through compound that will make NCO and OH radical reaction, residual 1 unreacted NCO in advance and comprise at least 1 (methyl) acryloyl group and the acrylate resin reaction that comprises carboxyl,
(2) acrylate resin through comprising carboxyl with in molecule, have the acryl resin that contains unsaturated group that the reaction of epoxy radicals with the compound of polymerism pair keys obtains simultaneously.
(3) acid suspension (pendant) type Epocryl.
(4) will comprise the acryl resin that contains the two keys of polymerism that the basic acryl resin of OH obtains with 2 yuan of anhydride reactions with the two keys of polymerism.
In above-mentioned resin, the resin of preferred especially (1) and (2).
As object lesson, can use the for example acrylic acid 2-hydroxyl ethyl ester that will have OH base, for example methacrylic acid with COOH base and can and the compound of the multipolymer of monomers such as the esters of acrylic acid of their copolymerization or vinylic, acquisition etc. with comprising the compound that has unsaturated link group between reactive epoxide ring of OH base and carbon compounds such as (for example) glycidyl acrylates reaction.With the reaction of OH base in, except epoxide ring, can also use compound with acid anhydrides, NCO, acryloyl group.In addition, can also use and open flat 6-102669 communique, spy the spy and open the reactant that compound that compound that making of putting down in writing in the flat 6-1938 communique have epoxide ring obtains with the such unsaturated carboxylic acid reaction of acrylic acid and saturated or unsaturated multi-anhydride react acquisition.As the compound that has unsaturated group between such alkali-soluble group of COOH base and carbon simultaneously, can enumerate out for example ダ イ ヤ Na one Le NR シ リ one ズ (Mitsubishi's レ イ ヨ Application (strain) manufacturing); Photomer 6173 (contain oligomer, the Diamond Shamrock Co.Ltd. of the polyurethane acroleic acid of COOH base, make); PVC ス コ one ト R-264, KS レ ジ ス ト 106 (being Osaka organic chemistry industry (strain) manufacturing); サ イ Network ロ マ one P シ リ one ズ, プ ヲ Network セ Le CF200 シ リ one ズ (being ダ イ セ Le chemical industry (strain) manufacturing); Ebecry 13800 (manufacturing of ダ イ セ Le ユ one シ one PVC one (strain)) etc.
As the content of acrylic copolymer, with respect to the gross mass of the resinous principle that comprises above-mentioned dispersion resin contained in the curing colouration composition of the present invention, preferably in the scope of 0 quality %～50 quality %.If the content of acrylic copolymer in above-mentioned scope, even then contain under the situation of concentration increasing colorant, also can keep high sensitivity, make suitableization of developing powder and obtain good developing performance, can shorten the quiescent interval of operation.
< colorant >
Curing colouration composition of the present invention contains at least a colorant.Through containing colorant, can form the visual image of desired color.
As colorant, can also use the colored pixels that forms color filter colored based colorant such as R, G, B and form at the bottom of the fast black base with among the normally used black based colorant any.
In curing colouration composition of the present invention; Using the black based colorant to constitute under the situation of curing colouration composition; Especially can obtain effect of the present invention, promptly high photo sensitivity, edge and the development tolerance excellent effect to good development property better can realize developing.Therefore,, be preferably the colorant of black, also be preferably the big RGB of colour purity as colorant.
As the colorant of black, can enumerate out that carbon black, titanium are black, graphite, iron oxide, titanium dioxide and in addition after state pigment, dyestuff, do not have special qualification.Wherein, preferred carbon black, titanium black, graphite, more preferably carbon black.These colorants can use a kind separately, also can be with also using more than 2 kinds.
As and with the mass ratio under the situation more than 2 kinds (quality of carbon black: and the quality of the colorant of usefulness), preferably in 95: 5～60: 40 scope, more preferably 95: 5～70: 30, more preferably 90: 10～80: 20.Under black colorant is multiple situation, be multiple gross mass.If mass ratio in above-mentioned scope, does not then have the cohesion of dispersion liquid, can form does not have uneven stable filming.
As carbon black, can enumerate out power one ボ Application Block ヲ Star Network #2400, #2350, #2300, #2200, #1000, #980, #970, #960, #950, #900, #850, MCF88, #650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, #4000, #4010, #55, #52, #50, #47, #45, #44, #40, #33, #32, #30, #20, #10, #5, CF9, #3050, #3150, #3250, #3750, #3950, ダ イ ヤ Block ヲ Star Network A, ダ イ ヤ Block ヲ Star Network N220M, ダ イ ヤ Block ヲ Star Network N234, ダ イ ヤ Block ヲ Star Network I, ダ イ ヤ Block ヲ Star Network LI, ダ イ ヤ Block ヲ Star Network II, ダ イ ヤ Block ヲ Star Network N339, ダ イ ヤ Block ヲ Star Network SH, ダ イ ヤ Block ヲ Star Network SHA, ダ イ ヤ Block ヲ Star Network LH, ダ イ ヤ Block ヲ Star Network H, ダ イ ヤ Block ヲ Star Network HA, ダ イ ヤ Block ヲ Star Network SF, ダ イ ヤ Block ヲ Star Network N550M, ダ イ ヤ Block ヲ Star Network E, ダ イ ヤ Block ヲ Star Network G, ダ イ ヤ Block ヲ Star Network R, ダ イ ヤ Block ヲ Star Network N760M, the ダ イ ヤ Block ヲ Star Network LP of for example Mitsubishi Chemical society manufacturing; カ one ボ Application Block ヲ Star Network サ one マ Star Network ス N990, N991, N907, N908, N990, N991, N908 that キ ヤ Application カ one Block society makes; カ one ボ Application Block ヲ Star Network rising sun #80, rising sun #70, rising sun #70L, rising sun F-200, rising sun #66, rising sun #66HN, rising sun #60H, rising sun #60U, rising sun #60, rising sun #55, rising sun #50H, rising sun #51, rising sun #50U, rising sun #50, rising sun #35, rising sun #15, ア サ ヒ サ one マ Le that rising sun カ one ボ Application society makes; The カ one ボ Application Block ヲ Star Network Color Black Fw200 that デ ダ サ society makes, Color Black Fw2, Color Black Fw2V, Color Black Fw1, Color Black Fw18, Color BlackS170, Color Black S160, Specical Black6, Specical Black5, SpecicalBlack4, Specical Black4A, Printex U, Printex V, Printex 140U, Printex140V etc.
Carbon black preferably has insulativity.Carbon black with insulativity; It is the carbon black that under situation about measuring through following method, demonstrates insulativity as the volume resistance of powder; For example; Be through at surface of carbon black absorption, coating or chemical bonding (grafting) organism etc., thereby make surface of carbon black have the carbon black of organic compound.
As the carbon black except that above-mentioned, for example can use the special flat 11-60988 communique, spy opened to open flat 11-60989 communique, spy and open flat 10-330643 communique, spy and open flat 11-80583 communique, spy and open that flat 11-80584 communique, spy are opened flat 9-124969 communique, the spy opens the resin-coated carbon black of putting down in writing in the flat 9-95625 communique.In addition, can also improve above-mentioned dispersion resin and come carbon blacks.
In the present invention, as disperseing the pigment that applies, the mode of carbon black, can enumerate out powder, paste shape, ball shape, paste shape, laminar etc. through above-mentioned resin etc.
The pigment that disperses to apply through above-mentioned resin etc., the preferred mean grain size of carbon black are in the scope of 0.003 μ m～0.2 μ m, more preferably in the scope of 0.005 μ m～0.15 μ m, further preferably at 0.01 μ m～0.10 μ m.Can make various effect, especially development property of the present invention and development repeatability excellent more thus.
Pigment as as colorants such as RGB can use inorganic pigment or organic pigment.In addition, if no matter pigment is inorganic, organic, all consider preferred high permeability; Then preferably use the pigment of the as far as possible little nominal particle size of particle diameter; From the viewpoint of operability, preferred mean grain size is 0.010～0.100 μ m, the more preferably pigment of 0.010～0.050 μ m.
As above-mentioned inorganic pigment; Can enumerate out metallic compound by expressions such as metal oxide, metal complex salt; Specifically, can enumerate tap a blast furnace, the metal oxide of cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony etc. and the composite oxides of metal.
As above-mentioned organic pigment, can enumerate out:
C.I. pigment yellow 11,24, and 31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;
C.I. pigment orange 36,38,43,71;
C.I. pigment red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;
C.I. pigment violet 19,23, and 32,39;
C.I. pigment blue 1,2,15,15:1,15:3,15:6,16,22,60,66;
C.I. pigment Green 7,36,37;
C.I. pigment brown 25,28;
C.I. pigment black 1,7 etc.
In the present invention, especially can preferably use the pigment that in the structural formula of pigment, has alkaline N atom.These pigment with alkaline N atom demonstrate good dispersiveness in curing colouration composition of the present invention.Being not very clear for its reason, is the influential cause of good degree to the compatibility of photonasty polymerization composition and pigment but infer.
In above-mentioned pigment,, can enumerate out following pigment as preferred pigment.But be 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;
C.I. pigment black 1,7.
As organic pigment, except independent use is a kind of,, can also use various combinations in order to improve colour purity.Object lesson illustrates following.
As red pigment, can use anthraquione pigmentss 、 perylene pigment, diketopyrrolopyrrolecocrystals series pigments separately is that yellow uitramarine, isoindoline are that yellow uitramarine, quinophthalone are that yellow uitramarine, Huo person's perylene are uses such as red pigment mixing with their at least a and bisdiazo perhaps.For example, as anthraquinone class pigment, can enumerate out C.I. paratonere 177 Zuo Wei perylene class pigment; C.I. paratonere 155, C.I. paratonere 224 can be enumerated out,, C.I. paratonere 254 can be enumerated out as diketopyrrolopyrroles pigment; From the viewpoint of colorrendering quality, preferred mixed C .I. pigment yellow 83 or C.I. pigment yellow 13 9.The mass ratio of red pigment and yellow uitramarine is preferably 100: 5～and 100: 50.Less than 100: 5 can't suppress the transmittance of 400～500nm, can't improve colour purity.In addition, if surpass 100: 50, then predominant wavelength becomes near the short wavelength sometimes, becomes big with departing from of NTSC target tone.Be particularly suitable in 100: 10～100: 30 scope.Under the situation that is the combination between the red pigment, can combine colourity adjustment.
As viridine green, can use the halo phthualocyanine pigment separately, perhaps this viridine green and bisdiazo are that yellow uitramarine, quinophthalone are that yellow uitramarine, azomethine are that yellow uitramarine or isoindoline are that yellow uitramarine mixes use.The potpourri of preference such as C.I. pigment Green 7,36 or 37, C.I. pigment yellow 83, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 180 or C.I. pigment yellow 185.The mass ratio of viridine green and yellow uitramarine is preferably 100: 5～and 100: 150.Less than 100: 5 can't suppress the transmittance of 400～450nm, can't improve colour purity.In addition, if surpass 100: 150, then predominant wavelength becomes near the long wavelength sometimes, becomes big with departing from of NTSC target tone.Preferred mass ratio is in 100: 30～100: 120 scope.
As blue pigment, can use mixing of phthalocyanine pigment or itself Yu dioxazines violet pigment separately, be preferably for example C.I. pigment blue 15: 6 with the mixing of C.I. pigment Violet 23.The mass ratio of blue pigment and violet pigment is preferably 100: 0～and 100: 30, more preferably below 100: 10.
Using under the situation of dyestuff as colorant, can obtain the curing colouration composition of ability uniform dissolution.
Dyestuff as can be used as colorant has no particular limits, and can use the known dyestuff as present color filter purposes.For example be that the spy opens clear 64-90403 communique; The spy opens clear 64-91102 communique; Te Kaiping 1-94301 communique; Te Kaiping 6-11614 communique; The spy steps on No. 2592207; United States Patent (USP) 4808501A instructions; No. 5667920 instructions of United States Patent (USP); No. 5059500 instructions of United States Patent (USP); Te Kaiping 5-333207 communique; Te Kaiping 6-35183 communique; Te Kaiping 6-51115 communique; Te Kaiping 6-194828 communique; Te Kaiping 8-211599 communique; Te Kaiping 4-249549 communique; Te Kaiping 10-123316 communique; Te Kaiping 11-302283 communique; Te Kaiping 7-286107 communique; The spy opens the 2001-4823 communique; Te Kaiping 8-15522 communique; Te Kaiping 8-29771 communique; Te Kaiping 8-146215 communique; Te Kaiping 11-343437 communique; Te Kaiping 8-62416 communique; The spy opens the 2002-14220 communique; The spy opens the 2002-14221 communique; The spy opens the 2002-14222 communique; The spy opens the 2002-14223 communique; Te Kaiping 8-302224 communique; Te Kaiping 8-73758 communique; Te Kaiping 8-179120 communique; The dyestuff of record in the Te Kaiping 8-151531 communique etc.
