CN101930176B - Coloring photosensitive composition - Google Patents
Coloring photosensitive composition Download PDFInfo
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- CN101930176B CN101930176B CN201010217886.7A CN201010217886A CN101930176B CN 101930176 B CN101930176 B CN 101930176B CN 201010217886 A CN201010217886 A CN 201010217886A CN 101930176 B CN101930176 B CN 101930176B
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- 0 CC=CC(C(c(c(O1)c2)ccc2N*)=C(C=C2)C1=CC2=N*)=CC Chemical compound CC=CC(C(c(c(O1)c2)ccc2N*)=C(C=C2)C1=CC2=N*)=CC 0.000 description 4
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
-
- 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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- 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
- G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
-
- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- 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
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- 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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A coloring photosensitive composition contains a coloring agent, an adhesive resin, a photopolymerization compound, a photopolymerization initiator and a solvent, and the coloring agent contains a compound expressed in a formula (2). [In the formula (2), G<1> represents C2-C12 alkylidene, hydrogen atoms contained in the alkylidene can be substituted by C1-C4 alkyl,-CH2- contained in the alkylidene can be substituted by -O-, J<1> represents hydrogen atom, -NR<a>R<b> or -NR<a>R<b>H<+>Q<->, R<a> and R<b> respectively represents hydrogen atom or C1-C8 alkyl, Q<-> represents halide ion, BF4<->, PF6<->, ClO4<->, X-CO2<-> or Y-SO3<->, X and Y respectively represents univalent organic group, and n<a> represents integer of 1-4].
Description
Technical field
The present invention relates to coloring photosensitive combination and use the color filter of this coloring photosensitive combination.
Background technology
Color filter for display device such as display panels, electroluminescence (element), Plasmia indicating panels uses coloring photosensitive combination manufacture.Colorant contained by coloring photosensitive combination uses dyestuff or pigment.
Known such coloring photosensitive combination is the composition (patent documentation 1) containing xanthene dye, pigment, adhesive resin, photopolymerizable compound, Photoepolymerizationinitiater initiater and solvent.
A non-patent literature 1: " こ れ Ga デ イ ス プ レ イ overall picture だ! (display overall picture) " p.114 (spring Gu She etc. are outstanding; か ん I publishes distribution on April 18th, 2005)
Patent documentation 2: Japanese Patent Laid-Open 2010-32999 publication
Summary of the invention
Further, in order to reach the high-contrast of color filter, it is desirable to develop a kind of new coloring photosensitive combination.
The present inventor, in order to solve above-mentioned problem, discusses, and result completes the present invention.
Namely the invention provides following [1] ~ [10].
[1]. a kind of coloring photosensitive combination, it contains colorant, adhesive resin, photopolymerizable compound, Photoepolymerizationinitiater initiater and solvent, and colorant is the colorant comprising the compound that formula (2) represents,
[in formula (2), G
1represent the alkylidene of carbon number 2 ~ 12, the hydrogen atom contained by this alkylidene can be replaced by the alkyl of carbon number 1 ~ 4, this-CH contained by alkylidene
2-can be replaced by-O-,
J
1represent hydrogen atom ,-NR
ar
bor-NR
ar
bh
+q
-,
R
aand R
brepresent the alkyl of hydrogen atom or carbon number 1 ~ 8 independently of one another,
Q
-represent halide ion, BF
4 -, PF
6 -, ClO
4 -, X-CO
2 -or Y-SO
3 -,
X and Y represents the organic group of 1 valency independently of one another,
N
arepresent the integer of 1 ~ 4.]
[2]. the coloring photosensitive combination as described in [1], wherein, J
1-NR
ar
bor-NR
ar
bh
+q
-.
[3]. the coloring photosensitive combination as described in any one of [1] or [2], wherein, colorant is the colorant also containing the compound that formula (1) represents,
[in formula (1), R
1~ R
4represent hydrogen atom ,-R independently of one another
6or the aromatic hydrocarbyl of carbon number 6 ~ 10, the hydrogen atom contained by this aromatic hydrocarbyl can by halogen atom ,-R
6,-OH ,-OR
6,-SO
3 -,-SO
3h ,-SO
3m ,-CO
2h ,-CO
2r
6,-SO
3r
6,-SO
2nHR
8or-SO
2nR
8r
9replace,
R
5expression-SO
3 -,-SO
3h ,-SO
3m ,-CO
2h ,-CO
2r
6,-SO
3r
6,-SO
2nHR
8or-SO
2nR
8r
9,
M represents the integer of 0 ~ 5.When m is the integer of more than 2, multiple R
5can be the same or different,
X represents halogen atom, and a represents the integer of 0 or 1,
R
6represent the saturated hydrocarbyl of carbon number 1 ~ 10, the hydrogen atom contained by the saturated hydrocarbyl of this carbon number 1 ~ 10 can be replaced by halogen atom, this-CH contained by saturated hydrocarbyl
2-can by-O-,-CO-or-NR
10-replace,
R
10represent the saturated hydrocarbyl of hydrogen atom or carbon number 1 ~ 10, the hydrogen atom contained by this saturated hydrocarbyl can be replaced by halogen atom, this-CH contained by saturated hydrocarbyl
2-replaced by-O-or-CO-,
R
8and R
9represent the alkyl of carbon number 1 ~ 10, the naphthenic base of carbon number 3 ~ 30 or-Q independently of one another
1, this alkyl and the hydrogen atom contained by this naphthenic base can by hydroxyl, halogen atom ,-Q
1,-CH=CH
2or-CH=CHR
6replace, this alkyl and this-CH contained by naphthenic base
2-can by-O-,-CO-or-NR
10-replace, R
8and R
9can bonding and form the heterocycle of carbon number 1 ~ 10 mutually, the hydrogen atom contained by this heterocycle can by R
6,-OH or-Q
1replace,
Q
1represent the aromatic hydrocarbyl of carbon number 6 ~ 10 or the aromatic heterocycle of carbon number 3 ~ 10, this aromatic hydrocarbyl and the hydrogen atom contained by aromatic heterocycle can by-OH ,-R
6,-OR
6,-NO
2,-CH=CH
2,-CH=CHR
6or halogen atom replaces,
M represents sodium atom or potassium atom,
Wherein, the compound that represents of formula (1)+charge number with-charge number is identical.]
[4]. as the coloring photosensitive combination according to any one of [1] ~ [3], wherein, colorant is the colorant also containing organic pigment.
[5]. the coloring photosensitive combination as described in [4], wherein, organic pigment is containing C.I. pigment blue 15: the organic pigment of 6.
[6]. as the coloring photosensitive combination according to any one of [1] ~ [5], wherein, the content of the compound that formula (2) represents is 1 ~ 50 quality % relative to colorant.
[7]. as the coloring photosensitive combination according to any one of [1] ~ [6], wherein, Photoepolymerizationinitiater initiater is the compound with oxime structure.
[8]. a kind of film, it uses the coloring photosensitive combination according to any one of [1] ~ [7] to be formed.
[9]. a kind of color filter, it uses the photosensitive composition according to any one of [1] ~ [7] to be formed.
[10]. the color filter as described in [9], it is formed by photo-engraving process.
Accompanying drawing explanation
Fig. 1 is the skeleton diagram of the manufacture method that color filter of the present invention is described;
Fig. 2 is the skeleton diagram of the manufacture method that color filter of the present invention is described;
Fig. 3 is the skeleton diagram of the manufacture method that color filter of the present invention is described;
Fig. 4 is the skeleton diagram of the manufacture method that color filter of the present invention is described.
Embodiment
Coloring photosensitive combination of the present invention contains colorant (following, to be sometimes called " colorant (A) "), the compound that colorant (A) represents containing formula (2),
[in formula (2), G
1represent the alkylidene of carbon number 2 ~ 12, the hydrogen atom contained by this alkylidene can be replaced by the alkyl of carbon number 1 ~ 4, this-CH contained by alkylidene
2-can be replaced by-O-,
J
1represent hydrogen atom ,-NR
ar
bor-NR
ar
bh
+q
-,
R
aand R
brepresent the alkyl of hydrogen atom or carbon number 1 ~ 8 independently of one another,
Q
-represent halide ion, BF
4 -, PF
6 -, ClO
4 -, X-CO
2 -or Y-SO
3 -,
X and Y represents the organic group of 1 valency independently of one another,
N
arepresent the integer of 1 ~ 4.]
The alkylidene of carbon number 2 ~ 12 for example there are methylene, ethylidene, glyceryl (propylidene), Ding Erji (butylidene) etc.
-CH
2-group that formula (G-1) represents and the group that formula (G-2) represents can be for example there are by the alkylidene of carbon number 2 ~ 12 that-O-replaces.
[in formula (G-1) and formula (G-2), G
2~ G
5represent the alkylidene of carbon number 1 ~ 8 independently of one another.
N
1represent the integer of 1 ~ 3.
N
2represent the integer of 0 ~ 3.
Wherein, the total number of the carbon atom contained by group that formula (G-1) represents and oxygen atom is 3 ~ 12, and the total number of the carbon atom contained by group that formula (G-2) represents and oxygen atom is respectively 2 ~ 12.
* the bonding position with-NH-is represented.]
The alkyl of carbon number 1 ~ 4 is exemplified as methyl, ethyl, propyl group, butyl etc.
-SO
2-NH-G
1-J
1be exemplified as the group that such as following formula represents.
G
1during the group represented for formula (G-1) ,-SO
2-NH-G
1-J
1be exemplified as the group that such as following formula represents.
G
1during the group represented for formula (G-2) ,-SO
2-NH-G
1-J
1be exemplified as the group that such as following formula represents.。
J
1for-NR
ar
btime ,-SO
2-NH-G
1-J
1be exemplified as the group that following formula represents.
J
1for-NR
ar
bh
+q
-time ,-SO
2-NH-G
1-NR
ar
bh
+be exemplified as the group that following formula represents.
Q
-represent halide ion, BF
4 -, PF
6 -, ClO
4 -, X-CO
2 -or Y-SO
3 -.
X and Y represents the organic group of 1 valency.The organic group of 1 valency for example there are the alkyl of carbon number 1 ~ 20, the naphthenic base of carbon number 3 ~ 20, the aryl of carbon number 6 ~ 20 and their groups of combining.
The alkyl of carbon number 1 ~ 20 for example there are methyl, ethyl, propyl group, butyl, hexyl, decyl etc.
The naphthenic base of carbon number 3 ~ 20 for example there are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ring decyl etc.
The aryl of carbon number 6 ~ 20 for example there are phenyl, naphthyl, phenanthryl.
X-CO
2 -containing CO
2 -the organism negative ion of base, Y-SO
3 -containing SO
3 -the organism negative ion of base, such as, for example there are the negative ion that formula (Q-1) ~ formula (Q-4) represents.
[R
yrepresent the alkyl of carbon number 1 ~ 20.
M represents the integer of 0 ~ 5.]
Q
-preferred X-CO
2 -and Y-SO
3 -, the more preferably negative ion that represents of formula (Q-4).The tendency that these negative ion have the compound dissolubility in a solvent that formula (2) is represented to uprise.
The compound that formula (2) represents for example there are the compound that such as formula (2-1) ~ formula (2-92) represents.
Such as, the example more specifically of compound that formula (2-24) represents for example there are the compound that formula (2-24-1) and formula (2-24-2) represent.
The content of colorant (A), relative to the solid state component in coloring photosensitive combination, is preferably 10 ~ 70 quality %, is more preferably 15 ~ 55 quality %, more preferably 20 ~ 50 quality %.Here, solid state component refers to the total of the composition in addition to the solvents in coloring photosensitive combination.
The content of colorant (A) is when above-mentioned scope, and when being made color filter, colour saturation is abundant, and can make the adhesive resin containing necessary amount in composition, can form the sufficient pattern of physical strength, thus desirable.
Content preferably 1 ~ 50 quality % of the compound that the formula (2) in colorant (A) represents, more preferably 1 ~ 40 quality %, further preferred 2 ~ 30 quality %.
