[go: up one dir, main page]

CN101154038A - 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 PDF

Info

Publication number
CN101154038A
CN101154038A CNA2007101483945A CN200710148394A CN101154038A CN 101154038 A CN101154038 A CN 101154038A CN A2007101483945 A CNA2007101483945 A CN A2007101483945A CN 200710148394 A CN200710148394 A CN 200710148394A CN 101154038 A CN101154038 A CN 101154038A
Authority
CN
China
Prior art keywords
methyl
solvent
general formula
boiling point
quality
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA2007101483945A
Other languages
Chinese (zh)
Other versions
CN101154038B (en
Inventor
冲田务
冈部孝太郎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of CN101154038A publication Critical patent/CN101154038A/en
Application granted granted Critical
Publication of CN101154038B publication Critical patent/CN101154038B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • 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
    • 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

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Optical Filters (AREA)
  • Inks, Pencil-Leads, Or Crayons (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

The liquid crystal indicator of curing colouration composition, color filter and use color filter
Technical field
The present invention relates to be applicable to by 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 by 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 to 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 ethylene 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 to comprise bonding agent is the 1st mode with the color filter that contains the monomer of epoxy radicals with the Thermocurable ink composite, in addition, having stipulated wellability, and the specific composition of solvent species 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, 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 as the dispersing of pigments deficiency 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 color filter of flatness excellence 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 colored pixels portion of flatness excellence.
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 comprise boiling point under (A) normal pressure be 180 ℃～280 ℃ solvent and (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 following general formula (1) expression, comprise to come free following general formula (I) expression monomer copolymerization units polymkeric substance and contain by among the polymkeric substance of the structural unit of following general formula (a) expression more than a kind.
General formula (1)
(A 1-R 2nR 1P 1) m
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 oxygen atom, the carbon number that are selected from acidic-group, have basic nitrogen atom are the group among alkyl, alkoxysilyl, epoxy radicals, isocyanate group and the hydroxyl more than 4.N A 1Can be identical, also can be different.M represents 1～8, and n represents 2～9, and m+n satisfies 3～10.P 1The expression macromolecular scaffold.
General formula (I)
Figure A20071014839400091
In general formula (I), R 01Expression hydrogen atom or replacement or unsubstituted alkyl.R 02The expression alkylidene.W represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.X represents 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 represents to be selected from NR 03, among O, the 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)
Figure A20071014839400101
In general formula (a), R 1aExpression hydrogen or methyl, R 2aThe expression alkylidene, Z 1Expression nitrogen heterocyclic ring structure.
＜2〉as＜1〉described in curing colouration composition, 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 following general 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 represents 1～4 integer.
＜3〉as＜1〉or＜2 described in curing colouration composition, 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〉as＜1 〉～＜3〉each described curing colouration composition, 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 with respect to the total amount of this curing colouration composition, be 10 quality %～16 quality %, and be suitable for by the slot coated mode.
＜5〉as＜1 〉～＜3〉each described curing colouration composition, 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 with respect to the total amount of this curing colouration composition, be 25 quality %～60 quality %, and be suitable for by ink-jetting style.
＜6〉as＜1 〉～＜3〉each described curing colouration composition, it is characterized in that 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) dipropylene glycol n-propyl ether acetic acid esters (232 ℃ of boiling points)
(12) dipropylene glycol 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)
＜7〉as＜1 〉～＜3〉each described curing colouration composition, it is characterized in that under the situation of slot coated mode, the content of contained solvent (A) is 5～30 quality % in the above-mentioned curing colouration composition.
＜8〉as＜1 〉～＜3〉each described curing colouration composition, it is characterized in that under the situation of ink-jetting style, the content of contained solvent (A) is 20～80 quality % in the above-mentioned curing colouration composition.
＜9〉as＜1 〉～＜3〉each described curing colouration composition, it is characterized in that 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)
(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)
＜10〉as＜1 〉～＜3〉each described curing colouration composition, it is characterized in that under the situation of slot coated mode, the content of contained solvent (B) is 5～30 quality % in the above-mentioned curing colouration composition.
＜11〉as＜1 〉～＜3〉each described curing colouration composition, it is characterized in that 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〉as＜1 〉～＜3〉each described curing colouration composition, it is characterized in that, combination as solvent contained in the above-mentioned curing colouration composition (A) and solvent (B), be that solvent (A) 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, solvent (B) is the combination of ethyl lactate, propylene glycol methyl ether acetate.
＜13〉a kind of color filter, its contain use as＜1～＜12〉each described curing colouration composition preparation and the dyed layer that obtains.
＜14〉a kind of liquid crystal indicator, it has＜13 described in color filter.
Effect of the present invention is still indeterminate, infers as follows.
Can think; curing type coloured composition of the present invention by and with boiling point within the limits prescribed 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; adsorbability to granules of pigments strengthens; and be adsorbed on the strand of the dispersion resin on the granules of pigments by growth; can improve protecting colloid; dispersing of pigments has good stability; so the keeping quality excellence, and the levelability of coating fluid is good, can form the colored pixels portion of flatness excellence.
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 colored pixels portion of flatness excellence.
In addition, according to the present invention, can provide the color filter and the liquid crystal indicator that uses it of the high-contrast that forms by slot coated mode or ink-jetting style.
Embodiment
Below, to curing colouration composition of the present invention, use the color filter of this curing colouration composition preparation and use the liquid crystal indicator of this color filter preparation to be described in detail.
[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, this solvent comprise (A) boiling point under normal pressure be 180 ℃～280 ℃ solvent and (B) solubility parameter be 8.5～10.5, the boiling point under the normal pressure is 130～170 ℃ a solvent; This dispersion resin contain be selected from by the macromolecular compound of following general formula (1) expression, comprise to come free following general formula (I) expression monomer copolymerization units polymkeric substance and contain by among the polymkeric substance of the structural unit of following general formula (a) expression more than a kind.
General formula (1)
(A 1-R 2nR 1P 1) m
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 oxygen atom, the carbon number that are selected from acidic-group, have basic nitrogen atom are the group among alkyl, alkoxysilyl, epoxy radicals, isocyanate group and the hydroxyl more than 4.N A 1Can be identical, also can be different.M represents 1～8, and n represents 2～9, and m+n satisfies 3～10.P 1The expression macromolecular scaffold.
General formula (I)
In general formula (I), R 01Expression hydrogen atom or replacement or unsubstituted alkyl.R 02The expression alkylidene.W represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.X represents 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 represents to be selected from NR 03, among O, the 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)
Figure A20071014839400142
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 〉
Solvent contained in the curing colouration composition of the present invention comprise (A) boiling point under normal pressure be 180 ℃～280 ℃ solvent and (B) solubility parameter be 8.5～10.5, 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 ℃.By 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 following general 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 represents 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 list 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 list 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 list 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 list 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 listing 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, another the represented substituting group as not being hydrogen atom can list 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) dipropylene glycol n-propyl ether acetic acid esters (232 ℃ of boiling points)
(12) dipropylene glycol 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 forms on substrate is good, can shorten the quiescent interval in the painting process.
High boiling solvent among the present invention may be used alone, or two or more kinds may be used in combination.
((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 by 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, more preferably 9.0～10.0.
In addition, the SP value among the present invention is represented by following formula.
SP value (δ)=(Δ H/V) 1/2
Wherein, in formula, Δ H represents mole vaporization heat (cal), and V represents 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 and normal pressure under the situation of boiling point in these scopes under, can suppress shower nozzle and stop up, dispersion stabilization is good, keeping quality is also excellent.
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 ethylene 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 of using 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 (B) dispersion resin dissolving with the preferred compositions of 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, dipropylene glycol n-propyl ether acetic acid esters, dipropylene glycol n-butyl ether acetic acid esters, 1,3 butylene glycol diacetate esters; (B) the dispersion resin dissolving is ethyl lactate, 3-methoxy propyl acetoacetic ester, 3-ethoxyl ethyl propionate, acetate ethyl cellosolve, propylene glycol methyl ether acetate with solvent.
As particularly preferred 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) the dispersion resin dissolving is the combination of ethyl lactate, propylene glycol methyl ether acetate with solvent.
Under the situation of slot coated, the dispersion resin dissolving gross mass of the content of solvent among the present invention 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 forms on substrate is good, can shorten the quiescent interval in the painting process.
High boiling solvent among the present invention may be used alone, or two or more kinds may be used in combination.
Among the present invention (A) high boiling solvent and (B) dispersion resin dissolving in slot coated mode and ink-jetting style, 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.
Under the situation of slot coated, if (A) high boiling solvent and (B) dispersion resin dissolving be (A)/(B)=more than 5/100 with the mass ratio of solvent, then can suppress gap nozzle drying, be coated with striped, production of foreign matters.If (A) high boiling solvent and (B) dispersion resin dissolving be (A)/(B)=below 40/100 with the mass ratio of solvent, then the drying of coated substrates can be finished at short notice, during substrate after conveyance coating, substrate can be not 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 by slot coated.It is described in detail in the back.
Under the situation of ink-jetting style, if (A) high boiling solvent and (B) dispersion resin dissolving be that (A)/(B)=more than 50/100, the levelability of then beating after dripping is good with the mass ratio of solvent, can suppress the interior film thickness difference of pixel, can prevent the nozzle drying, spray nozzle clogging.If (A) high boiling solvent and (B) dispersion resin dissolving be that (A)/(B)=below 300/100, then the favorable solubility of dispersion resin, spreading agent etc. can keep dispersiveness with the mass ratio of solvent.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 by 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 described in detail in the back.
Curing colouration composition of the present invention in the scope of not damaging effect of the present invention, as required, can also and use except above-mentioned (A) have the high boiling solvent of ad hoc structure and (B) dispersion resin dissolving with the solvent the solvent.
As such high boiling solvent, can list 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 list ethers, for example 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, the oxo methyl acetate, oxo ethyl acetate, the oxo butyl acetate, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3-oxo methyl propionate, 3-oxo alkyl propionates classes such as 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, dimethylbenzene 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 following general formula (1) expression, comprise to come free following general formula (I) expression monomer copolymerization units polymkeric substance and contain by among the polymkeric substance of the structural unit of following general formula (a) expression more than a kind.
General formula (1)
(A 1-R 2nR 1P 1) m
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 oxygen atom, the carbon number that are selected from acidic-group, have basic nitrogen atom are the group among alkyl, alkoxysilyl, epoxy radicals, isocyanate group and the hydroxyl more than 4.N A 1Can be identical, also can be different.M represents 1～8, and n represents 2～9, and m+n satisfies 3～10.P 1The expression macromolecular scaffold.