As chemical constitution, can use dyestuffs such as pyrazoles azo class, aniline azo class, triphenylmethane, anthraquinone class, anthrapyridones, benzylidene class, oxonols class, pyrazoles triazole azo class, pyridone azo class, cyanine class, phenothiazines, pyrrolo-pyrazoles azomethine class, xanthene class, phthalocyanines, benzo pyran, indigo class.
The content of colorant is under the situation of black (BM) with respect to the quality of all solids composition in the curing colouration composition at colorant, is preferably above, above, the 50 quality %～75 quality % more preferably of 45 quality % more preferably of 40 quality %.
Be to be preferably more than the 25 quality % under red (R) situation, more preferably more than the 30 quality %, 35 quality %～50 quality % more preferably.
Under the situation that is green (G), be preferably more than the 35 quality %, more preferably more than the 40 quality %, 45 quality %～60 quality % more preferably.
Under the situation that is blue (B), be preferably more than the 25 quality %, more preferably more than the 28 quality %, 30 quality %～50 quality % more preferably.
Because the absorption of colorant etc. and can not arriving by the foot of exposure layer, curing colouration composition can't fully solidify under the situation of content in above-mentioned scope of colorant, as the ultraviolet ray (especially 365nm) of exposure light.Therefore, not enough by the curing owing to exposure of the foot of exposure layer, the identification (descry) in being difficult to obtain to develop, in addition, development edge (margine) diminishes or development tolerance (1atitude) diminishes.In addition, different according to the kind (RGB and BM) of colorant, the absorbance log of exposure light (even degree of cure of this dyed layer foot) is different.Curing colouration composition of the present invention can be brought into play effect when the content of colorant is big.Curing colouration composition of the present invention can obtain the colour purity height, the dyed layer that light-proofness is good, and it films and has high sensitivity, obtains development edge and the better development property of development tolerance.
< polymerization initiator >
Curing colouration composition of the present invention contains Photoepolymerizationinitiater initiater, thermal polymerization according to the coating process of dyed layer.Below describe in detail.
-Photoepolymerizationinitiater initiater-
Curing colouration composition of the present invention contains at least a Photoepolymerizationinitiater initiater passing through the slot coated mode under the situation of coating dyed layer on the substrate.Through using Photoepolymerizationinitiater initiater, can obtain the more degree of cure of height, and can also be according to expectation control curable.
As Photoepolymerizationinitiater initiater, for example can enumerate out Lu for Jia oxadiazole compound or halogenated methyl-s-compound in triazine class isoreactivity halogen compounds, 3-aryl substituted cumarin compound, at least a lophine dimer etc.
In the above-mentioned active halogen compound, for Jia oxadiazole compound, can enumerate out 2-halogenated methyl-5-vinyl-1,3 of representing by general formula I V of putting down in writing in the for example special public clear 57-6096 communique, 4-oxadiazole compound etc. as above-mentioned Lu.
As above-mentioned 2-halogenated methyl-5-vinyl-1,3, the object lesson of 4-oxadiazole compound; Can enumerate out 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(right-the cyano styrene base)-1; 3; 4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyrene base)-1,3,4-oxadiazole etc.
As above-mentioned halogenated methyl-s-compound in triazine class; Can enumerate out the vinyl-halogenated methyl-s-triaizine compounds, the spy that represent by general formula V that put down in writing in the for example special public clear 59-1281 communique and open the 2-(naphthalene-1-yl)-4 that representes by general formula VI that puts down in writing in the clear 53-133428 communique; 6-pair-halogenated methyl-s-triaizine compounds and the 4-(right-aminophenyl)-2 that representes by general formula VII, 6-pair-halogenated methyl-s-triaizine compounds etc.
Object lesson as above-mentioned vinyl-halogenated methyl-s-triaizine compounds; For example can enumerate out 2; 4-two (trichloromethyl)-6-p-methoxystyrene base-s-triazine, 2; 4-two (trichloromethyl)-6-(1-right-dimethylamino phenyl-1,3-butadiene base)-s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyrene base-s-triazine etc.
As above-mentioned 2-(naphthalene-1-yl)-4, the object lesson of 6-pair-halogenated methyl-s-triaizine compounds can be enumerated out for example 2-(naphthalene-1-yl)-4; 6-couple-trichloromethyl-s-triazine, 2-(4-methoxyl-naphthalene-1-yl)-4; 6-couple-trichloromethyl-s-triazine, 2-(4-ethoxy-naphthalene-1-yl)-4,6-couple-trichloromethyl-s-triazine, 2-(4-butoxy-naphthalene-1-yl)-4,6-couple-trichloromethyl-s-triazine, 2-[4-(2-methoxy ethyl)-naphthalene-1-yl]-4; 6-couple-trichloromethyl-s-triazine, 2-[4-(2-ethoxyethyl group)-naphthalene-1-yl]-4; 6-couple-trichloromethyl-s-triazine, 2-[4-(2-butoxyethyl group)-naphthalene-1-yl]-4,6-couple-trichloromethyl-s-triazine, 2-(2-methoxyl-naphthalene-1-yl)-4,6-couple-trichloromethyl-s-triazine, 2-(6-methoxyl-5-methyl-naphthalene-2-yl)-4; 6-couple-trichloromethyl-s-triazine, 2-(6-methoxyl-naphthalene-2-yl)-4; 6-couple-trichloromethyl-s-triazine, 2-(5-methoxyl-naphthalene-1-yl)-4,6-couple-trichloromethyl-s-triazine, 2-(4,7-dimethoxy-naphthalene-1-yl)-4; 6-couple-trichloromethyl-s-triazine, 2-(6-ethoxy-naphthalene-2-yl)-4; 6-couple-trichloromethyl-s-triazine, 2-(4,5-dimethoxy-naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine etc.
As above-mentioned 4-(right-aminophenyl)-2, the object lesson of 6-two-halogenated methyl-s-triaizine compounds can be enumerated out 4-[right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2; 6-two (trichloromethyl)-s-triazine, 4-[neighbour-methyl-right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[right-N, N-two (chloroethyl) aminophenyl]-2; 6-two (trichloromethyl)-s-triazine, 4-[neighbour-methyl-right-N, N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-(right-N-chloroethyl amino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-(right-N-ethoxy carbonyl methylamino phenyl)-2; 6-two (trichloromethyl)-s-triazine, 4-[right-N, N-two (phenyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-(right-N-chloroethyl carbonylamino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-[right-N-(right-methoxyphenyl) carbonylamino phenyl] 2; 6-two (trichloromethyl)-s-triazine, 4-[-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[-bromo-is right-N, and N-two (ethoxy carbonyl methyl) aminophenyl]-2; 6-two (trichloromethyl)-s-triazine, 4-[-chloro-is right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[-fluoro-is right-N; N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-bromo-is right-N, and N-two (ethoxy carbonyl methyl) aminophenyl]-2; 6-two (trichloromethyl)-s-triazine, 4-[neighbour-chloro-is right-N, and N-two (ethoxy carbonyl methyl) aminophenyl-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-fluoro-is right-N; N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-bromo-is right-N, and N-two (chloroethyl) aminophenyl]-2; 6-two (trichloromethyl)-s-triazine, 4-[neighbour-chloro-is right-N, N-two (chloroethyl) aminophenyl]-2, and 6-two (trichloromethyl)-s-triazine, 4-[neighbour-fluoro-is right-N; N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[-bromo-is right-N, and N-two (chloroethyl) aminophenyl]-2; 6-two (trichloromethyl)-s-triazine, 4-[-chloro-is right-N, N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[-fluoro-is right-N; N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-(-bromo-is right-N-ethoxy carbonyl methylamino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-(-chloro-is right-N-ethoxy carbonyl methylamino phenyl) and-2; 6-two (trichloromethyl)-s-triazine, 4-(-fluoro-is right-N-ethoxy carbonyl methylamino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-(neighbour-bromo-right-N-ethoxy carbonyl methylamino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-(neighbour-chloro-right-N-ethoxy carbonyl methylamino phenyl)-2; 6-two (trichloromethyl)-s-triazine, 4-(neighbour-fluoro-right-N-ethoxy carbonyl methylamino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-(-bromo-is right-N-chloroethyl amino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-(-chloro-is right-N-chloroethyl amino phenyl) and-2; 6-two (trichloromethyl)-s-triazine, 4-(-fluoro-is right-N-chloroethyl amino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-(neighbour-bromo-right-N-chloroethyl amino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-(neighbour-chloro-right-N-chloroethyl amino phenyl)-2; 6-two (trichloromethyl)-s-triazine, 4-(neighbour-fluoro-right-N-chloroethyl amino phenyl)-2,6-two (trichloromethyl)-s-triazine, 2,4-two (trichloromethyl)-6-[3-bromo-4-[N; N-two (ethoxy carbonyl methyl) amino] phenyl]-1,3,5-triazines etc.
Above-mentioned 3-aryl substituted cumarin compound particularly preferably is { (s-triazine-2-yl) amino }-3-aryl-coumarin compounds.
Above-mentioned lophine dimer be meant by 2 lophine residues constitute 2,4,5-triphenyl imidazole radicals dimer.
As object lesson; Can enumerate out 2-(neighbour-chlorphenyl)-4,5-diphenyl-imidazole base dimer, 2-(ortho-fluorophenyl base)-4,5-diphenyl-imidazole base dimer, 2-(neighbour-methoxyphenyl)-4; 5-diphenyl-imidazole base dimer, 2-(right-methoxyphenyl)-4; 5-diphenyl-imidazole base dimer, 2-(right-Dimethoxyphenyl)-4,5-diphenyl-imidazole base dimer, 2-(2, the 4-Dimethoxyphenyl)-4; 5-diphenyl-imidazole base dimer, 2-(right-the methyl mercapto phenyl)-4,5-diphenyl-imidazole base dimer etc.
Except above-mentioned Photoepolymerizationinitiater initiater, can also use other known initiating agent.
Can enumerate out the for example vicinalpolyketoaldonyl compound of United States Patent (USP) 2367660A record; The alpha-carbonyl compound of putting down in writing in No. 2367661 instructionss of United States Patent (USP) and the US2367670 instructions; The acyloin ether of putting down in writing in No. 2448828 instructionss of United States Patent (USP); Put down in writing in No. 2722512 instructionss of United States Patent (USP) by the aromatic series acyloin compound of α-hydrocarbyl substituted; The multinuclear naphtoquinone compounds of putting down in writing in No. 3046127 instructionss of United States Patent (USP) and No. 2951758 instructionss of United States Patent (USP); The combination of triallyl imidazole dimer/right-aminophenyl ketone of putting down in writing in No. 3549367 instructionss of United States Patent (USP); Benzothiazole compound/three halos methylol-s-compound in triazine class of putting down in writing in the special public clear 51-48516 communique etc.
In addition; Can also use ア デ カ オ プ ト マ one SP-150, ア デ カ オ プ ト マ one SP-151, ア デ カ オ プ ト マ one SP-170, ア デ カ オ プ ト マ one SP-171, ア デ カ オ プ ト マ one SP-N-1717, ア デ カ オ プ ト マ one SP-N1414 etc. (above be rising sun electrification (strain) manufacturing), OXE-01, OXE-02, CGI113, IR369, IR907, IR184, IR819 (above be Ciba Speciaities Chemicals Co.Ltd., manufacturing) etc. as Photoepolymerizationinitiater initiater.
With respect to all solids composition of curing colouration composition, the content of Photoepolymerizationinitiater initiater is preferably 0.5 quality %～20.0 quality %, more preferably 1.0 quality %～15.0 quality %.If the content of Photoepolymerizationinitiater initiater in above-mentioned scope, then can carry out polymerizing curable well, obtain the film strength of height.
In Photoepolymerizationinitiater initiater, as required, can also be also with following sensitizer.
As object lesson; Can enumerate out benzoin, benzoin methyl ether, 9-Fluorenone, 2-chloro-9-Fluorenone, 2-methyl-9-Fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone, 9; 10-anthraquinone, 2-ethyl-9; 10-anthraquinone, the 2-tert-butyl group-9; 10-anthraquinone, 2; 6-two chloro-9; 10-anthraquinone, xanthone, 2-methyl xanthone, 2-methoxyl xanthone, 2-ethoxy xanthone, thioxanthones, dibenzoyl, dibenzylidene benzophenone, right-(dimethylamino) styryl phenyl base ketone, right-(dimethylamino) phenyl-p-methylstyrene base ketone, benzophenone, right-(dimethylamino) benzophenone (or michler ' s ketone), right-(diethylamino) benzophenone, benzanthrone, 7-{L-4-chloro-6-(diethylamino)-S-triazinyl (2), 1-is amino }-benzothiazole compound put down in writing in 3-phenyl cumarin etc. or the special public clear 51-48516 communique etc.