The content of the compound that the formula (2) in colorant (A) represents, when above-mentioned scope, easily reaches the optimization penetrating spectrum, and can obtain high-contrast and the color filter of high brightness.
Colorant (A) is selected according to the color of object color filter, also can contain multiple dyestuff or pigment.
Colorant (A), preferably except the compound represented containing formula (2), also contains the colorant of xanthene dye.
Xanthene dye concrete example have such as rhodamine B, Sulfo rhodamine 101, Sulfo rhodamine B, rhodamine 6G,
C.I. CI 45430,91,92,289
C.I. acid violet 102
C.I. solvent red 49,72
C.I. alkali red 1:1 etc.
Xanthene dye is preferably the compound represented by formula (1).
(in formula (1), R
1~ R
4represent hydrogen atom ,-R independently of one another
6or the aromatic hydrocarbyl of carbon number 6 ~ 10, the hydrogen atom contained by this aromatic hydrocarbyl can by halogen atom ,-R
6,-OH ,-OR
6,-SO
3 -,-SO
3h ,-SO
3m ,-CO
2h ,-CO
2r
6,-SO
3r
6,-SO
2nHR
8or-SO
2nR
8r
9replace,
R
5expression-SO
3 -,-SO
3h ,-SO
3m ,-CO
2h ,-CO
2r
6,-SO
3r
6,-SO
2nHR
8or-SO
2nR
8r
9,
M represents the integer of 0 ~ 5.When m is the integer of more than 2, multiple R
5can be the same or different,
X represents halogen atom.A represents the integer of 0 or 1,
R
6represent the saturated hydrocarbyl of carbon number 1 ~ 10, the hydrogen atom contained by the saturated hydrocarbyl of this carbon number 1 ~ 10 can be replaced by halogen atom, this-CH contained by saturated hydrocarbyl
2-can by-O-,-CO-or-NR
10-replace.
R
10represent the saturated hydrocarbyl of hydrogen atom or carbon number 1 ~ 10, the hydrogen atom contained by this saturated hydrocarbyl can be replaced by halogen atom, this-CH contained by saturated hydrocarbyl
2-can be replaced by-O-,-CO-.
R
8and R
9represent the alkyl of carbon number 1 ~ 10, the naphthenic base of carbon number 3 ~ 30 or-Q independently of one another
1, this alkyl and the hydrogen atom contained by this naphthenic base can by hydroxyl, halogen atom ,-Q
1,-CH=CH
2or-CH=CHR
6replace, this alkyl and the-CH contained by naphthenic base
2-can by-O-,-CO-or-NR
10-replace.Or R
8and R
9can bonding and form the heterocycle of carbon number 1 ~ 10 mutually, the hydrogen atom contained by this heterocycle can by R
6,-OH or-Q
1replace.
Q
1represent the aromatic hydrocarbyl of carbon number 6 ~ 10 or the aromatic heterocycle of carbon number 5 ~ 10, above-mentioned aromatic hydrocarbyl and the hydrogen atom contained by aromatic heterocycle can by-OH ,-R
6,-OR
6,-NO
2,-CH=CH
2,-CH=CHR
6or halogen atom replaces,
M represents sodium atom or potassium atom.
Wherein, the compound that represents of formula (1)+charge number with-charge number is identical.)
R
6for example there are methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, amyl group, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, suberyl, octyl group, 2-ethylhexyl, ring octyl group, nonyl, decyl (decanyl), three ring decyls, methoxy-propyl, ethoxycarbonyl propyl, own oxygen base propyl group, 2-ethyl hexyl oxy propyl group, methoxyethyl, ethoxycarbonyl propyl etc.
The aromatic hydrocarbyl of carbon number 6 ~ 10 for example there are phenyl, naphthyl etc.
As the aromatic hydrocarbyl of this carbon number 6 ~ 10 substituting group for the halogen atom of example, for example there are fluorine, chlorine, bromine etc.
-SO
3r
6for example there are methoxysulfonyl, ethoxysulfonyl, own oxygen base sulfonyl, the last of the ten Heavenly stems oxygen base sulfonyl etc.
-CO
2r
6for example there are methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, isopropoxy carbonyl, butoxy carbonyl, isobutoxy carbonyl, pentyloxy carbonyl, isoamoxy carbonyl, neopentyl oxygen carbonyl, cyclopentyloxy carbonyl, hexyloxy carbonyl, cyclohexyloxy carbonyl, heptan oxygen base carbonyl, ring oxygen in heptan base carbonyl, carbonyl octyloxy, 2-ethylhexyl oxygen base carbonyl, ring octyl group oxygen base carbonyl, nonyl oxygen base carbonyl, decyl (decanyl) oxygen base carbonyl, three ring decyl (decanyl) oxygen base carbonyls, methoxy propoxy carbonyl, ethoxy propoxycarbonyl, own oxygen base propoxycarbonyl, 2-ethyl hexyl oxy propoxycarbonyl, methoxyl hexyloxy carbonyl etc.
-SO
2nHR
8for example there are sulfamoyl, N-(methyl) sulfamoyl, N-(ethyl) sulfamoyl, N-(propyl group) sulfamoyl, N-(isopropyl) sulfamoyl, N-(butyl) sulfamoyl, N-(isobutyl) sulfamoyl, N-(amyl group) sulfamoyl, N-(isopentyl) sulfamoyl, N-(neopentyl) sulfamoyl, N-(cyclopentyl) sulfamoyl, N-(hexyl) sulfamoyl, N-(cyclohexyl) sulfamoyl, N-(heptyl) sulfamoyl, N-(suberyl) sulfamoyl, N-(octyl group) sulfamoyl, N-(2-ethylhexyl) sulfamoyl, N-(1,5-dimethylhexanyl) sulfamoyl, N-(ring octyl group) sulfamoyl, N-(nonyl) sulfamoyl, N-(decyl) sulfamoyl, N-(three ring decyls) sulfamoyl, N-(methoxy-propyl) sulfamoyl, N-(ethoxycarbonyl propyl) sulfamoyl, N-(propoxypropyl) sulfamoyl, N-(isopropoxide propyl) sulfamoyl, N-(own oxygen base propyl group) sulfamoyl, N-(2-ethyl hexyl oxy propyl group) sulfamoyl, N-(methoxyethyl) sulfamoyl, N-(3-phenyl-1-methyl-propyl) sulfamoyl etc.
-SO
2nHR
8and-SO
2nR
8r
9the group that citing also has following formula to represent.
In above-mentioned formula, X
1represent halogen atom.X
1in halogen atom for example there are fluorine atom, chlorine atom and bromine atoms.
In above-mentioned formula, X
3represent the alkyl of carbon number 1 ~ 3 or the alkoxy of carbon number 1 ~ 3, the hydrogen atom of this alkyl and alkoxy can be replaced by halogen atom.
The alkyl of the carbon number 1 ~ 3 that can be replaced by halogen atom for example there are methyl, ethyl, propyl group, isopropyl, trifluoromethyl etc.
The alkoxy of the carbon number 1 ~ 3 that can be replaced by halogen atom for example there are methoxyl, ethoxy, propoxyl group, fluoro-methoxy etc.
In above-mentioned formula, X
2represent the alkoxy of the alkyl of carbon number 1 ~ 3, carbon number 1 ~ 3, halogen atom or nitro, the hydrogen atom of this alkyl and alkoxy can be replaced by halogen atom.
X
2in halogen atom for example there are fluorine atom, chlorine atom and bromine atoms.
The alkyl of the carbon number 1 ~ 3 that can be replaced by halogen atom for example there are methyl, ethyl, propyl group, isopropyl, trifluoromethyl etc.
The alkoxy of the carbon number 1 ~ 3 that can be replaced by halogen atom for example there are methoxyl, ethoxy, propoxyl group, fluoro-methoxy etc.
In above-mentioned formula, X
2the meaning represented is same as described above.
In above-mentioned formula, X
3the meaning represented is same as described above.
-SO
2nR
8r
9contained R
8and R
9the alkyl or aryl containing alkoxy of the branch-like alkyl of preferred carbon number 6 ~ 8, the naphthenic base of carbon number 5 ~ 7, allyl, phenyl, the aralkyl of carbon number 8 ~ 10, the hydroxyl alkyl of carbon number 2 ~ 8 and aryl and carbon number 2 ~ 8, especially preferably 2-ethylhexyl.
The preferred ethyl of substituting group of the aromatic hydrocarbyl of carbon number 6 ~ 10, propyl group, phenyl, 3,5-dimethylphenyl ,-SO
3r
6or-SO
2nHR
8.
The aromatic hydrocarbyl with substituent carbon number 6 ~ 10 for example there are aminomethyl phenyl, 3,5-dimethylphenyl, trimethylphenyl, ethylphenyl, hexyl phenyl, decyl phenyl, fluorophenyl, chlorphenyl, bromophenyl, hydroxy phenyl, methoxyphenyl, Dimethoxyphenyl, ethoxyl phenenyl, Hexyloxy-phenyl, the last of the ten Heavenly stems oxygen base phenyl, trifluoromethyl etc.
R
1and R
2in one of at least or R
3and R
4in the alkyl of one of at least preferably carbon number 1 ~ 4 or the aromatic hydrocarbyl of carbon number 6 ~ 10 that can be substituted.
R
1and R
2in one of at least and R
3and R
4in the alkyl of one of at least preferably carbon number 1 ~ 4 or the aromatic hydrocarbyl of carbon number 6 ~ 10 that can be substituted.
R
1and R
2in one of at least and R
3and R
4in the aromatic hydrocarbyl of the carbon number 6 ~ 10 that one of at least more preferably can be substituted.
R
5be preferably carboxyl, ethoxy carbonyl, sulfo group, N-(2-ethyl hexyl oxy propyl group) sulfamoyl, N-(1,5-dimethylhexanyl) sulfamoyl, N-(3-phenyl-1-methyl-propyl) sulfamoyl, N-(isopropoxide propyl) sulfamoyl.
The compound that the compound preferred formula (1-1) that formula (1) represents represents,
[in formula (1-1), R
11~ R
14represent hydrogen atom ,-R independently of one another
6or the aromatic hydrocarbyl of carbon number 6 ~ 10, the hydrogen atom contained by this aromatic hydrocarbyl can by halogen atom ,-R
6,-OH ,-OR
6,-SO
3 -,-SO
3h ,-SO
3na ,-CO
2h ,-CO
2r
6,-SO
3r
6,-SO
2nHR
8or-SO
2nR
8r
9replace,
R
15represent hydrogen atom ,-SO
3 -,-SO
3h ,-SO
2nHR
8or-SO
2nR
8r
9,
R
16expression-SO
3 -,-SO
3h ,-SO
2nHR
8or-SO
2nR
8r
9,
R
6, R
8, R
9, the meaning that represents of m, X and a is same as described above.
Wherein, the compound that represents of formula (1-1)+charge number with-charge number is identical.]
The compound that the compound preferred formula (1-2) that formula (1) represents represents,
[(in formula (1-2), R
21~ R
24represent hydrogen atom ,-R independently of one another
26or the aromatic hydrocarbyl of carbon number 6 ~ 10, the hydrogen atom contained by this aromatic hydrocarbyl can by halogen atom ,-R
26,-OH ,-OR
26,-SO
3 -,-SO
3na ,-CO
2h ,-CO
2r
26,-SO
3h ,-SO
3r
26or-SO
2nHR
28replace,
R
25expression-SO
3 -,-SO
3na ,-CO
2h ,-CO
2r
26,-SO
3h or-SO
2nHR
28,
R
26represent the saturated hydrocarbyl of carbon number 1 ~ 10, the hydrogen atom contained by this saturated hydrocarbyl can by-OR
27or halogen atom replaces,
R
27represent the saturated hydrocarbyl of carbon number 1 ~ 10.
R
28represent hydrogen atom ,-R
26,-CO
2r
26or the aromatic hydrocarbyl of carbon number 6 ~ 10, the hydrogen atom contained by this aromatic hydrocarbyl can by-R
26or-OR
26replace,
The meaning that m, X and a represent is same as described above.