General formula (I)
Figure A20071014839400221
In the formula, R 01Expression hydrogen atom or replacement or unsubstituted alkyl.R 02The expression alkylidene.W represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.X represents to be selected from-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-,-appointing among the NHCO--individual.Y represents to be selected from NR 03, among O, the 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)
Figure A20071014839400222
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 the polymkeric substance of copolymerization units of monomer of free general formula (I) expression and the polymkeric substance that (B-3) contains describe by the structural unit of general formula (a) expression by macromolecular compound, (B-2) of general formula (1) expression.
[(B-1) macromolecular compound of representing by general formula (1): (B-1) specific dispersion resin]
At first, following macromolecular compound by general formula (1) expression (below, suitably be called " (B-1) specific dispersion resin ") is described.
General formula (1)
(A 1-R 2nR 1P 1) m
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 oxygen atom, the carbon number that are selected from acidic-group, have basic nitrogen atom are the group among alkyl, alkoxysilyl, epoxy radicals, isocyanate group and the hydroxyl more than 4.N A 1Can be identical, also can be different.
Though there is no particular limitation, but more particularly, as above-mentioned " organic group that contains 1 valency of organic pigment structure ", can list and for example have phthalocyanines, insoluble azo class, the azo lake class, the anthraquinone class, quinacridine ketone; dioxazines, the diketopyrrolo-pyrrole class, the anthracene pyridines, the anthanthrone class, the indanthrone class, flavanthrones, purple perilla ketone; perylene class, the organic group of 1 valency of the pigment structure of thioindigo class etc. is as preferred example, more preferably has phthalocyanines, the azo lake class, anthraquinone class dioxazines, the organic group of 1 valency of diketopyrrolo-pyrrole class pigment structure etc. is preferably especially and has phthalocyanines, the anthraquinone class, the organic group of 1 valency of diketopyrrolo-pyrrole class pigment structure etc.
In addition, as above-mentioned " organic group that contains 1 valency of heterocycle ", can list and for example have thiophene, furans, xanthene, the 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, the organic group of 1 valency of anthraquinone etc. more preferably has pyrrolin as preferred example, pyrrolidine, pyrazoles, pyrazoline, pyrazolidine, imidazoles, triazole, pyridine, piperidines, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindoline, isoindolinone, Benzimidazolinone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoins, carbazole, acridine, acridone, the organic group of 1 valency of anthraquinone etc.
In addition, above-mentioned organic pigment structure or heterocycle also can have substituting group, as this substituting group, can list 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; Cyano group; 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 by the following structures unit.
As above-mentioned " organic group that contains 1 valency of acidic-group ", can list 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 list 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.
Figure A20071014839400251
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 list-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, R17 represents that 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.)。
" urethane groups " as above-mentioned for example can list-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 list for example acetylacetone based, crown ether etc. with coordination oxygen atom.
As above-mentioned " carbon number is the alkyl more than 4 ", can list carbon number and be the alkyl more than 4, carbon number is the aryl more than 6, carbon number is the preferred examples of conduct such as the aralkyl more than 7, more preferably carbon number is 4～20 alkyl, carbon number is 6～20 aryl, carbon number is 7～20 a aralkyl etc., is preferably carbon number especially and is 4～15 alkyl (octyl group for example, dodecyl etc.), carbon number is 6～15 an aryl (phenyl for example, naphthyl etc.), carbon number is aralkyl (for example benzyl etc.) of 7～15 etc.
As above-mentioned " alkoxysilyl ", can list 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 not have to replace, and also replacement can be arranged.
As the object lesson of this organic connection base, can list the group that the following structures unit maybe constitutes this structural unit combination.
Figure A20071014839400271
Have under the substituent situation at above-mentioned organic connection base, as this substituting group, can list for example methyl, carbon numbers such as ethyl are 1～20 alkyl, phenyl, carbon numbers such as naphthyl are 6～16 aryl, hydroxyl, amino, carboxyl, sulfoamido, the N-sulfoamido, carbon numbers such as acetoxyl group are 1～6 acyloxy, methoxyl, carbon numbers such as ethoxy are 1～6 alkoxy, chlorine, halogen atoms such as bromine, methoxycarbonyl, ethoxy carbonyl, carbon numbers such as cyclohexyloxy carbonyl are 2～7 alkoxy carbonyl, cyano group, carbonate groups such as 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 following general formula (4) expression.
General formula (4)
(B 1aR 24-
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 oxygen atom, carbon number is the position of alkyl, alkoxysilyl, epoxy radicals, isocyanate group and hydroxyl more than 4), R 24Expression singly-bound or (a+1) organic connection base of valency.A represents 1～10 integer, a B 1Can be identical, also can be different.
As above-mentioned by B 1The adsorption site of expression can list 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 the sulphur atom by 1～100 carbon atom, 0～10 nitrogen-atoms, 0～50 oxygen atom, 1～200 hydrogen atom and 0～20 constitutes, can be not have to replace, also can have substituting group.
As the object lesson of organic connection base of above-mentioned (a+1) valency, can list the group (also can form ring structure) that following structural unit maybe constitutes this structural unit combination.
Figure A20071014839400281
As R 24Be preferably singly-bound or by 1～50 carbon atom, 0～8 nitrogen-atoms, 0～25 oxygen atom, organic base that is connected of 1～100 hydrogen atom and (a+1) valency of 0～10 sulphur atom formation, singly-bound or more preferably by 1～30 carbon atom, 0～6 nitrogen-atoms, 0～15 oxygen atom, organic base that is connected of (a+1) valency that 1～50 hydrogen atom and 0～7 s' sulphur atom constitutes is preferably singly-bound or especially by 1～10 carbon atom, 0～5 nitrogen-atoms, 0～10 oxygen atom, organic base that is connected of 1～30 hydrogen atom and (a+1) valency of 0～5 sulphur atom formation.
In above-mentioned group, organic connection base at (a+1) valency has under the substituent situation, as this substituting group, can list for example methyl, carbon numbers such as ethyl are 1～20 alkyl, phenyl, carbon numbers such as naphthyl are 6～16 aryl, hydroxyl, amino, carboxyl, sulfoamido, the N-sulfoamido, carbon numbers such as acetoxyl group are 1～6 acyloxy, methoxyl, carbon numbers such as ethoxy are 1～6 alkoxy, chlorine, halogen atoms such as bromine, methoxycarbonyl, ethoxy carbonyl, carbon numbers such as cyclohexyloxy carbonyl are 2～7 alkoxy carbonyl, cyano group, carbonate groups such as 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 the sulphur atom by 1～100 carbon atom, 0～10 nitrogen-atoms, 0～50 oxygen atom, 1～200 hydrogen atom and 0～20 constitutes, can be not have to replace, also can have substituting group.
As the object lesson of organic connection base of above-mentioned divalent, can list the group that the following structures unit maybe constitutes this structural unit combination.
Figure A20071014839400291
As R 2Be preferably singly-bound or by 1～50 carbon atom, 0～8 nitrogen-atoms, 0～25 oxygen atom, organic base that is connected of 1～100 the hydrogen atom and the divalent of 0～10 sulphur atom formation, singly-bound or more preferably by 1～30 carbon atom, 0～6 nitrogen-atoms, 0～15 oxygen atom, organic base that is connected of the divalent that 1～50 hydrogen atom and 0～7 s' sulphur atom constitutes is preferably singly-bound or especially by 1～10 carbon atom, 0～5 nitrogen-atoms, 0～10 oxygen atom, organic base that is connected of 1～30 the hydrogen atom and the divalent of 0～5 sulphur atom formation.
In above-mentioned group, organic connection base at divalent has under the substituent situation, as this substituting group, can list for example methyl, carbon numbers such as ethyl are 1～20 alkyl, phenyl, carbon numbers such as naphthyl are 6～16 aryl, hydroxyl, amino, carboxyl, sulfoamido, the N-sulfoamido, carbon numbers such as acetoxyl group are 1～6 acyloxy, methoxyl, carbon numbers such as ethoxy are 1～6 alkoxy, chlorine, halogen atoms such as bromine, methoxycarbonyl, ethoxy carbonyl, carbon numbers such as cyclohexyloxy carbonyl are 2～7 alkoxy carbonyl, cyano group, carbonate groups such as 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 the sulphur atom by 1～100 carbon atom, 0～10 nitrogen-atoms, 0～50 oxygen atom, 1～200 hydrogen atom and 0～20 constitutes, can be not have to replace, also can have substituting group.
As the object lesson of organic connection base of above-mentioned (m+n) valency, can list the group (also can form ring structure) that the following structures unit maybe constitutes this structural unit combination.
Figure A20071014839400301
Organic connection base as (m+n) valency, be preferably carbon atom by 1～60,0～10 nitrogen-atoms, 0～40 oxygen atom, the group that 1～120 hydrogen atom and 0～10 s' sulphur atom constitutes, more preferably by 1～50 carbon atom, 0～10 nitrogen-atoms, 0～30 oxygen atom, organic base that is connected of 1～100 hydrogen atom and (m+n) valency of 0～7 sulphur atom formation is preferably the carbon atom by 1～40 especially, 0～8 nitrogen-atoms, 0～20 oxygen atom, the group that 1～80 hydrogen atom and 0～5 s' sulphur atom constitutes.
In above-mentioned group, organic connection base at (m+n) valency has under the substituent situation, as this substituting group, can list for example methyl, carbon numbers such as ethyl are 1～20 alkyl, phenyl, carbon numbers such as naphthyl are 6～16 aryl, hydroxyl, amino, carboxyl, sulfoamido, the N-sulfoamido, carbon numbers such as acetoxyl group are 1～6 acyloxy, methoxyl, carbon numbers such as ethoxy are 1～6 alkoxy, chlorine, halogen atoms such as bromine, methoxycarbonyl, ethoxy carbonyl, carbon numbers such as cyclohexyloxy carbonyl are 2～7 alkoxy carbonyl, cyano group, carbonate groups such as 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.
Figure A20071014839400311
In above-mentioned object lesson, from acquired, the synthetic easiness of raw material, to the deliquescent viewpoint of all kinds of solvents, organic connection base of most preferred (m+n) valency is following group.
Figure A20071014839400321
In above-mentioned general formula (1), m represents 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 represents 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, be preferably and be selected from polymer of vinyl monomer or multipolymer, esters polymer, ether polymer, polyurethane polymer, acylamide polymer, epoxide polymer, the modifier of polysiloxane base polymer and these materials, or multipolymer [for example, comprise polyethers/polyurethane copolymer, the multipolymer of polyethers/polymer of vinyl monomer etc. (can be a random copolymers, segmented copolymer, in the graft copolymer any)] at least a among, more preferably be selected from polymer of vinyl monomer or multipolymer, esters polymer, ether polymer, at least a among the modifier of polyurethane polymer and these materials or the multipolymer is 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 list (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 list 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 list dimethyl maleate, diethyl maleate and dibutyl maleate etc.
As the example of dimethyl ester class, can list dimethyl fumarate, DEF and dibutyl fumarate etc.
As the example of itaconic acid diester class, can list dimethyl itaconate, diethyl itaconate and dibutyl itaconate etc.
As (methyl) acrylic amide; can list (methyl) acrylamide; N-methyl (methyl) acrylamide; N-ethyl (methyl) acrylamide; N-propyl group (methyl) acrylamide; N-isopropyl (methyl) acrylamide; N-normal-butyl (methyl) acrylamide; the N-tert-butyl group (methyl) acrylamide; N-cyclohexyl (methyl) acrylamide; N-(2-methoxy ethyl) (methyl) acrylamide; N; N-dimethyl (methyl) acrylamide; N; N-diethyl (methyl) acrylamide; N-phenyl (methyl) acrylamide; N-nitrobenzophenone acrylamide; N-ethyl-N phenyl acrylamide; N-benzyl (methyl) acrylamide; (methyl) acryloyl morpholine; diacetone acrylamide; N hydroxymethyl acrylamide; N-hydroxyethyl acrylamide; vinyl (methyl) acrylamide; N, N-diallyl (methyl) acrylamide; N-allyl (methyl) acrylamide etc.
As the example of phenylethylene, can list 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, by can be by hydroxy styrenes, vinyl benzoic acid methyl esters and the α-Jia Jibenyixi etc. of the group of acidic materials deprotection (for example t-Boc etc.) protection.
As the example of vinyl ethers, can list 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 list methyl vinyl ketone, ethyl vinyl ketone, propyl ethylene base ketone, phenyl vinyl ketone etc.
As the example of olefines, can list ethene, propylene, isobutylene, butadiene, isoprene etc.
As the example of maleimide, can list 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, vinylcarbazole etc.), N-vinyl formamide, N-vinyl acetamide, N-acetyl imidazole, vinyl caprolactone etc.
Except above-claimed cpd, can also use to have 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 isocyanate group and hydroxyl or amino addition reaction suitably to synthesize.Specifically, monomer that can be by containing isocyanate group with contain the compound of 1 hydroxyl or contain 1 uncle or secondary amino group compound 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 list vinyl monomer or have sulfonic vinyl monomer with carboxylic acid group with vinyl monomer of acidic-group.
As vinyl monomer, can list (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) acrylate of the such cyclic acid anhydride of the monomer of hydroxyl and maleic anhydride or phthalic anhydride, cyclohexane dicarboxylic acid acid anhydride 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 or cost, dissolubilities.
In addition, as having sulfonic vinyl monomer, 2-acrylamide-2-methyl propane sulfonic acid etc. can be listed,, mono phosphoric acid ester (2-acryloxy ethyl ester), mono phosphoric acid ester (1-methyl-2-acryloxy ethyl ester) etc. can be listed as vinyl monomer with phosphate.