-thermal polymerization-
Curing colouration composition of the present invention is containing at least a of thermal polymerization polymerization initiator through ink-jetting style under the situation of base plate coating dyed layer.Through using the optical polymerism initiating agent, can obtain the more degree of cure of height, and can also be according to expectation control curable.
Wherein, also can use above-mentioned Photoepolymerizationinitiater initiater as thermal polymerization.
For example, in above-mentioned thermal polymerization, for the Jia oxadiazole, can enumerate out 2-halogenated methyl-5-vinyl-1 of putting down in writing in the special public clear 57-6096 communique as Lu; 3,4-oxadiazole compound, specifically can be enumerated out 2-trichloromethyl-5-styryl-1; 3,4-oxadiazole, 2-trichloromethyl-5-(right-the cyano styrene base)-1,3; 4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyrene base)-1,3,4-oxadiazole etc.
In addition, can enumerate out the spy and open the 2-(naphthalene-1-yl)-4 that puts down in writing in the clear 53-133428 communique, 6-couple-halogenated methyl-s-triaizine compounds, 4-(right-aminophenyl)-2; 6-two-halogenated methyl-s-triaizine compounds, specifically can be enumerated out 2-(naphthalene-1-yl)-4, and 6-is two-trichloromethyl-s-triazine, 2-(4-methoxyl-naphthalene-1-yl)-4; 6-couple-trichloromethyl-s-triazine, 2-(4-ethoxy-naphthalene-1-yl)-4,6-couple-trichloromethyl-s-triazine, 2-(4-butoxy-naphthalene-1-yl)-4,6-couple-trichloromethyl-s-triazine, 2-[4-(2-ethoxyethyl group)-naphthalene-1-yl]-4; 6-couple-trichloromethyl-s-triazine, 2-(2-methoxyl-naphthalene-1-yl)-4,6-couple-trichloromethyl-s-triazine, 2-(6-methoxyl-5-methyl-naphthalene-2-yl)-4,6-couple-trichloromethyl-s-triazine, 2-(6-methoxyl-naphthalene-2-yl)-4; 6-couple-trichloromethyl-s-triazine, 2-(5-methoxyl-naphthalene-1-yl)-4,6-couple-trichloromethyl-s-triazine, 2-(4,7-dimethoxy-naphthalene-1-yl)-4; 6-couple-trichloromethyl-s-triazine, 2-(6-ethoxy-naphthalene-2-yl)-4,6-couple-trichloromethyl-s-triazine, 2-(4,5-dimethoxy-naphthalene-1-yl)-4; 6-couple-trichloromethyl-s-triazine, 4-[right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4 is [right-N; N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-methyl-right-N, N-two (chloroethyl) aminophenyl]-2; 6-two (trichloromethyl)-s-triazine, 4-(right-N-chloroethyl amino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-(right-N-ethoxy carbonyl methylamino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-are [right-N; N-two (phenyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[right-N-(right-methoxyphenyl) carbonylamino phenyl] 2,6-two (trichloromethyl)-s-triazine, 4-[-N; N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-bromo-is right-N, and N-two (chloroethyl) aminophenyl]-2; 6-two (trichloromethyl)-s-triazine, 4-[neighbour-chloro-is right-N, N-two (chloroethyl) aminophenyl]-2, and 6-two (trichloromethyl)-s-triazine, 4-[neighbour-fluoro-is right-N; N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[-bromo-is right-N, and N-two (chloroethyl) aminophenyl]-2; 6-two (trichloromethyl)-s-triazine, 4-[-chloro-is right-N, N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[-fluoro-is right-N; N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-(-chloro-is right-N-ethoxy carbonyl methylamino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-(neighbour-bromo-right-N-ethoxy carbonyl methylamino phenyl)-2; 6-two (trichloromethyl)-s-triazine, 4-(neighbour-chloro-right-N-ethoxy carbonyl methylamino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-(-bromo-is right-N-chloroethyl amino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-(-chloro-is right-N-chloroethyl amino phenyl) and-2; 6-two (trichloromethyl)-s-triazine, 4-(neighbour-chloro-right-N-chloroethyl amino phenyl)-2, and 6-two (trichloromethyl)-s-triazine, 4-[neighbour-bromo-is right-N, and N-two (ethoxy carbonyl) aminophenyl] 2; 6-two (trichloromethyl)-S-triazine, 2,4-two (trichloromethyl)-6-p-methoxystyrene base-s-triazine etc.
In these materials; As being suitable for the material of making curing colouration composition of the present invention, can enumerate out 4-[neighbour-bromo-is right-N, N-two (ethoxy carbonyl) aminophenyl] 2; 6-two (trichloromethyl)-S-triazine, 2,4-two (trichloromethyl)-6-p-methoxystyrene base-s-triazine.
In curing colouration composition of the present invention, except above-mentioned thermal polymerization, as required, can also add other thermal polymerization.
As other thermal polymerization; Be usually known organic peroxide compounds, azo compound, Lu for Jia oxadiazole or halogenated methyl-s-triazine isoreactivity halogen compounds etc., it is higher, stable and produce the compound as polymerization initiator of free radical through decomposes at normal temperatures to be preferably decomposition temperature.
The organic peroxide compounds is meant in molecule to have-organic compound of O-O-key.
If classify, then can enumerate out ketone peroxide, ketal peroxide, hydroperoxides, dialkyl peroxide, diacyl peroxide, peroxyester, peroxy dicarbonate etc. with chemical constitution.
Specifically, can enumerate out 3,3 ', 4; 4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, benzoyl peroxide, 2,2-two (4,4-two-tert-butyl hydroperoxide cyclohexyl) propane, 1; 1-two (peroxidating uncle hexyl)-3,3,5-trimethyl-cyclohexane, peroxidating benzoic acid tertiary butyl ester, peroxidating benzoic acid di-t-butyl ester, peroxidating m-phthalic acid di-t-butyl ester, peroxidating ra-butyl acetate, peroxidating benzoic acid uncle hexyl ester, peroxidating-3; 5,5-tri-methyl hexanoic acid tertiary butyl ester, peroxidating lauric acid tertiary butyl ester, peroxidating isopropyl list carbonic acid tertiary butyl ester, peroxidating-2-ethylhexyl list carbonic acid tertiary butyl ester, 2,5-dimethyl-2; 5-two (tolyl between peroxidating) hexane, 2,5-dimethyl-2,5-two (benzoyl peroxide base) hexane, peroxidating isopropyl list carbonic acid uncle hexyl ester, peroxidating isobutyric acid tertiary butyl ester, peroxidating-2 ethyl hexanoic acid 1; 1,3,3-tetramethyl butyl ester,, 2; 5-dimethyl-2,5-two (peroxidating 2-ethyl hexanoyl base) hexane, peroxidating-2 ethyl hexanoic acid tertiary butyl ester, tert-butyl hydroperoxide maleic amide, cyclohexanone superoxide, methyl-acetoacetic ester superoxide, methyl hexanone superoxide, acetyl acetone peroxide, 1,1-two (uncle's hexyl peroxide)-3; 3,5-trimethyl-cyclohexane, 1,1-two (peroxidating uncle hexyl) cyclohexane, 1; 1-two (tert-butyl peroxide)-3,3,5-trimethyl-cyclohexane, 1; 1-two (tert-butyl hydroperoxide)-2-methylcyclohexane, 1,1-two (tert-butyl hydroperoxide) cyclohexane, 2,2-two (tert-butyl peroxide) butane, diisopropyl benzene hydroperoxides, hydroperoxides, 1; 1,3,3-tetramethyl butyl hydroperoxides, cumene hydroperoxide, tert butyl hydroperoxide etc.; Be preferably 2, ketal peroxide compounds such as 2-two (4,4-two-tert-butyl hydroperoxide cyclohexyl) propane; Diacyl peroxide compounds such as benzoyl peroxide; Peroxyester compounds such as tert butyl peroxy benzoate.
As azo compound, can enumerate out 1,1 '-azo two (cyclohexane-1-nitrile), 1-[(1-cyanic acid-1-Methylethyl) azo] formamide (2-(carbamyl azo) isobutyronotrile) etc.
As triaizine compounds, can enumerate out the vinyl-halogenated methyl-s-triaizine compounds, the spy that put down in writing in the special public clear 59-1281 communique and open the 2-(naphthalene-1-yl)-4 that puts down in writing in the clear 53-133428 communique, 6-pair-halogenated methyl-s-triaizine compounds and 4-(right-aminophenyl)-2; 6-two-halogenated methyl-s-triaizine compounds specifically, can enumerate out 2; 4-two (trichloromethyl)-6-p-methoxystyrene base-s-triazine, 2,4-two (trichloromethyl)-6-(1-right-dimethylamino phenyl-1,3-butadiene base)-s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyrene base-s-triazine, 2-[4-(2-methoxy ethyl)-naphthalene-1-yl]-4; 6-couple-trichloromethyl-s-triazine, 2-[4-(2-butoxyethyl group)-naphthalene-1-yl]-4; 6-couple-trichloromethyl-s-triazine, 4-[neighbour-methyl-right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-(right-N-chloroethyl carbonylamino phenyl)-2; 6-two (trichloromethyl)-s-triazine, 4-[-bromo-is right-N; N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[-chloro-is right-N, and N-two (ethoxy carbonyl methyl) aminophenyl]-2; 6-two (trichloromethyl)-s-triazine, 4-[-fluoro-is right-N; N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-bromo-is right-N, and N-two (ethoxy carbonyl methyl) aminophenyl]-2; 6-two (trichloromethyl)-s-triazine, 4-[neighbour-chloro-is right-N; N-two (ethoxy carbonyl methyl) aminophenyl-, and 6-two (trichloromethyl)-s-triazine, 4-[neighbour-fluoro-is right-N, and N-two (ethoxy carbonyl methyl) aminophenyl]-2; 6-two (trichloromethyl)-s-triazine, 4-(-bromo-is right-N-ethoxy carbonyl methylamino phenyl) and-2,6-two (trichloromethyl)-s-triazine etc.
In the present invention, unqualified to above thermal polymerization, can also use other known material.
If the content of thermal polymerization is more than the 1 quality % with respect to all solids composition of curing colouration composition of the present invention; Then dyed layer fully solidifies; If all solids composition with respect to curing colouration composition of the present invention is below the 30 quality % in addition, then the viscosity of composition keeps certain, time dependent excellent in stability.In addition, if use the material of the higher material of half life temperature (be preferably more than 50 ℃, more preferably more than 80 ℃), then can form can time dependent preferred formation for the viscosity of composition.These initiating agents can use a kind, or combination more than 2 kinds is used.
< polymerizable compound >
Curing colouration composition of the present invention is according to different optical polymerism compound, the thermal polymerization property compounds of containing of the coating process of dyed layer.Below describe in detail.
-optical polymerism compound-
Curing colouration composition of the present invention contains a kind of optical polymerism compound at least.Through using, can obtain more the degree of cure of height with above-mentioned optical polymerism initiating agent, and can also be according to expectation control curable.
The optical polymerism compound receives from the effect of the spike of above-mentioned Photoepolymerizationinitiater initiater and polymerizing curable, formation image.
As the optical polymerism compound, boiling point is the compound with at least 1 olefinic unsaturated group more than 100 ℃ under the preferred normal pressure, and wherein, more preferably 4 officials can above acrylate compounds.
As boiling point under the normal pressure is the compound with at least 1 olefinic unsaturated group more than 100 ℃, can enumerate out the for example acrylic ester or the methacrylate of simple functions such as polyethyleneglycol (methyl) acrylic ester, polypropylene glycol list (methyl) acrylic ester, phenoxy group ethyl (methyl) acrylic ester; Polyglycol two (methyl) acrylic ester; Trimethylolethane trimethacrylate (methyl) acrylic ester; Neopentyl glycol two (methyl) acrylic ester; Pentaerythrite three (methyl) acrylic ester; Pentaerythrite four (methyl) acrylic ester; Dipentaerythritol six (methyl) acrylic ester; Hexane diol (methyl) acrylic ester; Trimethylolpropane tris (acryloyl group oxygen base propyl group) ether; Three (acryloxy ethyl) chlorinated isocyanurates; Material with (methyl) acroleic acid esterification after polyfunctional alcohols such as glycerine or trimethylolethane and oxirane or the epoxypropane addition; The material that gathers (methyl) acroleic acid esterification of pentaerythrite or dipentaerythritol; Special public clear 48-41708 communique; Special public clear 50-6034 communique; The spy opens the urethane acrylate class of putting down in writing in the clear 51-37193 communique; The spy opens clear 48-64183 communique; Special public clear 49-43191 communique; Put down in writing in the special public clear 52-30490 communique as polyester acrylate class class; Polyfunctional acrylic ester or methacrylate as the epoxy acrylate class of epoxy resin and (methyl) acrylic acid reaction product etc.