Wherein, the compound that represents of formula (1-2)+charge number with-charge number is identical.]
The compound that the compound preferred formula (1-3) that formula (1) represents represents,
[in formula (1-3), R
31and R
32represent phenyl independently of one another, the hydrogen atom contained by this phenyl can by halogen atom ,-R
26,-OR
26,-CO
2r
26,-SO
3r
26or-SO
2nHR
28replace,
R
33expression-SO
3 -or-SO
2nHR
28,
R
34represent hydrogen atom ,-SO
3 -or-SO
2nHR
28,
R
26, R
28, the meaning that represents of X and a is same as described above.
Wherein, the compound that represents of formula (1-3)+charge number with-charge number is identical.]
The compound that the compound preferred formula (1-4) that formula (1) represents represents,
[in formula (1-4), R
41and R
42represent phenyl independently of one another, the hydrogen atom contained by this phenyl can by-R
26or-SO
2nHR
28replace,
R
43expression-SO
3 -or-SO
2nHR
28,
R
26, R
28, X and a represent meaning same as described above.
Wherein, the compound that represents of formula (1-4)+charge number with-charge number is identical.]
The compound that formula (1) represents for example there are the compound that such as formula (1a) ~ formula (1f) represents.
[in formula (1a), R
band R
cseparately represent hydrogen atom ,-SO
3 -,-CO
2h or-SO
2nHR
a.R
arepresent 2-ethylhexyl.The meaning that X and a represents is same as described above.]
[in formula (1b), R
bthe meaning represented is same as described above.]
The compound that formula (1b) represents is the dynamic isomer of the compound that formula (1b-1) represents.
[in formula (1b-1), R
b, the meaning that represents of X and a is same as described above.]
[in formula (1c) and formula (1d), R
d, R
cand R
fseparately expression-SO
3 -,-SO
3na or-SO
2nHR
a.R
arepresent 2-ethylhexyl.]
[in formula (1e) and formula (1f), R
g, R
hand R
iseparately represent hydrogen atom ,-SO
3 -,-SO
3h or-SO
2nHR
a.R
arepresent 2-ethylhexyl.]
In the compound that formula (1) represents, there is-SO
2nHR
8compound can obtain by the following method, such as by conventional method to having-SO
3pigment or the pigment intermediate of H carry out chlorination, then make to obtain there is-SO
2the pigment of Cl or pigment intermediate and R
8-NH
2the amine reaction represented.Also can be obtained by such method, the method recorded by the upper right hurdle ~ hurdle, lower-left of the 3rd page, Japanese Patent Laid-Open 3-78702 publication manufactures a kind of pigment, by the chlorination as above-mentioned of this pigment, then makes it to react with amine.
The colorant of colorant (A) preferably also containing organic pigment.
As organic pigment, for example there are particularly such as: C.I. pigment blue 15,15:3,15:4,15:6, the blue pigments such as 60; C.I. pigment violet 1,19,23,29,32,36, the violet pigment etc. of 38 etc.Wherein, preferred C.I. pigment purple 23, C.I. pigment blue 15: 3 or 15:6, especially preferably containing C.I. pigment blue 15: 6.These pigment may be used alone, can also be two or more kinds in combination.
As required, rosin process can be carried out to the organic pigment in above-mentioned pigment, use and be imported with the surface treatment of the pigment derivative of acidic groups or basic group etc., the grafting process utilizing macromolecular compound to carry out surface of pigments, the micronize process utilizing sulfuric acid particles method etc. to carry out or utilize the cleaning treatment of the removing organic solvent of impurity or water etc., utilize the removing process etc. of the removing ionic impurity of ion exchange process etc.
Preferably, the uniform particle diameter of organic pigment.By making it to carry out dispersion treatment containing pigment dispersing agent, the dispersible pigment dispersion that pigment disperses state so in the solution equably can be obtained.
For example there are the surfactants etc. such as kation system, negative ion system, nonionic system, both sexes, Polyester, polyamine system, acrylic acid series as above-mentioned pigment dispersing agent.Only can use a kind, also can two or more combinationally use.
When using pigment dispersing agent, in the pigment of every 1 mass parts, its use amount is preferably below 1 mass parts, more preferably more than 0.05 mass parts, below 0.5 mass parts.The use amount of pigment dispersing agent, when above-mentioned scope, has the tendency of the dispersible pigment dispersion that can obtain homogeneous disperse state.
Especially, preferred C.I. pigment blue 15: the mass ratio of 6 compounds represented with formula (1) is 97: 3 ~ 50: 50.
When the content of the organic pigment in colorant (A) is in above-mentioned scope, penetrate the easy optimization of spectrum, and owing to obtaining high-contrast, high brightness, thus well, and thermotolerance, drug resistance are good, therefore more satisfactory.
Coloring photosensitive combination of the present invention contains adhesive resin (B).Adhesive resin can use known.
Adhesive resin is the resin with alkali-solubility, is containing being derived from the Component units of compound (B0) (hereinafter sometimes referred to " (B0) ") and being derived from the multipolymer of Component units of compound (B2) (hereinafter sometimes referred to " (B2) ").Above-claimed cpd (B0) possesses carbon-to-carbon unsaturated double-bond and cyclic ether structure, and compound (B2) is selected from least a kind in unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides.
As the cyclic ether structure of (B0), can enumerate such as, epoxy construction, oxetanes structure and tetrahydrofuran structure.
The structure that epoxy construction can be enumerated the structure obtained by chain olefin epoxidation, the structure obtained by monocyclic cycloalkenyl hydrocarbon epoxidation and be obtained by multi-ringed cycloolefin hydrocarbon epoxidation, preferably by structure that multi-ringed cycloolefin hydrocarbon epoxidation obtains.
(B0) compound preferably containing carbon-to-carbon unsaturated double-bond and epoxy construction, the compound of structure that more preferably there is carbon-to-carbon unsaturated double-bond and multi-ringed cycloolefin hydrocarbon epoxidation is obtained.(B0) time for these compounds, the film obtained and the solvent resistance of color filter, excellent heat resistance.
Specifically can enumerate containing carbon-to-carbon unsaturated double-bond and the compound of structure that chain olefin epoxidation is obtained, the compound etc. that the following formula (IV) that diglycidyl (methyl) acrylate, Beta-methyl diglycidyl (methyl) acrylate, β-ethyl glycidyl (methyl) acrylate, glycidyl vinyl ether, Japanese Patent Laid-Open 7-248625 publication are recorded represents.
[in formula (IV), R
61~ R
63represent the alkyl of hydrogen atom or carbon number 1 ~ 10 independently of one another, m1 is the integer of 1 ~ 5.]
The compound that above formula (IV) represents can be enumerated such as, adjacent vinylbenzyl glycidyl ether, between vinylbenzyl glycidyl ether, to vinylbenzyl glycidyl ether, the adjacent vinylbenzyl glycidyl ether of Alpha-Methyl, vinylbenzyl glycidyl ether between Alpha-Methyl, Alpha-Methyl is to vinylbenzyl glycidyl ether, 2, 3-diepoxy propoxy methyl styrene, 2, 4-diepoxy propoxy methyl styrene, 2, 5-diepoxy propoxy methyl styrene, 2, 6-diepoxy propoxy methyl styrene, 2, 3, 4-tri-glycidyl oxy methyl styrene, 2, 3, 5-tri-glycidyl oxy methyl styrene, 2, 3, 6-tri-glycidyl oxy methyl styrene, 3, 4, 5-tri-glycidyl oxy methyl styrene and 2, 4, 6-tri-glycidyl oxy methyl styrene.
The compound of the structure that containing carbon-to-carbon unsaturated double-bond and the compound of structure that obtained by monocyclic cycloalkenyl hydrocarbon epoxidation, preferably there is (methyl) acryloxy and obtained by monocyclic cycloalkenyl hydrocarbon epoxidation.Above-mentioned monocyclic cycloalkenyl hydrocarbon for example there are cyclopentene, cyclohexene, cycloheptene, cyclooctene etc.
Containing carbon-to-carbon unsaturated double-bond and the compound of structure that monocyclic cycloalkenyl hydrocarbon epoxidation is obtained, can enumerate such as, vinyl cyclohexene list oxidation 1, 2-epoxy-4-vinyl cyclohexane (such as, セ ロ キ サ イ De 2000, ダ イ セ Le chemical industry (strain) manufactures), acrylic acid-3, 4-epoxycyclohexyl-methyl ester (such as, サ イ Network ロ マ mono-A400, ダ イ セ Le chemical industry (strain) manufactures), methacrylic acid-3, 4-epoxycyclohexyl-methyl ester (such as, サ イ Network ロ マ mono-M100, ダ イ セ Le chemical industry (strain) manufactures) etc.
Here, " (methyl) acryloxy " in this instructions represents at least one of acryloxy and methacryloxy.The statement such as " (methyl) acrylic acid ... ester " and " (methyl) acrylic acid " also has same meaning.
The compound of the structure that containing carbon-to-carbon unsaturated double-bond and the compound (B1) (hereinafter sometimes referred to " (B1) ") of structure that obtained by multi-ringed cycloolefin hydrocarbon epoxidation, preferably there is (methyl) acryloxy and obtained by multi-ringed cycloolefin hydrocarbon epoxidation.Above-mentioned multi-ringed cycloolefin hydrocarbon can enumerate dicyclopentenyl, tricyclo decene, norbornane, different norborene, bicyclooctene, bicyclononene, two ring undecylenes, three ring undecylenes, two cyclododecenes, three cyclododecenes etc.
(B1) can enumerate such as, acrylic acid-3,4-epoxynorborn ester, methacrylic acid-3, the compound that 4-epoxynorborn ester, formula (B1-1) represent and the compound that formula (B1-2) represents, at least a kind of compound selected the compound that the compound preferably represented from formula (B1-1) and formula (B1-2) represent.
[in formula (B1-1) and formula (B1-2), R
71and R
72represent the alkyl of the carbon number 1 ~ 4 that hydrogen atom or its hydrogen atom can be optionally substituted by a hydroxyl group independently of one another.
X
1and X
2represent the alkylidene of singly-bound or carbon number 1 ~ 6 independently of one another or represent *-(CH
2)
s-X
3-(CH
2)
t-.
X
3represent-S-,-O-or-NH-.
S represents the integer of 1 ~ 6, and t represents the integer of 0 ~ 6.Wherein s+t≤6.
* the bonding position with O is represented.]
As the alkyl of the carbon number 1 ~ 4 that can be optionally substituted by a hydroxyl group, specifically can enumerate hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyl-1-Methylethyl, 2-hydroxyl-1-Methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl etc., preferable methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, more preferably methyl.
R
71and R
72preferred hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, more preferably hydrogen atom, methyl.
The heteroatoms that can contain the alkylidene of heteroatomic carbon number 1 ~ 6 can be enumerated, oxygen atom, sulphur atom and nitrogen-atoms.In addition, heteroatoms number is not contained in carbon number.
The alkylidene of carbon number 1 ~ 6 can be enumerated, methylene, ethylidene, propane-1,2-bis-base (i.e. 1,2-propylidene), propane-1,3-bis-base (namely 1,3-propylidene), butane-Isosorbide-5-Nitrae-two base (i.e. Isosorbide-5-Nitrae-butylidene), pentane-1,5-bis-base (namely 1,5-pentylidene), hexane-1,6-bis-base (i.e. 1,6-hexylidene),
X
1and X
2preferred singly-bound, methylene, ethylidene ,-O-CH
2-or-O-(CH
2)
2-, more preferably singly-bound or-O-(CH
2)
2-.
The compound that formula (B1-1) represents can enumerate the compound etc. that formula (B1-1-1) ~ formula (B1-1-15) represents, the compound that preferred formula (B1-1-1), formula (B1-1-3), formula (B1-1-5), formula (B1-1-7), formula (B1-1-9), formula (B1-1-11) ~ formula (B1-1-15) represents, the more preferably compound that represents of formula (B1-1-1), formula (B1-1-7), formula (B1-1-9) or formula (B1-1-15).