In addition, as vinyl monomer, can also use the vinyl monomer that contains the phenol hydroxyl or contain vinyl monomer of sulfoamido etc. with acidic-group.
In the above-mentioned macromolecular compound second month in a season, be preferably macromolecular compound by following general formula (2) expression by general formula (1) expression.
General formula (2)
(A 2-R 4-S nR 3S-R 5-P 2) m
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 oxygen atom, carbon number be the 1 valency organic group at the position of alkyl, alkoxysilyl, epoxy radicals, isocyanate group 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 the sulphur atom by 1～60 carbon atom, 0～10 nitrogen-atoms, 0～50 oxygen atom, 1～100 hydrogen atom and 0～20 constitutes, can be not have to replace, also can have substituting group.
As above-mentioned by R 3Organic connection base of (m+n) valency of expression, specifically, can list 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 represents 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 represents 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, most preferably be and all satisfy R shown below by above-mentioned general formula (2) expression 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: singly-bound, organic base that is connected of the divalent that is made of " 1～10 carbon atom; 0～5 nitrogen-atoms; 0～10 oxygen atom; 1～30 hydrogen atom and 0～5 sulphur atom " that following structural unit maybe constitutes the combination of this structural unit (also can have substituting group, as this substituting group, can list for example methyl, carbon numbers such as ethyl are 1～20 alkyl, phenyl, carbon numbers such as naphthyl are 6～16 aryl, hydroxyl, amino, carboxyl, sulfoamido, the N-sulfoamido, carbon numbers such as acetoxyl group are 1～6 acyloxy, methoxyl, carbon numbers such as ethoxy are 1～6 alkoxy, chlorine, halogen atoms such as bromine, methoxycarbonyl, ethoxy carbonyl, carbon numbers such as cyclohexyloxy carbonyl are 2～7 alkoxy carbonyl, cyano group, carbonate groups such as tert-butyl group carbonic ester etc.)
Figure A20071014839400371
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.
Figure A20071014839400381
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, 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 by 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 easiness 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 under macromolecular compound of the present invention has situation by the structure of general formula (2) expression, the easiness 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 following general formula (3) expression, makes the method for vinyl monomer generation free radical polymerization.
General formula (3)
(A 3-R 7-S nR 6SH) m
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 waited syntheticly by the following method by the compound of above-mentioned general formula (3) expression, the easiness angle on synthetic 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 list 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 vinyl that replace.
Object lesson (object lesson (18)～(34)) as have the compound of 3～10 sulfydryls in-molecule can list following compound.
Figure A20071014839400401
In above-mentioned group, from acquired, the synthetic easiness of raw material, to the deliquescent viewpoint of all kinds of solvents, particularly preferred compound is following compound.
Figure A20071014839400411
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 oxygen atom, carbon number be the position of alkyl, alkoxysilyl, epoxy radicals, isocyanate group and hydroxyl more than 4 and the compound with carbon-to-carbon double bond) there is no particular limitation, can list following material.
Figure A20071014839400412
Figure A20071014839400421
Figure A20071014839400441
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 by 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 list 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, by known method, polymerization and obtaining according to conventional methods.In addition, the compound of being represented by above-mentioned general formula (3) among the present invention has the function as chain-transferring agent, below, only be called " chain-transferring agent " sometimes.
For example, can obtain by following method, described 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 list 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 represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.X represents-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-or-NHCO-.Y represents-NR 03-,-O-,-S-or-N=, being connected with the N atom by 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 list for example hydroxyl, alkoxy, aryloxy group, acyloxy, halogen group etc.
As by R 01The preferred alkyl of expression specifically, can list 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 list for example hydroxyl, alkoxy, aryloxy group, acyloxy etc.
As by R 02The preferred alkylidene of expression specifically, can list methylene, ethylidene, propylidene, trimethylene, tetramethylene etc.
W represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene, be preferably-C (=O) O-or-CONH-.
Y represents-NR 03-,-O-,-S-or-N=, being connected with the N atom by 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 by the atomic group that is adjacent as Y, can list 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 list benzimidazole ring, benzothiazole ring, benzoxazole ring.
X represents-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 list 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 the following description, 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 of the part of the polymerizable functional group with ethylenical unsaturated double bonds of polymeric chain part and its end.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 following general formula (II).
General formula (II)
Figure A20071014839400501
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 by 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 by 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 represents 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 list poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate and poly-(methyl) isobutyl acrylate, the molecule of polystyrene-individual end in the polymkeric substance of poly-(methyl) acryloyl group of bonding.As this polyreactive oligomers that can in market, obtain, can list the polystyrene oligomer (Mn=6000 that has carried out the metering system acidylate at single end; trade name: AS-6; East Asia synthetic chemical industry (strain) is made); carried out poly-(methyl) methyl acrylate (Mn=6000 of metering system acidylate at single end; trade name: AA-6; East Asia synthetic chemical industry (strain) is made) and carried out poly-(methyl) n-butyl acrylate (Mn=6000 of metering system acidylate at single end; trade name: AB-6; East Asia synthetic chemical industry (strain) is made).
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 list 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, there is no particular limitation, for example is 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 list following compound.
Promptly, as (methyl) esters of acrylic acid, can list (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 list butyl crotonate and the own ester of crotonic acid etc.
As the example of vinyl ester, can list 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 list dimethyl maleate, diethyl maleate and dibutyl maleate etc.
As the example of dimethyl ester class, can list dimethyl fumarate, DEF and dibutyl fumarate etc.
As the example of itaconic acid diester class, can list dimethyl itaconate, diethyl itaconate and dibutyl itaconate etc.
As (methyl) acrylic amide; can list (methyl) acrylamide; N-methyl (methyl) acrylamide; N-ethyl (methyl) acrylamide; N-propyl group (methyl) acrylamide; N-isopropyl (methyl) acrylamide; N-normal-butyl (methyl) acrylamide; the N-tert-butyl group (methyl) acrylamide; N-cyclohexyl (methyl) acrylamide; N-(2-methoxy ethyl) (methyl) acrylamide; N; N-dimethyl (methyl) acrylamide; N, N-diethyl (methyl) acrylamide; N-phenyl (methyl) acrylamide; N-benzyl (methyl) acrylamide; (methyl) acryloyl morpholine; diacetone acrylamide; Deng.
As the example of phenylethylene, can list 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, by can be by hydroxy styrenes, vinyl benzoic acid methyl esters and the α-Jia Jibenyixi etc. of the group of acidic materials deprotection (for example t-Boc etc.) protection.
As the example of vinyl ethers, can list 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 list 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 as above-mentioned multipolymer by 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-mercaptoacetic acid, lauryl mercaptan) and synthesize.
(B-2) content of specific dispersion resin is preferably 0.5～100 quality % with respect to the quality of aftermentioned colorant, 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 list 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 list 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 following general formula (b) or general formula (c) expression.
Figure A20071014839400562
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 represents hydrogen atom or alkyl, represents alkyl under the alkyl situation can list for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl, n-octyl, 2-ethylhexyl, n-octadecane base etc. as R.
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 list 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 list 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.
Figure A20071014839400571
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 list 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 list (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 list 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 list 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, list 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 by 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 is preferably 0.5～100 quality % with respect to the quality of colorant described later, 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 into-go on foot the effect that improves even pigment dispersing agent adds.
In order to disperse the aftermentioned colorant 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 by 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, can use spreading agent described later.
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 list spreading agent as described later.Spreading agent may be used alone, and can also use a variety of combinations.Can destroy the cohesion of colorant, carbon black granules simultaneously at colorant, black carbon surface polymeric adsorbent by 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.Can use following illustrative compound.But be not limited to these compounds.
EFKA-1101,1120,1125,4008,4009,4046,4047,4520,4010,4015,4020,4050,4055,4060,4080,4300,4330,4400,4401,4402,4403,4406,4800,5010,5044,5244,5054,5055,5063,5064,5065,5066,5070,5207 (above make for EFKAADDITIVES society), Anti-Terra-U, Anti-Terra-U 100, 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 is that nanmu originally changes into society's manufacturing), ソ Le ス パ one ス 3000,5000,9000,12000,13240,13940,17000,22000,24000,26000,28000 etc. (above make for AVECIA society), キ ャ リ ボ Application B, キ ャ リ ボ Application L-400, ェ レ ミ ノ one Le MBN-1, サ Application ス パ one Le PS-2, サ Application ス パ one Le PS-8, ィ ォ ネ ッ ト S-20 (Sanyo changes into manufacturing) デ ィ ス パ one ス ェ ィ De 6, デ ィ ス パ one ス ェ ィ De 8, デ ィ ス パ one ス ェ ィ De 15, デ ィ ス パ one ス ェ ィ De 9100 (サ Application ノ プ コ manufacturing) etc.These materials can use separately, also can will also use 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 list 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 ァ デ カ プ Le ロ ニ ッ Network シ リ-ズ for example, ァ デ カ ノ one Le シ リ one ズ ィ, テ ト ロ ニ ッ Network シ リ one ズ (above make for ADEKA), ェ マ Le ゲ Application シ リ one ズ, レ ォ De one Le シ リ one ズ (above) for spending king's (strain) to make, ェ レ ミ ノ one Le シ リ one ズ, ノ ニ Port one Le シ リ one ズ, ォ Network Port one Le シ リ one ズ, De デ カ Port-Le シ リ one ズ, ニ ュ-Port-Le シ リ one ズ (above make) for Sanyo changes into (strain), パ ィ ォ ニ Application シ リ one ズ (above this grease of bamboo (strain) manufacturing), ニ ッ サ Application ノ ニ ォ 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 product, can list for example メ ガ Off ァ ッ Network F142D, メ ガ Off ァ ッ Network F172, メ ガ Off ァ ッ Network F173, メ ガ Off ァ ッ Network F176, メ ガ Off ァ ッ Network F177, メ ガ Off ァ ッ Network F183, メ ガ Off ァ ッ Network 780, メ ガ Off ァ ッ Network 781, メ ガ Off ァ ッ Network R30, メ ガ Off ァ ッ Network R08 (big Japanese ink (strain) is made), Off ロ ラ one De FC-135, Off ロ ラ one De FC-170C, Off ロ ラ one De FC-430, Off ロ ラ one De FC-431 (manufacturing of Sumitomo ス リ one ェ 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), ェ Off ト ッ プ EF351, ェ Off ト ッ プ 352, ェ Off ト ッ プ 801, ェ Off ト ッ プ 802 (JEMCO (strain) manufacturing) etc.
As polysiloxane-based surfactant, can list for example ト one レ シ リ コ one Application DC3PA, ト one レ シ リ コ one Application DC7PA, ト one レ シ リ コ one Application SH11PA, ト one レ シ リ コ one Application SH21PA, ト one レ シ リ コ one Application SH28PA, ト one レ シ リ コ one Application SH29PA, ト one レ シ リ コ one Application SH30PA, ト one レ シ リ コ one Application SH-190, ト one レ シ リ コ one Application SH-193, ト one レ シ リ コ one Application SZ-6032, ト one レ シ リ コ one Application SF-8428, ト one レ シ リ コ one Application DC-57, ト one レ シ リ コ one Application DC-190 (East レ ダ ゥ コ one ニ Application グ シ リ コ one Application (strain) of Weiing Yi Shang manufacturing), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above is GE East sesame シ リ コ one Application (strain) manufacturing) etc.
These surfactants preferably use below 5 weight portions with respect to 100 weight portions liquid against corrosion, more preferably use below 2 weight portions.Amount at surfactant surpasses under the situation of 5 weight portions, is easy to generate check surface in the coating drying, 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 list the polymkeric substance that has carboxylic acid at side chain, for example be to open clear 59-44615 number as the spy, special public clear 54-34327 number, special public clear 58-12577 communique, special public clear 54-25957 number, the spy opens clear 59-53836 communique, the spy opens the methacrylic acid copolymer of being put down in writing in each communique of clear 59-71048 number, acrylic copolymer, itaconic acid copolymer, the citraconic acid multipolymer, maleic acid, partial esterification maleic acid etc., and the acid cellulose derivant that has carboxylic acid at side chain, the acrylic copolymers such as material that have the polymkeric substance of hydroxyl and acid anhydrides addition and obtain.