The material that in addition, can also use Japan then to introduce as photo-curable monomer and oligomer among the magazine Vol.20 of association, NO.7,300～308 pages.
In addition, can also use the spy to open in the flat 10-62986 communique and put down in writing, with the compound of (methyl) acroleic acid esterification after above-mentioned polyfunctional alcohol and oxirane or the epoxypropane addition with its object lesson with the form of general formula (1) and (2).
Wherein, preferred dipentaerythritol five (methyl) acrylic ester, dipentaerythritol six (methyl) acrylic ester and these acryloxies are through the structure of monoethylene glycol, the formation of propylene glycol residue.Can also use the oligomer types of these materials.
The optical polymerism compound can use a kind of, also can combination more than 2 kinds be used.
As the content of optical polymerism compound, with respect to all solids composition of 100 mass parts curing colouration composition of the present invention, be preferably 20 mass parts～200 mass parts, more preferably 50 mass parts～120 mass parts.If this content in above-mentioned scope, then can be cured well.
-thermal polymerization property compound-
Curing colouration composition of the present invention contains a kind of thermal polymerization property compound at least.Through using with above-mentioned thermal polymerization property initiating agent, can obtain the more degree of cure of height, and can also be according to expectation control curable.
Wherein, above-mentioned optical polymerism compound can be used as thermal polymerization property compound.
Wherein preferred compound is the compound with 2 above ethylenically unsaturated groups, and molecular weight is that the material below 1000 is good in the flatness of beating after dripping, and is preferred.Specifically, can enumerate out trimethylolethane trimethacrylate (methyl) acrylic ester, neopentyl glycol two (methyl) acrylic ester, dipentaerythritol six (methyl) acrylic ester, hexanediol (methyl) acrylic ester, trimethylolpropane tris (acryloyl group oxygen base propyl group) ether etc.
In curing colouration composition of the present invention, as required, can contain epoxy compound.
Above-mentioned epoxy compound has at least 2 epoxide rings in 1 molecule.If 2 of the number deficiency of the epoxide ring in 1 molecule, then degree of cure is not enough, in addition, can't guarantee solvent resistance, the voltage retention of height.
As the number of the epoxide ring that in 1 molecule, has, be preferably 2～10, more preferably 2～5.
As having at least 2 epoxide rings, calculated value epoxide equivalent (molecular weight/epoxy number of rings) in 1 molecule is 100～500 epoxy compound (epoxy compound of the present invention), can enumerate out bisphenol A-type, cresols phenol aldehyde type, biphenyl type, alicyclic epoxy compound etc.For example, as above-mentioned bisphenol A-type, can enumerate out エ Port ト one ト YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 etc. (above make), デ Na コ one Le EX-1101, EX-1102, EX-1103 etc. (above make), プ ヲ Network セ Le GL-61, GL-62, G101, G102 (above make for ダ イ セ Le chemistry society) for Na ガ セ changes into society for Dongdu changes into society and with Bisphenol F type, bisphenol S type like these material types.In addition, can also use Ebecryl3700, Ebecryl3701, Ebecryl600 epoxy acrylates such as (above are that ダ イ セ Le サ イ テ Star Network society makes).In addition; As above-mentioned cresols phenol aldehyde type, can enumerate out エ Port ト one ト YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704 etc. (above make), デ Na コ one Le EM-125 etc. (above make), as above-mentioned biphenyl type for Na ガ セ changes into society for Dongdu changes into society; Can enumerate out 3; 5,3 ', 5 '-tetramethyl-4; 4 '-diglycidyl biphenyl etc.; In addition, as above-mentioned alicyclic epoxy compound, can enumerate out セ ロ キ サ イ De 2021, セ ロ キ サ イ De 2081, セ ロ キ サ イ De 2083, セ ロ キ サ イ De 2085, エ Port リ one De GT-301, GT-302, GT-401, GT-403, EHPE-3150 (above make for ダ イ セ Le chemistry society), サ Application ト one ト ST-3000, ST-4000, ST-5080, ST-5100 etc. (above make) etc. for Dongdu changes into society.In addition; 1; 1; 2,2-four (right-glycidyl oxygen base phenyl) ethane, three (right-glycidyl oxygen base phenyl) methane, three-glycidyl machine three (hydroxyethyl) chlorinated isocyanurates, phthalic acid diglycidyl ester, terephthalic acid (TPA) diglycidyl ester, エ Port ト one ト YH-434, YH-434L as other amine type epoxy resin, in the skeleton of bisphenol A type epoxy resin through dimer acid modified glycidyl esters etc.
In ink-jetting style, the addition of epoxy compound can be in the scope of 50 quality % at all solids composition of the pigment that is no more than with respect to remove curing colouration composition.If this content of resin is in above-mentioned scope, the effect that suppresses volumetric contraction when then solidifying is high, as ink-jet method, giving drop to cut zone and forming under the situation of cured film, can obtain the tabular surface of uniform thickness, and the solvent resistance of film is also excellent.Under the situation of slot coated mode, can significantly improve solvent resistance, the mar resistance of film with the interpolation below the 10 quality %.
< other composition >
Curing colouration composition of the present invention is except mentioned component; As required; Can also mix various additives; For example, the macromolecular compound beyond the filling agent, above-mentioned alkali soluble resins, the surfactant beyond above-mentioned, adhesion promotor, antioxidant, ultraviolet light absorber, anti-polycoagulant etc.
As the object lesson of various additives, can enumerate out filling agents such as glass, aluminium oxide; Adhesion promotors such as vinyltrimethoxy silane, VTES, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, (methyl) acryloyl group propyl trimethoxy silicane, (methyl) acryloyl group propyl-triethoxysilicane, 3-aminopropyltriethoxywerene werene, 3-glycidyl ether oxygen propyl trimethoxy silicane, 3--glycidyl ether oxygen propyl methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-metacryloxy propyl trimethoxy silicane, 3-sulfydryl propyl trimethoxy silicane; 2,2-sulfo-two (4-methyl-6-tert butyl phenol), 2, antioxidants such as 6-two-tert-butyl phenol; Ultraviolet light absorbers such as 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, alkoxy benzophenone.
In addition, in order to promote the alkali dissolution property of uncured portion, further improve under the situation of development property of curing colouration composition, can add organic carboxyl acid, preferred molecular weight is the low-molecular-weight organic carboxyl acid below 1000.
Specifically, for example can enumerate out formic acid, acetate, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethacetic acid, enanthic acid, aliphatic monocarboxylic acid such as sad; Aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, brazilic acid, methylmalonic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl succinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoronic acid; Benzic acid, toluic acid, cumic acid, 2,3-mesitylenic acid, 3, aromatic monocarboxylates such as 5-mesitylenic acid; Aromatic multi-carboxy acids such as phthalic acid, terephthalic acid (TPA), m-phthalic acid, trimellitic acid, trimesic acid, mellophanic acid, PMA; Other carboxylic acids such as phenylacetic acid, phenoxyacetic acid, methoxybenzene ethoxyacetic acid, hydrogenation atropic acid, hydrogenation cinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, cinnamic acid benzyl ester, cinnamylidene acetate, coumaric acid, umbellic acid.
In curing colouration composition of the present invention, except above-mentioned, preferred further interpolation thermal polymerization prevents agent.Prevent agent as thermal polymerization; For example quinhydrones, Hydroquinone monomethylether, right-metoxyphenol, di-t-butyl-p-Cresol, pyrogallol, tert-butyl catechol, benzoquinones, 4; 4 '-sulfo-two (3 methy 6 tert butyl phenol), 2,2 '-methylene two (4-methyl-6-tert butyl phenol), 2-mercaptobenzimidazole etc. are useful.
< color filter and liquid display element >
Color filter of the present invention is provided with usually at the bottom of the different a plurality of colored pixels of tone and the fast black base of isolating colored pixels and constitutes.These (especially at the bottom of fast black bases) can form dyed layer through the above-mentioned curing colouration composition of the present invention of coating on substrate, after dry (prebake), make public into the pattern of expectation, prepare through development treatment.
Color filter of the present invention uses above-mentioned curing colouration composition of the present invention to constitute; For example can on the substrate of expectation, coating be modulated into liquid curing colouration composition etc. and form photosensitive layer; The photo-curable layer that forms is made public into pattern-like, wait through developing to form.In addition, owing to use above-mentioned curing colouration composition to constitute, so the optical concentration of black is high, constitutes the good bright-coloured pattern of cross section rectangle at the bottom of the fast black base.
Below, an example of manufacturing method of color filter of the present invention is shown.
The preparation of-curing colouration composition-
Curing colouration composition of the present invention is through mixed colorant, acrylic copolymer of the present invention (alkali soluble resins), polymerizable compound and Photoepolymerizationinitiater initiater and other composition (preferably with solvent) that uses as required and use various mixers or the dispersion machine mixed and dispersed prepares.
In addition, the operation of mixed and dispersed (mixed and dispersed operation) is preferably loose to handle through mixing dispersion and the differential that then carries out thereafter and is constituted, and also can omit mixing dispersion.In addition, the pigment type that in mixing, dispersion step, uses preferably through the mixing method of salt etc. with the particle size miniaturization.The mixing method of salt is known in special permission 3130217, special table 2003-504480 etc.In addition, can also use the pigment of the particulate that forms through aggregation method.
In mixing dispersion step; Infiltration between the constituent that promotes the particle surface of raw material colorant and be the main body with the resinous principle of vehicles is converted into the solid/gas interface of coloring agent particle and air the solid/solution interface of coloring agent particle and vehicles solution.In differential looses process, mix stirring through dispersion in the lump with medium, thereby coloring agent particle is dispersed to the small state near primary particle the particulate of glass, zirconia or pottery.Therefore, owing in mixing dispersion step, must the interface that the coloring agent particle surface forms be converted to solution from air; Therefore strong shearing force force of compression must be arranged; Expect mixing roll corresponding, be full-bodied by mixing thing with it, on the other hand, in differential day labor preface; Must uniform particles stably be scattered in small state, expectation can give the dispersion machine of impulsive force and shearing force, is lower viscosity by disperse object the coloring agent particle of cohesion.
The mixing dispersion step that is used for preparing the color filter that uses curing colouration composition of the present invention at first is that the part of colorants such as organic pigment or carbon black, the present invention's dispersion resin and the spreading agent that uses as required or surface conditioning agent and partial solvent is mixing in the lump.The machinery that uses in mixing is 2 beaming rollers, 3 beaming rollers, bowl mill, roll grinding machine (ト ロ Application ミ Le), decollator, kneader, is total to kneader (コ ニ one ダ one), homogenizer, mixer, single shaft or 2 extruders etc., disperses while give strong shearing force.Then; Add dispersion resin among remaining solvent and the present invention (above-mentioned do not have in mixing use remainder); The main sand milling bed that uses longitudinal type or horizontal type, pin grinding, slit grinding, ultrasonic dispersing machine etc., pearls such as the glass through 0.01～1mm particle diameter, zirconium dioxide disperse.In addition, can also omit above-mentioned mixing operation.In this case, spreading agent or the surface conditioning agent with dispersion resin among colorants such as pigment, the present invention and use as required carries out the pearl dispersion with solvent.Use the dispersion resin among the present invention of part preferably in dispersion process, to add when in this case, mixing.
Also, " Paint Flow andPigment Dispersion (the John Wiley and Sons society periodical in 1964) " of T.C.Patton work put down in writing in waiting for detailed description mixing, that disperse.
The coating of-curing colouration composition-
Through on substrate directly or across coating method coating curing colouration compositions such as the spin coating of other layers, slot coated mode, curtain coating coating method, roll coating model, ink-jetting styles; Thereby form the light solidification pigmentation layer; Curing colouration composition of the present invention especially under the situation through slot coated mode, ink-jetting style coating, can be brought into play effect of the present invention.
[slot coated mode]
Spin coating (spin), slit and the spin mode of using at present is with the necessary condition that rotates to be of substrate, and the thickness of the curing colouration composition that on substrate, drips is through the rotation homogenising of substrate.Because the maximization of glass substrate in making its rotation, produce a large amount of loads, so large substrate is difficult to rotation.Therefore, developed the slit-shaped nozzle that uses necessary width in the slot coated, on glass substrate, evenly sprayed curing colouration composition, with even velocity travelling slit nozzle or the method (slot coated) of glass substrate to be coated with.