As the compound that formula (B1-2) represents, can enumerate, the compound etc. that formula (B1-2-1) ~ formula (B1-2-15) represents, the compound that preferred formula (B1-2-1), formula (B1-2-3), formula (B1-2-5), formula (B1-2-7), formula (B1-2-9), formula (B1-2-11) ~ formula (B1-2-15) represents, the more preferably compound that represents of formula (B1-2-1), formula (B1-2-7), formula (B1-2-9) or formula (B1-2-15).
Be selected from least a kind of compound in compound that formula (B1-1) represents and the compound that formula (B1-2) represents, can be used alone separately.In addition, they also can mix with arbitrary ratio.During mixing, its mixture ratio is formula (B1-1): the mol ratio of formula (B1-2), preferably 5: 95 ~ 95: 5, more preferably 10: 90 ~ 90: 10, particularly preferably 20: 80 ~ 80: 20.
The compound with above-mentioned carbon-to-carbon unsaturated double-bond and oxetanes structure preferably has the compound of oxetanylmethoxy and (methyl) acryloxy.
The compound concrete example with carbon-to-carbon unsaturated double-bond and oxetanes structure has 3-methyl-3-methacryloxymethyl oxetanes, 3-methyl-3-acryloyloxymethyl oxetanes, 3-ethyl-3-methacryloxymethyl oxetanes, 3-ethyl-3-acryloyloxymethyl oxetanes, 3-methyl-3-methacryloxyethyl oxetanes, 3-methyl-3-acryloyl-oxyethyl oxetanes, 3-ethyl-3-methacryloxyethyl oxetanes or 3-ethyl-3-acryloyl-oxyethyl oxetanes.
The compound with above-mentioned carbon-to-carbon unsaturated double-bond and tetrahydrofuran structure preferably has the monomer of tetrahydrofuran base and (methyl) acryloxy.
The compound concrete example with carbon-to-carbon unsaturated double-bond and tetrahydrofuran structure has acrylic acid tetrahydro furfuryl ester (such as, PVC ス コ mono-ト V#150, Osaka Organic Chemical Industry (strain) manufactures), methacrylic acid tetrahydro furfuryl ester etc.
(B2) can enumerate such as, the unsaturated monocarboxylic class of acrylic acid, methacrylic acid, butenoic acid etc.;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2, the unsaturated dicarboxylic classes such as 3,6-tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid, Isosorbide-5-Nitrae-cyclohexene dicarboxylic acid;
Methyl-5-norborene-2, the two ring unsaturated compound classes containing carboxyl such as 3-dicarboxylic acid, 5-carboxyl two ring [2.2.1]-2-heptene, 5,6-dicarboxyl two ring [2.2.1]-2-heptene, 5-carboxyl-5-methyl bicyclic [2.2.1]-2-heptene, 5-carboxyl-5-ethyl two ring [2.2.1]-2-heptene, 5-carboxyl-6-methyl bicyclic [2.2.1]-2-heptene, 5-carboxyl-6-ethyl two ring [2.2.1]-2-heptene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic acid acid anhydride, 4-vinylphthalic acid acid anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2, the acid anhydrides of the unsaturated dicarboxylic classes such as 3,6-tetrahydrophthalic anhydride, dimethyl tetrahydro phthalic anhydride, 5,6-dicarboxyl two ring [2.2.1]-2-heptene acid anhydrides (carbic anhydride);
Unsaturated list [(methyl) acryloxyalkyl] the ester class of the polybasic carboxylic acid of succinic acid list [2-(methyl) acryloyl-oxyethyl] ester, phthalic acid list [2-(methyl) acryloyl-oxyethyl] ester etc. more than 2 yuan;
The unsaturated esters of acrylic acid etc. of hydroxyl and carboxyl is contained in same a part that acrylic acid-α-(hydroxymethyl) ester is such.
Wherein, based on copolyreaction, dissolubility in aqueous alkali, preferred acrylic acid, methacrylic acid, maleic anhydride.They can be used alone or in combination.
Adhesive resin (B) is containing the multipolymer from the Component units of (B0) and the Component units from (B2), Component units from (B0) and the ratio from the Component units of (B2) are relative to the words being aggregated in following scope of Component units forming above-mentioned multipolymer, owing to possessing the good tendency of storage stability, thermotolerance and physical strength, therefore ideal.
Component units from (B0): 2 ~ 98 % by mole
Component units from (B2): 2 ~ 98 % by mole
In addition, the ratio of above-mentioned Component units is in following scope, based on the angle of developability and solvent resistance, more desirable.
Component units from (B0): 40 ~ 85 % by mole
Component units from (B2): 15 ~ 60 % by mole
The manufacture of above-mentioned adhesive resin (B) can be see, for example, the method that document " experimental method of Polymer Synthesizing " (grand row work sale room (strain) chemistry in large Tianjin is with people's the 1st edition the 1st printing distribution on March 1st, 1972) is recorded and the citing document that the document is recorded.
Concrete, by by a certain amount of (B0) and (B2), polymerization initiator and solvent loading reaction vessel, nitrogen displace oxygen, when there is not oxygen, carrying out stirring, heating, being incubated, obtain multipolymer.In addition, for the multipolymer obtained, can directly use reacted solution, also can use solution that is concentrated or dilution, also take out solid (powder) use by methods such as precipitations again.
In addition, adhesive resin (B) is except containing from except the Component units of (B0) and the Component units from (B2), also containing from can with the Component units of the compound of (B0) and (B2) copolymerization (but, except (B1) and (B2)) (B3) (hereinafter sometimes referred to " (B3) ").
Above-mentioned (B3) can enumerate, (methyl) alkyl-acrylates of (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate etc.;
The alkyl-acrylates of methyl acrylate, isopropyl acrylate etc.;
(methyl) cyclohexyl acrylate, (methyl) acrylic acid-2-methyl cyclohexyl, (methyl) acrylic acid three ring [5.2.1.0
2,6] decane-8-base ester (in this technical field, trivial name is called (methyl) acrylic acid bicyclopentyl ester (ジ シ Network ロ ペ Application タ ニ Le (メ タ) ア Network リ レ mono-ト)), (methyl) acrylic acid cyclic alkyl ester class such as (methyl) acrylic acid bicyclopentyl oxygen base ethyl ester (ジ シ Network ロ ペ Application タ ニ Le オ キ シ エ チ Le (メ タ) ア Network リ レ mono-ト), (methyl) isobornyl acrylate;
(methyl) benzyl acrylate class of (methyl) phenyl acrylate etc.;
(methyl) acrylic acid aralkyl ester class of (methyl) benzyl acrylate etc.;
The dicarboxylic diester of diethyl maleate, DEF, diethyl itaconate etc.;
The hydroxyalkyl acrylate class of (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate etc.;
Two rings [2.2.1]-2-heptene, 5-methyl bicyclic [2.2.1]-2-heptene, 5-ethyl two ring [2.2.1]-2-heptene, 5-hydroxyl two ring [2.2.1]-2-heptene, 5-hydroxymethyl two ring [2.2.1]-2-heptene, 5-(2 '-hydroxyethyl) two ring [2.2.1]-2-heptene, 5-methoxyl two ring [2.2.1]-2-heptene, 5-ethoxy two ring [2.2.1]-2-heptene, 5,6-dihydroxy two ring [2.2.1]-2-heptene, 5.6-bis-(hydroxymethyl) two ring [2.2.1]-2-heptene, 5,6-bis-(2 '-hydroxyethyl) two ring [2.2.1]-2-heptene, 5,6-dimethoxy two ring [2.2.1]-2-heptene, 5,6-diethoxy two ring [2.2.1]-2-heptene, 5-hydroxy-5-methyl base two ring [2.2.1]-2-heptene, 5-hydroxyl-5-ethyl two ring [2.2.1]-2-heptene, 5-hydroxymethyl-5-methyl bicyclic [2.2.1]-2-heptene, 5-tert-butoxycarbonyl two ring [2.2.1]-2-heptene, 5-cyclohexyl oxygen carbonyl two ring [2.2.1]-2-heptene, 5-phenyloxycarbonyl two ring [2.2.1]-2-heptene, 5,6-bis-(tert-butoxycarbonyl) two ring [2.2.1]-2-heptene, two ring unsaturated compound classes of 5-6-bis-(cyclohexyl oxygen carbonyl) two rings [2.2.1]-2-heptene etc.,
The dicarbonyl imides derivant class of N-phenylmaleic anhydride contracting imines, N-cyclohexyl maleic anhydride contracting imines, N-benzyl maleic anhydride contracting imines, N-succinimido-3-maleic anhydride contracting imines benzoic ether, N-succinimido-4-maleic anhydride contracting imines butyric ester, N-succinimide-6-maleic anhydride contracting imines capronate, N-succinimide-3-maleic anhydride contracting imines propionic ester and N-(9-acridinyl) maleic anhydride contracting imines etc.;
Styrene, α-methyl styrene, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxy styrene, vinyl cyanide, methacrylonitrile, vinyl chloride, dichloroethylene, acrylamide, Methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc.
Wherein, preferred benzyl acrylate, styrene, N-phenylmaleic anhydride contracting imines, N-cyclohexyl maleic anhydride contracting imines, N-benzyl maleic anhydride contracting imines, two rings [2.2.1]-2-heptene etc.
Above-mentioned (B3) can be used alone or in combination.
During containing (B3), from the Component units of (B0) ~ (B3) ratio preferably for the total molal quantity of the Component units of above-mentioned formation multipolymer in following scope.
Component units from (B0): 2 ~ 97 % by mole (more preferably 10 ~ 48 % by mole)
Component units from (B2): 2 ~ 97 % by mole (more preferably 10 ~ 48 % by mole)
Component units from (B3): 1 ~ 96 % by mole (more preferably 4 ~ 80 % by mole)
Adhesive resin (B) containing above-mentioned (B0) ~ (B3) can as above manufacture.
In addition; as the Component units in above-mentioned adhesive resin (B); the Component units etc. that the Component units represented containing the macromonomer class of acryloyl group or monomethacrylate acyl group, formula (II) containing end and formula (III) represent, from pattern tack, excellent solvent resistance.
(in formula (II) and formula (III), R
53and R
56represent the alkyl of hydrogen atom or carbon number 1 ~ 6 independently of one another.)
There is the adhesive resin (B) of the Component units that formula (II) represents, can obtain as follows: make (B2), (B3) copolymerization obtains multipolymer, by the compound that the multipolymer obtained and formula (III-1) represent, reaction in the carboxyl contained at (B2) or acid anhydrides and obtaining.
(in formula (II-1) and formula (III-1), R
54and R
56the same).
There is the adhesive resin of the constituent that formula (III) represents, can obtain as follows: make (B2) and (B3) copolymerization obtain multipolymer, the compound multipolymer obtained and formula (III-1) represented is by such as reacting and obtain identically with the method that Japanese Patent Laid-Open 2005-189574 publication is recorded.
The weight-average molecular weight of the polystyrene conversion of adhesive resin (B) preferably 3,000 ~ 100,000, more preferably 5,000 ~ 50,000.The weight-average molecular weight of adhesive resin (B), in above-mentioned scope, has the tendency that coating is good, not easily occurs that film reduces during development, and the tendency having the removal of non-pixel portion good during development.
The molecular weight distribution [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] of adhesive resin (B) preferably 1.1 ~ 6.0, more preferably 1.2 ~ 4.0.Molecular weight distribution, in above-mentioned scope, has the tendency of developability excellence.
The content of adhesive resin (B) is relative to preferably 10 ~ 35 quality % of the solid constituent in coloring photosensitive combination, more preferably 15 ~ 30 quality %.The content of adhesive resin (B) is in the words of above-mentioned scope, there is following tendency: its dissolubility in developer solution is abundant, not easily there is development residue in the substrate of non-pixel portion, and the film of the pixel portion of exposure part reduces when not easily occurring developing, the removal of non-pixel portion is good.
Coloring photosensitive combination of the present invention contains photopolymerizable compound (C).Photopolymerizable compound (C) utilizes Photoepolymerizationinitiater initiater (D) to be irradiated by light and the living radical, acid etc. that produce and the compound that can be polymerized, such as, for example there are the compound etc. of the carbon-to-carbon unsaturated bond with polymerism.