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 and can with the multipolymer of other monomer of its copolymerization.As above-mentioned can with other monomer of (methyl) acrylic acid copolymer, can list (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 list (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), the hydroxyl glycidyl methacrylate, tetrahydrofurfuryl methacrylate etc.
In addition, can also list 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 has the polyalkylene oxide chain on these side chains is that for example methoxy poly (ethylene glycol) list (methyl) acrylate, ethoxy polypropylene glycol list (methyl) acrylate, single (methyl) acrylate etc. of methoxyl poly-(ethylene glycol and 1,2-propylene glycol) are the acrylic acid esters co-polymer of copolymer composition with for example polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, poly-(ethylene glycol and 1,2-propylene glycol) single (methyl) acrylate etc. with the OH base of these materials compound with alkyl envelope chain.
In addition, as above-mentioned vinyl compound, can list 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 list styrene, α-Jia Jibenyixi, 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 will be used in combination more than 2 kinds.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 mentioned above, 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, need to spend the excessive time in development, 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 suitably adjust and easily carry out 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 by use appropriate amount chain-transferring agent and easily carry out.
Acrylic resin for example can be with himself by 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 by 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.
(1) the polyurethane-modified acryl resin that contains polymerism pair keys that obtains by compound that will make isocyanate group and OH radical reaction, residual 1 unreacted isocyanate group in advance and comprise at least 1 (methyl) acryloyl group and the acrylate resin reaction that comprises carboxyl,
(2) acryl resin that contains unsaturated group that obtains of the reaction of the acrylate resin by comprising carboxyl and the compound that in molecule, has the two keys of epoxy radicals and polymerism simultaneously.
(3) (pendant) type Epocryl is hung in acid.
(4) acryl resin that contains the two keys of polymerism that obtains with 2 yuan of anhydride reactions of the acryl resin that will comprise the OH base with the two keys of polymerism.
In above-mentioned resin, the resin of preferred especially (1) and (2).
As object lesson, can use for example acrylic acid 2-hydroxyl ethyl ester that will have the OH base, for example methacrylic acid and can and the multipolymer of monomers such as the esters of acrylic acid of their copolymerization or vinylic chemical compound, and comprise the compound that has unsaturated link group between reactive epoxide ring of OH base and carbon compounds such as (for example) glycidyl acrylates reaction and the compound that obtains etc. with COOH base.With the reaction of OH base in, except epoxide ring, can also use compound with acid anhydrides, isocyanate group, acryloyl group.In addition, can also use the spy and open that flat 6-102669 communique, spy are opened the such unsaturated carboxylic acid reaction of compound that making of putting down in writing in the flat 6-1938 communique have epoxide ring and acrylic acid and the reactant of the compound that obtains and saturated or unsaturated multi-anhydride reaction acquisition.Compound as having unsaturated group between such alkali-soluble group of COOH base and carbon simultaneously can list for example ダ ィ ャ Na one Le NR シ リ one ズ (Mitsubishi's レ ィ ョ Application (strain) manufacturing); Photomer 6173 (oligomer, the Diamond Shamrock Co.Ltd. that contain the polyurethane acroleic acid of COOH base make); PVC ス コ one ト R-264, KS レ シ ス ト 106 (being Osaka organic chemistry industry (strain) manufacturing); サ ィ Network ロ マ one P シ リ one ズ, プ ラ Network セ Le CF200 シ リ one ズ (being ダ ィ セ Le chemical industry (strain) manufacturing); Ebecry 13800 (manufacturing of ダ ィ セ Le ュ 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.By 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 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 list that carbon black, titanium are black, graphite, iron oxide, titanium dioxide and in addition aftermentioned pigment, dyestuff, there is no particular limitation.Wherein, preferred carbon black, titanium black, graphite, more preferably carbon black.These colorants can use a kind separately, also can will also use 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 list for example カ one ボ Application Block ラ ッ Network #2400 of Mitsubishi Chemical society manufacturing, #2350, #2300, #2200, #1000, #980, #970, #960, #950, #900, #850, MCF88, #650, MA600, MA7, MA8, MA11, MA 100, 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 ィ ャ Block ラ ッ Network A, ダ ィ ャ Block ラ ッ Network N220M, ダ ィ ャ Block ラ ッ Network N234, ダ ィ ャ Block ラ ッ Network I, ダ ィ ャ Block ラ ッ Network LI, ダ ィ ャ Block ラ ッ Network II, ダ ィ ャ Block ラ ッ Network N339, ダ ィ ャ Block ラ ッ Network SH, ダ ィ ャ Block ラ ッ Network SHA, ダ ィ ャ Block ラ ッ Network LH, ダ ィ ャ Block ラ ッ Network H, ダ ィ ャ Block ラ ッ Network HA, ダ ィ ャ Block ラ ッ Network SF, ダ ィ ャ Block ラ ッ Network N550M, ダ ィ ャ Block ラ ッ Network E, ダ ィ ャ Block ラ ッ Network G, ダ ィ ャ Block ラ ッ Network R, ダ ィ ャ Block ラ ッ Network N760M, ダ ィ ャ Block ラ ッ Network LP; カ one ボ Application Block ラ ッ Network サ one マ ッ Network ス N990, N991, N907, N908, N990, N991, N908 that キ ャ Application カ one Block society makes; カ one ボ Application Block ラ ッ 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, ァ サ ヒ サ one マ Le that rising sun カ one ボ Application society makes; カ one ボ Application Block ラ ッ Network Color Black Fw200, Color Black Fw2, Color Black Fw2V, Color Black Fw1, Color Black Fw18, Color BlackS170, Color Black S160, Specical Black6, Specical Black5, SpecicalB lack4, Specical B lack4A, Printex U, Printex V, Printex 140U, Printex140V etc. that デ グ サ society makes.
Carbon black preferably has insulativity.Carbon black with insulativity, it is the carbon black that under situation about measuring by following method, demonstrates insulativity as the volume resistance of powder, for example, be by 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-coating 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 list powder, paste shape, ball shape, paste shape, laminar etc. by above-mentioned resin etc.
The pigment that disperses to apply by 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 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 list 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 list:
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 list 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 being used alone,, 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 or be that yellow uitramarine, isoindoline are that yellow uitramarine, quinophthalone are that yellow uitramarine, Huo person's perylene are uses such as red pigment mixing their at least a and bisdiazo.For example, as anthraquinone class pigment, can list C.I. paratonere 177 Zuo Wei perylene class pigment, C.I. paratonere 155, C.I. paratonere 224 can be listed,, C.I. paratonere 254 can be listed 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 adjust in conjunction with colourity.
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 energy 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 arrive the foot that is exposed 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, be exposed the curing deficiency owing to exposure of the foot of 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 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.By 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 list 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 list 2-halogenated methyl-5-vinyl-1,3 of representing by general formula I V of putting down in writing in 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 list 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 list the vinyl-halogenated methyl-s-triaizine compounds, the spy that represent by general formula V that put down in writing in for example special public clear 59-1281 communique and open the 2-(naphthalene-1-yl)-4 that represents 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 represents 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 list 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 list for example 2-(naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(4-methoxyl-naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(4-ethoxy-naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(4-butoxy-naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-[4-(2-methoxy ethyl)-naphthalene-1-yl]-4,6-pair-trichloromethyl-s-triazine, 2-[4-(2-ethoxyethyl group)-naphthalene-1-yl]-4,6-pair-trichloromethyl-s-triazine, 2-[4-(2-butoxyethyl group)-naphthalene-1-yl]-4,6-pair-trichloromethyl-s-triazine, 2-(2-methoxyl-naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(6-methoxyl-5-methyl-naphthalene-2-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(6-methoxyl-naphthalene-2-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(5-methoxyl-naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(4,7-dimethoxy-naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(6-ethoxy-naphthalene-2-yl)-4,6-pair-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 list 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-[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-[is 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-[is right-N-(right-methoxyphenyl) carbonylamino phenyl] and 2,6-two (trichloromethyl)-s-triazine, between 4-[-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and bromo-is right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and chloro-is right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and fluoro-is right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-bromo-is right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-chloro-is right-N, 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, N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-chloro-is right-N, N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-fluoro-is right-N, N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and bromo-is right-N, N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and chloro-is right-N, N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and fluoro-is right-N, N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-(-bromo-is right-N-ethoxy carbonyl methylamino phenyl) and-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) and-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) and-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) and-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-triazine 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 list 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 list 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), the aromatic series acyloin compound of putting down in writing in No. 2722512 instructionss of United States Patent (USP) that is replaced by α-alkyl, 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 ァ デ カ ォ プ ト マ-SP-150, ァ デ カ ォ プ ト マ-SP-151, ァ デ カ ォ プ ト マ-SP-170, ァ デ カ ォ プ ト マ-SP-171, ァ デ カ ォ プ ト マ-SP-N-1717, ァ デ カ ォ プ ト マ-SP-N1414 etc. (above make for rising sun electrification (strain)), OXE-01, OXE-02, CGI113, IR 369, 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 list benzoin, benzoin methyl ether, the 9-Fluorenone, 2-chloro-9-Fluorenone, 2-methyl-9-Fluorenone, the 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone, 9, the 10-anthraquinone, 2-ethyl-9, the 10-anthraquinone, the 2-tert-butyl group-9, the 10-anthraquinone, 2,6-two chloro-9, the 10-anthraquinone, xanthone, 2-methyl xanthone, 2-methoxyl xanthone, 2-ethoxy xanthone, thioxanthones, dibenzoyl, the 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-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 contain under the situation of base plate coating dyed layer by ink-jetting style the thermal polymerization polymerization initiator at least-kind.By 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, as Lu for the Jia oxadiazole, can list 2-halogenated methyl-5-vinyl-1 of putting down in writing in the special public clear 57-6096 communique, 3,4-oxadiazole compound, specifically can list 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 list the spy 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, 4-(right-aminophenyl)-2,6-two-halogenated methyl-s-triaizine compounds, specifically, can list 2-(naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(4-methoxyl-naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(4-ethoxy-naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(4-butoxy-naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-[4-(2-ethoxyethyl group)-naphthalene-1-yl]-4,6-pair-trichloromethyl-s-triazine, 2-(2-methoxyl-naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(6-methoxyl-5-methyl-naphthalene-2-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(6-methoxyl-naphthalene-2-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(5-methoxyl-naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(4,7-dimethoxy-naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(6-ethoxy-naphthalene-2-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(4,5-dimethoxy-naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 4-[is 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-[is right-N, N-two (phenyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[is right-N-(right-methoxyphenyl) carbonylamino phenyl] and 2,6-two (trichloromethyl)-s-triazine, between 4-[-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-bromo-is right-N, N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-chloro-is right-N, N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-fluoro-is right-N, N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and bromo-is right-N, N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and chloro-is right-N, N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and fluoro-is right-N, N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-(-chloro-is right-N-ethoxy carbonyl methylamino phenyl) and-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) and-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)-2,6-two (trichloromethyl)-s-triazine, 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 etc.
In these materials, as being suitable for the material of making curing colouration composition of the present invention, can list 4-[neighbour-bromo-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 by 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 list ketone peroxide, ketal peroxide, hydroperoxides, dialkyl peroxide, diacyl peroxide, peroxyester, peroxy dicarbonate etc. with chemical constitution.