The translational speed of gap nozzle is generally 50～200mm/sec.Slot coated is not continuous, but individual coating of many ground coated substrates produces the gap between coating and coating.Needing can be betwixt because the drying of the cohesion of colorant or nozzle produce the curing colouration composition of foreign matter that kind.Requirement can not produce the curing colouration composition of the sagging such liquid rerum natura of liquid from nozzle in the terminal ejection that suppresses liquid of coating under the state that does not spray.In addition, for the homogeneity that can between drying, curing, guarantee to film, curing colouration composition must have high flowability (levelability).
In order to carry out individual coating, the equipment that the gap nozzle that need will be coated with cleans at every turn.The method of this each wiping nozzle is before coating, to flow through a spot of coating fluid earlier, carries out pre-coating, thereby makes method of nozzle cleaningization etc.The all methods of the present invention all are effectively, and special expectation is the method for ejection in advance.
The formation of-pattern-
Photomask through regulation carries out pattern exposure to the dyed layer like above-mentioned formation, only exposed portion is solidified, and through developer solution unexposed portion is developed and removes; The aforesaid operations of the tone number that only repeats to expect, thus can prepare the color filter that the colored pixels (comprising at the bottom of pixel and the fast black base) of the tone (for example 3 looks or 4 looks such as R, G, B, black) that expectation is set forms.
At this moment, the light source that uses in the exposure is preferably high-pressure mercury-vapor lamp.Ultraviolet rays such as preferred especially g line, h line, i line, j line more preferably are major component, comprise the ultraviolet ray of j line with i line, h line.Exposure machine can use the exposure machine near mode (プ ロ キ シ ミ テ イ one), also can use mirror projection pattern or move mode one by one.
Use the thickness (dry back) of the dyed layer of curing colouration composition formation to be preferably 0.3～5.0 μ m usually, more preferably 0.5～3.5 μ m is preferably 1.0～2.5 μ m especially.
The drying of dyed layer (prebake) heats in 50～140 ℃ temperature province and carried out in 10～300 seconds through in hot scraping blade, baking oven etc.Wherein, preferably in 70～130 ℃ temperature province, heated 60～180 seconds, more preferably in 90～120 ℃ temperature province, heat 90～120 ℃.Vacuum drying can also after prebake, be carried out, to finish drying.
-development treatment-
Development treatment is preferably alkaline development and handles, and wash-out passes through the uncured part of exposure in alkaline aqueous solution, only the cured portion of residual light curing.
As developer solution, so long as can dissolve uncured portion, can not dissolve the solvent of the cured portion that becomes filter portion, just can use arbitrarily.Specifically, can use the combination or the alkaline aqueous solution of various organic solvents, wherein, be preferably alkaline-based developer.
As above-mentioned alkaline aqueous solution; For example; The preferred use dissolved NaOH, potassium hydroxide, sodium carbonate, soda mint, sodium silicate, sodium metasilicate, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, tetramethyl-ammonium oxyhydroxide, tetraethyl ammonium oxyhydroxide, choline, pyrroles, piperidines, 1,8-diazabicyclo-[5,4; 0]-and alkali compounds such as 7-hendecene, make concentration be 0.001～10 quality %, be preferably the alkaline aqueous solution of 0.01～1 quality %.
As development temperature, be generally 20 ℃～30 ℃, as development time, preferably in 20～90 seconds scope.In addition, under the situation of using the developer solution that constitutes by such alkaline aqueous solution, after development, wash (flushing) usually.
After development treatment, as required, cure processing after can also carrying out.After to cure be the heat treated that is used for after the completely crued development, can under about 200～220 ℃, heat (curing firmly) usually.After cure that to handle be that layer after using hot scraping blade or heating arrangements such as convection oven (heated air circulation type dryer), high frequency heating machine to video picture under these conditions carries out with continous way or batch (-type).
[ink-jetting style]
The characteristic of color filter of the present invention is to pass through ink-jetting style after forming pattern of pixels on the substrate, under 150～250 ℃, carrying out heat treated.
In more detail; Manufacturing method of color filter of the present invention is following operation is set at least and constitutes, that is, and and on substrate in the recess of the separator lined of light-proofness; Give the drop of the curing colouration composition of the invention described above through ink-jetting style; Thereby form painted areas (pixel), the painted areas that forms is carried out heat treated and the operation of heat curing (below, be sometimes referred to as " pixel formation operation ").
In color filter of the present invention, use the structure of the above-mentioned curing colouration composition of the present invention through formation, thereby can not produce obstruction on the top of inkjet nozzle, operating efficiency is excellent, and the color filter of preparation is also excellent as above-mentioned.
Above-mentioned ink-jetting style can be from charged printing ink of continuous injection and the method through electric field controls, use piezoelectric element to carry out the method for interrupted injection printing ink, foaming when utilizing heating printing ink carries out selecting the known method such as method of interrupted injection.
See that on the viewpoint of when ejection stability the ejection condition optimization when spraying curing colouration composition of the present invention is: the temperature of above-mentioned composition is 20～50 ℃, and the viscosity of composition is reduced.If consider influence and image quality deterioration, then expect the above-mentioned composition temperature is kept constant as far as possible to drop size, drop spouting velocity.
In inkjet head (also only being called shower nozzle), can adopt known device.In hot shower nozzle,, preferably has the type of opening the operating pumps of record in flat 9-323420 number like the spy in order to spray.In piezo jets, can use the shower nozzle of record in European patent A277703 number, European patent A278590 etc.Shower nozzle preferably has the temperature adjustment function of the temperature that can manage printing ink.Injection temperation is set, makes that the viscosity when spraying is the scope of 5～25mPas, be preferably the control ink temperature, make the change amplitude of viscosity in ± 5%.In addition, as the driving frequency number, preferably operation under 1～500kHz.
The drying of polishing after stain layer is 100～200 ℃ of 30～120 seconds (prebake) of heating down, then 180～260 ℃ dry down, solidify (afterwards curing).Wherein, as required, can also pass through the vacuum drying operation.Also can omit prebake.
-substrate-
As aforesaid substrate; Can enumerate out the alkali-free glass that uses in the liquid crystal indicator for example etc., alkali glass, Pyrex (graded marks) glass, quartz glass and it is adhered to nesa coating and the glass that obtains, or the photo-electric conversion element substrate that uses in the solid-state imaging element etc. silicon substrate etc. for example.In addition, can also be plastic base.Under the situation of preparation color filter, usually form on these substrates at the bottom of a plurality of painted pixels and the fast black base of isolating each pixel.
Raw material as above-mentioned plastic base; From the viewpoint of optical characteristics, thermotolerance, physical strength, preferred unformed polyolefin, polyethersulfone, gather glutarimide, polycarbonate, polyethylene terephthalate, PEN, norbornene polymer, with the diphenylamine fluorenes be the polyimide of two amine components, the polyester that constitutes by bisphenol fluorene and dibasic acid etc.Wherein, preferred, polyethers sulfone, polycarbonate, polyethylene terephthalate and norbornene polymer.Above-mentioned raw materials is particularly preferably in using in the LCD purposes.
Characteristic as the plastic base requirement; Be low-thermal-expansion (deterioration of the display precision of the cured when preventing to be accompanied by the preparation color filter), optical characteristics, surface smoothing property etc. such as gas barrier (guaranteeing stability of liquid crystal), transmittance and optical isotropy.For thermal expansion, preferred thermal expansivity is 10
-4Below.In addition, in plastic base, preferably have barrier layer for gases and/or solvent resistance layer on its surface.
Curing colouration composition of the present invention is fit at the bottom of the fast black base that colored pixels that formation will constitute color filter isolates and the colored pixels of colour such as RGB.
On the color filter that uses curing colouration composition of the present invention to form, coating layer (planarization layer) can be set.As forming the resin (OC agent) of going up coating layer, can enumerate out acrylic resin composition, composition epoxy resin, polyimide resin composition etc.
In addition, be adapted at the bottom of the above-mentioned fast black base using in the liquid crystal indicator (LCD).Can be useful in the purposes such as carried terminals such as TV, PC, liquid crystal projection apparatus, game machine, portable phone, digital camera, fashionable dress with having no particular limits.
Embodiment
Below, embodiments of the invention are described, but the present invention is not done any qualification by these embodiment.In addition, do not particularly point out, " part " is quality criteria.
In an embodiment of the present invention, to coated face for preparing through the slot coated mode and the color filter through ink-jetting style preparation, estimate changing as the situation of the component of the curing colouration composition of coating fluid separately.
[embodiment 1]
< forming coated face>through the slot coated mode
" the 1. preparation of red solidification compound "
Under the condition of 3000rpm, use homogenizer to stir 1 hour the following red A of composition.Pearl dispersion machine (trade name: デ イ ス パ one マ Star ト, GETZMANN society make) through using 0.3mm zirconium dioxide pearl carries out 4 hours diffusing processing of differential to the gained mixed solution, obtains disperse object.In addition, the mean grain size of pigment is observed through SEM and is measured with usual method.
-red A-the dispersion liquid of forming
Pigment: 11 parts of paratoneres 254 (mean grain size 20nm)
Pigment: 4 parts of paratoneres 177 (mean grain size 18nm)
5 parts of dispersion resins (B-1-3) (following structure)
The mixed solvent of 3 parts of methoxyl butylacetic acid esters of spreading agent (trade name: Disperbyk-161, PVC Star Network ケ ミ one society make) and butyl acetate
Alkali soluble resins: 4 parts of methyl ether acetate solution of propylene glycol (solid constituent: 50 quality %) of methacrylic acid benzyl ester/methacrylic acid copolymer=75/25 [mass ratio] multipolymer, weight molecular weight Mw:5000
(B) solvent is used in the dispersion resin dissolving: 73 parts of propylene glycol methyl ether acetates (SP value 9.2,146 ℃ of boiling points)
-red B-the coating fluid of forming
100 parts of the dispersion liquids of red composition A
Epoxy resin: (trade name EHPE3150 ダ イ セ Le chemistry is made) 2 parts
Polymerizable compound: 8 parts of dipentaerythritol five/six acrylic ester
Polymerization initiator: 4-(neighbour-bromo-is right-N, N-two (ethoxy carbonyl methyl) amino-phenyl)-2,1 part of 6-two (trichloromethyl)-s-triazine
Polymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1 1 part
Polymerization initiator: 0.5 part of diethyl thioxanthone
Polymerization inhibitor: 0.001 part of p methoxy phenol
Fluorine class surfactant (trade name: the big Japanese ink manufacturing of Megafac R30) 0.01 part
0.2 part in nonionic class surfactant (trade name: テ ト ロ ニ Star Network R150, ADEKA manufacturing)
(A) high boiling solvent: 50 parts of 1,3 butylene glycol diacetate esters (232 ℃ of boiling points)
(B) solvent is used in the dispersion resin dissolving: 80 parts of propylene glycol methyl ether acetates (SP value 9.2,146 ℃ of boiling points)
Mix and stir the above-mentioned red B of composition, obtain the coating fluid of curing colouration composition.
[embodiment 2]
" preparation of green solidification compound "
Thereby the redness of embodiment 1 is formed A replace to the following green A of composition acquisition disperse object.
-green A-the dispersion liquid of forming
Pigment: 11 parts of pigment green 36s (mean grain size 19nm)
7 parts of pigment: Pigment Yellow 150 (mean grain size 22nm)
5 parts of dispersion resins (B-1-26) (following structure)
3 parts of spreading agents (trade name: Disperbyk-161, PVC Star Network ケ ミ one society make 30% solution)
Alkali soluble resins: methacrylic acid benzyl ester/methacrylic acid copolymer=75/25 [mass ratio] multipolymer, weight molecular weight Mw:5000 4 parts
Propylene glycol methyl ether acetate solution (solid constituent: 50 quality %)
(B) solvent is used in the dispersion resin dissolving: 70 parts of 3-ethoxy-propionic acid methyl esters (SP value 9.3,165 ℃ of boiling points)
-green B-the coating fluid of forming
100 parts of the dispersion liquids of green composition A
Epoxy resin: (trade name EHPE3150 ダ イ セ Le chemistry is made) 2 parts
Polymerizable compound: 8 parts of dipentaerythritol five/six acrylic ester
Polymerization initiator: 1,2 parts of two trihalomethyl groups of 3--5-coumarone triazine
Polymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1 1 part
Polymerization initiator: 0.5 part of diethyl thioxanthone
Polymerization inhibitor: 0.001 part of p methoxy phenol
0.02 part in fluorine class surfactant (trade name: Megafac R08, big Japanese ink manufacturing)
0.5 part in nonionic class surfactant (trade name: エ マ Le ゲ Application A-60, flower king manufacturing)
(A) high boiling solvent: 50 parts of 1,3 butylene glycol diacetate esters (232 ℃ of boiling points)
(B) solvent is used in the dispersion resin dissolving: 100 parts of 3-ethoxy-propionic acid methyl esters (SP value 9.3,165 ℃ of boiling points)
Mix and stir the above-mentioned green B of composition, obtain the coating fluid of curing colouration composition.