Above-mentioned photopolymerizable compound (C) preferably has the multi-functional photopolymerizable compound of the functional group of more than 3.Multi-functional photopolymerizable compound as the functional group with more than 3 for example there are tetramethylol methane tetraacrylate, pentaerythritol tetramethylacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol pentamethacrylates, dipentaerythritol acrylate, dipentaerythritol hexamethacrylate etc.Above-mentioned photopolymerizable compound (C) can be used alone, also can combine two or more to use, its content relative to preferably 7 ~ 65 quality % of the solid constituent in coloring photosensitive combination, more preferably 13 ~ 60 quality %, preferred 17 ~ 55 quality % further.The content of above-mentioned photopolymerizable compound (C), in above-mentioned scope, has that the film thickness ratio of solidification fully, before and after development improves, undercutting (undercut) is difficult to enter pattern and adaptation becomes good tendency.
Photosensitive composition of the present invention contains Photoepolymerizationinitiater initiater (D).Photoepolymerizationinitiater initiater is the compound being irradiated by light and producing living radical, acid etc., polymerizable compound (C) can be made to be polymerized, and preferably produces the compound of free radical with ultraviolet.Above-mentioned Photoepolymerizationinitiater initiater (D) for example there are living radical and produces agent, acid producing agent etc.
Living radical is produced agent and is penetrated by illumination and produce living radical.Above-mentioned living radical produces agent and for example there are acetophenone based compound, benzoin based compound, benzophenone based compound, thioxanthones based compound, triazine based compound, oxime compound etc.
From the viewpoint of sensitivity, Photoepolymerizationinitiater initiater (D) preferably has the compound of oxime structure.
Above-mentioned oxime compound for example there are such as O-acyl group oxime compound, its object lesson for example there are N-benzoyloxy-1-(4-phenyl sulphur aminoacyl phenyl)-1-butanone-2-imines, N-benzoyloxy-1-(4-phenyl sulphur aminoacyl phenyl)-1-octanone-2-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methyl-4-(3, 3-dimethyl-2, 4-dioxo cyclopentyl (ペ Application タ ニ Le) methoxyl) benzoyl)-9H-carbazole-3-base] ethane-1-imines etc., preferred N-benzoyloxy-1-(4-phenyl sulphur aminoacyl phenyl)-1-octanone-2-imines.Oxime compound is N-benzoyloxy-1-(4-phenyl sulphur aminoacyl phenyl)-1-octanone-2-imines, can obtain the color filter of high brightness.
Oxime compound also can use the commercially available products such as イ Le ガ キ ユ ア OXE01, イ Le ガ キ ユ ア OXE02 (being that チ バ ジ ヤ パ Application society manufactures above), N-1919 (manufacture of ADEKA society).
Above-mentioned acetophenone based compound for example there are such as diethoxy acetophenone, 2-methyl-2-morpholino base-1-(4-methyl sulphur aminoacyl phenyl)-1-acetone, 2-dimethylamino-1-(4-morpholino base phenyl)-2-benzyl-1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-1-acetone, 1-hydroxycyclohexyl phenyl ketone, the oligomer etc. of 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl]-1-acetone, preferred 2-methyl-2-morpholino base-1-(4-methyl sulphur aminoacyl phenyl)-1-acetone.
Above-mentioned acyloin based compound for example there are benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether etc.
Above-mentioned benzophenone based compound for example there are such as benzophenone, o-benzoyl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl base sulphur, 3; 3 '; 4; 4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 2; 4,6-tri-methyl benzophenone etc.
Above-mentioned thioxanthones based compound for example there are such as ITX, ITX, 2,4-diethyl thioxanthones, 2,4-dichloro-thioxanthones, the chloro-4-propoxythioxanthone of 1-etc.
Above-mentioned triazine based compound for example there are 2, two (the trichloromethyl)-6-(4-methoxyphenyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl naphthyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(5-methylfuran-2-base) vinyl]-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(furans-2-base) vinyl]-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-1 of 4-, 3, 5-triazine, 2, two (trichloromethyl)-6-[2-(3 of 4-, 4-Dimethoxyphenyl) vinyl]-1, 3, 5-triazine etc.
Living radical beyond above-mentioned illustration produces agent and also can use as 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 2,2 '-bis-(adjacent chlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bis-imidazoles, 10-butyl-2-chloro acridone, 2-EAQ, dibenzoyl, 9,10-phenanthrenequione, camphorquinone, phenylglyoxalates methyl esters, two cyclopentadiene titanium compounds etc.
As above-mentioned acid producing agent, for example there are salt or toluenesulfonic acid nitrobenzyl salt (or ester) class, toluenesulfonic acid benzoin salt (or ester) class etc. of 4-hydroxy phenyl dimethyl sulfonium tosilate, 4-hydroxy phenyl dimethyl sulfonium hexafluoro stibate, 4-acetoxyl group phenyl dimethyl sulfonium tosilate, 4-acetoxyl group phenyl methyl benzyl sulfonium hexafluoro stibate, triphenylsulfonium tosilate, triphenylsulfonium hexafluoro stibate, diphenyl iodine tosilate, diphenyl iodine hexafluoro stibate etc.
In addition, also have in the compound producing agent as above-mentioned living radical and to produce while living radical also acidic compound.Such as, triazine system Photoepolymerizationinitiater initiater also uses as acid producing agent.
The content of Photoepolymerizationinitiater initiater (D) is relative to total amount preferably 0.1 ~ 30 quality % of adhesive resin (B) and photopolymerizable compound (C), more preferably 1 ~ 20 quality %.The content of Photoepolymerizationinitiater initiater is in above-mentioned scope, and high-sensitivity, time shutter shorten, and throughput rate improves.
Auxiliary agent (F) can be caused containing photopolymerization further in coloring photosensitive combination of the present invention.Photopolymerization cause auxiliary agent (F) usually and Photoepolymerizationinitiater initiater (D) combine to use, be for promoting by the compound of the polymerization of the photopolymerizable compound of Photoepolymerizationinitiater initiater initiated polymerization or sensitizer.
Cause auxiliary agent (F) as photopolymerization and for example there are amine compound, alkoxy anthracene based compound, thioxanthones based compound etc.
As above-mentioned amine compound, for example there are such as triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylamino benzoic acid methyl esters, 4-dimethylamino ethyl benzoate, 4-dimethylamino benzoic acid isopentyl ester, benzoic acid-2-dimethylamino ethyl ester, 4-dimethylamino benzoic acid-2-Octyl Nitrite, N, N-dimethyl-p-toluidine, 4, 4 '-bis-(dimethylamino) benzophenone (common name Michler's keton), 4, 4 '-bis-(diethylamino) benzophenone, 4, 4 '-bis-(ethylmethylamino) benzophenone etc., wherein, preferably 4, 4 '-bis-(diethylamino) benzophenone.
As above-mentioned alkoxy anthracene based compound, for example there are such as 9,10-dimethoxy anthracenes, 2-ethyl-9,10-dimethoxy anthracene, 9,10-diethoxy anthracenes, 2-ethyl-9,10-diethoxy anthracene, 9,10-dibutoxy anthracene, 2-ethyl-9,10-dibutoxy anthracene etc.
As above-mentioned thioxanthones based compound, for example there are such as ITX, ITX, 2,4-diethyl thioxanthones, 2,4-dichloro-thioxanthones, 1-chloro-4-propoxythioxanthone etc.
Photopolymerization causes auxiliary agent (F) and can be used alone, and also can combine two or more and use.In addition, cause auxiliary agent (F) as photopolymerization and also can use commercially available product, commercially available photopolymerization causes auxiliary agent (F) and for example there are such as trade name " EAB-F " (hodogaya chemical industry (strain) manufacture) etc.
The combination of auxiliary agent (F) is caused as the Photoepolymerizationinitiater initiater (D) in coloring photosensitive combination of the present invention and photopolymerization, for example there are diethoxy acetophenone/4, 4 '-bis-(diethylamino) benzophenone, 2-methyl-2-morpholino-1-(4-methyl sulphur aminoacyl phenyl)-1-acetone/4, 4 '-bis-(diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone/4, 4 '-bis-(diethylamino) benzophenone, benzyl dimethyl ketal/4, 4 '-bis-(diethylamino) benzophenone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-1-acetone/4, 4 '-bis-(diethylamino) benzophenone, 1-hydroxycyclohexyl phenyl ketone/4, 4 '-bis-(diethylamino) benzophenone, oligomer/4 of 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl]-1-acetone, 4 '-bis-(diethylamino) benzophenone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-1-butanone/4, 4 '-bis-(diethylamino) benzophenone etc., preferable examples has 2-methyl-2-morpholino-1-(4-methyl sulphur aminoacyl phenyl)-1-acetone/4, 4 '-bis-(diethylamino) benzophenone.
When using these photopolymerization to cause auxiliary agent (F), relative to every 1 mole of Photoepolymerizationinitiater initiater (D), its use amount preferably 0.01 ~ 10 mole, more preferably 0.01 ~ 5 mole.
Coloring photosensitive combination of the present invention contains solvent (E).As solvent (E), for example there are ethers, aromatic hydrocarbon based, above-mentioned outside ketone, alcohols, ester class, amide-type, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO) etc.
As above-mentioned ethers, for example there are tetrahydrofuran, oxinane, 1, 4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol list propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, propylene glycol monopropyl ether acetic acid esters, propylene glycol monomethyl ether, methylcellosolve acetate, ethyl cellosolve acetate, ethylcarbitol acetate, acetate of butyl carbitol, anisole (methyl phenyl ethers anisole), phenetol, methyl anisole etc.
As above-mentioned aromatic hydrocarbon based, for example there are such as benzene,toluene,xylene, mesitylene etc.
As above-mentioned ketone, for example there are such as acetone, 2-butanone, 2-HEPTANONE, 3-heptanone, 4-heptanone, 4-methyl-2 pentanone, 4-hydroxy-4-methyl-2-pentanone, cyclopentanone, cyclohexanone etc.
As above-mentioned alcohols, for example there are such as methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, glycerine etc.
As above-mentioned ester class, for example there are such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methoxy menthyl acetate, ethyl methoxyacetate, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, 2 hydroxy propanoic acid methyl esters, 2-methoxy methyl propionate, 2-methoxypropionate, 2-methoxy propyl propyl propionate, 2-ethoxypropanoate, 2-ethoxyl ethyl propionate, 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-Oxobutyric acid methyl esters, 2-Oxobutyric acid ethyl ester, acetic acid-3-methoxybutyl, acetic acid-3-methyl-3-methoxybutyl, gamma-butyrolacton etc.
As above-mentioned amide-type, for example there are such as DMF, DMA, 1-METHYLPYRROLIDONE etc.
Wherein, preferred ethers, ketone and ester class.More preferably propylene glycol methyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and 4-hydroxy-4-methyl-2-pentanone, by these and with then better.
Again, above-mentioned solvent can be used alone, also two or more use capable of being combined.
The content of the solvent (E) in coloring photosensitive combination is relative to coloring photosensitive combination preferably 70 ~ 95 quality %, more preferably 75 ~ 90 quality %.The content of solvent (E) is in above-mentioned scope, and flatness when having a coating is good and when forming color filter, colour saturation can not be not enough and display characteristic is good tendency.
Photosensitive composition of the present invention also can contain surfactant (G) further.The polysiloxane series surfactant being selected from polysiloxane series surfactant, fluorine system surfactant and there is fluorine atom is for example there are as surfactant (G).
As above-mentioned polysiloxane series surfactant, for example there are the surfactant etc. with siloxane bond.Particularly, for example there are ト mono-レ シ リ コ mono-Application DC3PA, same to SH7PA, same to DC11PA, same to SH21PA, same to SH28PA, same to SH29PA, same to SH30PA, polyether modified silicon oil SH8400 (trade name: ト mono-レ シ リ コ mono-Application; East レ ダ ウ コ mono-ニ Application ゲ (strain) manufacture), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacture), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufacture of モ メ Application テ イ Block パ Off オ mono-マ Application ス マ テ リ ア Le ズ ジ ヤ パ Application contract commercial firm) etc.