Specifically, can list 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, the 5-trimethyl-cyclohexane, peroxidating benzoic acid tertiary butyl ester, peroxidating benzoic acid di-t-butyl ester, peroxidating m-phthalic acid di-t-butyl ester, the 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, the tert-butyl hydroperoxide maleic amide, the cyclohexanone superoxide, the methyl-acetoacetic ester superoxide, methyl hexanone superoxide, acetyl acetone peroxide, 1,1-two (uncle's hexyl peroxide)-3,3, the 5-trimethyl-cyclohexane, 1,1-two (peroxidating uncle hexyl) cyclohexane, 1,1-two (tert-butyl peroxide)-3,3, the 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, the 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 list 1,1 '-azo two (cyclohexane-1-nitrile), 1-[(1-cyano group-1-Methylethyl) azo] formamide (2-(carbamyl azo) isobutyronotrile) etc.
As triaizine compounds, can list vinyl-halogenated methyl-s-triaizine compounds of putting down in writing in the special public clear 59-1281 communique, the spy opens 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 list 2,4-two (trichloromethyl)-6-p-methoxystyrene base-s-triazine, 2,4-two (trichloromethyl)-6-(1-is right-dimethylamino phenyl-1, the 3-butadienyl)-the s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyrene base-s-triazine, 2-[4-(2-methoxy ethyl)-naphthalene-1-yl]-4,6-pair-trichloromethyl-s-triazine, 2-[4-(2-butoxyethyl group)-naphthalene-1-yl]-4,6-pair-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, between 4-[-and bromo-is right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and chloro-is right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and fluoro-is right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-bromo-is right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-chloro-is right-N, N-two (ethoxy carbonyl methyl) aminophenyl-, 6-two (trichloromethyl)-s-triazine, 4-[neighbour-fluoro-is right-N, 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 will be used in combination more than 2 kinds.
＜polymerizable compound 〉
Curing colouration composition of the present invention is according to different optical polymerism compound, the thermal polymerization 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.By 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 is subjected to 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 list for example acrylate or the methacrylate of simple functions such as polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, phenoxy group ethyl (methyl) acrylate; Polyglycol two (methyl) acrylate; trimethylolethane trimethacrylate (methyl) acrylate; neopentyl glycol two (methyl) acrylate; pentaerythrite three (methyl) acrylate; pentaerythrite four (methyl) acrylate; dipentaerythritol six (methyl) acrylate; hexane diol (methyl) acrylate; 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 of poly-(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.
In addition, can also use Japan then the magazine Vol.20 of association, NO.7, the material introduced as photo-curable monomer and oligomer in 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) acrylate, dipentaerythritol six (methyl) acrylate and these acryloxies are by the structure of ethylene 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 will be used in combination more than 2 kinds.
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 compound-
Curing colouration composition of the present invention contains a kind of thermal polymerization compound at least.By using with above-mentioned thermal polymerization 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 the thermal polymerization 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 list trimethylolethane trimethacrylate (methyl) acrylate, neopentyl glycol two (methyl) acrylate, dipentaerythritol six (methyl) acrylate, hexanediol (methyl) acrylate, 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 the degree of cure deficiency in addition, can't be guaranteed 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 list bisphenol A-type, cresols phenol aldehyde type, biphenyl type, alicyclic epoxy compound etc.For example, as above-mentioned bisphenol A-type, can list ェ 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 ラ Network セ Le GL-61, GL-62, G101, G102 (above make for ダ ィ 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 Ebecryl 3700, Ebecryl 3701, Ebecryl 600 epoxy acrylates such as (above are that ダ ィ セ Le サ ィ テ ッ Network society makes).In addition, as above-mentioned cresols phenol aldehyde type, can list ェ Port ト one ト YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704 etc. (above make) for Dongdu changes into society, デ Na コ one Le EM-125 etc. (the above Na ガ セ of being changes into society and makes), as above-mentioned biphenyl type, can list 3,5,3 ', 5 '-tetramethyl-4,4 '-diglycidyl biphenyl etc., in addition, as above-mentioned alicyclic epoxy compound, can list セ ロ キ サ ィ De 2021, セ ロ キ サ ィ De 2081, セ ロ キ サ ィ De 2083, セ ロ キ サ ィ De 2085, ェ Port リ one De GT-301, GT-302, GT-401, GT-403, EHPE-3150 (above is that ダ ィ セ Le chemistry society makes), 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, as ェ Port ト one ト YH-434, the YH-434L of other amine type epoxy resin, in the skeleton of bisphenol A type epoxy resin by 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 that is no more than with respect to the face material of removing curing colouration composition.If this content of resin in above-mentioned scope, suppresses the effect height of volumetric contraction when then solidifying, as ink-jet method, giving drop and forming under the situation of cured film, can obtain the tabular surface of uniform thickness to cut zone, 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 list filling agents such as glass, aluminium oxide; Vinyltrimethoxy silane, vinyltriethoxysilane, 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, the 3-aminopropyltriethoxywerene werene, the 3-glycidyl ether oxygen propyl trimethoxy silicane, 3--glycidyl ether oxygen propyl methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, 3-metacryloxy propyl trimethoxy silicane, adhesion promotors such as 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 of uncured portion, further improve under the situation of development 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 list 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, pyromellitic acid; 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, preferably advance-go on foot to add thermal polymerization and prevent 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 〉
At the bottom of color filter of the present invention is provided with the different a plurality of colored pixels of tone usually and isolates the fast black base of colored pixels and constitute.These (especially at the bottom of fast black bases) can form dyed layer by the above-mentioned curing colouration composition of the present invention of coating on substrate, after dry (prebake), expose into the pattern of expectation, prepare by 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 exposed into pattern-like, wait by developing to form.In addition, owing to use above-mentioned curing colouration composition to constitute, so optical concentration height of black 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 by 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 dispersion machine mixes and disperses to prepare.
In addition, the operation (mixing dispersion step) of mix disperseing is preferably loose by mixing dispersion and the differential that then carries out thereafter and is handled formation, also can omit mixing dispersion.In addition, the pigment type that in mixing, dispersion step, uses preferably by 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 by aggregation method.
In mixing dispersion step, promote the particle surface of raw material colorant and, the solid/gas interface of coloring agent particle and air is converted into the solid/solution interface of coloring agent particle and vehicles solution based on the infiltration between the constituent of the resinous principle of vehicles.In differential looses process, mix stirring by dispersion in the lump with medium, thereby coloring agent particle is dispersed to small state near primary particle the particulate of glass, zirconia or pottery.Therefore, because in mixing dispersion step, the interface that the coloring agent particle surface must be formed is 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, uniform particles stably must be scattered in small state, expectation can give the dispersion machine of impulsive force and shearing force to the coloring agent particle of cohesion, by to be disperseed thing be lower viscosity.
The mixing dispersion step that is used for preparing the color filter that uses curing colouration composition of the present invention at first be with 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 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 by 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 in waiting, " Paint Flow andPigment Dispersion (the John Wiley and Sons society periodical in 1964) " of T.C.Patton work put down in writing for detailed description mixing, that disperse.
The coating of-curing colouration composition-
By 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 by 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 is with the necessary condition that rotates to be of substrate at present, and the thickness of the curing colouration composition that drips on substrate is by the rotation homogenising of substrate.Because the maximization of glass substrate produce a large amount of loads in making its rotation, 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, the method (slot coated) to be coated with even velocity travelling slit nozzle or glass substrate.
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.Need not can be betwixt owing to the cohesion of colorant or the drying of nozzle produce the such curing colouration composition of foreign matter.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 guarantee to film between drying, curing, 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 to flow through a spot of coating fluid before coating earlier, carries out pre-coating, thereby makes method of nozzle cleaningization etc.The all methods of the present invention all are effectively, the method for the pre-ejection of special expectation.
The formation of-pattern-
Photomask by regulation carries out pattern exposure to the dyed layer as above-mentioned formation, only exposed portion is solidified, and by developer solution unexposed portion is developed and removes; Only repeat the aforesaid operations of the tone number expected, thereby 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 ィ 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 by 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 be carried out, to finish drying after prebake.
-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, sodium bicarbonate, 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 feature of color filter of the present invention be by ink-jetting style after forming pattern of pixels on the substrate, under 150～250 ℃, carry out heat treated.
In more detail, manufacturing method of color filter of the present invention is following operation is set at least and constitutes, promptly, 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 by 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 by formation, thereby can not produce obstruction on the top of inkjet nozzle, the operating efficiency excellence, the color filter of preparation is also excellent as described above.
Above-mentioned ink-jetting style can be from charged printing ink of continuous injection and the method by 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 as the spy in order to spray.In piezo jets, can use the shower nozzle of record in No. 277703, European patent A, 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 under 1～500kHz, operate.
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 list 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 a plurality of painted pixels on these substrates and isolate at the bottom of the fast black base of each pixel.
Raw material as above-mentioned plastic base, from the viewpoint of optical characteristics, thermotolerance, physical strength, preferred unformed polyolefin, polyethersulfone, poly-glutarimide, polycarbonate, polyethylene terephthalate, Polyethylene Naphthalate, 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 that the curing when preventing to be accompanied by the preparation color filter is handled), optical characteristics, surface smoothings etc. such as gas barrier (guaranteeing stability of liquid crystal), transmittance and optical isotropy.For thermal expansion, preferred thermal expansivity is below the 10-4.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 list 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, at coated face for preparing by the slot coated mode and the color filter by ink-jetting style preparation, estimate changing as the situation of the component of the curing colouration composition of coating fluid separately.
[embodiment 1]
＜form coated face by 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 ィ ス パ one マ ッ ト, GETZMANN society make) by using the 0.3mm zirconium oxide bead carries out 4 hours diffusing processing of differential to the gained mixed solution, obtains to disperse thing.In addition, the mean grain size of pigment is observed by SEM and is measured with usual method.
-red A-the dispersion liquid of forming
Face material: 11 parts of paratoneres 254 (mean grain size 20nm)
Face material: 4 parts of red 177 (the mean grain size 18nm) of face material
5 parts of dispersion resins (B-1-3) (following structure)
3 parts of spreading agents (trade name: Disperbyk-161, PVC ッ Network ケ ミ one society make)
3 parts of the mixed solvents of methoxyl butylacetic acid ester and butyl acetate
Alkali soluble resins: methacrylic acid benzyl ester/methacrylic acid copolymer=75/25[mass ratio] 4 parts of methyl ether acetate solution of propylene glycol (solid constituent: 50 quality %) of multipolymer, weight molecular weight Mw:5000
(B) dispersion resin dissolving solvent: 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 ィ セ Le chemistry is made) 2 parts
Polymerizable compound: 8 parts of dipentaerythritol five/six acrylate
Polymerization initiator: 4-(neighbour-bromo-is right-N, and N-two (ethoxy carbonyl first
1 part of base) amino-phenyl)-2,6-two (trichloromethyl)-s-triazine
Polymerization initiator: 1 part of 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
Nonionic class surfactant (trade name: テ ト ロ ニ ッ Network R150,
0.2 part ADEKA makes)
(A) high boiling solvent: 50 parts of 1,3 butylene glycol diacetate esters (232 ℃ of boiling points)
(B) dispersion resin dissolving solvent: propylene glycol methyl ether acetate
80 parts (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 dispersion thing.
-green A-the dispersion liquid of forming
Face material: 11 parts of pigment green 36s (mean grain size 19nm)