[embodiment 3]
" preparation of blue solidification compound "
Thereby the redness of embodiment 1 is formed A replace to the following blue A of composition acquisition disperse object.
-blue A-the dispersion liquid of forming
Pigment: pigment blue 15: 14 parts of 6 (mean grain size 15nm)
Pigment: 1 part of pigment Violet 23 (mean grain size of observing through SEM is 23nm)
5 parts of dispersion resins (B-1-35) (following structure)
Spreading agent (trade name: Disperbyk-161, PVC Star Network ケ ミ one society make 3 part of 30% solution)
Alkali soluble resins: methacrylic acid benzyl ester/methacrylic acid copolymer=75/25 [mass ratio] multipolymer, weight molecular weight Mw:5000 4 parts
Propylene glycol methyl ether acetate solution (solid constituent: 50 quality %)
(B) solvent is used in the dispersion resin dissolving: 73 parts of propylene glycol methyl ether acetates (SP value 9.2,146 ℃ of boiling points)
-blue B-the coating fluid of forming
100 parts of the dispersion liquids of blue composition A
Alkali soluble resins: 6 parts of propylene glycol methyl ether acetate solution of methacrylic acid benzyl ester/methacrylic acid copolymer=75/25 [mass ratio] multipolymer, weight molecular weight Mw:5000 (solid constituent: 50 quality %)
Epoxy resin: (trade name EHPE3150 ダ イ セ Le chemistry is made) 2 parts
UV curable resin: (trade name サ イ Network ロ マ one P ACA-250, ダ イ セ Le chemistry is made)
The propylene glycol methyl ether acetate solution (solid constituent 50 quality %) that comprises 4 parts of the acrylic copolymers of alicyclic ring, COOH base, acryloyl group at side chain
Polymerizable compound: 12 parts of dipentaerythritol five/six acrylic ester
3 parts of polymerization initiator: 1-(9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl)-1-(O-acetyl group oxime) ethyl ketone
Polymerization inhibitor: 0.001 part of p methoxy phenol
Fluorine class surfactant (trade name: the big Japanese ink manufacturing of Megafac R08) 0.02 part
1.0 parts in nonionic class surfactant (trade name: エ マ Le ゲ Application A-60 flower king makes)
(A) high boiling solvent: 20 parts of propylene glycol n-butyl ether acetic acid esters (211 ℃ of boiling points)
(B) solvent is used in the dispersion resin dissolving: 150 parts of propylene glycol methyl ether acetates (SP value 9.2,146 ℃ of boiling points)
Mix and stir the above-mentioned blue B of composition, obtain the coating fluid of curing colouration composition.
[embodiment 4]
" preparation of red solidification compound "
Mix and stir following red the composition, obtain the coating fluid of curing colouration composition.
100 parts of the dispersion liquids of above-mentioned red composition A
Epoxy resin: (trade name EHPE3150 ダ イ セ Le chemistry is made) 2 parts
Polymerizable compound: 8 parts of dipentaerythritol five/six acrylic ester
Polymerization initiator: 4-(neighbour-bromo-is right-N, N-two (ethoxy carbonyl methyl) amino-phenyl)-2,1 part of 6-two (trichloromethyl)-s-triazine
Polymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1 1 part
Polymerization initiator: 0.5 part of diethyl thioxanthone
Polymerization inhibitor: 0.001 part of p methoxy phenol
Fluorine class surfactant (trade name: the big Japanese ink manufacturing of Megafac R30) 0.01 part
0.2 part in nonionic class surfactant (trade name: テ ト ロ ニ Star Network R150 ADEKA makes)
(A) high boiling solvent: 35 parts of 1,3 butylene glycol diacetate esters (232 ℃ of boiling points)
(B) solvent is used in the dispersion resin dissolving: 30 parts of propylene glycol methyl ether acetates (SP value 9.2,146 ℃ of boiling points)
[embodiment 5]
" preparation of red solidification compound "
Mix and stir following red the composition, obtain the coating fluid of curing colouration composition.
100 parts of the dispersion liquids of above-mentioned red composition A
Epoxy resin: (trade name EHPE3150 ダ イ セ Le chemistry is made) 2 parts
Polymerizable compound: 8 parts of dipentaerythritol five/six acrylic ester
Polymerization initiator: 4-(neighbour-bromo-is right-N, N-two (ethoxy carbonyl methyl) amino-phenyl)-2,1 part of 6-two (trichloromethyl)-s-triazine
Polymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1
Polymerization initiator: 0.5 part of diethyl thioxanthone
Polymerization inhibitor: 0.001 part of p methoxy phenol
Fluorine class surfactant (trade name: the big Japanese ink manufacturing of Megafac R30) 0.01 part
0.2 part in nonionic class surfactant (trade name: テ ト ロ ニ Star Network R150 ADEKA makes)
(A) high boiling solvent: 102 parts of 1,3 butylene glycol diacetate esters (232 ℃ of boiling points)
(B) solvent is used in the dispersion resin dissolving: 28 parts of propylene glycol methyl ether acetates
(SP value 9.2,146 ℃ of boiling points)
[comparative example 1]
" preparation of red solidification compound "
Form among the B in redness,, form B with redness and likewise prepare curing colouration composition except (A) high boiling solvent is replaced with the propylene glycol methyl ether acetate.This composition does not comprise (A) of the present invention high boiling solvent.
[comparative example 2]
" preparation of red solidification compound "
80 parts of (B) dispersion resins dissolvings forming B with solvent and redness except 73 parts of (B) dispersion resin dissolvings redness being formed A replace with 73 part 1 respectively with solvent; 3-butylene glycol diacetate esters and 80 part 1; Beyond the 3-butylene glycol diacetate esters, likewise prepare curing colouration composition with redness composition A, the red B that forms.This composition is except the solvent that in spreading agent and alkali soluble resins solution, comprises, and solvent is used in (B) dispersion resin dissolving that does not contain among the present invention.Using the content of solvent with respect to the dissolving of (B) dispersion resin in whole solvents of coating fluid is 2 quality %.
[comparative example 3]
" preparation of red solidification compound "
In redness is formed A, part dispersion resin (B-1-3) is replaced with the composition of alkali soluble resins 1, promptly prepare dispersion liquid with the following red C that forms.
-red C-the dispersion liquid of forming
Pigment: 11 parts of paratoneres 254 (mean grain size 20nm)
Pigment: 4 parts of paratoneres 177 (mean grain size 18nm)
3 parts of spreading agents (trade name: Disperbyk-161, PVC Star Network ケ ミ one society make 30% solution)
Alkali soluble resins 1: 14 parts of methacrylic acid benzyl ester/methacrylic acid copolymers
The propylene glycol methyl ether acetate solution of=75/25 [mass ratio] multipolymer, weight molecular weight Mw:5000 (solid constituent: 50 quality %)
68 parts of propylene glycol methyl ether acetates (SP value 9.2,146 ℃ of boiling points)
Except using the red C of composition to replace the redness among the red B of composition to form the A, form B with redness and likewise prepare curing colouration composition.
[comparative example 4]
" preparation of red solidification compound "
(B) dispersion resin dissolving of forming B with solvent and redness except (B) dispersion resin dissolving of redness being formed A replaces with DIBK (SP:8.2 respectively with solvent; Bp:169 ℃) and DIBK (SP:8.2; Bp:169 ℃) in addition, form A with redness and likewise prepare curing colouration composition with the red B of composition.
[comparative example 5]
" preparation of red solidification compound "
(B) dispersion resin dissolving of forming B with solvent and redness except (B) dispersion resin dissolving of redness being formed A replaces with ethylene glycol monoethyl ether (SP value: 10.6 respectively with solvent; Bp:136 ℃) and ethylene glycol monoethyl ether (SP value: 10.6; Bp:136 ℃) in addition, form A with redness and likewise prepare curing colouration composition with the red B of composition.
[comparative example 6]
" preparation of red solidification compound "
(B) dispersion resin dissolving of forming B with solvent and redness except (B) dispersion resin dissolving of redness being formed A replaces with propylene glycol monomethyl ether (SP value: 10.4 respectively with solvent; Bp:120 ℃) and propylene glycol monomethyl ether (SP value: 10.4; Bp:120 ℃) in addition, form A with redness and likewise prepare curing colouration composition with the red B of composition.
The contained solvent, solvent is used in (B) dispersion resin dissolving that does not contain among the present invention to the composition of comparative example 4～comparative example 6 in resin solution.The content of propylene glycol methyl ether acetate is 2 quality % with respect to whole solvents of coating fluid.
[comparative example 7]
" preparation of red solidification compound "
(A) high boiling solvent of red composition B is replaced with 3-ethoxyethyl group propionic ester (bp:169 ℃), the preparation curing colouration composition.
< slot coated is fitted the evaluation of property >
1. coating striped
Use has the slot coated device of the slit shower nozzle of slit separation 100 μ m, coating effective width 500mm, slot coated is fitted property estimate.Regulate interval, spray volume between slit and glass substrate, make that dried coating thickness is 2 μ m, with coating speed 100mm/ second be the coating condition.Through usual way after 10 glass substrates (width 550mm, length 650mm, thickness 0.7mm) are gone up coating; Aloft with above-mentioned slit shower nozzle standby 5 minutes; After standby, carried out virtual assigned (dummy dispense) in 3 seconds, on glass substrate, intermittently be coated with 10 with previous status.Below same per 10 be coated with, amount to 100 coated substrates of preparation.After carrying out after the coating, cure after carrying out 60 seconds prebake under 90 ℃, use the striated of the visual calculating coated face of the sodium lamp inhomogeneous bar number of (below, suitably be called " coating striped ").
Be not coated with fully striped be evaluated as " zero ", have 1～5 be evaluated as " △ ", more than 6 for " * ".
2. foreign matter number
Through the foreign matter of size more than the above-mentioned visual calculating 20 μ m, estimate with the foreign matter number of per 1 substrate.
3. contrast
Through the contrast of contrast analyzer (trade name: BM-7, ト プ コ Application society make) the above-mentioned coated substrates of mensuration, as the index of dispersiveness.With with the recently expression of embodiment 1 as 100 o'clock.Yet,, therefore can't compare, thereby abandon with embodiment 1 because embodiment 2 is different in beam split with 3.
The result is shown in the table 1.
[embodiment 6]
" preparation of red solidification compound "
Replace with the following red D of composition except redness being formed A, form A with redness and likewise handle, obtain dispersion liquid.
-red D-the dispersion liquid of forming
Pigment: 11 parts of paratoneres 254 (mean grain size 20nm)
Pigment: 4 parts of paratoneres 177 (mean grain size 18nm)
Dispersion resin (B-2-1) (following structure)
(following monomer M-2/ methacrylic acid/end has carried out the metering system acidylate
5 parts of polymethyl methacrylate copolymer (10/15/75 quality %, weight-average molecular weight 25000))
(trade name: Disperbyk-161, PVC Star Network ケ ミ one society make 30% to spreading agent
3 parts of solution)
Alkali soluble resins: 4 parts of propylene glycol methyl ether acetate solution of methacrylic acid benzyl ester/methacrylic acid copolymer=75/25 [mass ratio] multipolymer, weight molecular weight Mw:5000 (solid constituent: 50 quality %)
(A) high boiling solvent: 30 parts of 1,3 butylene glycol diacetate esters (232 ℃ of boiling points)
(B) solvent is used in the dispersion resin dissolving: propylene glycol methyl ether acetate
23 parts (SP value 9.2,146 ℃ of boiling points)
Monomer (M-2)
-red E-the printing ink of forming
80 parts of the dispersion liquids of red composition D
Epoxy resin: (trade name EHPE3150 ダ イ セ Le chemistry is made) 2 parts
Polymerizable compound: 8.3 parts of dipentaerythritol five/six acrylic ester
Polymerization initiator: 1,1.5 parts of two trihalomethyl groups of 3--5-coumarone triazine
Polymerization inhibitor: 0.001 part of p methoxy phenol
Nonionic class surfactant (trade name: エ マ Le ゲ Application A-60, flower king system
0.8 part is made)
Fluorine class surfactant (trade name: the big Japanese ink manufacturing of Megafac R08) 0.02 part
(A) high boiling solvent: 40 parts of 1,3 butylene glycol diacetate esters (232 ℃ of boiling points)
Mix and stir the above-mentioned red E of composition, obtain the printing ink of curing colouration composition.