As above-mentioned fluorine system surfactant, for example there are the surfactant etc. with fluorocarbon chain.For example there are Off ロ ラ mono-De (trade name) FC430 particularly, same FC431 (Sumitomo ス リ mono-エ system (strain) manufacture), メ ガ Off ア Star Network (registered trademark) F142D, same F171, same F172, same F173, same F177, same F183, same R30 (DIC (strain) manufacture), エ Off ト Star プ (trade name) EF301, same EF303, EF351, EF352 (Mitsubishi マ テ リ ア Le electronics changes into (strain) and manufactures), サ mono-Off ロ Application (trade name) S381, same S382, same SC101, same SC105 (Asahi Glass (strain) manufacture), E5844 (manufacture of (strain) ダ イ キ Application Off ア イ Application ケ ミ カ Le research institute), BM-1000, BM-1100 (being all trade name: BM Chemie society manufactures) etc.
As the above-mentioned polysiloxane series surfactant with fluorine atom, for example there are the surfactant etc. with siloxane bond and fluorocarbon chain.Particularly, メ ガ Off ア Star Network (registered trademark) R08, same to BL20, same to F475, same to F477, same to F443 (DIC (strain) manufacture) etc.
These surfactants can be used alone, also two or more use capable of being combined.
The content of surfactant (G) is relative to coloring photosensitive combination preferably 0.00001 ~ 0.1 quality %, more preferably 0.00005 ~ 0.01 quality %.The content of surfactant (G), in above-mentioned scope, has the tendency that flatness is good.
As the method using coloring photosensitive combination of the present invention to form the pattern of color filter, for example there are following method and use the method etc. without the need to the ink jet technique of photo-engraving process, said method is, coloring photosensitive combination of the present invention is coated on substrate or another resin bed (such as, another coloring photosensitive combination layer etc. first formed on substrate) on, except the volatile ingredient of desolventizing etc., form dyed layer, expose this dyed layer via photomask and develop.
By known methods such as optical lithographies, several TFT22 (see Fig. 1) are formed on glass substrate 21 for every pixel.TFT22 by grid (gate) electrode 22a, grid (gate) dielectric film 22b, be formed at polysilicon film 22c on this gate insulating film 22b and by such as oxide film (SiO
2) and nitride film (SiN
x) laminated film formed diaphragm 22d form, this gate electrode 22a is such as formed on glass substrate 21 by molybdenum (Mo), forms a part for grid (gate) line simultaneously; This gate insulating film 22b is formed on gate electrode 22a, such as, by nitride film (SiN
x) and oxide film (SiO
2) laminated film form.The region relative with gate electrode 22a of polysilicon film 22c is raceway groove (channel) region of TFT22, and the two side areas of this channel region is (source) region, source or leakage (drain) region.By the connecting hole (contact hole) that diaphragm 22d is arranged, the source region of polysilicon film 22c is electrically connected with the signal wire 27 such as formed by aluminium.In addition, by connecting hole described later (contact hole) 201, the drain region of polysilicon film 22c is electrically connected with pixel electrode 24.
For each pixel, when glass substrate 21 is formed several TFT22, while glass substrate 21 forms TFT22, form calibration symbol (not shown).This calibration symbol is as the positioning datum in the formation process of colour filter 23 described later.In addition, these calibration symbols can dual-purpose be also the symbol of the laminating benchmark driving substrate and counter substrate.Calibration symbol is formed when can form the metal levels such as distribution or polysilicon layer in the manufacturing process of TFT22, at least utilizes its one deck to be formed in same operation.
Then, by spin-coating method or additive method TFT22 and be formed with calibration symbol glass substrate 21 on form thickness 0.5 ~ 5.0 μm, the coloring photosensitive combination layer 23A of such as 1.0 μm.This coloring photosensitive combination layer 23A corresponds to color filter of the present invention.
Then, by preferably heat-treating at 60 ~ 110 DEG C at the temperature of 30 DEG C ~ 120 DEG C of scopes, make coloring photosensitive combination layer 23A dry.In order to dry coloring photosensitive combination layer 23A, drying under reduced pressure can be combined and heat drying carries out.Then, via photomask (not shown) to coloring phototonus composition layer 23A irradiation ultraviolet radiation, not important part (i.e. non-exposed portion) is optionally removed again by developer solution, form the connecting hole (contacthole) 201 of the drain region arriving polysilicon film 22c, then wash.Then, in order to make coloring photosensitive combination layer 23A flow again (reflow), and the curability composition contained by coloring photosensitive combination layer 23A being solidified, heating at 150 ~ 230 DEG C under the range temperature of 100 DEG C ~ 300 DEG C, preferably.
Thus, coloring photosensitive combination layer 23A becomes the colour filter 23 (see Fig. 2) containing Red lightscreening plate 23a, green color filter 23b, blue color filter 23c corresponding to each pixel column.Region between each optical filter of colour filter 23 is the Mixed Zone of adjacent look, but these regions are lightproof areas relative with signal wire 27, so especially no problem in quality.In addition, the region between these each optical filters can not be painted.
Then, form by such as spin-coating method the diaphragm photosensitive resin film 29 that such as thickness is 0.3 ~ 2.0 μm, cover colour filter 23 (see Fig. 3).Then, via photomask (not shown) to photosensitive resin film 29 irradiation ultraviolet radiation, region corresponding to connecting hole 201 and non-important part is optionally removed again by developer solution, form the connecting hole (contact hole) 202 of the drain region arriving polysilicon film 22c, then wash.Then, in order to make photosensitive resin film 29 flow again (reflow), heat at such as 200 DEG C under the range temperature of 100 DEG C ~ 300 DEG C.Then, in order to remove the residue and organism piled up in connecting hole 202, etch with oxygen plasma, then in order to remove the oxide film because oxygen plasma is formed, such as, etch with rare fluoric acid.
Then, on photosensitive resin film 29, transparent conductive material is formed as ITO (Indium-TinOxide: the oxide hybrid films of indium and tin) by such as splash method, by optical lithography and etching method, design producing is carried out to this ito film, forms transparent pixel electrode 24 (see Fig. 4).This pixel electrode 24 can be formed by metals such as aluminium (Al) or silver (Ag) according to method for making.Then, after forming oriented film by known method, bond this driving substrate and counter substrate, manufacture liquid crystal indicator.
The high film of contrast can be obtained according to coloring photosensitive combination of the present invention.
Embodiment
Below, the present invention is illustrated in greater detail according to embodiment." % " and " part " in example, as long as no special record, is exactly quality % and mass parts.
Synthesis example 1
[synthesis example of the compound that formula (2) represents]
The synthesis > of the compound that < formula (2-24-1a) represents
In the flask with cooling tube and stirring apparatus, drop into 75 parts of 4-nitrobenzene dimethoxy nitriles, 375 parts of DMAs, under agitation maintain less than 20 DEG C, slowly add 68.9 parts of sodium carbonate on one side.Under agitation maintain less than 20 DEG C on one side again, drip 68.9 parts of 3-mercapto-propionates.After dropping liquid terminates, at room temperature stir 3.5 hours, reaction solution is filtered, filtrate is injected into the 1 equivalent hydrochloric acid of 2250 parts, isolated by filtration precipitates, and carefully cleans with ion exchange water, drying under reduced pressure at 50 DEG C, obtains the compound that 104.4 parts of formulas (2-24-1a) represent.
The synthesis > of the compound that < formula (2-24-1b) represents
52.0 parts of compounds (2-24-1a), 104.0 parts of N are dropped in the flask with cooling tube and stirring apparatus, dinethylformamide, under agitation maintain less than 20 DEG C on one side, 40.2 part of 1,8-diazabicyclo [5.4.0]-7-undecylene (DBU) while drip.After dropping liquid terminates, at room temperature stir 2.5 hours.Reaction solution is injected into the water of 208.0 parts, then adds concentrated hydrochloric acid to pH below 2.Filter out precipitation, carefully clean with ion exchange water, drying under reduced pressure at 50 DEG C, obtain 33.6 parts of compounds (2-24-1b).
The synthesis > of the compound that < formula (2-24-1c) represents
In the flask with cooling tube and stirring apparatus, drop into 33.0 parts of compounds (2-24-1b), 396 parts of acetic acid, at room temperature stir, while add 4.2 parts of sodium tungstates.Under agitation maintain less than 30 DEG C on one side again, instill 87.5 part of 30% hydrogen peroxide.After dropping liquid terminates, be warming up to 50 DEG C, stir 2 hours.By reaction solution cool to room temperature, be dissolved in the solution obtained in 396 parts of methyl alcohol potassium acetate 60.7 parts and inject reaction solution, stir 1 hour.Filter out precipitation, by washed with methanol, drying under reduced pressure at 50 DEG C, obtains the compound that 35.0 parts of formulas (2-24-1c) represent.
The synthesis > of the compound that < formula (2-24-1d) represents
5.0 parts of compounds (2-24-1c), 0.82 part of cupric chloride, 0.40 part of ammonium molybdate, 19.1 parts of quinoline are dropped in the flask with cooling tube and stirring apparatus.Flask is placed on and is redefined in 100 DEG C of oil baths, stir and be warming up to 160 DEG C.Continue stirring again 3 hours, be cooled to 100 DEG C, add 66.5 parts of methyl alcohol.Filter out precipitation, by washed with methanol, drying under reduced pressure at 50 DEG C, obtains the compound that 2.0 parts of formulas (2-24-1d) represent.
The synthesis > of the compound that < formula (2-24-1) represents
57.6 parts of anhydrous DMAs, 1.5 parts of anhydrous DMFs are dropped in the flask with cooling tube and stirring apparatus.Be cooled to 0 DEG C, drip 2.3 parts of thionyl chlorides, at 0 DEG C, continue stirring 1 hour.Add 1.8 parts of compounds (2-24-1d) again, at room temperature stir 30 minutes, stir 1.5 hours at 50 DEG C, stir 4 hours at 80 DEG C.Be cooled to 0 DEG C, drip the mixed solution of 2.8 parts of N, N-dimethyl-1,3-propane diamine and 4.2 parts of triethylamines.At room temperature stir 15 minutes, stir 4 hours at 80 DEG C, add 506.9 parts of methyl alcohol.Filter out precipitation, carefully clean with methyl alcohol, drying under reduced pressure at 50 DEG C, obtain the compound that 1.6 parts of formulas (2-24-1) represent.
Synthesis example 2
The synthesis example > of the compound that < formula (1) represents
The potpourri (middle tank formation manufacture) of the compound that the compound shown in 15 parts of formulas (A0-1) and formula (A0-2) represent, 150 parts of chloroforms and 8.9 parts of N are dropped in the flask with cooling tube and stirring apparatus, dinethylformamide, under agitation maintain less than 20 DEG C on one side, drip 10.9 parts of thionyl chlorides.After dropping liquid terminates, be warming up to 50 DEG C, maintain this temperature and within 5 hours, make it reaction, be then cooled to 20 DEG C.While cooled reaction solution is under agitation maintained less than 20 DEG C, drip the mixed liquor of 12.5 parts of 2 ethyl hexylamines and 22.1 parts of triethylamines.Then, reaction within 5 hours, is made it in synthermal lower stirring.Then, remove the solvent in the reaction mixture obtained with rotary evaporator distillation, then add a small amount of methyl alcohol, carry out high degree of agitation.This potpourri is added in the mixed liquor of 375 parts of ion exchange waters while stirring, makes crystallization.Filter out the crystallization of precipitation, carefully clean with ion exchange water, drying under reduced pressure at 60 DEG C, obtains the potpourri (potpourri of the compound that formula (A1-1) ~ formula (A1-8) represents of compound that 11.3 parts of formulas (A1-a) represent and the compound that formula (A2-b) represents; Dyestuff A1)
[in formula (A1-a) and formula (A1-b), R
g, R
hand R
irepresent hydrogen atom ,-SO independently of one another
3 -,-SO
3h or N-(2-ethylhexyl) sulphur aminoacyl].