7 parts of face material: Pigment Yellow 150 (mean grain size 22nm)
5 parts of dispersion resins (B-1-26) (following structure)
(trade name: Disperbyk-161, PVC ッ Network ケ ミ one society make 30% to spreading agent
3 parts of solution)
Alkali soluble resins: methacrylic acid benzyl ester/methacrylic acid copolymer
4 parts=75/25[mass ratio] the propylene glycol methyl ether acetate solution (solid constituent: 50 quality %) of multipolymer, weight molecular weight Mw:5000
(B) dispersion resin dissolving solvent: 3-ethoxy-propionic acid methyl esters
70 parts (SP value 9.3,165 ℃ of boiling points)
Figure A20071014839400941
-green B-the coating fluid of forming
100 parts of the dispersion liquids of green composition A
Epoxy resin: (trade name EHPE3150 ダ ィ セ Le chemistry is made) 2 parts
Polymerizable compound: 8 parts of dipentaerythritol five/six acrylate
Polymerization initiator: 1,2 parts of two trihalomethyl groups of 3--5-coumarone triazine
Polymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholine
1 part of phenyl)-] ketone-1
Polymerization initiator: 0.5 part of diethyl thioxanthone
Polymerization inhibitor: 0.001 part of p methoxy phenol
Fluorine class surfactant (trade name: Megafac R08, big Japanese ink system
0.02 part is made)
Nonionic class surfactant (trade name: ェ マ Le ゲ Application A-60, flower
0.5 part king makes)
(A) high boiling solvent: 50 parts of 1,3 butylene glycol diacetate esters (232 ℃ of boiling points)
(B) dispersion resin dissolving solvent: 3-ethoxy-propionic acid methyl esters
100 parts (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 dispersion thing.
-blue A-the dispersion liquid of forming
Face material: pigment blue 15: 14 parts of 6 (mean grain size 15nm)
Face material: 1 part of pigment Violet 23 (mean grain size of observing by SEM is 23nm)
5 parts of dispersion resins (B-1-35) (following structure)
Spreading agent (trade name: Disperbyk-161, PVC ッ Network ケ ミ one society make,
3 part of 30% solution)
Alkali soluble resins: methacrylic acid benzyl ester/methacrylic acid copolymer
4 parts=75/25[mass ratio] the propylene glycol methyl ether acetate solution (solid constituent: 50 quality %) of multipolymer, weight molecular weight Mw:5000
(B) dispersion resin dissolving solvent: propylene glycol methyl ether acetate
73 parts (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: methacrylic acid benzyl ester/methacrylic acid copolymer
=75/25[mass ratio] multipolymer, weight molecular weight Mw:5000 6 parts
Propylene glycol methyl ether acetate solution (solid constituent: 50 quality %)
Epoxy resin: (trade name EHPE3150 ダ ィ セ Le chemistry is made) 2 parts
UV curable resin: (trade name サ ィ Network ロ マ one P ACA-250, ダ ィ セ Le chemistry is made)
4 parts
The propylene glycol methyl ether acetate solution (solid constituent 50 quality %) that comprises the acrylic copolymer of alicyclic ring, COOH base, acryloyl group at side chain
Polymerizable compound: 12 parts of dipentaerythritol five/six acrylate
Polymerization initiator: 1-(9-ethyl-6-(2-methyl benzoyl)-9H
3 parts-carbazole-the 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
Nonionic class surfactant (trade name: ェ マ Le ゲ Application A-60 flower king system
1.0 part is made)
(A) high boiling solvent: 20 parts of propylene glycol n-butyl ether acetic acid esters (211 ℃ of boiling points)
(B) dispersion resin dissolving solvent: propylene glycol methyl ether acetate
150 parts (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 ィ セ Le chemistry is made) 2 parts
Polymerizable compound: 8 parts of dipentaerythritol five/six acrylate
Polymerization initiator: 4-(neighbour-bromo-is right-N, and N-two (ethoxy carbonyl first
1 part of base) amino-phenyl)-2,6-two (trichloromethyl)-s-triazine
Polymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)
1 part-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
Nonionic class surfactant (trade name: テ ト ロ ニ ッ Network R150ADEKA
0.2 part manufacturing)
(A) high boiling solvent: 35 parts of 1,3 butylene glycol diacetate esters (232 ℃ of boiling points)
(B) dispersion resin dissolving solvent: propylene glycol methyl ether acetate
30 parts (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 ィ セ Le chemistry is made) 2 parts
Polymerizable compound: 8 parts of dipentaerythritol five/six acrylate
Polymerization initiator: 4-(neighbour-bromo-is right-N, and N-two (ethoxy carbonyl first
1 part of base) amino-phenyl)-2,6-two (trichloromethyl)-s-triazine
Polymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)
1 part-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
Nonionic class surfactant (trade name: テ ト ロ ニ ッ Network R150ADEKA
0.2 part manufacturing)
(A) high boiling solvent: 102 parts of 1,3 butylene glycol diacetate esters (232 ℃ of boiling points)
(B) dispersion resin dissolving solvent: 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, except (A) high boiling solvent being replaced with propylene glycol methyl ether acetate, form B with redness and similarly prepare curing colouration composition.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, similarly prepare curing colouration composition with redness composition A, the red B that forms.This composition does not contain (B) dispersion resin dissolving solvent among the present invention except the solvent that comprises in spreading agent and alkali soluble resins solution.The content that dissolves with solvent with respect to (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
Face material: 11 parts of paratoneres 254 (mean grain size 20nm)
Face material: 4 parts of paratoneres 177 (mean grain size 18nm)
(trade name: Disperbyk-161, ピ Star Network ケ ミ one society make 30% to spreading agent
3 parts of solution)
Alkali soluble resins 1: 14 parts=75/25[of methacrylic acid benzyl ester/methacrylic acid copolymer mass ratio] multipolymer, weight molecular weight Mw:5000
Propylene glycol methyl ether acetate solution (solid constituent: 50 quality %)
68 parts of propylene glycol methyl ether acetates (SP value 9.2,146 ℃ of boiling points)
Redness in using the red B of composition of the red C of composition replacement is formed the A, forms B with redness and similarly prepares 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 diisobutyl ketone (SP:8.2 respectively with solvent, bp:169 ℃) and diisobutyl ketone (SP:8.2, bp:169 ℃) in addition, form A with redness and similarly 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 similarly 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 similarly prepare curing colouration composition with the red B of composition.
The composition of comparative example 4～comparative example 6 the contained solvent, does not contain (B) dispersion resin dissolving solvent among the present invention 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.
The evaluation of the suitable property of＜slot coated 〉
1. coating striped
Use has the slot coated device of the slit shower nozzle of slit separation 100 μ m, coating effective width 500mm, and the suitable property of slot coated is estimated.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.By 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
By 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
By 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 similarly handle, obtain dispersion liquid.
-red D-the dispersion liquid of forming
Face material: 11 parts of paratoneres 254 (mean grain size 20nm)
Face material: 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, ピ 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 4 parts
Propylene glycol methyl ether acetate solution (solid constituent: 50 quality %)
(A) high boiling solvent: 30 parts of 1,3 butylene glycol diacetate esters (232 ℃ of boiling points)
(B) dispersion resin dissolving solvent: propylene glycol methyl ether acetate
23 parts (SP value 9.2,146 ℃ of boiling points)
Figure A20071014839401021
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 ィ セ Le chemistry is made) 2 parts
Polymerizable compound: 8.3 parts of dipentaerythritol five/six acrylate
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: ェ 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 similarly handle, obtain dispersion liquid.
-green C-the dispersion liquid of forming
Face material: 10 parts of pigment green 36s (mean grain size 19nm)
6 parts of face material: 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 ッ 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] 3 parts of propylene glycol methyl ether acetate solution (solid constituent: 50 quality %) of multipolymer, weight molecular weight Mw:5000
(A) high boiling solvent: 33 parts of propylene glycol n-butyl ether acetate solution (211 ℃ of boiling points)
(B) dispersion resin dissolving solvent: propylene glycol methyl ether acetate
20 parts (SP value 9.2,146 ℃ of boiling points)
Figure A20071014839401041
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 ィ セ Le chemistry is made) 2 parts
Polymerizable compound: 8 parts of dipentaerythritol five/six acrylate
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: ェ 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: 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 similarly handle, obtain dispersion liquid.
-blue C-the dispersion liquid of forming
Face material: pigment blue 15: 12 parts of 6 (mean grain size 15nm)
Face material: 1 part of pigment Violet 23 (mean grain size 23nm)
7 parts of dispersion resins (B-1-46) (following structure)
(trade name: Disperbyk-161, PVC ッ 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] 6 parts of propylene glycol methyl ether acetate solution (solid constituent: 50 quality %) of multipolymer, weight molecular weight Mw:5000
(A) high boiling solvent: 20 parts of propylene glycol n-butyl ether acetate solution (211 ℃ of boiling points)
(B) dispersion resin dissolving solvent: propylene glycol methyl ether acetate
31 parts (SP value 9.2,146 ℃ of boiling points)
Figure A20071014839401061
-blue D-the printing ink of forming
80 parts of the dispersion liquids of blue composition C
Epoxy resin: (trade name EHPE3150 ダ ィ セ Le chemistry is made) 2 parts
Polymerizable compound: 10 parts of dipentaerythritol five/six acrylate
Polymerization initiator: 1,2 parts of two trihalomethyl groups of 3--5-coumarone triazine
Polymerization inhibitor: 0.001 part of p methoxy phenol
Nonionic class surfactant (trade name: ェ 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: 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 ィ セ Le chemistry is made) 2 parts
Polymerizable compound: 8.3 parts of dipentaerythritol five/six acrylate
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: ェ 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: 70 parts of 1,3 butylene glycol diacetate esters (232 ℃ of boiling points)
(B) dispersion resin dissolving solvent: 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, similarly 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) dispersion resin dissolving solvent: propylene glycol methyl ether acetate
43 parts (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 ィ セ Le chemistry is made) 2 parts
Polymerizable compound: 8.3 parts of dipentaerythritol five/six acrylate
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: ェ 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) dispersion resin dissolving solvent: 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 propylene glycol methyl ether acetate, form E with redness and similarly 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 solvent replacing of redness being formed D and the red E of composition is the 1,3 butylene glycol diacetate esters, forms E with redness and similarly 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 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, except dispersion resin (B-2-1) being replaced with alkali soluble resins 2, form the dispersion liquid that D similarly prepares the following red G of composition with redness.
-red G-the dispersion liquid of forming
Face material: 11 parts of paratoneres 254 (mean grain size 20nm)
Face material: 4 parts of paratoneres 177 (mean grain size 18nm)
Spreading agent (trade name: Disperbyk-161, PVC ッ 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] 14 parts of propylene glycol methyl ether acetate solution (solid constituent: 50 quality %) of multipolymer, weight molecular weight Mw:5000
(A) high boiling solvent: 30 parts of 1,3 butylene glycol diacetate esters (232 ℃ of boiling points)
(B) dispersion resin dissolving solvent: propylene glycol methyl ether acetate
18 parts (SP value 9.2,146 ℃ of boiling points)
In redness composition E, except using the red composition of red composition dispersion liquid G replacement dispersion liquid D, form E with redness and similarly prepare curing colouration composition.
[comparative example 11]
" preparation of red solidification compound "
Except (B) dispersion resin dissolving of redness being formed D with solvent with replace with the diisobutyl ketone, D similarly 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 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 "
Except (B) dispersion resin dissolving of redness being formed D and the red E of composition is the ethylene glycol monoethyl ether with solvent replacing, D similarly 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 solvent.The content of propylene glycol methyl ether acetate is 4 quality % with respect to whole solvents of coating fluid.
The 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) by 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, carries out 30 minutes thermal treatment again under 220 ℃, the preparation color filter.
-estimate-
1. flatness
Measure near the black resin the thickness and the thickness of pixel middle body by DECTAK-III (manufacturing of ァ Le バ ッ Network), calculating with middle body is near 100% o'clock thickness.
2. ejection
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 by 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, therefore embodiment 12,13 abandons because the beam split difference can't compare.
The result is shown in the table 2.
Table 1
Resin (A) high boiling solvent and other solvent (B) dispersion resin dissolves 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:8.2bp169 ℃) 14.7 - × 6 89
Comparative example 5 Dispersion resin (B-1-3) The 1,3 butylene glycol diacetate esters Ethylene glycol monoethyl ether (SP:10.6bp136 ℃) 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) dispersion resin dissolves 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:8.2bp169 ℃) 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:10.6bp136 ℃) 30 - 85 6 minutes 86
By found that of table 1, table 2, use solvent and dispersion resin among the present invention, compare with comparative example with the color filter that ink-jetting style forms by the slot coated mode, there be not the inhomogeneous of striated on the coated face, slot coated adaptability excellence in addition, has excellent the dripping property of beating, flatness is good, and the contrast of color filter is also excellent.