[embodiment 7]
" preparation of green solidification compound "
Replace with the following green C of composition except redness being formed D, form D with redness and likewise handle, obtain dispersion liquid.
-green C-the dispersion liquid of forming
Pigment: 10 parts of pigment green 36s (mean grain size 19nm)
6 parts of pigment: Pigment Yellow 150 (mean grain size 22nm)
Dispersion resin (B-3-3) (following structure)
(following illustration monomer (M-6)/methacrylic acid/end has carried out metering system
The polymethyl methacrylate copolymer of 5 parts of acidylates (10/15/75 quality %, weight-average molecular weight 25000))
(trade name: Disperbyk-161, PVC Star Network ケ ミ one society make 30% to spreading agent
3 parts of solution)
Alkali soluble resins: methacrylic acid benzyl ester/methacrylic acid copolymer=75/25 [mass ratio] multipolymer, weight molecular weight Mw:5000's
3 parts of propylene glycol methyl ether acetate solution (solid constituents: 50 quality %)
(A) high boiling solvent: 33 parts of propylene glycol n-butyl ether acetate solution (211 ℃ of boiling points)
(B) solvent is used in the dispersion resin dissolving: propylene glycol methyl ether acetate
20 parts (SP value 9.2,146 ℃ of boiling points)
Illustration monomer (M-6)
-green D-the printing ink of forming
80 parts of the dispersion liquids of green composition C
Epoxy resin: (trade name EHPE3150 ダ イ セ Le chemistry is made) 2 parts
Polymerizable compound: 8 parts of dipentaerythritol five/six acrylic ester
Polymerization initiator: 1,1.5 parts of two trihalomethyl groups of 3--5-coumarone triazine
Polymerization inhibitor: 0.001 part of p methoxy phenol
Nonionic class surfactant (trade name: エ マ Le ゲ Application A-60 flower king system is made for 0.8 part)
Fluorine class surfactant (trade name: the big Japanese ink manufacturing of Megafac R08) 0.02 part
(A) high boiling solvent: 30 parts of propylene glycol n-butyl ether acetic acid esters (211 ℃ of boiling points)
Mix and stir the above-mentioned green D of composition, obtain the printing ink of curing colouration composition.
[embodiment 8]
" preparation of blue solidification compound "
Replace with the following blue C of composition except redness being formed D, form D with redness and likewise handle, obtain dispersion liquid.
-blue C-the dispersion liquid of forming
Pigment: pigment blue 15: 12 parts of 6 (mean grain size 15nm)
Pigment: 1 part of pigment Violet 23 (mean grain size 23nm)
7 parts of dispersion resins (B-1-46) (following structure)
(trade name: Disperbyk-1 61, PVC Star Network ケ ミ one society make 30% to spreading agent
3 parts of solution)
Alkali soluble resins: methacrylic acid benzyl ester/methacrylic acid copolymer
The propylene glycol methyl ether acetate solution of 6 parts=75/25 [mass ratio] multipolymer, weight molecular weight Mw:5000 (solid constituent: 50 quality %)
(A) high boiling solvent: 20 parts of propylene glycol n-butyl ether acetate solution (211 ℃ of boiling points)
(B) solvent is used in the dispersion resin dissolving: propylene glycol methyl ether acetate
31 parts (SP value 9.2,146 ℃ of boiling points)
-blue D-the printing ink of forming
80 parts of the dispersion liquids of blue composition C
Epoxy resin: (trade name EHPE3150 ダ イ セ Le chemistry is made) 2 parts
Polymerizable compound: 10 parts of dipentaerythritol five/six acrylic ester
Polymerization initiator: 1,2 parts of two trihalomethyl groups of 3--5-coumarone triazine
Polymerization inhibitor: 0.001 part of p methoxy phenol
0.8 part in nonionic class surfactant (trade name: エ マ Le ゲ Application A-60, flower king manufacturing)
Fluorine class surfactant (trade name: the big Japanese ink manufacturing of Megafac R08) 0.02 part
(A) high boiling solvent: 30 parts of propylene glycol n-butyl ether acetic acid esters (211 ℃ of boiling points)
Mix and stir the above-mentioned blue D of composition, obtain the printing ink of curing colouration composition.
[embodiment 9]
" preparation of red solidification compound "
Mix and stir following red the composition, obtain the coating fluid of curing colouration composition.
80 parts of the dispersion liquids of red composition D
Epoxy resin: (trade name EHPE3150 ダ イ セ Le chemistry is made) 2 parts
Polymerizable compound: 8.3 parts of dipentaerythritol five/six acrylic ester
Polymerization initiator: 1,1.5 parts of two trihalomethyl groups of 3--5-coumarone triazine
Polymerization inhibitor: 0.001 part of p methoxy phenol
0.8 part in nonionic class surfactant (trade name: エ マ Le ゲ Application A-60, flower king manufacturing)
Fluorine class surfactant (trade name: the big Japanese ink manufacturing of Megafac R08) 0.02 part
(A) high boiling solvent: 70 parts of 1,3 butylene glycol diacetate esters (232 ℃ of boiling points)
(B) solvent is used in the dispersion resin dissolving: propylene glycol methyl ether acetate
15 parts (SP value 9.2,146 ℃ of boiling points)
[embodiment 10]
" preparation of red solidification compound "
Except the solvent composition of redness being formed D by the following replacement, likewise handle with the above-mentioned red D that forms, obtain the dispersion liquid of red combination F.
-red solvent composition-dispersion liquid of forming F
(A) high boiling solvent: 10 parts of 1,3 butylene glycol diacetate esters (232 ℃ of boiling points)
(B) solvent is used in the dispersion resin dissolving: 43 parts of propylene glycol methyl ether acetates (SP value 9.2,146 ℃ of boiling points)
Mix and stir following red the composition, obtain the coating fluid of curing colouration composition.
80 parts of the dispersion liquids of red composition F
Epoxy resin: (trade name EHPE3150 ダ イ セ Le chemistry is made) 2 parts
Polymerizable compound: 8.3 parts of dipentaerythritol five/six acrylic ester
Polymerization initiator: 1,1.5 parts of two trihalomethyl groups of 3--5-coumarone triazine
Polymerization inhibitor: 0.001 part of p methoxy phenol
Nonionic class surfactant (trade name: エ マ Le ゲ Application A-60 flower king system
0.8 part is made)
Fluorine class surfactant (trade name: the big Japanese ink manufacturing of Megafac R08) 0.02 part
(A) high boiling solvent: 10 parts of 1,3 butylene glycol diacetate esters (232 ℃ of boiling points)
(B) solvent is used in the dispersion resin dissolving: propylene glycol methyl ether acetate
30 parts (SP value 9.2,146 ℃ of boiling points)
[comparative example 8]
" preparation of red solidification compound "
Except the 1,3 butylene glycol diacetate esters of redness being formed D and the red E of composition replaces with the propylene glycol methyl ether acetate, form E with redness and likewise prepare curing colouration composition.This composition does not contain (A) of the present invention high boiling solvent.
[comparative example 9]
" preparation of red solidification compound "
Except (B) dispersion resin of redness being formed D and the red E of composition uses solvent replacing as the 1,3 butylene glycol diacetate esters, form E with redness and likewise prepare curing colouration composition.This is formed the solvent contained in spreading agent and resin solvent, does not contain (B) of the present invention dispersion resin and uses solvent.The content of propylene glycol methyl ether acetate is 4 quality % with respect to whole solvents of coating fluid.
[comparative example 10]
" preparation of red solidification compound "
Form among the D in redness,, form the dispersion liquid that D likewise prepares the following red G of composition with redness except dispersion resin (B-2-1) is replaced with the alkali soluble resins 2.
-red G-the dispersion liquid of forming
Pigment: 11 parts of paratoneres 254 (mean grain size 20nm)
Pigment: 4 parts of paratoneres 177 (mean grain size 18nm)
Spreading agent (trade name: Disperbyk-161, PVC Star Network ケ ミ one society make,
3 part of 30% solution)
Alkali soluble resins 2: methacrylic acid benzyl ester/methacrylic acid copolymer=75/25 [mass ratio] multipolymer, weight molecular weight Mw:5000's
14 parts of propylene glycol methyl ether acetate solution (solid constituents: 50 quality %)
(A) high boiling solvent: 30 parts of 1,3 butylene glycol diacetate esters (232 ℃ of boiling points)
(B) solvent is used in the dispersion resin dissolving: propylene glycol methyl ether acetate
18 parts (SP value 9.2,146 ℃ of boiling points)
Form among the E in redness, replace red the composition the dispersion liquid D, form E with redness and likewise prepare curing colouration composition except using the red dispersion liquid G that forms.
[comparative example 11]
" preparation of red solidification compound "
Except (B) dispersion resin dissolving of redness being formed D with solvent with replace with the DIBK, D likewise prepares curing colouration composition with the redness composition.This is formed the solvent contained in spreading agent and resin solvent, does not contain (B) of the present invention dispersion resin and uses solvent.The content of propylene glycol methyl ether acetate is 4 quality % with respect to whole solvents of coating fluid.
[comparative example 12]
" preparation of red solidification compound "
Use solvent replacing as the ethylene glycol monoethyl ether except (B) dispersion resin dissolving of redness being formed D and the red E of composition, form D with redness and likewise prepare curing colouration composition.This is formed the solvent contained in spreading agent and resin solvent, does not contain (B) of the present invention dispersion resin and uses solvent.The content of propylene glycol methyl ether acetate is 4 quality % with respect to whole solvents of coating fluid.
< evaluation of the preparation of color filter and the flatness of dyed layer, ejection property >
The preparation of-color filter-
On glass substrate,, the resin black (thickness is 2.0 μ m) of 20 μ m width is set with clathrate (peristome is 100 μ m * 200 μ m) through photoetching method.Use has the ink-jet of the piezoelectric element of nozzle (aperture 30 μ m
) and makes a testing machine, sprays from peristome.Ejection be drip the back to beat at 1 minute, stop 1 minute, spray 1 minute again, the sequence that stops 1 minute carries out 20 times spout test at intermittence (time of ejection always is 20 minutes).Substrate to ejection under 70 ℃ carries out thermal treatment in 30 minutes, carries out the initial stage drying, under 220 ℃, carries out 30 minutes thermal treatment again, the preparation color filter.
-estimate-
1. flatness
Measure thickness and the thickness of pixel middle body near the black resin through DECTAK-III (manufacturing of ア Le バ Star Network), calculating with middle body is near 100% o'clock thickness.
2. ejection property
Observe the substrate of ejection at above-mentioned intermittence, beating a time till calculating when not having painted pixel to occur, with it as the drying property of nozzle, the index of blockage.
3. contrast
On the glass substrate that does not have the resin black dividing plate, beat and drip above-mentioned printing ink, make that dyed layer is 2.0 μ m.Measure contrast through contrast analyzer (trade name: BM-7, ト プ コ Application society make).Numerical value in the table is at the ratio that is at 100 o'clock with embodiment 11.In addition, embodiment 12,13 can't compare because beam split is different, therefore abandons.
The result is shown in the table 2.