[in above-mentioned formula, * represents the bonding position with-NH-.]
Synthesis example 3
Divide with 0.02L/ in the 1L flask with backflow cooling tube, tap funnel and stirring machine and pass into nitrogen, become nitrogen atmosphere, add 200 mass parts 3-methoxyl-n-butyl alcohols and 105 mass parts 3-methoxybutyl acetic acid esters, be heated to 70 DEG C while stirring.Then, 60 mass parts methacrylic acids, 240 mass parts 3,4-epoxy three ring [5.2.1.0 are dissolved
2.6] decyl acrylate (compound that formula (B1-1-1) represents and the compound that formula (B1-2-1) represents mix with mol ratio 50: 50) and 140 mass parts 3-methoxybutyl acetic acid esters, spend 4 hours this lysate being added drop-wise to insulation with tap funnel is in the flask of 70 DEG C.On the other hand, 30 mass parts polymerization initiator 2,2-azos two (2,4-methyl pentane nitrile) are dissolved in 225 mass parts 3-methoxybutyl acetic acid esters, spend within 4 hours, be added drop-wise in flask another tap funnel of this solution.Polymerization initiator drip terminate after, keep 70 DEG C 4 hours, then cool to room temperature, obtaining weight-average molecular weight Mw is 1.3 × 10
4, the resin solution B1 that molecular weight distribution (Mw/Mn) is 2.5, solid constituent is 33 quality %, acid number is 34mg-KOH/g (acid number of solution).
The mensuration > of < molecular weight
The weight-average molecular weight (Mw) of the resin B 1 obtained and the mensuration of number-average molecular weight (Mn) use GPC method, carry out under the following conditions.
Device: HLC-8120GPC (eastern ソ mono-(strain) manufactures)
(chromatogram) post: TSK-GELG2000HXL
(chromatogram) column temperature: 40 DEG C
Solvent: THF
Flow velocity: 1.0mL/ divides
Detected liquid solid component concentration: 0.001 ~ 0.01 quality %
Injection rate IR: 50 μ L
Detecting device: RI
Calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500,
A-500 (eastern ソ mono-(strain) manufactures)
Embodiment 1
Mix following material, use perforated glass ball mill (PVC one ズ ミ Le) that pigment is disperseed fully,
(A) colorant C.I. pigment blue 15: 6 27 parts
Acrylic acid series pigment dispersing agent 9.1 parts
Propylene glycol monomethyl ether 196 parts
Then, mix following material, obtain coloring photosensitive combination.
(A) colorant: the compound that formula (2-24-1) represents 27 parts
(A) colorant: the compound that formula (1) represents: dyestuff A1 6.0 parts
(B) resin: resin solution B1 152 parts
(C) photopolymerizable compound: dipentaerythritol acrylate 50 parts
(KAYARAD DPHA; Japan's chemical drug (strain) manufactures)
(D) Photoepolymerizationinitiater initiater: N-benzoyloxy-1-(4-phenyl sulphur aminoacyl phenyl)-1-octanone
Ketone-2-imines 15 parts
(manufacture of イ Le ガ キ ユ ア OXE01 チ バ ジ ヤ パ Application society)
(E) solvent: 4-hydroxy-4-methyl-2-pentanone 376 parts
Embodiment 2
Mix following material, use perforated glass ball mill that pigment is disperseed fully,
(A) colorant C.I. pigment blue 15: 6 27 parts
Acrylic acid series pigment dispersing agent 9.1 parts
Propylene glycol monomethyl ether 196 parts
Then, mix following material, obtain coloring photosensitive combination.
(A) salt 27 parts of colorant: C.I. direct blue 264 and dodecylbenzene sulfonic acid
(オ リ ヱ Application ト chemical industry (strain) manufacture)
(A) colorant: the compound that formula (1) represents: dyestuff A1 6.0 parts
(B) resin: resin solution B1 152 parts
(C) photopolymerizable compound: dipentaerythritol acrylate 50 parts
(KAYARAD DPHA; Japan's chemical drug (strain) manufactures)
(D) Photoepolymerizationinitiater initiater: N-benzoyloxy-1-(4-phenyl sulphur aminoacyl phenyl)-1-octanone
-2-imines 15 parts
(イ Le ガ キ ユ ア OXE01; チ バ ジ ヤ パ Application society manufactures)
(E) solvent: 4-hydroxy-4-methyl-2-pentanone 376 parts
Embodiment 3
Mix following material, use perforated glass ball mill that pigment is disperseed fully,
(A) colorant C.I. pigment blue 15: 6 31 parts
Acrylic acid series pigment dispersing agent 11 parts
Propylene glycol monomethyl ether 226 parts
Then, mix following material, obtain coloring photosensitive combination.
(A) salt 13 parts of colorant: C.I. direct blue 264 and dodecylbenzene sulfonic acid
(オ リ ヱ Application ト chemical industry (strain) manufacture)
(A) colorant: the compound that formula (1) represents: dyestuff A1 5.0 parts
(B) resin: resin solution B1 152 parts
(C) photopolymerizable compound: dipentaerythritol acrylate 50 parts
(KAYARAD DPHA; Japan's chemical drug (strain) manufactures)
(D) Photoepolymerizationinitiater initiater: N-benzoyloxy-1-(4-phenyl sulphur aminoacyl phenyl)-1-octanone
-2-imines 15 parts
(イ Le ガ キ ユ ア OXE01; チ バ ジ ヤ パ Application society manufactures)
(E) solvent: 4-hydroxy-4-methyl-2-pentanone 312 parts
Embodiment 4
Mix following material, obtain coloring photosensitive combination.
(A) salt 57 parts of colorant: C.I. direct blue 264 and dodecylbenzene sulfonic acid
(オ リ ヱ Application ト chemical industry (strain) manufacture)
(A) colorant: the compound that formula (1) represents: dyestuff A1 5.0 parts
(B) resin: resin solution B1 152 parts
(C) photopolymerizable compound: dipentaerythritol acrylate 50 parts
(KAYARAD DPHA; Japan's chemical drug (strain) manufactures)
(D) Photoepolymerizationinitiater initiater: N-benzoyloxy-1-(4-phenyl sulphur aminoacyl phenyl)-1-octanone
-2-imines 15 parts
(イ Le ガ キ ユ ア OXE01; チ バ ジ ヤ パ Application society manufactures)
(E) solvent: 4-hydroxy-4-methyl-2-pentanone 526 parts
Reference example 1
Mix following material, use perforated glass ball mill that pigment is disperseed fully,
(A) colorant C.I. pigment blue 15: 6 18 parts
(A) colorant C.I. pigment Violet 23 5.7 parts
Acrylic acid series pigment dispersing agent 6.1 parts
Propylene glycol monomethyl ether 154 parts
Then, mix following material, obtain coloring photosensitive combination.
(B) resin: resin solution B1 136 parts
(C) photopolymerizable compound: dipentaerythritol acrylate 55 parts
(KAYARAD DPHA; Japan's chemical drug (strain) manufactures)
(D) Photoepolymerizationinitiater initiater: N-benzoyloxy-1-(4-phenyl sulphur aminoacyl phenyl)-1-octanone
-2-imines 15 parts
(イ Le ガ キ ユ ア OXE01; チ バ ジ ヤ パ Application society manufactures)
(E) solvent: propylene glycol monomethyl ether 319 parts
[formation of pattern]
At glass substrate (the イ mono-ゲ Le 2000 of the length of side 2 inches; コ mono-ニ Application ゲ society manufactures] upper be coated with coloring photosensitive combination with spin-coating method after, preliminary drying 3 minutes at 100 DEG C.After cooling, the interval of figuratum to the substrate and tool that are coated with this coloring photosensitive combination quartz glass photomask is set as 100 μm, uses exposure machine (TME-150RSK; ト プ コ Application (strain) manufactures), under air atmosphere, with 150mJ/cm
2exposure (365nm benchmark) carry out illumination and penetrate.After illumination is penetrated, above-mentioned film is flooded 80 seconds at 23 DEG C in the water system developer solution containing nonionic system surfactant 0.12% and potassium hydroxide 0.04%, develops, after washing, carry out rear baking 20 minutes at 220 DEG C in an oven.After letting cool, use determining film thickness device (DEKTAK3; Japan's vacuum technique (strain) manufactures) measure the thickness of pattern obtained, result is 2.0 μm.
[chromaticity evaluation]
For the pattern on the glass substrate obtained, use colour examining machine (OSP-SP-200; Olympus (strain) manufactures) measure light splitting, use the isochrome function of illuminant-C, measure the xy chromaticity coordinate (Bx, By) in the XYZ color specification system of CIE and brightness.Result display in Table 1.
[contrast evaluation]
Except not using except photomask exposes, other operate in the same manner as the formation of pattern, for the film on obtained glass substrate, use contrast colour examining machine (CT-1; Hu Ban motor society manufactures, detecting device, BM-5A, light source; F-10), blank value is set as 10000, measures contrast.With light polarizing film (POLAX-38S; Le ケ オ society manufactures) clamp film on glass substrate, it can be used as sample.Result display in Table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Reference example 1 | |
| Bx | 0.141 | 0.141 | 0.141 | 0.143 | 0.143 |
| By | 0.085 | 0.085 | 0.085 | 0.085 | 0.085 |
| Brightness | 9.4 | 9.2 | 9.4 | 8.8 | 8.8 |
| Contrast | 6900 | 6740 | 6960 | 7020 | 5150 |
Embodiment 5
Mix following material, use perforated glass ball mill that pigment is disperseed fully,
(A) colorant C.I. pigment blue 15: 6 17 parts
Acrylic acid series pigment dispersing agent 5.7 parts
Propylene glycol monomethyl ether 122 parts
Then, mix following material, obtain coloring photosensitive combination.
(A) salt 3.6 parts of colorant: C.I. direct blue 264 and dodecylbenzene sulfonic acid
(オ リ ヱ Application ト chemical industry (strain) manufacture)
(A) colorant: the compound that formula (1) represents: dyestuff A1 3.6 parts
(B) resin: resin solution B1 152 parts
(C) photopolymerizable compound: dipentaerythritol acrylate 50 parts
(KAYARAD DPHA; Japan's chemical drug (strain) manufactures)
(D) Photoepolymerizationinitiater initiater: N-benzoyloxy-1-(4-phenyl sulphur aminoacyl phenyl)-1-octanone
-2-imines 15 parts
(イ Le ガ キ ユ ア OXE01; チ バ ジ ヤ パ Application society manufactures)
(E) solvent: 4-hydroxy-4-methyl-2-pentanone 320 parts
Embodiment 6
Mix following material, use perforated glass ball mill that pigment is disperseed fully,
(A) colorant C.I. pigment blue 15: 6 15 parts
Acrylic acid series pigment dispersing agent 5.2 parts
Propylene glycol monomethyl ether 111 parts
Then, mix following material, obtain coloring photosensitive combination.
(A) salt 6.4 parts of colorant: C.I. direct blue 264 and dodecylbenzene sulfonic acid
(オ リ ヱ Application ト chemical industry (strain) manufacture)
(A) colorant: the compound that formula (1) represents: dyestuff A1 3.8 parts
(B) resin: resin solution B1 152 parts
(C) photopolymerizable compound: dipentaerythritol acrylate 50 parts
(KAYARAD DPHA; Japan's chemical drug (strain) manufactures)
(D) Photoepolymerizationinitiater initiater: N-benzoyloxy-1-(4-phenyl sulphur aminoacyl phenyl)-1-octanone
-2-imines 15 parts
(イ Le ガ キ ユ ア OXE01; チ バ ジ ヤ パ Application society manufactures)
(E) solvent: 4-hydroxy-4-methyl-2-pentanone 320 parts
[formation of pattern]
Carry out operation similarly to Example 1, be made pattern.Use determining film thickness device to measure the thickness of the pattern obtained, result is 3.0 μm.