Claims (14)

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 comprise boiling point under (A) normal pressure be 180 ℃～280 ℃ solvent and (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 following general formula (1) expression, comprise to come free following general formula (I) expression monomer copolymerization units polymkeric substance and contain by among the polymkeric substance of the structural unit of following general formula (a) expression more than a kind;
General formula (1)
Figure A2007101483940002C1
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 oxygen atom, the carbon number that are selected from acidic-group, have basic nitrogen atom are the group among alkyl, alkoxysilyl, epoxy radicals, isocyanate group and the hydroxyl more than 4; N A 1Can be identical, also can be different; M represents 1～8, and n represents 2～9, and m+n satisfies 3～10; P 1The expression macromolecular scaffold;
General formula (I)
Figure A2007101483940002C2
In general formula (I), R 01Expression hydrogen atom or replacement or unsubstituted alkyl; R 02The expression alkylidene; W represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene; X represents 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 represents to be selected from NR 03, among O, the 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 according to claim 1, it is characterized in that, with respect to the all-mass of solvent contained in the described curing colouration composition, containing being selected from of 5 quality %～80 quality % among the compound of (ii) (iii) being represented with general formula by following general formula (i), general formula more than a kind is 180 ℃～280 ℃ solvent as the boiling point under described (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)
Described 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 alkyl, aralkyl, the carbonyl of 1～8 straight or branched; R 1, R 2Do not represent hydrogen atom simultaneously; N represents 1～4 integer.
3. curing colouration composition according to claim 1, 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 described dispersion resin.
4. according to each described curing colouration composition in the claim 1～3, it is characterized in that, contained polymerization initiator is a Photoepolymerizationinitiater initiater in the described 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 by the slot coated mode.
5. according to each described curing colouration composition in the claim 1～3, it is characterized in that, contained polymerization initiator is a thermal polymerization in the described 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 by ink-jetting style.
6. according to each described curing colouration composition in the claim 1～3, it is characterized in that contained solvent (A) comprises the solvent that is selected among following (1)～(15) in the described curing colouration composition;
(1) diethylene glycol diethyl ether, boiling point are 188 ℃;
(2) diethylene glycol monoethyl ether acetic acid esters, boiling point are 217 ℃;
(3) diethylene glycol monobutyl ether, boiling point are 231 ℃;
(4) butyl carbitol acetate, boiling point are 247 ℃;
(5) propylene glycol n-propyl ether acetic acid esters, boiling point are 187 ℃;
(6) propylene-glycol diacetate, boiling point are 190 ℃;
(7) propylene glycol n-butyl ether acetic acid esters, boiling point are 211 ℃;
(8) propylene glycol phenyl ether, boiling point are 243 ℃;
(9) propylene glycol phenyl ether acetic acid ester, boiling point is 258 ℃;
(10) dipropylene glycol monomethyl ether acetic acid esters, boiling point are 209 ℃;
(11) dipropylene glycol n-propyl ether acetic acid esters, boiling point are 232 ℃;
(12) dipropylene glycol n-butyl ether acetic acid esters, boiling point are 250 ℃;
(13) tripropylene glycol list n-butyl ether, boiling point are 274 ℃;
(14) tripropylene glycol methyl ether acetate, boiling point are 263 ℃;
(15) 1,3 butylene glycol diacetate esters, boiling point are 232 ℃.
7. according to each described curing colouration composition in the claim 1～3, it is characterized in that under the situation of slot coated mode, the content of contained solvent (A) is 5～30 quality % in the described curing colouration composition.
8. according to each described curing colouration composition in the claim 1～3, it is characterized in that under the situation of ink-jetting style, the content of contained solvent (A) is 20～80 quality % in the described curing colouration composition.
9. according to each described curing colouration composition in the claim 1～3, it is characterized in that contained solvent (B) comprises the solvent that is selected among following (1)～(12) in the described curing type coloured composition,
(1) ethyl lactate, SP value are 10.0, boiling point is 154 ℃;
(2) 3-methoxy propyl acetoacetic ester, SP value are 10.1, boiling point is 158 ℃;
(3) 3-ethoxyl ethyl propionate, SP value are 8.8, boiling point is 169 ℃;
(4) 3-ethoxy-propionic acid methyl esters, SP value are 9.3, boiling point is 165 ℃;
(5) 3-methoxypropionic acid methyl esters, SP value are 9.5, boiling point is 145 ℃;
(6) 2-ethoxy-propionic acid methyl esters, SP value are 9.2, boiling point is 162 ℃;
(7) acetate ethyl cellosolve, SP value are 9.4, boiling point is 156 ℃;
(8) isoamyl propionate, SP value are 8.5, boiling point is 160 ℃;
(9) 2-heptanone, SP value are 8.8, boiling point is 152 ℃;
(10) cyclohexanone, SP value are 9.9, boiling point is 156 ℃;
(11) propylene glycol methyl ether acetate, SP value are 9.2, boiling point is 146 ℃;
(12) propylene-glycol ethyl ether acetic acid esters, SP value are 9.1, boiling point is 156 ℃.
10. according to each described curing colouration composition in the claim 1～3, it is characterized in that under the situation of slot coated mode, the content of contained solvent (B) is 5～30 quality % in the described curing colouration composition.
11., it is characterized in that under the situation of ink-jetting style, the content of contained solvent (B) is 20～80 quality % in the described curing colouration composition according to each described curing colouration composition in the claim 1～3.
12. according to each described curing colouration composition in the claim 1～3, it is characterized in that, combination as solvent contained in the described curing colouration composition (A) and solvent (B), be following combination: solvent (A) 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, solvent (B) is ethyl lactate, propylene glycol methyl ether acetate.
13. a color filter, it contains the dyed layer that uses each described curing colouration composition preparation in the claim 1～12 and obtain.
14. a liquid crystal indicator, it has the color filter described in the claim 13.
CN2007101483945A 2006-09-29 2007-08-31 Curing colouration composition, color filtering device and liquid crystal display using the color filtering device Active CN101154038B (en)