Table 1
| Resin | (A) high boiling solvent and other solvent | (B) the dispersion resin dissolving is with solvent and other solvent | Solid constituent in the curing colouration constituent [quality %] | (A) high boiling solvent and the dissolving of (B) dispersion resin are with containing of solvent of proportional (A) * 100/ ((A)+B)) [%] | The coating striped | The foreign matter number | Contrast | |
| Embodiment 1 | Dispersion resin (B-1-3) | The 1,3 butylene glycol diacetate esters | Propylene glycol methyl ether acetate | 14.7 | 24.1 | ○ | 0 | 100 |
| Embodiment 2 | Dispersion resin (B-1-26) | The 1,3 butylene glycol diacetate esters | 3-ethoxy-propionic acid methyl ether acetate | 15.1 | 22.3 | ○ | 0 | - |
| Embodiment 3 | Dispersion resin (B-1-35) | Propylene glycol butyl ether acetic acid esters | Propylene glycol methyl ether acetate | 15.4 | 7.9 | ○ | 0 | - |
| Embodiment 4 | Dispersion resin (B-1-3) | The 1,3 butylene glycol diacetate esters | Propylene glycol methyl ether acetate | 20.0 | 24.0 | ○ | 1 | 95 |
| Embodiment 5 | Dispersion resin (B-1-3) | The 1,3 butylene glycol diacetate esters | Propylene glycol methyl ether acetate | 14.7 | 50.2 | ○ | 2 | 95 |
| Comparative example 1 | Dispersion resin (B-1-3) | - | Propylene glycol methyl ether acetate | 14.7 | 0 | × | 3 | 90 |
| Comparative example 2 | Dispersion resin (B-1-3) | The 1,3 butylene glycol diacetate esters | - | 14.7 | 100 | × | 5 | 88 |
| Comparative example 3 | Alkali soluble resins 1 | The 1,3 butylene glycol diacetate esters | Propylene glycol methyl ether acetate | 14.7 | 24.1 | × | 10 | 70 |
| Comparative example 4 | Dispersion resin (B-1-3) | The 1,3 butylene glycol diacetate esters | Diisobutyl ketone (SP:8.2 bp169 ℃) | 14.7 | - | × | 6 | 89 |
| Comparative example 5 | Dispersion resin (B-1-3) | The 1,3 butylene glycol diacetate esters | Ethylene glycol monoethyl ether (SP:10.6 bp136 ℃) | 14.7 | - | △ | 5 | 90 |
| Comparative example 6 | Dispersion resin (B-1-3) | The 1,3 butylene glycol diacetate esters | PGME (120 ℃ of SP=10.4 boiling points) | 14.7 | - | × | 7 | 94 |
| Comparative example 7 | Dispersion resin (B-1-3) | 3-ethoxyethyl group propionic ester (bp:169) | Propylene glycol methyl ether acetate | 14.7 | 0 | △ | 5 | 93 |
Table 2
| Resin | (A) high boiling solvent and other solvent | (B) the dispersion resin dissolving is with solvent and other solvent | Solid constituent in the curing colouration constituent [quality %] | (A) high boiling solvent and the dissolving of (B) dispersion resin are with containing of solvent of proportional (A) * 100/ ((A)+(B)) [%] | Flatness | Ejection property | Contrast | |
| Embodiment 6 | Dispersion resin (B-2-1) | The 1,3 butylene glycol diacetate esters | Propylene glycol methyl ether acetate | 30 | 72.1 | 99 | ＞20 minutes | 100 |
| Embodiment 7 | Dispersion resin (B-3-3) | Propylene glycol butyl ether acetic acid esters | Propylene glycol methyl ether acetate | 32 | 75.9 | 98 | ＞20 minutes | - |
| Embodiment 8 | Dispersion resin (B-1-46) | The propylene glycol n-butyl ether acetic acid esters | Propylene glycol methyl ether acetate | 35 | 58.1 | 98 | ＞20 minutes | - |
| Embodiment 9 | Dispersion resin (B-2-1) | The 1,3 butylene glycol diacetate esters | Propylene glycol methyl ether acetate | 20 | 70.4 | 95 | ＞20 minutes | 95 |
| Embodiment 10 | Dispersion resin (B-2-1) | The 1,3 butylene glycol diacetate esters | Propylene glycol methyl ether acetate | 30 | 20.6 | 96 | ＞20 minutes | 96 |
| Comparative example 8 | Dispersion resin (B-2-1) | - | Propylene glycol methyl ether acetate | 30 | 0 | 70 | 3 minutes | 90 |
| Comparative example 9 | Dispersion resin (B-2-1) | The 1,3 butylene glycol diacetate esters | - | 30 | 100 | 90 | 2 minutes | 90 |
| Comparative example 10 | Alkali soluble resins 2 | The 1,3 butylene glycol diacetate esters | Propylene glycol methyl ether acetate | 30 | 70 | 85 | 3 minutes | 73 |
| Comparative example 11 | Dispersion resin (B-2-1) | The 1,3 butylene glycol diacetate esters | Diisobutyl ketone (SP:8.2 bp169 ℃) | 30 | - | 88 | 5 minutes | 85 |
| Comparative example 12 | Dispersion resin (B-2-1) | The 1,3 butylene glycol diacetate esters | Ethylene glycol monoethyl ether (SP:10.6 bp136 ℃) | 30 | - | 85 | 6 minutes | 86 |
Result by table 1, table 2 finds, uses solvent and dispersion resin among the present invention, compares with comparative example with the color filter that ink-jetting style forms through the slot coated mode; There is not the inhomogeneous of striated on the coated face; Slot coated adaptability is excellent, in addition, has excellent the dripping property of beating; Flatness is good, and the contrast of color filter is also excellent.
Claims (10)
1. curing colouration composition, it is the curing colouration composition that contains colorant, dispersion resin, polymerization initiator, polymerizable compound and solvent, it is characterized in that,
This solvent comprises boiling point under (A) normal pressure be 180 ℃～280 ℃ solvent with (B) solubility parameter be 8.5～10.5 and normal pressure under boiling point be 130～170 ℃ solvent,
Boiling point under said (A) normal pressure is that 180 ℃～280 ℃ solvent comprises the solvent that is selected among following (1)～(10):
(1) diethylene glycol monoethyl ether acetic acid esters, boiling point are 217 ℃;
(2) butyl carbitol acetate, boiling point are 247 ℃;
(3) propylene glycol n-propyl ether acetic acid esters, boiling point are 187 ℃;
(4) propylene-glycol diacetate, boiling point are 190 ℃;
(5) propylene glycol n-butyl ether acetic acid esters, boiling point are 211 ℃;
(6) dipropylene glycol monomethyl ether acetic acid esters, boiling point are 209 ℃;
(7) DPG n-propyl ether acetic acid esters, boiling point are 232 ℃;
(8) DPG n-butyl ether acetic acid esters, boiling point are 250 ℃;
(9) tripropylene glycol methyl ether acetate, boiling point are 263 ℃;
(10) 1,3 butylene glycol diacetate esters, boiling point are 232 ℃,
Said (B) solubility parameter be 8.5～10.5 and normal pressure under boiling point be that 130～170 ℃ solvent comprises the solvent that is selected among following (1)～(7):
(1) 3-methoxy propyl acetoacetic ester, SP value are 10.1, boiling point is 158 ℃;
(2) 3-ethoxyl ethyl propionate, SP value are 8.8, boiling point is 169 ℃;
(3) 3-ethoxy-propionic acid methyl esters, SP value are 9.3, boiling point is 165 ℃;
(4) 3-methoxypropionic acid methyl esters, SP value are 9.5, boiling point is 145 ℃;
(5) 2-ethoxy-propionic acid methyl esters, SP value are 9.2, boiling point is 162 ℃;
(6) propylene glycol methyl ether acetate, SP value are 9.2, boiling point is 146 ℃;
(7) propylene-glycol ethyl ether acetic acid esters, SP value are 9.1, boiling point is 156 ℃,
This dispersion resin contain be selected from by the macromolecular compound of formula (1) expression, comprise to come free formula (I) expression monomer copolymerization units polymkeric substance and contain by among the polymkeric substance of the structural unit of formula (a) expression more than a kind;
General formula (1)
In general formula (1), R
1Organic connection base of representing following (m+n) valency,
R
2Expression-CH
2-, phenylene ,-S-or group that their combinations are constituted,
A
1Expression contains 1 valency organic group of organic pigment structure or heterocycle or contains 1 valency organic group of the group among the group that is selected from acidic-group, has basic nitrogen atom;
The said 1 valency organic group that contains heterocycle is the organic group with 1 valency of naphthalimide or acridone;
The said organic group that contains 1 valency of acidic-group is the organic group with carboxylic acid group or sulfonic 1 valency;
The said organic group that contains 1 valency of the group with basic nitrogen atom is the organic group with 1 amino valency, the organic group with 1 valency of substituted imido, and said substituted imido is by-NHR
8Or-NR
9R
10The organic group of 1 valency of expression, wherein, R
8, R
9, R
10Be that carbon number is 1～5 alkyl independently of one another;
N A
1Can be identical, also can be different; M representes 1～8, and n representes 2～9, and m+n satisfies 3～10;
P
1The expression macromolecular scaffold is polymer soluble in organic solvent, and for being selected from least a among polymer of vinyl monomer or multipolymer, esters polymer, the ether polymer;
General formula (I)
In general formula (I), R
01The expression hydrogen atom, or replace or unsubstituted carbon number is 1～12 alkyl; R
02The expression carbon number is 1～12 alkylidene; W representes-C (=O) O-; X representes-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-or-NHCO-; Y representes-NR
03-, being connected with the N atom through the atomic group that is adjacent forms ring texture, and this ring texture is imidazole ring, pyrimidine ring, triazole ring, tetrazole ring, thiazole ring Huo oxazole ring; R
03Expression hydrogen atom, alkyl or aryl; In the formula, N and the Y formation ring texture that is connected to each other; M, n are 0 or 1 independently of one another;
General formula (a)
In general formula (a), R
1aExpression hydrogen or methyl, R
2aExpression methylene, ethylidene, trimethylene, tetramethylene, hexa-methylene, 2-hydroxy propylidene, methylene oxygen base, ethyleneoxy group, methylene oxygen base carbonyl or methylene sulfenyl,
Z
1Expression has the nitrogen heterocyclic ring structure of pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, quinoline ring, acridine ring, phenothiazine ring 、 Fen oxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benzotriazole structure, benzothiazole structure, cyclic amide structure, ring-type urethane structure or cyclic imide structure.
2. curing colouration composition according to claim 1; It is characterized in that; Said curing colouration composition also contains alkali soluble resins, be selected from contain be selected from (methyl) acrylic acid, maleic acid, maleic anhydride, the crotonic acid more than a kind and this alkali soluble resins more than a kind that is selected among the multipolymer more than a kind in (methyl) butyl acrylate, (methyl) phenyl acrylate, (methyl) benzyl acrylate, the styrene be 5 quality %～50 quality % with respect to the all-mass of the resinous principle that comprises said dispersion resin.
3. curing colouration composition according to claim 1 and 2; It is characterized in that; Contained polymerization initiator is a Photoepolymerizationinitiater initiater in the said curing colouration composition; The quality of all solids composition of this curing colouration composition is 10 quality %～16 quality % with respect to the total amount of this curing colouration composition, and uses through the slot coated mode.
4. curing colouration composition according to claim 1 and 2; It is characterized in that; Contained polymerization initiator is a thermal polymerization in the said curing colouration composition; The quality of all solids composition of this curing colouration composition is 25 quality %～60 quality % with respect to the total amount of this curing colouration composition, and uses through ink-jetting style.
5. curing colouration composition according to claim 1 and 2; It is characterized in that; Under the situation of slot coated mode, the boiling point in the said curing colouration composition under contained said (A) normal pressure is that the content of 180 ℃～280 ℃ solvent is 5～30 quality %.
6. curing colouration composition according to claim 1 and 2; It is characterized in that; Under the situation of ink-jetting style, the boiling point in the said curing colouration composition under contained said (A) normal pressure is that the content of 180 ℃～280 ℃ solvent is 20～80 quality %.
7. curing colouration composition according to claim 1 and 2; It is characterized in that; Under the situation of slot coated mode, in the said curing colouration composition contained said (B) solubility parameter be 8.5～10.5 and normal pressure under boiling point be that the content of 130～170 ℃ solvent is 5～30 quality %.
8. curing colouration composition according to claim 1 and 2; It is characterized in that; Under the situation of ink-jetting style, in the said curing colouration composition contained said (B) solubility parameter be 8.5～10.5 and normal pressure under boiling point be that the content of 130～170 ℃ solvent is 20～80 quality %.
9. color filter, it contains the dyed layer that uses each described curing colouration composition preparation in the claim 1～8 and obtain.
10. liquid crystal indicator, it has the color filter described in the claim 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006270029A JP2008088272A (en) | 2006-09-29 | 2006-09-29 | Curable colored composition, color filter, and liquid crystal display using the color filter |
| JP270029/2006 | 2006-09-29 |
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| Publication Number | Publication Date |
|---|---|
| CN101154038A CN101154038A (en) | 2008-04-02 |
| CN101154038B true CN101154038B (en) | 2012-06-13 |
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| CN2007101483945A Active CN101154038B (en) | 2006-09-29 | 2007-08-31 | Curing colouration composition, color filtering device and liquid crystal display using the color filtering device |
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|---|---|
| JP (1) | JP2008088272A (en) |
| KR (1) | KR20080029787A (en) |
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| CN107614630A (en) * | 2015-06-05 | 2018-01-19 | 昭和电工株式会社 | Composition for forming insulating protective film by offset printing |
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|---|---|
| JP2008088272A (en) | 2008-04-17 |
| KR20080029787A (en) | 2008-04-03 |
| CN101154038A (en) | 2008-04-02 |
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