[chromaticity evaluation]
Carry out operation similarly to Example 1, measure xy chromaticity coordinate (Bx, By) and brightness.Result display in table 2.
[contrast evaluation]
Carry out operation similarly to Example 1, the contrast of the film on the glass substrate that mensuration obtains.Result display in table 2.
Table 2
| Embodiment 5 | Embodiment 6 | |
| Bx | 0.144 | 0.145 |
| By | 0.085 | 0.085 |
| Brightness | 9.6 | 9.6 |
| Contrast | 6200 | 6450 |
Synthesis example 4
There is stirring machine, thermometer, backflow cooling tube, in the flask of tap funnel and nitrogen ingress pipe, import 182g propylene glycol monomethyl ether, to make in flask atmosphere from after air becomes nitrogen, be warming up to 100 DEG C, then, instill a kind of solution, continue again to stir at 100 DEG C, this solution is by 70.5g (0.40 mole) benzyl methacrylate, 43.0g (0.5 mole) methacrylic acid, 3.6g 2 is with the addition of in the potpourri that the monomethacrylates of 22.0g (0.10 mole) tricyclodecane skeleton (Hitachi changes into (strain) FA-513M processed) and 136g propylene glycol monomethyl ether are formed, 2 '-azobis isobutyronitrile forms.Then, atmosphere in flask is become air from nitrogen, 35.5g [0.25 mole, (be 50 % by mole relative to the carboxyl of the methacrylic acid for this reaction)] glycidyl methacrylate, 0.9g tri-(dimethylaminomethyl) phenol and 0.145g quinhydrones is dropped in flask, at 110 DEG C, continue reaction, obtain solid constituent 32%, resin solution B2 that solid constituent acid number is 79mgKOH/g.The weight-average molecular weight of the polystyrene conversion measured by GPC is 30,000.
Embodiment 7
Mix following material, use perforated glass ball mill that pigment is disperseed fully,
(A) colorant C.I. pigment blue 15: 6 27 parts
Acrylic acid series pigment dispersing agent 9.1 parts
Propylene glycol monomethyl ether 196 parts
Then, mix following material, obtain coloring photosensitive combination.
(A) salt 1.1 parts of colorant: C.I. direct blue 264 and dodecylbenzene sulfonic acid
(オ リ ヱ Application ト chemical industry (strain) manufacture)
(A) colorant: the compound that formula (1) represents: dyestuff A1 4.8 parts
(B) resin: resin solution B1 152 parts
(C) photopolymerizable compound: dipentaerythritol acrylate 50 parts
(KAYARAD DPHA; Japan's chemical drug (strain) manufactures)
(D) Photoepolymerizationinitiater initiater: N-benzoyloxy-1-(4-phenyl sulphur aminoacyl phenyl)-1-octanone
-2-imines 15 parts
(イ Le ガ キ ユ ア OXE01; チ バ ジ ヤ パ Application society manufactures)
(E) solvent: ethyl lactate 280 parts
Embodiment 8
Mix following material, use perforated glass ball mill that pigment is disperseed fully,
(A) colorant C.I. pigment blue 15: 6 25 parts
Acrylic acid series pigment dispersing agent 8.4 parts
Propylene glycol monomethyl ether 181 parts
Then, mix following material, obtain coloring photosensitive combination.
(A) salt 2.3 parts of colorant: C.I. direct blue 264 and dodecylbenzene sulfonic acid
(オ リ ヱ Application ト chemical industry (strain) manufacture)
(A) colorant: the compound that formula (1) represents: dyestuff A1 4.8 parts
(B) resin: resin solution B1 152 parts
(C) photopolymerizable compound: dipentaerythritol acrylate 50 parts
(KAYARAD DPHA; Japan's chemical drug (strain) manufactures)
(D) Photoepolymerizationinitiater initiater: N-benzoyloxy-1-(4-phenyl sulphur aminoacyl phenyl)-1-octanone
-2-imines 15 parts
(イ Le ガ キ ユ ア OXE01; チ バ ジ ヤ パ Application society manufactures)
(E) solvent: ethyl lactate 308 parts
Comparative example 1
Mix following material, use perforated glass ball mill that pigment is disperseed fully,
(A) colorant C.I. pigment blue 15: 6 20 parts
Acrylic acid series pigment dispersing agent 5 parts
Propylene glycol monomethyl ether 137 parts
Then, mix following material, obtain coloring photosensitive combination.
(A) colorant: the compound that formula (1) represents: dyestuff A1 3.5 parts
(B) resin: resin solution B1 157 parts
(C) photopolymerizable compound: dipentaerythritol acrylate 50 parts
(KAYARAD DPHA; Japan's chemical drug (strain) manufactures)
(D) Photoepolymerizationinitiater initiater: N-benzoyloxy-1-(4-phenyl sulphur aminoacyl phenyl)-1-octanone
-2-imines 15 parts
(イ Le ガ キ ユ ア 0XE01; チ バ ジ ヤ パ Application society manufactures)
(E) solvent: 4-hydroxy-4-methyl-2-pentanone 289 parts
[formation of pattern]
Carry out operation similarly to Example 1, be made pattern.Use determining film thickness device to measure the thickness of the pattern obtained, result is 2.2 μm.
[chromaticity evaluation]
Carry out operation similarly to Example 1, measure xy chromaticity coordinate (Bx, By) and brightness.Result display in table 3.
[contrast evaluation]
Carry out operation similarly to Example 1, the contrast of the film on the glass substrate that mensuration obtains.Result display in table 3.
Table 3
| Embodiment 7 | Embodiment 8 | Comparative example 1 | |
| Bx | 0.141 | 0.141 | 0.141 |
| By | 0.085 | 0.085 | 0.085 |
| Brightness | 9.7 | 9.7 | 9.7 |
| Contrast | 6360 | 6420 | 5750 |
In the film formed using the coloring photosensitive combination of embodiment, confirm high-contrast.
Utilizability in industry
According to the present invention, can manufacture the color filter of high-contrast, this color filter is applicable to the formation of the rendered image forming the color filter used in liquid crystal display cells or solid-state imager.
Symbol description
21 glass substrates
22TFT (on-off element)
22a gate electrode
22b gate insulating film
22c polysilicon film
22d diaphragm 23 colour filter
23A coloring photosensitive combination layer (color filter)
23a Red lightscreening plate
23b green color filter
23c blue color filter
24 pixel electrodes
27 signal wires
29 photosensitive resin films (diaphragm)
201,202 connecting holes
Claims (9)
1. a coloring photosensitive combination, it contains colorant, adhesive resin, photopolymerizable compound, Photoepolymerizationinitiater initiater and solvent, it is characterized in that, described colorant is the colorant of the compound represented containing formula (2),
In formula (2), G
1represent the alkylidene of carbon number 2 ~ 12, the hydrogen atom contained by this alkylidene can be replaced by the alkyl of carbon number 1 ~ 4, J
1expression-NR
ar
bh
+q
-,
R
aand R
brepresent the alkyl of hydrogen atom or carbon number 1 ~ 8 independently of one another,
Q
-represent Y-SO
3,
Y represents the organic group of 1 valency,
N
arepresent the integer of 1 ~ 4.
2. coloring photosensitive combination as claimed in claim 1, wherein, colorant is the colorant also containing the compound that formula (1) represents,
In formula (1), R
1~ R
4represent hydrogen atom ,-R independently of one another
6or the aromatic hydrocarbyl of carbon number 6 ~ 10, the hydrogen atom contained by this aromatic hydrocarbyl can by halogen atom ,-R
6,-OH ,-OR
6,-SO
3 -,-SO
3h ,-SO
3m ,-CO
2h ,-CO
2r
6,-SO
2nHR
8or-SO
2nR
8r
9replace,
R
5expression-SO
3 -,-SO
3h ,-SO
3m ,-CO
2h ,-CO
2r
6,-SO
2nHR
8or-SO
2nR
8r
9,
M represents the integer of 0 ~ 5, when m is the integer of more than 2, and multiple R
5can be the same or different,
X represents halogen atom, and a represents the integer of 0 or 1,
R
6represent the saturated hydrocarbyl of carbon number 1 ~ 10, the hydrogen atom contained by the saturated hydrocarbyl of this carbon number 1 ~ 10 can be replaced by halogen atom, this-CH contained by saturated hydrocarbyl
2-can by-O-,-CO-or-NR
10-replace,
R
10represent the saturated hydrocarbyl of hydrogen atom or carbon number 1 ~ 10, the hydrogen atom contained by this saturated hydrocarbyl can be replaced by halogen atom, this-CH contained by saturated hydrocarbyl
2-can be replaced by-O-or-CO-,
R
8and R
9represent the alkyl of carbon number 1 ~ 10, the naphthenic base of carbon number 3 ~ 30 or-Q independently of one another
1, this alkyl and the hydrogen atom contained by this naphthenic base can by hydroxyl, halogen atom ,-Q
1replace, this alkyl and this-CH contained by naphthenic base
2-can by-O-,-CO-or-NR
10-replace, R
8and R
9can bonding and form the heterocycle of carbon number 1 ~ 10 mutually, the hydrogen atom contained by this heterocycle can by R
6,-OH or-Q
1replace,
Q
1represent the aromatic hydrocarbyl of carbon number 6 ~ 10 or the aromatic heterocycle of carbon number 3 ~ 10, this aromatic hydrocarbyl and the hydrogen atom contained by aromatic heterocycle can by-OH ,-R
6,-OR
6or halogen atom replaces,
M represents sodium atom or potassium atom,
Wherein, the compound that represents of formula (1)+charge number with-charge number is identical.
3. coloring photosensitive combination as claimed in claim 1, wherein, colorant is the colorant also containing organic pigment.
4. coloring photosensitive combination as claimed in claim 3, wherein, organic pigment is containing C.I. pigment blue 15: the organic pigment of 6.
5. coloring photosensitive combination as claimed in claim 1, wherein, the content of the compound that formula (2) represents is 1 ~ 50 quality % relative to colorant.
6. coloring photosensitive combination as claimed in claim 1, wherein, Photoepolymerizationinitiater initiater is the compound with oxime structure.
7. a film, it uses the coloring photosensitive combination described in claim 1 to be formed.
8. a color filter, it uses the coloring photosensitive combination described in claim 1 to be formed.
9. color filter as claimed in claim 8, it is formed by photo-engraving process.
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| KR101574089B1 (en) | 2011-12-23 | 2015-12-03 | 제일모직 주식회사 | Photosensitive resin composition and color filter using the same |
| KR101413077B1 (en) * | 2011-12-30 | 2014-07-01 | 제일모직 주식회사 | Photosensitive resin composition for color filter and color filter using the same |
| KR102155239B1 (en) * | 2012-05-29 | 2020-09-11 | 스미또모 가가꾸 가부시키가이샤 | Colored curable resin composition |
| JP6115281B2 (en) | 2012-06-07 | 2017-04-19 | Jsr株式会社 | Coloring composition, color filter and display element |
| KR102066287B1 (en) * | 2012-06-11 | 2020-01-14 | 스미또모 가가꾸 가부시키가이샤 | Colored photosensitive resin composition |
| JP6155809B2 (en) * | 2013-04-26 | 2017-07-05 | 東洋インキＳｃホールディングス株式会社 | Photosensitive coloring composition and color filter using the same |
| JP6566901B2 (en) * | 2015-03-30 | 2019-08-28 | 住友化学株式会社 | Colored curable resin composition |
| JP2016191915A (en) * | 2015-03-30 | 2016-11-10 | 住友化学株式会社 | Colored curable resin composition |
| JP7184518B2 (en) * | 2016-02-12 | 2022-12-06 | 三菱ケミカル株式会社 | Photosensitive coloring composition for forming colored spacer, cured product, colored spacer, image display device |
| JP2017203899A (en) * | 2016-05-12 | 2017-11-16 | Dic株式会社 | Organic pigment composition for color filter, and color filter |
| JP7374985B2 (en) | 2019-02-28 | 2023-11-07 | 住友化学株式会社 | Cyan colored curable composition |
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| JP5621337B2 (en) | 2014-11-12 |
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