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

Publications (2)

Publication Number Publication Date
CN101154038A true CN101154038A (en) 2008-04-02
CN101154038B CN101154038B (en) 2012-06-13

Family

ID=39255764

Family Applications (1)

Application Number Title Priority Date Filing Date
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

Country Status (3)

Country Link
JP (1) JP2008088272A (en)
KR (1) KR20080029787A (en)
CN (1) CN101154038B (en)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102043337A (en) * 2009-10-23 2011-05-04 富士胶片株式会社 Colored curable composition, colored pattern, color filter, method of producing color filter and liquid crystal display element
CN101763911B (en) * 2008-12-23 2012-08-22 比亚迪股份有限公司 Preparation method of nanometer conductive carbon black suspension, battery anode and battery
CN102839518A (en) * 2011-06-22 2012-12-26 海尔集团公司 Household dry cleaning machine and clothes dry cleaning method
US8507585B2 (en) 2008-05-23 2013-08-13 Riso Kagaku Corporation Non-aqueous pigment ink
CN104603210A (en) * 2012-08-31 2015-05-06 富士胶片株式会社 Dispersion composition, and curable composition, transparent film, microlens and solid-state imaging element using same
CN104603209A (en) * 2012-08-31 2015-05-06 富士胶片株式会社 Dispersion composition, and curable composition, transparent film, microlens and solid-state imaging element using same
CN104914669A (en) * 2014-03-11 2015-09-16 东友精细化工有限公司 Blue photosensitive resin composition, blue color filter and display device comprising the same
CN106459238A (en) * 2014-05-27 2017-02-22 富士胶片株式会社 sunscreen composition
CN106959580A (en) * 2015-12-29 2017-07-18 东友精细化工有限公司 Colored photosensitive resin composition and the column spacer including it
CN107272331A (en) * 2016-03-30 2017-10-20 住友化学株式会社 Hardening resin composition and cured film
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
CN109491147A (en) * 2017-09-11 2019-03-19 夏普株式会社 The manufacturing method of alignment films, liquid crystal display panel and liquid crystal display panel
CN109804312A (en) * 2016-12-16 2019-05-24 株式会社Lg化学 Be used to form the photopolymerizable composition of frame pattern, the manufacturing method of the frame pattern of display panel, manufacture frame pattern
CN109814335A (en) * 2017-11-21 2019-05-28 东友精细化工有限公司 Photosensitive composition, colour filter and image display device
CN109891320A (en) * 2016-10-26 2019-06-14 东友精细化工有限公司 Metal oxide photosensitive polymer combination and the colour filter and image display device manufactured using it
CN110352221A (en) * 2017-03-02 2019-10-18 富士胶片株式会社 Composition, film, infrared intercepting filter, solid-state imager, infrared sensor, camera model and new compound
TWI675889B (en) * 2015-02-09 2019-11-01 日商富士軟片股份有限公司 Pigment dispersion composition and method for producing the same, polymerizable composition,shielding film, and solid state image sensor
TWI783432B (en) * 2021-03-03 2022-11-11 長春人造樹脂廠股份有限公司 Etch-resistant composition

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009019117A (en) * 2007-07-12 2009-01-29 Seiko Epson Corp Color filter ink, color filter, color filter manufacturing method, image display device, and electronic device
JP5399013B2 (en) * 2008-06-30 2014-01-29 新日鉄住金化学株式会社 Ink composition for inkjet color filter excellent in inkjet ejection stability, and color filter cured film and color filter obtained using this ink composition
JP4602462B2 (en) * 2008-09-22 2010-12-22 富士フイルム株式会社 Ink composition
JP5919830B2 (en) * 2011-02-08 2016-05-18 住友化学株式会社 Colored photosensitive resin composition
JP2013231878A (en) * 2012-04-27 2013-11-14 Fujifilm Corp Method for forming cured layer or cured pattern, method for manufacturing color filter, and color filter, solid-state imaging device and liquid crystal display device manufactured by using the same
KR102012524B1 (en) 2013-08-22 2019-08-20 동우 화인켐 주식회사 A color photosensitive resin composition, color filter and display device comprising the same
CN104650281A (en) * 2014-12-26 2015-05-27 北京鼎材科技有限公司 Alkali-soluble resin polymer for color light filter and light-sensitive resin composition
JP7560970B2 (en) 2019-07-31 2024-10-03 住友化学株式会社 Colored curable resin composition

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10186637A (en) * 1996-12-26 1998-07-14 Clariant Internatl Ltd Radiation sensitive composition for roll coating
CN1294429C (en) * 2002-03-27 2007-01-10 阪田油墨株式会社 Pigment-dispersed resist composition for color filters
JP2004138995A (en) * 2002-08-21 2004-05-13 Fuji Photo Film Co Ltd Plate making method for planographic printing plate
JP4627617B2 (en) * 2003-05-23 2011-02-09 東洋インキ製造株式会社 Coloring composition, method for producing color filter, and method for producing black matrix substrate
JP4322608B2 (en) * 2003-09-19 2009-09-02 富士フイルム株式会社 Color filter and manufacturing method thereof
JP2005234045A (en) * 2004-02-17 2005-09-02 Fujifilm Electronic Materials Co Ltd Color resin composition
JP4494061B2 (en) * 2004-03-30 2010-06-30 東京応化工業株式会社 Positive resist composition
KR101112545B1 (en) * 2004-12-16 2012-03-13 스미또모 가가꾸 가부시끼가이샤 Photosensitive resin and thin film panel comprising pattern made of the photosensitive resin and method for manufacturing the thin film panel

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8507585B2 (en) 2008-05-23 2013-08-13 Riso Kagaku Corporation Non-aqueous pigment ink
CN102015924B (en) * 2008-05-23 2013-09-25 理想科学工业株式会社 Non-aqueous pigment ink
CN101763911B (en) * 2008-12-23 2012-08-22 比亚迪股份有限公司 Preparation method of nanometer conductive carbon black suspension, battery anode and battery
CN102043337A (en) * 2009-10-23 2011-05-04 富士胶片株式会社 Colored curable composition, colored pattern, color filter, method of producing color filter and liquid crystal display element
CN102839518A (en) * 2011-06-22 2012-12-26 海尔集团公司 Household dry cleaning machine and clothes dry cleaning method
CN102839518B (en) * 2011-06-22 2017-06-20 海尔集团公司 A kind of dry-cleaning method of Domestic dry washing machine and clothing
CN104603210B (en) * 2012-08-31 2017-10-17 富士胶片株式会社 Dispersive composition, use the solidification compound of the dispersive composition, hyaline membrane, lenticule and solid-state imager
CN104603210A (en) * 2012-08-31 2015-05-06 富士胶片株式会社 Dispersion composition, and curable composition, transparent film, microlens and solid-state imaging element using same
CN104603209A (en) * 2012-08-31 2015-05-06 富士胶片株式会社 Dispersion composition, and curable composition, transparent film, microlens and solid-state imaging element using same
US10287422B2 (en) 2012-08-31 2019-05-14 Fujifilm Corporation Dispersion composition, curable composition using the same, transparent film, microlens, and solid-state imaging device
TWI585134B (en) * 2012-08-31 2017-06-01 富士軟片股份有限公司 Dispersion composition and method of manufacturing the same, curable composition using the same, transparent film, micro lens, and solid-state image sensing device
CN104603209B (en) * 2012-08-31 2017-11-24 富士胶片株式会社 Dispersive composition, use the solidification compound of the dispersive composition, hyaline membrane, lenticule and solid-state imager
CN104914669A (en) * 2014-03-11 2015-09-16 东友精细化工有限公司 Blue photosensitive resin composition, blue color filter and display device comprising the same
CN104914669B (en) * 2014-03-11 2021-02-19 东友精细化工有限公司 Blue photosensitive resin composition, blue filter and display device having the same
CN106459238A (en) * 2014-05-27 2017-02-22 富士胶片株式会社 sunscreen composition
TWI671596B (en) * 2014-05-27 2019-09-11 日商富士軟片股份有限公司 Shielding composition
US10290669B2 (en) 2014-05-27 2019-05-14 Fujifilm Corporation Light screening composition
TWI675889B (en) * 2015-02-09 2019-11-01 日商富士軟片股份有限公司 Pigment dispersion composition and method for producing the same, polymerizable composition,shielding film, and solid state image sensor
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
CN106959580A (en) * 2015-12-29 2017-07-18 东友精细化工有限公司 Colored photosensitive resin composition and the column spacer including it
CN107272331A (en) * 2016-03-30 2017-10-20 住友化学株式会社 Hardening resin composition and cured film
CN107272331B (en) * 2016-03-30 2021-09-24 住友化学株式会社 Curable resin composition and cured film
CN109891320B (en) * 2016-10-26 2023-06-20 东友精细化工有限公司 Metal oxide photosensitive resin composition, color filter and image display device manufactured using the same
CN109891320A (en) * 2016-10-26 2019-06-14 东友精细化工有限公司 Metal oxide photosensitive polymer combination and the colour filter and image display device manufactured using it
CN109804312A (en) * 2016-12-16 2019-05-24 株式会社Lg化学 Be used to form the photopolymerizable composition of frame pattern, the manufacturing method of the frame pattern of display panel, manufacture frame pattern
CN110352221A (en) * 2017-03-02 2019-10-18 富士胶片株式会社 Composition, film, infrared intercepting filter, solid-state imager, infrared sensor, camera model and new compound
US11066537B2 (en) 2017-03-02 2021-07-20 Fujifilm Corporation Composition, film, infrared cut filter, solid image pickup element, infrared sensor, camera module, and novel compound
CN109491147A (en) * 2017-09-11 2019-03-19 夏普株式会社 The manufacturing method of alignment films, liquid crystal display panel and liquid crystal display panel
CN109814335A (en) * 2017-11-21 2019-05-28 东友精细化工有限公司 Photosensitive composition, colour filter and image display device
CN109814335B (en) * 2017-11-21 2022-03-04 东友精细化工有限公司 Colored photosensitive resin composition, color filter and image display device
TWI783432B (en) * 2021-03-03 2022-11-11 長春人造樹脂廠股份有限公司 Etch-resistant composition

Also Published As

Publication number Publication date
JP2008088272A (en) 2008-04-17
CN101154038B (en) 2012-06-13
KR20080029787A (en) 2008-04-03

Similar Documents

Publication Publication Date Title
CN101154038B (en) Curing colouration composition, color filtering device and liquid crystal display using the color filtering device
CN1991584B (en) Light solidification pigmentation composition and color filter, and liquid crystal display device
CN101842444B (en) Pigment dispersion composition, curable color composition, color filter and method for producing the same
KR101559828B1 (en) Resin, pigment dispersion liquid, coloring curable composition, color filter produced by using the composition, and method for producing the color filter
CN101397429B (en) Pigment dispersion composition, photocurable composition and color filter
JP5555415B2 (en) Curable coloring composition and method for producing the same, color filter, and solid-state imaging device
CN101295134B (en) Colored photopolymerizable composition, color filter using the same and method of producing color filter
TWI463253B (en) Colored curable composition, color filter, and method for producing color filter
CN101959923B (en) Curable composition and color filter
CN102236256B (en) Coloring photonasty resin composition, pattern forming method, color filter and producing method thereof and display device
JP5191194B2 (en) Processed pigment, pigment dispersion composition using the same, colored photosensitive composition, and color filter
CN104513498B (en) Dye dispersion liquid
JP7170732B2 (en) Coloring composition, film, color filter, method for producing color filter, solid-state imaging device, and image display device
CN101105546A (en) Coloring resin composition and color filter used for liquid crystal display element
CN101546006A (en) Color filter slice, method for manufacturing the same and liquid crystal display device
CN103959109A (en) Colored composition for color filter, and color filter
CN102073216A (en) Colored photosensitive resin composition, pattern forming method, manufacture method for color filter, color filter, and display apparatus
CN101515114B (en) Coloring curable composition, coloring pattern, color filter and method of manufacturing the same and liquid crystal display element
JP2010085457A (en) Colored curable composition, color filter and production method thereof, and solid-state imaging device
CN101231467B (en) Curable composition, color filter and method for producing same
JP2008233244A (en) Curable colored composition, color filter and liquid crystal display device
JP2008083594A (en) Colored photosensitive composition, color filter and method for producing the same
CN101520526B (en) Color filter for liquid display element
JP2010015056A (en) Coloring composition for color filter, its set, color filter, and manufacturing method of color filter
CN102043337A (en) Colored curable composition, colored pattern, color filter, method of producing color filter and liquid crystal display element

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant