CN103998532A - Colored photosensitive composition, color filter and method for producing same, and display device - Google Patents

Colored photosensitive composition, color filter and method for producing same, and display device Download PDF

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Publication number
CN103998532A
CN103998532A CN201280062389.1A CN201280062389A CN103998532A CN 103998532 A CN103998532 A CN 103998532A CN 201280062389 A CN201280062389 A CN 201280062389A CN 103998532 A CN103998532 A CN 103998532A
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China
Prior art keywords
group
coloring photosensitive
pigment
dyestuff
composition
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片山晃男
长田崇一郎
福重裕一
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Fujifilm Corp
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Fujifilm Corp
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Publication of CN103998532A publication Critical patent/CN103998532A/en
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    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
    • C09B29/0029—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom
    • C09B29/0037—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom containing a five-membered heterocyclic ring with two nitrogen atoms
    • 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
    • C09B67/006—Preparation of organic pigments
    • 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
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • 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
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/32—Monoazo dyes prepared by diazotising and coupling from coupling components containing a reactive methylene group
    • C09B29/33—Aceto- or benzoylacetylarylides
    • C09B29/331—Aceto- or benzoylacetylarylides containing acid groups, e.g. COOH, SO3H, PO3H2, OSO3H2, OPO2H2; salts thereof
    • C09B29/334—Heterocyclic arylides, e.g. acetoacetylaminobenzimidazolone
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    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
    • C09B29/3617—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom
    • C09B29/3621—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring
    • C09B29/3626—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring from a pyridine ring containing one or more hydroxyl groups (or = O)
    • C09B29/363—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring from a pyridine ring containing one or more hydroxyl groups (or = O) from diazotized amino carbocyclic rings
    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
    • C09B29/3665—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic ring with two nitrogen atoms
    • C09B29/3669—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic ring with two nitrogen atoms from a pyrimidine ring
    • 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
    • C09B63/00—Lakes
    • C09B63/005—Metal lakes of dyes
    • 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
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0022—Wet grinding of pigments
    • 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
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0022—Wet grinding of pigments
    • C09B67/0023—Wet grinding of pigments of phthalocyanines
    • 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
    • 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
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • 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
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • C09B67/0085—Non common dispersing agents
    • C09B67/009—Non common dispersing agents polymeric dispersing agent
    • 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
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters

Abstract

This colored photosensitive composition contains: (A) a green pigment; (B) a dye having a base skeleton that differs from that of the green pigment; and (C) a polymerizable compound. At least 15 mass% of the dye (B) is adsorbed on the surface of the green pigment (A).

Description

Coloring photosensitive combination, colour filter and manufacture method thereof and display unit
Technical field
The present invention relates to coloring photosensitive combination, colour filter and manufacture method thereof and display unit.
Background technology
One of method of the coloring photosensitive combination using in making the colour filter that liquid crystal indicator, solid-state image pickup (CCD, CMOS etc.) use as preparation, known have a colo(u)rant dispersion method.
This colo(u)rant dispersion method be with making colo(u)rant dispersion in various photosensitive composites and coloring photosensitive combination and the method for making colour filter by photolithography.Owing to forming pattern by photolithography, so the positional precision of the method is high, is the method that is applicable to the colour filter of the large picture of making, fine.When making colour filter by colo(u)rant dispersion legal system, utilize the coating coloring photosensitive combinations such as spin coater, roller coating machine and form and film, by this is filmed, expose, developing forms colored pattern, by repeating to color one by one this operation, obtains thus colour filter.As coloring photosensitive combination, the known green coloring photosensitive composite (reference example is as No. 3387541 communique of Japanese Patent) for colour filter that for example contains phthualocyanine pigment.
In recent years, for the performance requriements of colour filter, become more and more stricter, especially tone, brightness have been subject to attention.
Corresponding to this situation, (reference example is as No. 3387541 communique of Japanese Patent, TOHKEMY 2008-292970 communique, TOHKEMY 2009-86375 communique to have proposed to substitute the technology of pigment in the past with dyestuff.)。But known dye is generally compared with pigment, its poor heat resistance, in order to give full play to the performance of dyestuff, need to further improve.
Therefore, also developed the technology of dyestuff and pigment use.For example proposed to use absorption to have the aqueous inkjet of the pigment of dyestuff to record with black liquid (for example, with reference to Japanese kokai publication hei 9-151344 communique and No. 4167053 communique of Japanese Patent.), but be not the technology that can tolerate colour filter purposes, thereby expect further technological development.In addition, following proposal was also proposed: utilize macromolecule dispersing agent to disperse pigment, make the dispersive composition that comprises the surperficial dyestuff that is not adsorbed in pigment, with this dispersive composition, provide coloring photosensitive combination.(for example, with reference to TOHKEMY 2011-178865 communique.)
Summary of the invention
Invent problem to be solved
In addition, as the method for using pigment and preparation of dyestuff coloring photosensitive combination, can consider the method for the dyestuff of direct mixed powder in the dispersible pigment dispersion that colo(u)rant dispersion is formed.In the method, in the situation that solid component concentration in composition is high, in the situation that for pigment the quality ratio of dyestuff large, if directly the dyestuff of powder is added in dispersible pigment dispersion, in the stirring and dissolving operation after interpolation make dyestuff be dissolved in the process of solvent in the dispersion state of pigment change, exist dispersiveness, the dispersion stabilization of pigment that deteriorated trend occurs.
In addition, with regard to the method, also exist dissolving as the dyestuff of powder to need long-time or dyestuff dissolves completely or dyestuff is not difficult to mix such situation.And then also existence is difficult to the worry of confirming whether dyestuff dissolves, also has obstacle on manufacturing.
Utilize the above-mentioned prepared coloring photosensitive combination of these methods cannot tackle fully that thermotolerance is high, the requirement of the colour filter of the image that can demonstrate high image quality, expectation is improvement further.
The present invention completes in view of above-mentioned condition.That is, problem of the present invention is, the coloring photosensitive combination that can form the pigmented layer that thermotolerance is good, brightness is high, contrast gradient is high when forming the pigmented layer of colour filter etc. is provided.
In addition, problem of the present invention is, the display unit that can demonstrate good image quality of using above-mentioned coloring photosensitive combination colour filter and manufacture method thereof that form, that can demonstrate the image that brightness is high, contrast gradient is high and possessing this colour filter is provided.
For solving the means of problem
Above-mentioned problem of the present invention realizes by following method.
< 1 > coloring photosensitive combination, it comprises (A) veridian, (B) and has the dyestuff of the female skeleton different from above-mentioned veridian and (C) polymerizable compound, and the 15 quality % of above-mentioned (B) dyestuff are adsorbed in the surface of above-mentioned (A) veridian above.
< 2 > are according to the coloring photosensitive combination described in < 1 >, its be included in same system to above-mentioned (A) veridian and above-mentioned (B) dyestuff carry out dispersion treatment and dispersive composition.
< 3 > are according to the coloring photosensitive combination described in < 1 > or < 2 >, wherein, above-mentioned dispersive composition is when the concentration of disperseing above-mentioned (B) dyestuff in the dispersive composition at initial stage being made as to Ci, the concentration of above-mentioned (B) dyestuff in the dispersive composition after disperseing to finish is made as to Cf, meets the dispersive composition of the relation of Ci > Cf.
< 4 > are according to the coloring photosensitive combination described in any one in < 1 >～< 3 >, wherein, above-mentioned (B) dyestuff be by be selected from following general formula (a-1), (a-2), (b) and (c) in the represented compound of at least one general formula.
[changing 1]
General formula (a-1) and (a-2) in, R 1～R 5represent independently of one another hydrogen atom or monovalence substituting group.
[changing 2]
In general formula (b), R 6and R 7the substituting group that represents independently of one another hydrogen atom or 1 valency.R 8represent hydrogen atom, fatty group, aryl, heterocyclic radical, formamyl, carbalkoxy, aryloxy carbonyl, acyl group, alkyl sulphonyl, aryl sulfonyl or sulfamyl.Q represents diazonium composition residue.
The represented pigment of general formula (b) can form polymer more than dipolymer in position arbitrarily.
[changing 3]
In general formula (c), R 9and R 10the substituting group that represents independently of one another hydrogen atom or 1 valency.R 11represent hydrogen atom, fatty group, aryl, heterocyclic radical, formamyl, carbalkoxy, aryloxy carbonyl, acyl group, alkyl sulphonyl, aryl sulfonyl or sulfamyl, A represents diazonium composition residue.
< 5 > are according to the coloring photosensitive combination described in any one in < 1 >～< 4 >, it comprises after above-mentioned (A) veridian and above-mentioned (B) dyestuff ready-mixed, the look material mixture that makes gained disperse and dispersive composition.
< 6 > are according to the coloring photosensitive combination described in any one in < 1 >～< 5 >, and it also contains (D) Photoepolymerizationinitiater initiater.
< 7 > are according to the coloring photosensitive combination described in any one in < 1 >～< 6 >, and it also contains (E) alkali-soluble tackiness agent.
< 8 > colour filter, it uses the coloring photosensitive combination described in any one in < 1 >～< 7 > to make.
The manufacture method of a < 9 > colour filter, it has following operation:
Pigmented layer forms operation, the coloring photosensitive combination described in any one in < 1 >～< 7 > is given on supporter and is formed pigmented layer;
Exposure process is pattern-like by formed pigmented layer exposure; With
Developing procedure, develops and forms colored pattern the pigmented layer after exposure.
< 10 > display unit, the colour filter that it possesses the colour filter described in < 8 > or makes by the manufacture method described in < 9 >.
The manufacture method of a < 11 > coloring photosensitive combination, wherein, the dyestuff that makes (A) veridian and (B) have the female skeleton different from above-mentioned veridian disperses and prepares dispersive composition, with above-mentioned dispersive composition, prepares coloring photosensitive combination.
The manufacture method of a < 12 > coloring photosensitive combination, wherein, make (A) veridian and (B) there is the dyestuff mixing of the female skeleton different from above-mentioned veridian and prepare look material composition, above-mentioned look material composition disperseed and prepare dispersive composition, with above-mentioned dispersive composition, preparing coloring photosensitive combination.
In the present invention, can infer: by as tinting material, used veridian and dyestuff (thering is the female skeleton different from pigment), in a part for the surface adsorption dyestuff of veridian, by dye molecule, covered thus the surface of veridian.Can think: dye adsorption in pigment by making, thereby dyestuff is adhered in surface of pigments, therefore can suppress the molecular motion of dyestuff, thus, even if be heated, also can suppress the decomposition of dyestuff, and can think: the pigmented layer forming for using coloring photosensitive combination of the present invention, even if heat, also can suppress variable color.On the other hand; veridian is covered by dyestuff; therefore; can infer: even if veridian becomes particulate because disperseing to wait; the dyestuff covering also plays a role as protective colloid; the dispersion state of pigment is stably kept, can improve thus veridian dispersion stabilization, contrast gradient etc. is uprised.
With regard to the method for mixing colouring agent in dispersible pigment dispersion (dyestuff powder or be dissolved in the dye solution forming in organic solvent), generally speaking, dyestuff is not adsorbed in pigment, even or adsorb, adsorption rate is also little.On the other hand, previously prepared directly veridian and dyestuff dispersions and dispersive composition or comprise veridian and the look material mixture of dyestuff, the dispersive composition obtaining with this look material mixture is disperseed is prepared coloring photosensitive combination, obtain thus coloring photosensitive combination of the present invention, with regard to painted photosensitive composition of the present invention, can infer that therefore, the thermotolerance of the pigmented layer of gained is high and can obtain high-contrast because the adsorption rate of dyestuff to surface of pigments becomes greatly.
Invention effect
According to the present invention, can provide the coloring photosensitive combination that can form the pigmented layer that thermotolerance is good, brightness is high and contrast gradient is high when forming the pigmented layer of colour filter etc.
In addition, according to the present invention, can provide the display unit that can demonstrate good image quality of using above-mentioned coloring photosensitive combination colour filter and manufacture method thereof that form, that can demonstrate the image that brightness is high, contrast gradient is high and possessing this colour filter.
Accompanying drawing explanation
Fig. 1 is the main electrode of making in the mensuration of the specific inductivity of embodiment and the concise and to the point figure of guard electrode.
Embodiment
Coloring photosensitive combination of the present invention is characterised in that, comprises the dyestuff that (A) veridian, (B) have the female skeleton different from above-mentioned veridian and (is suitably called below " particular dye ".) and (C) polymerizable compound, and 15 quality % of particular dye are adsorbed in the surface of above-mentioned (A) veridian above.
It should be noted that, more than the 15 quality % that the particular dye in coloring photosensitive combination is particular dye to the surperficial adsorption rate of veridian, be preferably 20 quality % more than.For the higher limit of adsorptive capacity, from purport of the present invention, more high better, if but with dyestuff, surface of pigments is too covered, there is the possibility of the absorption that hinders dispersion agent, therefore, be actually below 90 quality %.
In addition, in this manual, "～" represents the scope below the value of above and its upper limit of the value of its lower limit.In addition, for the statement of the group in this specification sheets, describe replacement and unsubstituted statement and comprise not thering is substituent situation and there is substituent situation.
And then in this manual, " the total solids composition of coloring photosensitive combination " refer to, from form the total composition of coloring photosensitive combination, remove the total of composition residual after organic solvent.
And then, in the present invention, adsorption rate for from dyestuff to surface of pigments, utilize ultracentrifugation separating machine (Hitachi's work machine (strain) system) to carry out centrifugal treating with 50000rpm dispersive composition, the supernatant liquor that collection comprises free composition, with HPLC, the amount of dye in the supernatant liquor of gained is measured, be defined as the dye adsorption rate being obtained by following formula, with %, represent.
[several 1]
< coloring photosensitive combination >
Below, for the essential component and any composition that form coloring photosensitive combination of the present invention, describe.
Coloring photosensitive combination of the present invention by (A) veridian, (B) particular dye and (C) polymerizable compound as essential component.
((A) veridian)
In coloring photosensitive combination of the present invention, contain (A) veridian, as this veridian, can use any in green pigment dyestuff, inorganic green pigment, but be preferably green pigment dyestuff.
As green pigment dyestuff, be for example preferably C.I. pigment Green 7,10,36,37 and 58, wherein, be preferably C.I. pigment Green 7,36,37 and 58.
In addition, as the average primary particle diameter of veridian, if consider, be preferably high permeability, the pigment of the little and small size of particles of preferable particle size as far as possible.If particularly also consider disposal, preferably average primary particle diameter is 0.01 μ m～0.3 μ m, the pigment of 0.01 μ m～0.15 μ m more preferably.If particle diameter is in above-mentioned scope, transmitance is high, colour characteristics is good, and is effective for the colour filter of formation high-contrast.
For average primary particle diameter, utilize SEM or TEM to observe, the part that cohesion does not occur at particle is measured 100 size of particles, calculates mean value, thereby obtains average primary particle diameter.
Coloring photosensitive combination of the present invention is as required in order to mix colours etc., also can and with pigment dyestuff, mineral dye beyond veridian.
As can and the veridian of use beyond pigment, can list for example following pigment dyestuff.But, be not limited in the present invention these pigment dyestuffs.
C.I. Pigment red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,
C.I. Pigment Yellow 73 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214
C.I. pigment orange 2,5,13,16,17:1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73
C.I. pigment blue 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,60,64,66,79,79 Cl substituting group is changed into the pigment, 80 that OH forms
C.I. pigment violet 1,19,23,27,32,37,42
C.I. pigment brown 25,28
C.I. Pigment black 1
As the pigment dyestuff that can preferably use in these, can list following pigment dyestuff.
C.I. Pigment Yellow 73 11,24,108,109,110,138,139,150,151,154,167,180,185
C.I. pigment orange 36,71
C.I. pigment red 122,150,171,175,177,209,224,242,254,255,264
C.I. pigment Blue 15: 1,15:3,15:6,16,22,60,66
C.I. pigment violet 19,23,32
C.I. Pigment black 1
In addition, as mineral dye, can list the metallic compound representing with metal oxide, metallic complex salt etc., specifically, can enumerate tap a blast furnace, the metal oxide of cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony etc. and the composite oxides of above-mentioned metal.
((B) particular dye)
Coloring photosensitive combination of the present invention comprises the dyestuff (=particular dye) with the female skeleton different from (A) veridian.
Described female skeleton refers to the structural portion of the structure of dyestuff and tone being given to feature, can list for example phthalocyanine, methylene pyrrole, the such structure of anthraquinone.
As particular dye, so long as there is the dyestuff of the female skeleton different from above-mentioned veridian, just be not particularly limited, as chemical structure, can use the dyestuffs such as methylene pyrrole class, pyrazoles azo, anilino azo, triphenylmethane, Anthraquinones, anthrapyridone (anthrapyridone) class, benzal base class, oxonols class, Pyrazolotriazole azo, pyridone azo, cyanine class, phenothiazines, pyrrolo-pyrazoles azomethine class, xanthene class, phthalocyanines, benzo pyran, indigo class.
As these concrete examples, it is for example Japanese kokai publication sho 64-90403 communique, Japanese kokai publication sho 64-91102 communique, Japanese kokai publication hei 1-94301 communique, Japanese kokai publication hei 6-11614 communique, Japan spy steps on No. 2592207, United States Patent (USP) the 4th, 808, No. 501 specification sheetss, United States Patent (USP) the 5th, 667, No. 920 specification sheetss, United States Patent (USP) the 5th, 059, No. 500 specification sheets, Japanese kokai publication hei 5-333207 communique, Japanese kokai publication hei 6-35183 communique, Japanese kokai publication hei 6-51115 communique, Japanese kokai publication hei 6-194828 communique, Japanese kokai publication hei 8-211599 communique, Japanese kokai publication hei 4-249549 communique, Japanese kokai publication hei 10-123316 communique, Japanese kokai publication hei 11-302283 communique, Japanese kokai publication hei 7-286107 communique, TOHKEMY 2001-4823 communique, Japanese kokai publication hei 8-15522 communique, Japanese kokai publication hei 8-29771 communique, Japanese kokai publication hei 8-146215 communique, Japanese kokai publication hei 11-343437 communique, Japanese kokai publication hei 8-62416 communique, TOHKEMY 2002-14220 communique, TOHKEMY 2002-14221 communique, TOHKEMY 2002-14222 communique, TOHKEMY 2002-14223 communique, Japanese kokai publication hei 8-302224 communique, Japanese kokai publication hei 8-73758 communique, Japanese kokai publication hei 8-179120 communique, the pigment of recording in Japanese kokai publication hei 8-151531 communique etc.
In addition, as the color of particular dye, preferably present yellow.
(preferred particular dye)
In these particular dye, Pyrazolotriazole methine dyes comprises one or more Pyrazolotriazole rings in molecule, and preferably each Pyrazolotriazole ring is across methine chain and comprise and amount to 2 Pyrazolotriazole rings.In addition, be also preferably the form with the methine chain being formed by odd number methyne.From the viewpoint of the color reproduction as object of the present invention, preferably the quantity of methyne is 1.Specifically, be following general formula (a-1) and (a-2) represented compound.
As preferred particular dye in coloring photosensitive combination of the present invention, from the viewpoint of color reproduction and brightness, be preferably and be selected from following general formula (a-1), (a-2), (b) and (c) at least one in represented compound.
Below, for general formula (a-1), (a-2), (b) and (c) represented compound at length describe.
[changing 4]
General formula (a-1) and (a-2) in, R 1～R 5represent independently of one another hydrogen atom or monovalence substituting group.
As R 1～R 5represented monovalence substituting group; specifically, can list alkyl, aryl, perfluoroalkyl carbonyl, alkyl sulphonyl, thiazolinyl alkylsulfonyl, aryl sulfonyl, heterocycle alkylsulfonyl, sulfamyl, alkylsulfamoyl group, ammonia aryl sulfonyl or heterocyclic sulfonamides base etc.
These each groups also can have substituting group, R 1～R 5the scope that the represented substituent total carbon atom number of each monovalence is 1～40, be preferably 3～25 scope.If be made as this scope, can obtain the good and high coloring photosensitive combination of brightness of the storage stability of coloring photosensitive combination.
Especially general formula (a-1) and (a-2) represented compound be preferably following form.
That is, be R 1, R 2alkyl, R for straight or branched 4, R 5for alkyl or aryl, R 3form for hydrogen atom, alkyl or aryl.
Below, general formula of the present invention (a-1) and (a-2) concrete example of represented Pyrazolotriazole methine dyes are shown, but the present invention is not limited thereto.
[changing 5]
[changing 6]
[changing 7]
[changing 8]
In general formula (b), R 6and R 7represent independently of one another hydrogen atom or monovalence substituting group.R 8represent hydrogen atom, fatty group, aryl, heterocyclic radical, formamyl, carbalkoxy, aryloxy carbonyl, acyl group, alkyl sulphonyl, aryl sulfonyl or sulfamyl.Q represents diazonium composition residue.The represented pigment of general formula (b) can form polymer more than dipolymer in position arbitrarily.
As R 6and R 7represented monovalence substituting group, specifically, represent independently of one another halogen atom, fatty group, aryl, heterocyclic radical, cyano group, carboxyl, formamyl, aliphatics oxygen base carbonyl, aryloxy carbonyl, acyl group, hydroxyl, aliphatics oxygen base, aryloxy, acyloxy, carbamoyloxy, heterocyclic oxy group, amino, aliphatics is amino, arylamino, heterocyclic amino group, acyl amino, carbamyl is amino, sulfamyl is amino, aliphatics oxygen base carbonylamino, aryloxy carbonylamino, aliphatics sulfuryl amino, arlysulfonylamino, nitro, aliphatics sulfenyl, artyl sulfo, aliphatics alkylsulfonyl, aryl sulfonyl, sulfamyl, sulfo group, imide, or heterocycle sulfenyl.In these; from giving deliquescent viewpoint, be mainly preferably fatty group, aryl, heterocyclic radical, cyano group, formamyl, aliphatics oxygen base carbonyl, aryloxy carbonyl, acyl group, aliphatics oxygen base, aryloxy, aliphatics amino or arylamino.
Above-mentioned each group can also be substituted, R 1～R 5the scope that the represented substituent total carbon atom number of each monovalence is 1～40, be preferably 3～25 scope.By being made as this scope, thereby can obtain the good and high coloring photosensitive combination of brightness of the storage stability of coloring photosensitive combination.
R 6～R 8represented aliphatic group can have substituting group, can be saturated, can be also undersaturated, can also be ring-type.Specifically, can list such as alkyl, substituted alkyl, thiazolinyl, substituted alkenyl, alkynyl, substituted alkynyl, aralkyl and substituted aralkyl etc.The total carbon atom number of aliphatic group is preferably 1～30, more preferably 1～16.As the concrete example of aliphatic group, can list such as methyl, ethyl, butyl, sec.-propyl, the tertiary butyl, hydroxyethyl, methoxy ethyl, cyanoethyl, trifluoromethyl, 3-sulfo group propyl group, 4-sulfo group butyl, cyclohexyl, benzyl, 2-styroyl, vinyl and allyl group etc.
R 6～R 8represented aryl can have substituting group, and total carbon atom number is preferably 6～30 aryl, 6～16 aryl more preferably.Specifically, can list such as phenyl, 4-tolyl, 4-p-methoxy-phenyl, 2-chloro-phenyl-, 3-(3-sulfo group propyl group is amino) phenyl, 4-sulfamyl, 4-ethoxyethyl group sulfamyl and 3-formyl-dimethylamino etc.
As R 6～R 8represented heterocyclic radical, can be saturated, also can be undersaturated, can list and comprise following aromatic heterocycle and comprise any the heteroatomic heterocyclic radical in the heteroatomss such as nitrogen-atoms, sulphur atom, Sauerstoffatom in ring, can also there is substituting group, the heterocyclic radical that preferably total carbon atom number is 1～30, the heterocyclic radical that more preferably total carbon atom number is 1～15.Specifically, can list such as 2-pyridine, 2-thienyl, 2-thiazolyl, 2-[4-morpholinodithio base, 2-benzoxazolyl and 2-furyl etc.
R 6～R 8represented formamyl can have substituting group, is preferably the formamyl of total carbon atom number 1～30, more preferably the formamyl of carbonatoms 1～16.Specifically, can list such as methylamino formyl radical, formyl-dimethylamino, phenyl amino formyl and N-methyl-N-phenyl amino formyl radical etc.
R 6～R 8represented aliphatics oxygen base carbonyl can have substituting group, can be saturated, can be also undersaturated, can also be ring-type, the aliphatics oxygen base carbonyl that preferably total carbon atom number is 2～30, further preferably total carbon atom number is 2～16 aliphatics oxygen base carbonyls.Specifically, can list such as methoxycarbonyl, ethoxycarbonyl and 2-methoxyl group ethoxycarbonyl etc.
R 6～R 8represented aryloxy carbonyl can have substituting group, the aryloxy carbonyl that preferably total carbon atom number is 7～30, the aryloxy carbonyl that more preferably carbonatoms is 7～16.Specifically, can list such as carbobenzoxy, 4-methylenedioxy phenoxy carbonyl and 3-chlorine carbobenzoxy etc.
R 6～R 8in represented acyl group, comprise aliphatics carbonyl, aryl carbonyl and heterocycle carbonyl, be preferably total carbon atom number and be 1～30 form, the form that more preferably total carbon atom number is 1～16.Specifically, can list such as ethanoyl, methoxyl group ethanoyl, thiophene acyl group (thienoyl) and benzoyl etc.
R 6～R 8represented aliphatics alkylsulfonyl can have substituting group, can be saturated, can be also undersaturated, can also be ring-type, is preferably total carbon atom number and is 1～30 form, the form that more preferably total carbon atom number is 1～16.Specifically, can list such as methane sulfonyl, methoxyl group methane alkylsulfonyl and Ethoxyethane alkylsulfonyl etc.
R 6～R 8represented aryl sulfonyl can have substituting group, is preferably the mode of total carbon atom number 6～30, the mode of total carbon atom number 6～18 more preferably.Specifically, can list such as benzenesulfonyl and tosyl group etc.
R 6～R 8represented sulfamyl can have substituting group, is preferably the mode of total carbon atom number 0～30, the mode of total carbon atom number 0～16 more preferably.Specifically, can list such as sulfamyl, dimethylamino alkylsulfonyl and two-(2-hydroxyethyl) sulfamyl etc.
R 6～R 8represented imide can have substituting group, is preferably the imide of 5～6 rings.In addition, be preferably the mode that the total carbon atom number of imide is 4～30, the mode that more preferably total carbon atom number of imide is 4～20.Specifically, can list such as succsinic acid imide and phthalic acid imides base etc.
The represented diazonium composition residue of Q refers to diazonium composition " B-NH 2" residue.Particularly, from the aspect of the colorrendering quality as target, preferably Q is aryl or aromatic heterocycle.
Here, aromatic heterocycle is in ring, to comprise any the aromatic ring in the heteroatomss such as nitrogen-atoms, sulphur atom, Sauerstoffatom, is preferably 5～6 rings.As the carbonatoms of aromatic heterocycle, be preferably 1～25, more preferably 1～15.As heteroaromatic, specifically, can list pyrazolyl, 1,2,4-triazolyl, isothiazolyl, benzisothiazole base, thiazolyl, benzothiazolyl, oxazolyl, 1,2,4-thiadiazolyl group etc.
In particular, the represented compound of general formula (b) is preferably following mode.
That is, be R 6cyano group, aliphatics oxygen base carbonyl or formamyl, R 7fatty group, R 8be fatty group, acyl group, aryl, aliphatics carbonyl, aliphatics alkylsulfonyl or aryl sulfonyl, Q is the mode of aryl.
Below, the concrete example of the represented pyridone azo dyes of general formula of the present invention (b) is shown, but the present invention is not limited thereto.
[changing 9]
[changing 10]
[changing 11]
[changing 12]
In general formula (c), R 9and R 10represent independently of one another hydrogen atom or monovalence substituting group.R 11represent hydrogen atom, fatty group, aryl, heterocyclic radical, formamyl, carbalkoxy, aryloxy carbonyl, acyl group, alkyl sulphonyl, aryl sulfonyl or sulfamyl, A represents diazonium composition residue.
As R 9and R 10represented monovalence substituting group, specifically, represent independently of one another halogen atom, fatty group, aryl, heterocyclic radical, cyano group, carboxyl, formamyl, aliphatics oxygen base carbonyl, aryloxy carbonyl, acyl group, hydroxyl, aliphatics oxygen base, aryloxy, acyloxy, carbamoyloxy, heterocyclic oxy group, amino, aliphatics is amino, arylamino, heterocyclic amino group, acyl amino, carbamyl is amino, sulfamyl is amino, aliphatics oxygen base carbonylamino, aryloxy carbonylamino, aliphatics sulfuryl amino, arlysulfonylamino, nitro, aliphatics sulfenyl, artyl sulfo, aliphatics alkylsulfonyl, aryl sulfonyl, sulfamyl, sulfo group, imide, or heterocycle sulfenyl, from giving deliquescent viewpoint, mainly be preferably fatty group, aryl, heterocyclic radical, cyano group, formamyl, aliphatics oxygen base carbonyl, aryloxy carbonyl, acyl group, aliphatics oxygen base, aryloxy, aliphatics is amino, arylamino.
Above-mentioned each group can further be substituted, R 1～R 5the scope that the represented substituent total carbon atom number of each monovalence is 1～40, is preferably 3～25 scope.By being made as this scope, thereby make the storage stability of coloring photosensitive combination good and can obtain the high coloring photosensitive combination of brightness.
R 9～R 11represented fatty group can have substituting group, can be saturated, can be also undersaturated, can also be ring-type.Specifically, can list such as alkyl, substituted alkyl, thiazolinyl, substituted alkenyl, alkynyl, substituted alkynyl, aralkyl and substituted aralkyl etc.The total carbon atom number of fatty group is preferably 1～30, more preferably 1～16.As the concrete example of fatty group, can list such as methyl, ethyl, butyl, sec.-propyl, the tertiary butyl, hydroxyethyl, methoxy ethyl, cyano ethyl, trifluoromethyl, 3-sulfo group propyl group, 4-sulfo group butyl, cyclohexyl, benzyl, 2-styroyl, vinyl and allyl group etc.
The represented diazonium composition residue of A refers to diazonium composition " B-NH 2" residue.Especially from the aspect of the colorrendering quality as target, A is preferably aryl or aromatic heterocycle.
Here, aromatic heterocycle is in ring, to comprise any the aromatic ring in the heteroatomss such as nitrogen-atoms, sulphur atom, Sauerstoffatom, is preferably 5～6 rings.As the carbonatoms of aromatic heterocycle, be preferably 1～25, more preferably 1～15.As heteroaromatic, specifically, can list pyrazolyl, 1,2,4-triazolyl, isothiazolyl, benzisothiazole base, thiazolyl, benzothiazolyl, oxazolyl, 1,2,4-thiadiazolyl group etc.
Below, the concrete example of the represented dyestuff of general formula of the present invention (c) is shown, but the present invention is not limited to this.
[changing 13]
(dispersive composition)
Coloring photosensitive combination of the present invention preferably comprises dispersive composition.As the method that makes coloring photosensitive combination of the present invention, for the dispersive composition preferably containing, describe.
In coloring photosensitive combination of the present invention, (B) 15 quality % of particular dye are adsorbed in the surface of (A) veridian above.By (B) particular dye is set as to above-mentioned scope to the surperficial adsorption rate of (A) veridian, thereby make the thermotolerance of the pigmented layer that made by coloring photosensitive combination of the present invention good and can demonstrate high-contrast.The method that makes particular dye be adsorbed in veridian can be any method, but the preferred previously prepared dispersive composition that comprises veridian and particular dye.
(look material composition)
In addition, in order to obtain this dispersive composition, preferably veridian and particular dye are carried out ready-mixed and make look material composition, then in same system, carry out dispersion treatment, thereby make dispersive composition.That is, preferably make in advance the slurry (look material composition) that pigment and dyestuff, the solvent using as required, dispersion agent, additive, abrasive etc. are mixed, then its disposable puts in dispersion system is carried out to dispersion treatment.Thereby, in the present invention, carry out salt grinding described later (salt milling) before or utilizing dispersion machine carry out dispersion treatment before and utilizing dispersion machine carry out multistage in each stage during dispersion treatment before in arbitrary situation under, the situation that the slurry all in advance mixing colouring agent being formed carries out dispersion treatment is called ready-mixed.It should be noted that, above-mentioned " in same system " refer to, in same diverting device and in same dispersion batch, carries out dispersion treatment.
Method as ready-mixed, can select the whole bag of tricks, can use (F) described later organic solvent that the particular dye of veridian and solid is mixed, or can dissolve by veridian with in aftermentioned (F) organic solvent the dye solution mixing that particular dye forms.
As the method for mixing, it can be the method for using common stirrer etc., can be use two roller roller mills, three roller roller mills, ball mill, Tron grinding machine (ト ロ Application ミ Le), decollator, kneader, be total to the forcing machine of kneader, clarifixator, mixing machine, single screw rod or twin screw etc., give strong shearing force on one side, carry out mixing method on one side, from making the adsorption rate of dyestuff become large viewpoint, preferably carry out mixing method.
(salt grinding)
Pigment condenses conventionally, in order to be pulverized before it is disperseed, preferably as pigment miniaturization processing, carries out salt milled processed described later.Now, as the blending means of dyestuff and pigment, also can when salt milled processed, with solution shape or solid state, add particular dye, thereby prepare above-mentioned look material composition.
The miniaturization of pigment is by realizing via following operation (salt grinding), that is, pigment, water-miscible organic solvent, together with water-soluble inorganic salt, are prepared to high viscosity liquid composition, use the stress applications such as case of wet attrition device, thus the operation grinding (salt grinding).Now, as required, can with solution shape or solid state, add particular dye together with pigment, thereby obtain look material mixture.
As the water-miscible organic solvent of the miniaturization operation for pigment, can list methyl alcohol, ethanol, Virahol, n-propyl alcohol, isopropylcarbinol, propyl carbinol, ethylene glycol, glycol ether, diglycol monotertiary methyl ether, carbiphene, diglycol monotertiary butyl ether, propylene glycol, propylene glycol monomethyl ether etc.
In addition, can use water-soluble low or do not there are water miscible other solvents, such as using benzene,toluene,xylene, ethylbenzene, chlorobenzene, oil of mirbane, aniline, pyridine, quinoline, tetrahydrofuran (THF), diox, ethyl acetate, isopropyl acetate, butylacetate, hexane, heptane, octane, nonane, decane, undecane, dodecane, hexanaphthene, methylcyclohexane, halohydrocarbon, acetone, methylethylketone, mibk, pimelinketone, dimethyl formamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone etc.
The solvent using in the miniaturization operation of pigment can, only for a kind of, also can mix use two or more as required.
The water-soluble inorganic salt using in miniaturization operation as pigment, can list sodium-chlor, Repone K, calcium chloride, bariumchloride, sodium sulfate etc.
The usage quantity of the water-soluble inorganic salt in miniaturization operation is 1～50 quality times of pigment, although have the effect of grinding when consumption is many, aspect productivity, preferred amount is 1～10 quality times.In addition, preferably using moisture is the inorganic salts below 1%.
The usage quantity of the water-miscible organic solvent in miniaturization operation with respect to pigment 100 mass parts be 50 mass parts～300 mass parts scope, be preferably the scope of 100 mass parts～200 mass parts.
Operating condition for the case of wet attrition device in the miniaturization operation of pigment, be not particularly limited, in order effectively to carry out grinding based on crushing medium, with regard to operating condition with regard to device during for kneader, the rotating speed of the cutter in device is preferably 10～200rpm, in addition, and when the speed ratio of twin screw is relatively large, grind effect large, thereby preferably.Be preferably 1 hour～8 hours runtime together with dry type grinding time, and the interior temperature of device is preferably 50～150 ℃.In addition, as the water-soluble inorganic salt of crushing medium preferably its grinding particle size be 5～50 μ m, size distribution is narrow, and is spherical.
Veridian in look material composition and the ratio of components of particular dye are preferably 1:1～10:1,2:1～10:1 more preferably in mass conversion.By being made as this scope, can make more than particular dye reaches 15 quality % of particular dye to the surperficial adsorption rate of veridian, can give play to effect of the present invention.
In addition, the summation of the pigment in look material composition and dyestuff is preferably 10 quality %～60 quality % with respect to the total mass of look material composition.
(manufacture method of dispersive composition)
Dispersive composition is to use (F) described later organic solvent that veridian and particular dye are disperseed and obtained.Now, preferably with above-mentioned look material composition, substitute veridian and particular dye.
And then, in dispersive composition, can add dispersion agent described later, pigment derivative and other compositions, can also add veridian pigment in addition.
Dispersive composition in the present invention is can be by above-mentioned each composition disposable or add in batches, such as by using the dispersion machines such as longitudinal type or horizontal molding sand turbine, needle mill, slit shredder (slit mill), ultrasonic dispersing machine, utilize the pearl being formed by glass, zirconium white etc. of 0.01mm～1mm particle diameter carry out micro-dispersion treatment and make.
First, veridian and particular dye are not carried out to ready-mixed, while disperseing not via look material composition in the situation that, preferably in the dispersion of pigment, dyestuff is put in diverting device, particularly preferably in the initial stage of disperseing, drop into.In this case, if disposable, dyestuff is fed into enoughly, easily forms dough, thus not preferred, therefore, preferably drop into gradually lentamente.
In addition, in the situation that particular dye is added in diverting device, can add the dye solution of particular dye, as long as be feasible at aspects such as solvabilities, just preferably under solid state, drop into.Even if the situation for adding with the form of dye solution, is also preferably the high as far as possible state of dye strength after interpolation.This is due to following reason, that is, the dye strength in the system of dispersive composition is higher state, promotes all the more the absorption to pigment, and result easily realizes the stable on heating effect of raising of the present invention.From this viewpoint, the in the situation that the interpolation of dyestuff preferably being carried out, disperseed in the utilization multistage described later at the dispersion initial stage (while disperseing to start), preferably at the dispersion initial stage of first stage, carry out.
As the method for the preparation of dye solution, can stir to dropping into organic solvent in dyestuff, the aspect from being easy to dissolve, is preferably the method that drops into the dyestuff of powder in the organic solvent stirring.The input method of dyestuff can, by the disposable input of total amount, can also drop in batches.
Method as the dissolving of dyestuff, can use bar-shaped object to stir the solution that comprises above-mentioned dyestuff and organic solvent, also can use magnetic stirrer to stir, in addition, can utilize the stirrer that makes propeller-like with constant speed and towards the common stirrer of a direction rotation, to dissolve in container.In addition, can utilize stirrer, dissolver etc. to apply shearing force dissolves.Can dissolve heatedly as required.
In addition, before the differential that utilizes pearl is loose, also can use two roller roller mills, three roller roller mills, ball mill, Tron grinding machine, decollator, kneader, be total to the forcing machine of kneader, clarifixator, mixing machine, single screw rod or twin screw etc., give strong shearing force on one side, Yi Bian carry out mixing processing.
It should be noted that, for detailed content mixing, that disperse, be recorded in T.C.Patton work " Paint Flow and Pigment Dispersion " (, John Wiley and Sons company periodical in 1964) etc., also can use the method for recording at this in the present invention.
And then, in dispersion, following method is also preferred mode,, solids component in the dispersive composition at dispersion initial stage is set as disperseing than the solids component highland in final dispersive composition, at the time point of the terminal approach disperseing, the composition with organic solvent, other macromolecular compound etc. except coloring components dilutes.
For the preparation method of this dispersive composition, be typically divided into that rough segmentation is loose and accurate to disperse these two stages or be further divided into a plurality of stages to implement to disperse be also preferred mode.
; preferably; the concentration of the particular dye in the dispersive composition after the concentration of the particular dye in the dispersive composition at dispersion initial stage is made as to Ci, dispersion being finished is (while carrying out concentration adjustment after disperseing to finish; while the concentration of the particular dye after concentration is adjusted) being made as Cf; to meet the mode of the relation of Ci > Cf; implement two steps more than stage, thereby disperse.
In the situation that implementing ready-mixed, Ci is the concentration of the particular dye in ready-mixed, in the situation that not implementing ready-mixed, in two stages dispersions or the dispersion of a plurality of stage, the concentration of the particular dye in the dispersion (in disperseing two stages for rough segmentation is fallen apart) in the 1st stage, the in the situation that of dispersion with one section not carrying out ready-mixed, be the concentration of disperseing the particular dye of beginning time point.In addition, Cf is the concentration of the particular dye in the terminal stage (disperseing for accurate in disperseing 2 stages) of disperseing, and the in the situation that of carrying out concentration adjustment after dispersion, the concentration of the particular dye after concentration adjustment is equivalent to above-mentioned Cf.
Thus, not only under high density, dyestuff is easier to be adsorbed in surface of pigments, and when carrying out colo(u)rant dispersion, dyestuff sucks lentamente in surface of pigments, thereby disperses when reaching adsorption equilibrium, therefore, can improve adsorption rate.If Ci=Cf, even if finally carry out above-mentioned concentration adjustment, but be just the state that dye strength is low during from input, therefore, reach adsorption equilibrium and need the time, and according to circumstances different, sometimes exist because the absorption causing because of dispersion agent or additive hinders the possibility that can cause final adsorption rate step-down, therefore not preferred.
In addition, according to the method, disperseing the solids component at initial stage large, therefore, dispersion liquid is applied to high shear force, utilize this shearing to be easy to carry out the dispersion of pigment, can obtain polymolecularity, is preferred mode.
In addition, as Ci, be preferably set to 1.1 times～10 times of Cf, more preferably 1.1～5 times.By being made as this scope, thereby easily obtain having the dispersive composition of polymolecularity.
(other compositions that dispersive composition is contained)
Below, for the dispersion agent preferably comprising in dispersive composition of the present invention, pigment derivative, describe.
(dispersion agent)
As dispersion agent, specifically, can use multiple compounds, can list positively charged ions such as organosiloxane polymer KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), (methyl) acrylic acid series (being total to) polymer P oly Flow No.75, No.90, No.95 (common prosperity society chemical industry (strain) system), W001 (abundant business (strain) society system) is tensio-active agent; The nonionics such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyl 10 oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylplenyl ether, polyethylene glycol dilaurate, polyglycol distearate, sorbitan fatty acid esters are tensio-active agent; The negatively charged ion such as W004, W005, W017 (abundant business (strain) society system) are tensio-active agent; The macromolecule dispersing agents such as EFKA-46, EFKA-47, EFKA-47EA, EFKA polymkeric substance 100, EFKA polymkeric substance 400, EFKA polymkeric substance 401, EFKA polymkeric substance 450 (being Ciba Specialty Chemicals company system), DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15, DISPERSE AID 9100 (being SAN NOPCO company system); The various SOLSPERSE dispersion agents (Japanese Lubrizol (strain) society system) such as SOLSPERSE 3000,5000,9000,12000,13240,13940,17000,24000,26000,28000; ADEKA PluronicL31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (rising sun electrification (strain) system) and Ionetto S-20 (Sanyo changes into (strain) system), Disperbyk101,103,106,108,109,111,112,116,130,140,142,162,163,164,166,167,170,171,174,176,180,182,2000,2001,2050,2150 (BYK-CHEMIE company systems).
-macromolecule dispersing agent-
Dispersive composition of the present invention preferably contains the macromolecule dispersing agent of following record as dispersion agent.
Dispersive composition of the present invention preferably contains following macromolecular compound and (is sometimes called below " particular polymers ".), described macromolecular compound has at least one in following general formula (II) or the represented structural unit of following general formula (III) and has at least one in the structural unit of acidic group.
[changing 14]
Above-mentioned general formula (II) and (III) in, R 1～R 6the organic group that represents independently of one another hydrogen atom or monovalence, X 1and X 2expression-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene independently of one another, L 1and L 2the organic concatenating group that represents independently of one another singly-bound or divalence, A 1and A 2the organic radical that represents independently of one another monovalence, m and n represent 2～8 integer independently of one another, p and q represent 1～100 integer independently of one another.
(general formula (II) or the represented structural unit of general formula (III))
Above-mentioned general formula (II) or the represented structural unit of general formula (III) are comprised in (A) macromolecular compound as repeating unit.
In above-mentioned general formula (II) and general formula (III), R 1～R 6the organic group that represents independently of one another hydrogen atom or monovalence.As the organic group of monovalence, be preferably and replace or unsubstituted alkyl.As alkyl, be preferably the alkyl of carbonatoms 1～12, more preferably carbonatoms 1～8 alkyl, be particularly preferably the alkyl of carbonatoms 1～4.
At alkyl, have in substituent situation, as this substituting group, for example can list hydroxyl, alkoxyl group (preferably carbonatoms 1～5, more preferably carbonatoms 1～3.) methoxyl group, oxyethyl group, cyclohexyloxy etc.
As preferred alkyl, specifically, can list for example methyl, ethyl, propyl group, normal-butyl, isobutyl-, the tertiary butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-methoxy ethyl.
As R 1, R 2, R 4, and R 5, be preferably hydrogen atom, as R 3and R 6, from the viewpoint of the adsorption efficiency to surface of pigments, most preferably be hydrogen atom or methyl.
X 1and X 2expression-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene independently of one another.Wherein, the viewpoint from the adsorptivity to pigment, is preferably-C (=O) O-,-CONH-, phenylene, most preferably is-C (=O) O-.
L 1and L 2the organic concatenating group that represents independently of one another singly-bound or divalence.As organic concatenating group of divalence, be preferably replace or unsubstituted alkylidene group, by this alkylidene group and heteroatoms or organic concatenating group of comprising the formed divalence of heteroatomic part-structure.Here, as alkylidene group, be preferably the alkylidene group of carbonatoms 1～12, more preferably carbonatoms 1～8 alkylidene group, be particularly preferably the alkylidene group of carbonatoms 1～4.In addition, as the heteroatoms comprising in heteroatomic part-structure, for example Sauerstoffatom, nitrogen-atoms, sulphur atom be can list, wherein, Sauerstoffatom, nitrogen-atoms are preferably.
As preferred alkylidene group, specifically, can list for example methylene radical, ethylidene, propylidene, trimethylene, tetramethylene.
At alkylidene group, have in substituent situation, as this substituting group, can list such as hydroxyl etc.
Organic concatenating group as divalence, the end of above-mentioned alkylidene group have be selected from-C (=O)-,-OC (=O)-,-NHC (=O)-in heteroatoms or comprise heteroatomic part-structure, Jie is by this heteroatoms or comprise heteroatomic part-structure and link with the Sauerstoffatom of adjacency, aspect the adsorptivity to pigment, organic concatenating group of the divalence obtaining is thus preferred.
A 1and A 2the organic radical that represents independently of one another monovalence.As the organic radical of monovalence, be preferably substituted or non-substituted alkyl or, substituted or non-substituted aryl.
Example as preferred alkyl, can list carbonatoms and be the alkyl of 1～20 straight chain shape, a chain and ring-type, as its concrete example, can list methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl, isopentyl, neo-pentyl, 1-methyl butyl, isohexyl, 2-ethylhexyl, 2-methyl hexyl, cyclohexyl, cyclopentyl, 2-norcamphyl.
As the substituting group of substituted alkyl, can use the group except the nonmetallic atom group of the monovalence after dehydrogenation, as preference, can list halogen atom (F,-Br,-Cl,-I), hydroxyl, alkoxyl group, aryloxy, sulfydryl, alkyl sulfenyl, artyl sulfo, alkyl disulfide group, aryl disulfide group, amino, N-alkylamino, N, N-dialkyl amido, N-arylamino, N, N-ammonia diaryl base, N-alkyl-N-arylamino, acyloxy, carbamoyloxy, N-alkyl carbamoyloxy base, N-arylamino methanoyl, N, N-dialkyl amido methanoyl, N, N-ammonia diaryl base methanoyl, N-alkyl-N-arylamino methanoyl, alkylsulfonyloxy (sulfoxy), aryl-sulfonyl oxygen, acyloxy, acyl mercapto, acyl amino, N-alkyl acyl is amino, N-aryl-acyl is amino, urea groups, N '-alkyl urea groups, N ', N '-dialkyl group urea groups, N '-aryl-ureido, N ', N '-diaryl urea groups, N '-alkyl-N '-aryl-ureido, N-alkyl urea groups, N-aryl-ureido, N '-alkyl-N-alkyl urea groups, N '-alkyl-N-aryl-ureido, N ', N '-dialkyl group-N-alkyl urea groups, N ', N '-dialkyl group-N-aryl-ureido, N '-aryl-N-alkyl urea groups, N '-aryl-N-aryl-ureido, N ', N '-diaryl-N-alkyl urea groups, N ', N '-diaryl-N-aryl-ureido, N '-alkyl-N '-aryl-N-alkyl urea groups, N '-alkyl-N '-aryl-N-aryl-ureido, alkoxycarbonyl amido, aryloxy carbonyl is amino, N-alkyl-N-alkoxycarbonyl amido, N-alkyl-N-aryloxy carbonyl is amino, N-aryl-N-alkoxycarbonyl amido, N-aryl-N-aryloxy carbonyl is amino, formyl radical, acyl group, carboxyl, carbalkoxy, aryloxy carbonyl, formamyl, N-alkyl-carbamoyl, N, N-dialkyl amido formyl radical, N-aryl-amino-carbonyl, N, N-ammonia diaryl base formyl radical, N-alkyl-N-aryl-amino-carbonyl, alkyl sulphinyl, aryl sulfonyl kia, alkyl sulphonyl, aryl sulfonyl, sulfo group (SO 3h) and conjugation base (hereinafter referred to as sulfonic acid foundation (ス Le ホ Na ト)), alkoxyl group alkylsulfonyl, aryloxy sulfonyl, sulfinamoyl (sulfinamoyl group), N-alkyl sulfinamoyl, N, N-dialkyl amino sulfinyl, N-aryl sulfinamoyl, N, N-ammonia diaryl sulfinyl, N-alkyl-N-aryl sulfinamoyl, sulfamyl, N-alkylsulfamoyl group, N, N-dialkyl sulfamine, N-ammonia aryl sulfonyl, N, N-ammonia diaryl alkylsulfonyl, N-alkyl-N-ammonia aryl sulfonyl, phosphonate group (PO 3h 2) and conjugation base (hereinafter referred to as phosphonate radical (phosphonato) base), dialkyl phosphine acidic group (PO 3(alkyl) 2), diaryl phosphonate group (PO 3(aryl) 2), alkylaryl phosphonate group (PO 3(alkyl) (aryl)), monoalkyl-phosphonic acid base (PO 3h (alkyl)) and conjugation base (hereinafter referred to as alkyl phosphonic acid foundation (alkylphosphonato) base), single aryl phosphine acidic group (PO 3h (aryl)) and conjugation base (hereinafter referred to as arylphosphonic acid foundation (arylphosphonato) base), phosphonate group oxygen base (OPO 3h 2) and conjugation base (hereinafter referred to as phosphonic acids foundation oxygen base), dialkyl phosphine acidic group oxygen base (OPO 3(alkyl) 2), diaryl phosphonate group oxygen base (OPO 3(aryl) 2), alkylaryl phosphonate group oxygen base (OPO 3(alkyl) (aryl)), monoalkyl-phosphonic acid base oxygen base (OPO 3h (alkyl)) and conjugation base (hereinafter referred to as alkyl phosphonic acid foundation oxygen base), single aryl phosphine acidic group oxygen base (OPO 3h (aryl)) and conjugation base (hereinafter referred to as arylphosphonic acid foundation oxygen base), cyano group, nitro, aryl, heteroaryl, thiazolinyl, alkynyl, silyl.
As the concrete example of the alkyl in these substituting groups, can enumerate described alkyl, they also can further have substituting group.
As substituting group; aspect from dispersion stabilization; be preferably alkoxyl group, aryloxy, alkyl sulfenyl, artyl sulfo, N, N-dialkyl amido, N, N-ammonia diaryl base, N-alkyl-N-arylamino, acyloxy, aryl, heteroaryl, thiazolinyl, alkynyl, silyl.
As the concrete example of aryl, can list phenyl, xenyl, naphthyl, tolyl, xylyl, base, cumenyl, chloro-phenyl-, bromophenyl, chloromethyl phenyl, hydroxy phenyl, p-methoxy-phenyl, ethoxyl phenenyl, Phenoxyphenyl, acetoxyl group phenyl, benzoyloxy phenyl, methyl thio-phenyl, phenyl thio-phenyl, methylamino phenyl, dimethylaminophenyl, acetylamino phenyl, carboxyl phenyl, methoxycarbonyl phenyl, ethoxyl phenenyl carbonyl, phenyloxycarbonyl phenyl, N-phenyl amino formylphenyl, phenyl, cyano-phenyl, sulfo group phenyl, sulfonic acid foundation phenyl, phosphonate group (phosphono) phenyl, phosphonic acids foundation phenyl etc.
As A 1and A 2viewpoint from dispersion stabilization and developability, be preferably the alkyl of the ring-type of the straight chain shape of carbonatoms 1～20, a chain of carbonatoms 3～20 and carbonatoms 5～20, more preferably the alkyl of the chain of the straight chain shape of carbonatoms 4～15, carbonatoms 4～15 and the ring-type of carbonatoms 6～10, the further preferred alkyl of a chain of the straight chain shape of carbonatoms 6～10, carbonatoms 6～12.
M and n represent 2～8 integer independently of one another.From the viewpoint of dispersion stabilization and developability, m and n are preferably 4～6, most preferably are 5.
P and q represent 1～100 integer independently of one another.The structural unit that p is different, the structural unit that q is different can mix two or more.From the viewpoint of dispersion stabilization and developability, p and q are preferably 5～60, more preferably 5～40, more preferably 5～20.
Particular polymers in the present invention comprises at least one in the represented structural unit of at least one or above-mentioned general formula (III) in the represented structural unit of above-mentioned general formula (II), or comprises at least one in the represented structural unit of at least one and above-mentioned general formula (III) in the represented structural unit of above-mentioned general formula (II).Here, at above-mentioned general formula (II) and (III), following be combined as particularly preferred mode.That is, R 1, R 2, R 4, and R 5be preferably hydrogen atom, R 3and R 6be preferably hydrogen atom or methyl.X 1and X 2be preferably-C (=O) O-.L 1and L 2be preferably end at the alkylidene group of carbonatoms 1～4 have be selected from-C (=O)-,-OC (=O)-,-NHC (=O)-in heteroatoms or comprise heteroatomic part-structure, Jie is by this heteroatoms or comprise heteroatomic part-structure and link with the Sauerstoffatom of adjacency, thereby forms organic concatenating group of divalence.M and n are preferably 5, p and q are preferably 5～20.
As the particular polymers in the present invention, from the aspect of dispersion stabilization, preferably comprise at least one in the represented structural unit of above-mentioned general formula (II).
In addition, as the represented structural unit of above-mentioned general formula (II), the represented structural unit of following general formula (II)-2 more preferably.
[changing 15]
In above-mentioned general formula (II)-2, R 1～R 3organic radical, the La that represents independently of one another hydrogen atom or monovalence represent represent-C of the alkylidene group of carbonatoms 2～10, Lb (=O)-or-NHC (=O)-, A 1the organic group, the m that represent monovalence represent that 2～8 integer, p represent 1～100 integer.
R 1～R 3, A 1detailed and the preferred mode of the organic radical of represented monovalence and m, p is identical with the situation in above-mentioned general formula (II).
La is alkylidene group, the alkylidene group of carbonatoms 2～4 more preferably of carbonatoms 2～8 more preferably.Specifically, can list for example ethylidene, propylidene, trimethylene, tetramethylene.When alkylidene group has substituting group, as this substituting group, can list such as hydroxyl etc.
By following general formula (i), (ii) or (i)-2 represented monomers being carried out to polymerization or copolymerization, the repeating unit as macromolecular compound is imported into respectively for above-mentioned general formula (II), (III) or (II)-2 represented structural units.
[changing 16]
In above-mentioned general formula (i), (ii) and (i)-2, R 1～R 6the organic group, the X that represent independently of one another hydrogen atom or monovalence 1and X 2expression-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene, L independently of one another 1and L 2organic concatenating group, the La that represents independently of one another singly-bound or divalence represent represent-C of the alkylidene group of carbonatoms 2～10, Lb (=O)-or-NHC (=O)-, A 1and A 2the organic radical, m and the n that represent independently of one another monovalence represent that 2～8 integer, p and q represent 1～100 integer independently of one another independently of one another.
R 1～R 6, X 1and X 2, L 1and L 2, A 1and A 2, m and n, p and q and above-mentioned general formula (II), (III) and (II)-2 same meaning.
Below, list the preferred concrete example (monomer (A-1)～(A-24)) of general formula (i), (ii) or (i)-2 represented monomers, but the present invention is not limited thereto.
[changing 17]
[changing 18]
[changing 19]
[changing 20]
[changing 21]
Particular polymers in the present invention comprises above-mentioned general formula (II) or (III) at least a kind of in represented structural unit, can only comprise a kind ofly, also can comprise two or more.
In addition, in particular polymers, above-mentioned general formula (II) or (III) content of represented structural unit are not particularly limited, when the contained entire infrastructure unit of polymkeric substance is made as to 100 quality %, from taking into account the dispersiveness of pigment and the aspect of developability, preferably contain said structure unit 5 quality % above, more preferably contain 30 quality % above, further preferably contain 40 quality %～60 quality %.
(structural unit with acidic group)
Particular polymers in the present invention comprises the structural unit (containing the structural unit of acidic group) with acidic group.The acidic group that contains the structural unit of acidic group plays a role as the adsorption group for pigment or pigment derivative.
Of the present invention, containing in the structural unit of acidic group, as acidic group, be preferably the acidic group below pKa10.As the concrete example of the acidic group below pKa10, can list such as sulfonic group, phosphate, carboxylic acid group, phenylol etc.Wherein, from taking into account the viewpoint of pigment-dispersing and developability, the most applicable use carboxylic acid group.
With regard to of the present invention, containing with regard to the structural unit of acidic group, acidic group can be bonded directly to the main chain of particular polymers, also can be situated between and by coupling chain, is bonded to the main chain of particular polymers.
As by the coupling chain of the main chain of particular polymers and acidic group link, preferably comprise the concatenating group that is selected from the functional group in aromatic nucleus, ether, ester group, amide group, urea groups and/or carbamate groups.Above-mentioned functional group himself demonstrates the adsorptivity to pigment, therefore, can think, containing in the structural unit of acidic group, if above-mentioned functional group is positioned at the position approaching with acidic group, has the effect with respect to the adsorptivity increase of pigment or pigment derivative.
Here, the main chain of particular polymers refers to, the position linking by polymerization when synthetic polymer, for example if by methacrylic ester in addition polymerization and polymkeric substance, refer to the alkylidene group position that methacryloyl position links by polymerization.
In addition, the multiple concatenating group of above-mentioned concatenating group use capable of being combined.Use capable of being combined is such as aromatic nucleus and ether, aromatic nucleus and ester group, aromatic nucleus and urea groups, ether and urea groups, aromatic nucleus and ether and urea groups etc.
At dispersive composition of the present invention, contain titanium black as pigment in the situation that, because titanium is black, there is nitrogen-atoms, so preferably use hydrogen bond functional group as the concatenating group of particular polymers, specifically, preferably use amide group, urea groups, carbamate groups.
In addition, the concatenating group using as the structural unit containing acidic group in the present invention, preferably imports aromatic nucleus.Coupling chain has aromatic nucleus, thus, compares with common alkyl chain etc., can alleviate by steric hindrance the winding of polymkeric substance, and aromatic nucleus becomes and is easy to the outside towards polymkeric substance from main chain portion, therefore, can improve the dispersiveness of pigment.
Here, aromatic nucleus represents to have the structure that the atomic arrangement of π-electron forms circlewise, can use well various phenyl ring, naphthalene nucleus, anthracene nucleus etc. not to comprise heteroatomic ring, pyridine ring, pyrrole ring, furan nucleus, carbazole ring, thiphene ring etc. and comprise heteroatomic ring etc.Wherein, can preferably use phenyl ring, naphthalene nucleus, pyridine ring that versatility is high, can more preferably use phenyl ring, more preferably the represented structure of following formula (2).
[changing 22]
In above-mentioned formula (2), Y represents and the concatenating group of the main chain of particular polymers, and S represents acidic functionality.R represents hydrogen atom, can have substituent alkyl, can have substituent aryl, can have substituent alkoxyl group, can have substituent aryloxy, can have substituent heteroaryl oxygen base, can have substituent alkyl oxy carbonyl, can have substituent aryloxy carbonyl, can have substituent alkylamidoalkyl, can have substituent aryl amido group, halogen radical, nitro.In addition, n represents 0～4 integer, and m represents 1～5 integer.
In above-mentioned formula (2), Y represents the concatenating group with the main chain of particular polymers.Structure as concatenating group, be not particularly limited, but from reducing the viewpoint of the pKa of acidic group, preferably utilize electron attractivity group that phenyl ring and main chain are linked, further preferably utilize ester group, amide group, sulfoamido etc. to link, more preferably utilize ester group to link.
The preferred concrete example of Y is as follows, and Y is not defined as these structures.X represents and the position of the main chain bonding of particular polymers, and Z represents the position with phenyl ring bonding.
[changing 23]
[changing 24]
In above-mentioned formula (2), R represents hydrogen atom, can have substituent alkyl, can have substituent aryl, can have substituent alkoxyl group, can have substituent aryloxy, can have substituent heteroaryl oxygen base, can have substituent alkyl oxy carbonyl, can have substituent aryloxy carbonyl, can have substituent alkylamidoalkyl, can have substituent aryl amido group, halogen radical, nitro.From reducing the viewpoint of the pKa of acidic group, preferably utilize hydrogen atom or electron attractivity group to replace, be preferably hydrogen atom, can there is substituent alkyl oxy carbonyl, can there is substituent aryloxy carbonyl, can there is substituent alkylamidoalkyl, can there is substituent aryl amido group, halogen radical, nitro, carboxyl, be further preferably hydrogen atom, can there is substituent alkyl oxy carbonyl, can there is substituent aryloxy carbonyl.
Structural unit containing acidic group of the present invention is preferably to be had carboxylic acid group and (is sometimes called below " containing carboxylic acid group's structural unit " as the structural unit of acidic group.)。More preferably have and be situated between by by removing the structural unit that atomicity after hydrogen atom is the carboxylic acid group of coupling chain that 4 above atomic groups the form main chain that is bonded to particular polymers.
Above-mentioned, containing in carboxylic acid group's structural unit, by being situated between, by coupling chain, carboxylic acid group is bonded to main chain, thereby can improves the flexible of carboxylic acid group's part, can interact with pigment or pigment derivative more expeditiously.In addition, carboxylic acid group also plays a role as developability group, therefore, is accompanied by flexible uprising, and developability also improves.In this, preferably link chain length.
On the other hand, if coupling chain is long, the quantity containing carboxylic acid group's structural unit that can import in polymkeric substance tails off, and therefore, and then the quantity that can import to the carboxylic acid group in polymkeric substance tails off.
Based on foregoing, in containing carboxylic acid group's structural unit, it is that the atomic group of 4～100 forms that the coupling chain that main chain and carboxylic acid group are linked is preferably by removing atomicity after hydrogen atom, by removing atomicity after hydrogen atom, being more preferably that the atomic group of 6～60 forms, is more preferably that the atomic group of 8～20 forms by removing atomicity after hydrogen atom.
With regard to above-mentioned containing with regard to carboxylic acid group's structural unit, the optimal way of the coupling chain that the main chain of particular polymers is linked with carboxylic acid group is identical with the above-mentioned coupling chain containing in the structural unit of acidic group, in addition, the multiple concatenating group of use capable of being combined is also identical as the situation of coupling chain.
As the above-mentioned concatenating group containing using in carboxylic acid group's structural unit, identical with the above-mentioned structural unit containing acidic group, preferably import aromatic nucleus, the preferred mode of aromatic nucleus is also identical.
As the part-structure of the above-mentioned structural unit containing carboxylic acid group, the more preferably represented structure of following formula (1).
[changing 25]
In above-mentioned formula (1), the same meaning of Y, R and n and above-mentioned formula (2).Carboxylic acid group can be situated between and be imported from phenyl ring by concatenating group.
The concrete example of the part-structure that above-mentioned formula (1) is represented is as follows, and this part-structure is not limited to these concrete examples.X represents the bonding position with main chain.
[changing 26]
[changing 27]
In the above-mentioned structural unit that contains carboxylic acid group, above-mentioned coupling chain preferably has aromatic nucleus, and is that 6 atomic groups above and below 60 form by removing hydrogen atom atomicity afterwards.More preferably above-mentioned aromatic nucleus is phenyl ring and is situated between by this phenyl ring or utilizes ester bond to be bonded to the coupling chain of main chain.
For particular polymers of the present invention, during from formation painted areas, be suppressed at the aspect that generates precipitate developing solution, more than the content of the above-mentioned structural unit containing carboxylic acid group is preferably 50mgKOH/g.In order effectively to suppress as the generation of 2 aggregates of the aggregate of 1 particle of pigment or effectively to weaken the cohesive force of 2 aggregates, containing the content of carboxylic acid group's structural unit, be preferably 50mgKOH/g～200mgKOH/g.
(other structural units)
The adsorptivity improving to pigment of take is object, particular polymers of the present invention be preferably further by the monomer with the adsorbable functional group in pigment in addition copolymerization and macromolecular compound.
Except acidic group, as the monomer with the adsorbable functional group in pigment, specifically, can list have organic pigment structure or heterocycle structure monomer, have basic nitrogen atom monomer, there is the monomer of ionic group etc.Wherein, aspect the adsorptive power to pigment, be preferably the monomer with organic pigment structure or heterocycle structure.
The monomer (monomer) with the adsorbable functional group in pigment can suitably be selected according to the kind of the pigment disperseing, and they can use separately, and also two or more kinds may be used.
Particular polymers in the present invention, in not damaging the scope of its effect, can further contain the structural unit from vinyl monomer that can copolymerization.
Here, as spendable vinyl monomer, be not particularly limited, preference is as being ester class, styrenic, (methyl) vinyl cyanide of (methyl) esters of acrylic acid, crotonate class, vinyl esters, maleic acid diester class, dimethyl ester class, methylene-succinic acid diester class, (methyl) acrylic amide, vinyl ethers, vinyl alcohol etc.As the concrete example of such vinyl monomer, can list for example following compound.It should be noted that, in this specification sheets, when representing in " acryl, methacryloyl " any one or both, be sometimes recited as " (methyl) acryl ".
As the example of (methyl) esters of acrylic acid, can list (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, the just own ester of (methyl) vinylformic acid, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid tertiary butyl cyclohexyl, (methyl) 2-EHA, the tertiary monooctyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid dodecane ester, (methyl) vinylformic acid octadecane ester, (methyl) vinylformic acid acetoxyl group ethyl ester, (methyl) phenyl acrylate, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-(2-methoxy ethoxy) ethyl ester, (methyl) vinylformic acid 3-phenoxy group-2-hydroxypropyl acrylate, (methyl) benzyl acrylate, (methyl) vinylformic acid diglycol monotertiary methyl ether, (methyl) vinylformic acid carbiphene, (methyl) vinylformic acid triglycol monomethyl ether, (methyl) vinylformic acid triglycol list ethyl ether, (methyl) polyalkylene glycol acrylate monomethyl ether, (methyl) polyalkylene glycol acrylate list ethyl ether, (methyl) vinylformic acid beta-phenoxy ethoxy ethyl ester, (methyl) vinylformic acid Nonylphenoxy macrogol ester, (methyl) vinylformic acid two cyclopentenes esters, (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester, (methyl) vinylformic acid trifluoro ethyl ester, (methyl) vinylformic acid octafluoro pentyl ester, (methyl) vinylformic acid perfluoro capryl ethyl ester, (methyl) vinylformic acid two cyclopentyl esters, (methyl) tribromophenyl acrylate, (methyl) vinylformic acid tribromo phenyl oxygen base ethyl ester etc.
As the example of crotonate class, can list butyl crotonate and the own ester of β-crotonic acid etc.
As the example of vinyl ester, can list vinylacetate, vinyl propionic ester, vinyl butyrate, vinyl methoxyacetic acid ester and M-nitro benzoic acid vinyl acetate etc.
As the example of maleic acid diester class, can list dimethyl maleate, ethyl maleate and dibutyl maleinate etc.
As the example of dimethyl ester class, can list dimethyl fumarate, DEF and dibutyl fumarate etc.
As the example of methylene-succinic acid diester class, can list dimethyl itaconate, diethyl itaconate and dibutyl itaconate etc.
As (methyl) acrylic amide, can list (methyl) acrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-propyl group (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, N-normal-butyl acryl (methyl) acrylamide, the N-tertiary butyl (methyl) acrylamide, N-cyclohexyl (methyl) acrylamide, N-(2-methoxy ethyl) (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N-phenyl (methyl) acrylamide, N-benzyl (methyl) acrylamide, (methyl) acryloyl morpholine, diacetone acrylamide etc.
As the example of vinyl ethers, can list methylvinylether, butyl vinyl ether, hexyl vinyl ether and methoxy ethyl vinyl ether etc.
As the example of styrenic, can list vinylbenzene, vinyl toluene, dimethyl styrene, Three methyl Benzene ethene, ethyl styrene, isopropyl benzene ethene, butylstyrene, hydroxy styrenes, methoxy styrene, butyl phenyl ether ethene, acetoxy-styrene, chloro-styrene, dichlorostyrene, bromstyrol, 1-chloro-4-methyl-benzene, utilization by acidic substance and hydroxy styrenes, vinyl M-nitro benzoic acid methyl esters and alpha-methyl styrene etc. that group (such as t-Boc etc.) that can deprotection is protected.
As the concrete example of the particular polymers in the present invention, can list following exemplary compounds 1～exemplary compounds 35.
[changing 28]
[changing 29]
[changing 30]
[changing 31]
[changing 32]
[changing 33]
[changing 34]
The preferred molecular weight of particular polymers of the present invention is counted 5000～100000 scope with weight-average molecular weight (Mw), with number-average molecular weight (Mn), counts 2500～50000 scope.In weight-average molecular weight (Mw) more preferably 10000～50000 scope, in number-average molecular weight (Mn) 5000～30000 scope more preferably.Especially in weight-average molecular weight (Mw), most preferably be 20000～40000 scope, in number-average molecular weight (Mn), most preferably be 5000～20000 scope.
That is,, from effectively 2 aggregates of the aggregate of 1 particle as pigment being disperseed or effectively weakening the viewpoint of cohesion again, the weight-average molecular weight of particular polymers (Mw) is preferably more than 1000.In addition, the viewpoint of the developability when coloring photosensitive combination that contains dispersive composition from utilization is manufactured colour filter, the weight-average molecular weight of particular polymers (Mw) is preferably below 50000.
Particular polymers of the present invention can utilize common radical polymerization to be manufactured.
In general, use and be suspended polymerization or solution polymerization process etc.As the solvent using when synthesizing such particular polymers, can list for example ethylene dichloride, pimelinketone, methylethylketone, acetone, methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, 2-methoxy ethyl acetic ester, 1-methoxy-2-propanol, 1-methoxyl group-2-propyl-acetic acid ester, N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), toluene, ethyl acetate, methyl lactate, ethyl lactate etc.These solvents can be used separately or mix two or more.It should be noted that, when carrying out radical polymerization, can use radical polymerization initiator, in addition, also can use chain-transfer agent (example: 2 mercapto ethanol and lauryl mercaptan).
Content in the dispersive composition of dispersion agent is preferably pigment: the scope of particular polymers (mass ratio)=1:0.1～1:2, more preferably scope, the scope of 1:0.4～1:0.7 more preferably of 1:0.2～1:1.
In addition, dispersive composition can contain pigment derivative.
Pigment derivative refers to that the side chain at pigment dyestuff imports acidic groups, basic group, aromatic series base as substituent compound, is the material different from particular dye.
In the present invention, with regard to veridian, in its surface adsorption, there is particular dye, but, make to have with above-mentioned particular polymers (macromolecule dispersing agent) and exist the pigment derivative at the position of affinity to be adsorbed in the surface of the pigment that particular dye do not adsorb, and used as the adsorption site of particular polymers, thus, pigment further can be made to fine particle, it is dispersed in coloured composition.In addition, can also prevent that its generation from condensing again.That is, pigment derivative, by not carrying out upgrading to adsorbing the surface of pigments of particular dye, thus, has the effect of the absorption that promotes the macromolecule dispersing agent as particular polymers of the present invention.
Particular polymers of the present invention has acidic group, and therefore, the basic color derivative that has basic group by use is as pigment derivative, thereby can further improve the dispersiveness of pigment, effectively fine pigment is disperseed.And, the coloring photosensitive combination that contains basic color derivative by use, thus the colour filter of the irregular little and look excellent of depth of shade can further be formed.
Pigment derivative is to import acidic groups, basic group, aromatic series base as substituent compound using pigment dyestuff as precursor skeleton and at side chain.Pigment dyestuff as precursor skeleton can list quinacridone pigment, phthualocyanine pigment, azo pigment, quinophthalone (quinophthalone) series pigments, isoindoline series pigments, isoindolinone pigment, quinoline pigment, diketopyrrolopyrroles (Diketopyrrolopyrrole) pigment, benzimidazolone pigment etc. specifically.In addition, as precursor skeleton, generally also comprise the faint yellow aromatic series polynuclear compound of the naphthalene system, anthraquinone system, triazine system, quinoline system etc. that are not known as pigment.
As pigment derivative, can use the pigment derivative of recording in Japanese kokai publication hei 11-49974 communique, Japanese kokai publication hei 11-189732 communique, Japanese kokai publication hei 10-245501 communique, TOHKEMY 2006-265528 communique, Japanese kokai publication hei 8-295810 communique, Japanese kokai publication hei 11-199796 communique, TOHKEMY 2005-234478 communique, TOHKEMY 2003-240938 communique, TOHKEMY 2001-356210 communique etc.
While using pigment derivative in dispersive composition of the present invention, as its usage quantity, preferably with respect to pigment be the scope of 1 quality %～80 quality %, more preferably 3 quality %～65 quality % scope, be particularly preferably the scope of 5 quality %～50 quality %.If content, within the scope of this, can suppress lowlyer by viscosity, can carry out well the dispersion of pigment, and can improve the dispersion stabilization after dispersion simultaneously.And, by this coloring photosensitive combination is applicable in the manufacture of colour filter, thus can access transmissivity high, there is excellent look characteristic, the colour filter of high-contrast.
And then, in not damaging the scope of effect of the present invention, as required, except particular polymers of the present invention, can also use other macromolecular compounds simultaneously.As other macromolecular compounds, can use natural resin, modified natural resin, synthetic resins, use the synthetic resins of natural resin modification etc.
As natural resin, take rosin as representative, as modified natural resin, can list rosin derivative, derivatived cellulose, rubber derivative, protein derivatives and their oligopolymer.As synthetic resins, can list epoxy resin, acrylic resin, maleic acid resin, butyral resin, vibrin, melmac, resol, urethane resin etc.As the synthetic resins with natural resin modification, Abietyl modified maleic acid resin, rosin modified phenolic resin etc.
As synthetic resins, daiamid and salt thereof, poly carboxylic acid and salt thereof, high molecular unsaturated acid ester, urethane, polyester, poly-(methyl) acrylate, (methyl) acrylic copolymer, naphthalene sulfonic acidformaldehyde condensation product.
As the content of the veridian in dispersive composition, with respect to the total solids composition (quality) of dispersive composition, be preferably 20～70 quality %, 30～60 quality % more preferably.If the content of veridian in above-mentioned scope, for guarantee depth of shade enough excellent look characteristic be effective.
In addition, as the content of the particular dye in dispersive composition, with respect to the total solids composition (quality) of dispersive composition, be preferably 5～40 quality %, 10～30 quality % more preferably.If the content of particular dye is in above-mentioned scope, the dispersion stabilization of dispersive composition is good, and for guarantee depth of shade enough excellent look characteristic be effective.
In addition, the content of the veridian in coloring photosensitive combination of the present invention is with respect to the total solids composition of said composition, is preferably 1～50 quality %, 1～30 quality % more preferably.
And then the content of the particular dye in coloring photosensitive combination of the present invention is preferably 0.1～25 quality %, 0.1～15 quality % more preferably with respect to the total solids composition of said composition.
The pigmented layer obtaining if the content of pigment and particular dye, in above-mentioned scope, is used coloring photosensitive combination has high brightness and high-contrast, in addition, and needed each characteristic of the coloring photosensitive combinations such as developability that are content with very little.
((C) polymerizable compound)
Coloring photosensitive combination of the present invention at least contains a kind of (C) polymerizable compound.
As polymerizable compound, it is for example the polymerizable compound with at least one ethylenical unsaturated double bonds, can be from the composition of known formation composition choice for use, can list the composition of recording in the composition recorded in [0010]～[0020] section in TOHKEMY 2006-23696 communique, the section of [0027]～[0053] in TOHKEMY 2006-64921 communique.
In addition, the polymerizable compound of the carbamate addition that also preferably utilizes the addition reaction of isocyanic ester and hydroxyl and manufacture, is also preferably the carbamate compounds class with ethylene oxide skeleton of recording in the urethane acrylate class recorded in Japanese kokai publication sho 51-37193 communique, Japanese Patent Publication 2-32293 communique, Japanese Patent Publication 2-16765 communique, Japanese Patent Publication 58-49860 communique, Japanese Patent Publication 56-17654 communique, Japanese Patent Publication 62-39417 communique, Japanese Patent Publication 62-39418 communique.
As other example, can list the polyester acrylate class recorded in Japanese kokai publication sho 48-64183 communique, Japanese Patent Publication 49-43191 communique, each communique of Japanese Patent Publication 52-30490 communique, epoxy resin is reacted with (methyl) vinylformic acid and polyfunctional acrylate or the methacrylic esters such as Epoxy Acrylates.And then also can use in Japanese bonding association will (Japanese Jie Association Hui Chi) vol.20, No.7,300th～308 pages (1984) polymerizable compound of being introduced as light solidified monomer and oligopolymer.
As concrete example, can list tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, three ((methyl) acryloxy ethyl) isocyanuric acid ester, tetramethylolmethane four (methyl) acrylate EO modification body, Dipentaerythritol six (methyl) acrylate EO modification body etc., in addition, as commercially available product, can list NK ESTER A-TMMT, NK ESTER A-TMM-3, NK oligo UA-32P, NK oligo UA-7200 (more than, Xin Zhong village chemical industry (strain) system), ARONIX M-305, ARONIX M-306, ARONIX M-309, ARONIX M-450, ARONIX M-402, TO-1382, TO-2349 (more than, East Asia synthetic (strain) system), V#802 (Osaka organic chemistry industry (strain) system) is as preference.
In addition, the compound of also recording in the section of (0031)～(0061) in preferred TOHKEMY 2009-265630 communique, is especially preferably the following compound of recording in the section of (0055)～(0059).
[changing 35]
[changing 36]
[changing 37]
[changing 38]
[changing 39]
These polymerizable compounds can be used separately, can also and use two or more.
As the content (being total content in situation of more than two kinds) of the polymerizable compound in the total solids composition in coloring photosensitive combination, be preferably 10 quality %～80 quality %, more preferably 15 quality %～75 quality %, be particularly preferably 20 quality %～60 quality %.
((D) Photoepolymerizationinitiater initiater)
Coloring photosensitive combination of the present invention preferably contains at least one Photoepolymerizationinitiater initiater.
Photoepolymerizationinitiater initiater, if can cross the material that makes above-mentioned polymerizable compound generation polymerization, is just not particularly limited, preferably from characteristic, efficiency of initiation, absorbing wavelength, enter the viewpoints such as chirality, cost and go out to send and select.
Photoepolymerizationinitiater initiater is to be carried out sensitization and caused and promote the compound of the polymerization of polymerizable compound by exposure light.Be preferably the compound of responding to the active ray more than wavelength 300nm and causing and promote the polymerization of polymerizable compound.In addition, for directly not responding to the Photoepolymerizationinitiater initiater of the active ray more than wavelength 300nm, can be preferably and sensitizing agent be used in combination.
Specifically, can list such as oxime ester compound, halogenated organic compound, oxygen base diazole compounds, carbonyl compound, ketal compound, bitter almond oil camphor compound, acridine compounds, organo-peroxide, azo-compound, coumarin compound, triazo-compound, Metallocenic compound, Hexaarylbiimidazole compound, organic boronic compound, disulfonic acid compound, salt compound, acylphosphanes (oxide compound), benzophenone cpd, acetophenone compound and derivative thereof etc.
Wherein, from the aspect of sensitivity, be preferably oxime ester compound, Hexaarylbiimidazole compound.
As oxime ester compound, can use the compound of recording in TOHKEMY 2000-80068 communique, TOHKEMY 2001-233842 communique, Japanese Unexamined Patent Application Publication 2004-534797 communique, No. 2005/080337th, International Publication, No. 2006/018973 specification sheets of International Publication, TOHKEMY 2007-210991 communique, TOHKEMY 2007-231000 communique, TOHKEMY 2007-269779 communique, TOHKEMY 2009-191061 communique, No. 2009/131189 specification sheets of International Publication.
As concrete example, can list 2-(O-benzoyl oxime)-1-[4-(thiophenyl) phenyl]-1, 2-dimethyl diketone, 2-(O-benzoyl oxime)-1-[4-(thiophenyl) phenyl]-1, 2-diacetylmethane, 2-(O-benzoyl oxime)-1-[4-(thiophenyl) phenyl]-1, 2-hexanedione, 2-(O-benzoyl oxime)-1-[4-(thiophenyl) phenyl]-1, 2-heptadione, 2-(O-benzoyl oxime)-1-[4-(thiophenyl) phenyl]-1, 2-acetyl caproyl, 2-(O-benzoyl oxime)-1-[4-(methylbenzene sulfenyl) phenyl]-1, 2-dimethyl diketone, 2-(O-benzoyl oxime)-1-[4-(ethylbenzene sulfenyl) phenyl]-1, 2-dimethyl diketone, 2-(O-benzoyl oxime)-1-[4-(butylbenzene sulfenyl) phenyl]-1, 2-dimethyl diketone, 1-(O-acetyl oxime)-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] ethyl ketone, 1-(O-acetyl oxime)-1-[9-methyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] ethyl ketone, 1-(O-acetyl oxime)-1-[9-propyl group-6-(2-methyl benzoyl)-9H-carbazole-3-yl] ethyl ketone, 1-(O-acetyl oxime)-1-[9-ethyl-6-(2-ethylamino benzonitrile acyl group)-9H-carbazole-3-yl] ethyl ketone, 1-(O-acetyl oxime)-1-[9-ethyl-6-(2-butylbenzene formyl radical)-9H-carbazole-3-yl] ethyl ketone etc.But, be not limited thereto.
In addition, in the present invention, the painted viewpoint from sensitivity, ageing stability, thermotolerance, as the oxime ester compound of Photoepolymerizationinitiater initiater, is also preferably the represented compound of following general formula (A).
[changing 40]
In general formula (A), X 1, X 2, and X 3independently represent respectively hydrogen atom, halogen atom or alkyl, R 1expression-R ,-OR ,-COR ,-SR ,-CONRR ' or-CN, R 2and R 3respectively independent expression-R ,-OR ,-COR ,-SR or-NRR '.R and R ' be independent alkyl, aryl, aralkyl or the heterocyclic radical of representing respectively, these groups can be selected from a kind of above replacement in halogen atom and heterocyclic radical, 1 of the carbon atom of the formation alkyl chain in this alkyl and aralkyl above can be substituted by unsaturated link(age), ehter bond or ester bond, and R and R ' be bonding and form ring mutually.
In general formula (A), as X 1, X 2, and X 3halogen atom while representing halogen atom, can list fluorine, chlorine, bromine, iodine, as X 1, X 2, and X 3alkyl while representing alkyl, can list for example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, tert-pentyl, hexyl, heptyl, octyl group, iso-octyl, 2-ethylhexyl, tertiary octyl group, nonyl, different nonyl, decyl, isodecyl, vinyl, allyl group, butenyl, vinyl, propenyl, methoxy ethyl, ethoxyethyl group, propoxy-ethyl, methoxyethoxyethyl, ethoxy ethoxy ethyl, propoxy-ethoxyethyl group, methoxy-propyl, single methyl fluoride, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluor ethyl, 2-(benzoxazole-2 '-yl) vinyl etc.
Wherein, X 1, X 2, and X 3all represent hydrogen atom, or X 1represent alkyl, X 2, and X 3all represent hydrogen atom.
In general formula (A), as R and the represented alkyl of R ', can list for example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, tert-pentyl, hexyl, heptyl, octyl group, iso-octyl, 2-ethylhexyl, tertiary octyl group, nonyl, different nonyl, decyl, isodecyl, vinyl, allyl group, butenyl, vinyl, propenyl, methoxy ethyl, ethoxyethyl group, propoxy-ethyl, methoxyethoxyethyl, ethoxy ethoxy ethyl, propoxy-ethoxyethyl group, methoxy-propyl, single methyl fluoride, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluor ethyl, 2-(benzoxazole-2 '-yl) vinyl etc.
As R and the represented aryl of R ', can list such as phenyl, tolyl, xylyl, ethylphenyl, chloro-phenyl-, naphthyl, anthryl, phenanthryl etc.
As R and the represented aralkyl of R ', can list such as benzyl, chlorobenzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, phenyl vinyl etc.
As R and the represented heterocyclic radical of R ', can list such as pyridyl, pyrimidyl, furyl, thio-phenyl etc.
In addition, as R and R ' bonding and the ring that forms can list such as piperidine ring, morpholine ring etc. mutually.
The R forming as containing above-mentioned R and R ' 2and R 3, particularly preferred mode be separately independent for methyl, hexyl, cyclohexyl ,-S-Ph ,-S-Ph-Cl and-S-Ph-Br.
In Photoepolymerizationinitiater initiater, as Photoepolymerizationinitiater initiater, particularly preferably be: in general formula (A), X 1, X 2, and X 3be hydrogen atom; R 1for alkyl, be particularly preferably methyl; R 2for alkyl, be particularly preferably methyl; R 3for alkyl, be particularly preferably ethyl.
Thereby, as the preferred concrete example of the represented Photoepolymerizationinitiater initiater of above-mentioned general formula (A), can list the following compd A～compound F 17-hydroxy-corticosterone exemplifying.But the present invention is not subject to any restriction of following compound.
[changing 41]
[changing 42]
[changing 43]
The represented Photoepolymerizationinitiater initiater of general formula (A) can synthesize by the method for recording in TOHKEMY 2005-220097 communique for example.
The represented compound of the general formula using in the present invention (A) is in the wavelength region may of 250nm～500nm, to have the compound of absorbing wavelength.More preferably can list the compound in the wavelength region may of 300nm～380nm with absorbing wavelength.Particularly preferably the absorbancy of 308nm and 355nm is high.
In addition, in the present invention, the painted viewpoint during from sensitivity, ageing stability, post-heating, as the oxime ester compound as Photoepolymerizationinitiater initiater, the represented compound of preferred following general formula (B) also.
[changing 44]
In general formula (B), R 22represent monovalence substituting group.A 22the concatenating group, the Ar that represent divalence represent aryl.N is 0～5 integer.X 22multiple X while representing that monovalence substituting group, n are 2～4 integers 22can be the same or different.
As above-mentioned R 22represented monovalence substituting group, is preferably monovalence nonmetallic atom group shown below.
As R 22represented monovalence nonmetallic atom group, can list and can have substituent alkyl, can have substituent aryl, can have substituent alkyl sulphonyl, can have substituent aryl sulfonyl, can have substituent acyl group, can have substituent heterocyclic radical etc.
As thering is substituent alkyl, be preferably the alkyl of carbonatoms 1～30, can list such as methyl, ethyl, propyl group, butyl, hexyl cyclopentyl, cyclohexyl, trifluoromethyl etc.
As thering is substituent aryl, be preferably the aryl of carbonatoms 6～30, can list such as phenyl, xenyl, 1-naphthyl, 2-naphthyl etc.
As thering is substituent alkyl sulphonyl, be preferably the alkyl sulphonyl of carbonatoms 1～20, can list such as methyl sulphonyl, ethylsulfonyl etc.
As thering is substituent aryl sulfonyl, be preferably the aryl sulfonyl of carbonatoms 6～30, can list such as phenyl sulfonyl, 1-naphthyl alkylsulfonyl etc.
As thering is substituent acyl group, be preferably the acyl group of carbonatoms 2～20, can list for example ethanoyl, propionyl, butyryl radicals, trifluoromethyl carbonyl, pentanoyl, benzoyl, 1-naphthoyl, 2-naphthoyl, 4-methyl sulfanyl (sulphanyl) benzoyl, 4-phenyl sulfanyl benzoyl, 4-dimethylamino benzoyl, 4-diethylamino benzoyl, 2-chlorobenzene formacyl, 2-methyl benzoyl, 2-anisoyl, 2-butyl phenyl ether formyl radical, 3-chlorobenzene formacyl, 3-trifluoromethyl benzoyl, 3-cyano group benzoyl, 3-nitro benzoyl, 4-fluoro benzoyl, 4-cyano group benzoyl, 4-anisoyl etc.
As can there is substituent heterocyclic radical, be preferably comprise nitrogen-atoms, Sauerstoffatom, sulphur atom, phosphorus atom, aromatic series or aliphatic heterocycle.Can list such as thienyl, furyl, pyranyl etc.
As above-mentioned R 22, from the aspect of high-sensitivity, more preferably unsubstituted or there is substituent acyl group, specifically, be preferably unsubstituted or there is substituent ethanoyl, propionyl, benzoyl, toluyl.
As above-mentioned substituting group, can list the represented group of routine structural formula described as follows, wherein, be preferably (d-1), (d-4) and (d-5) in any.
[changing 45]
As above-mentioned A 22represented bivalence linking base, can list can have substituent carbonatoms 1～12 alkylidene group, can there is substituent cycloethylene alkyl, can there is substituent alkynylene.
As the substituting group that can import in these groups, can list the carbalkoxys such as aryloxy, methoxycarbonyl, butoxy carbonyl, carbobenzoxy such as the alkoxyl groups such as halogen atom, methoxyl group, oxyethyl group, tert.-butoxy such as fluorine atom, chlorine atom, bromine atoms, iodine atom, phenoxy group, p-tolyloxy etc.
Wherein, as above-mentioned A 22from improving sensitivity, suppress because of heating through time the painted aspect that causes, be preferably unsubstituted alkylidene group, the alkylidene group for example, being replaced by alkyl (methyl, ethyl, the tertiary butyl, dodecyl), for example, by the alkylidene group of thiazolinyl (vinyl, allyl group), the alkylidene group that for example, replaced by aryl (phenyl, p-tolyl, xylyl, cumenyl, naphthyl, anthryl, phenanthryl, styryl).
As the represented aryl of above-mentioned Ar, be preferably the aryl of carbonatoms 6～30, in addition, can there is substituting group.
Specifically, Ar can list phenyl, xenyl, 1-naphthyl, 2-naphthyl, terphenyl, tetrad phenyl, o-, m-and p-tolyl, xylyl, o-, m-and p-cumenyl, base etc.Wherein, from improving sensitivity, suppress because of heating through time the painted aspect that causes, be preferably and replace or unsubstituted phenyl.
When above-mentioned phenyl has substituting group, as its substituting group, can list for example fluorine atom, chlorine atom, bromine atoms, the halogen atoms such as iodine atom, methoxyl group, oxyethyl group, the alkoxyl groups such as tert.-butoxy, phenoxy group, the aryloxies such as p-tolyloxy, methoxycarbonyl, butoxy carbonyl, the carbalkoxys such as carbobenzoxy, acetoxyl group, propionyloxy, the acyloxy such as benzoyl oxygen base, ethanoyl, benzoyl, isobutyryl, acryl, methacryloyl, the acyl groups such as methoxalyl (methoxalyl), methylamino, the amino alkylamino that waits of cyclohexyl, dimethylamino, diethylamino, morpholino base, the dialkyl amidos such as piperidyl, phenyl amino, methyl, ethyl, the tertiary butyl, the alkyl such as dodecyl, hydroxyl, carboxyl etc.
In general formula (B), if " SAr " structure being formed by the S of above-mentioned Ar and adjacency is structure shown below, preferred aspect sensitivity.
[changing 46]
As above-mentioned X 22represented monovalence substituting group, can list and can have substituent alkyl, can have substituent aryl, can have substituent thiazolinyl, can have substituent alkynyl, can have substituent alkoxyl group, can have substituent aryloxy, can have substituent alkyl sulfide oxygen base, can have substituent aryl sulphur oxygen base, halogen atom etc.
As thering is substituent alkyl, be preferably the alkyl of carbonatoms 1～30, can list such as methyl, ethyl, propyl group, butyl, hexyl, cyclopentyl, cyclohexyl, trifluoromethyl, 2-ethylhexyl, phenacyl etc.
As thering is substituent aryl, be preferably the aryl of carbonatoms 6～30, can list such as phenyl, xenyl, 1-naphthyl, 2-naphthyl, terphenyl, tetrad phenyl, o-, m-and p-tolyl, xylyl etc.
As thering is substituent thiazolinyl, be preferably the thiazolinyl of carbonatoms 2～10, can list such as vinyl, allyl group, styryl etc.
As thering is substituent alkynyl, be preferably the alkynyl of carbonatoms 2～10, can list such as vinyl, propenyl, propargyl etc.
As thering is substituent alkoxyl group, be preferably the alkoxyl group of carbonatoms 1～30, can list such as methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, benzyloxy etc.
As thering is substituent aryloxy, be preferably the aryloxy of carbonatoms 6～30, can list such as phenoxy group, 1-naphthyloxy, 2-naphthyloxy, 2-chlorophenoxy, 2-methylphenoxy, 2-methoxyphenoxy etc.
As thering is substituent alkyl sulfide oxygen base, be preferably the thioalkoxy group of carbonatoms 1～30, can list such as methyl sulphur oxygen base, ethyl sulphur oxygen base, propylthio oxygen base, sec.-propyl sulphur oxygen base, fourth sulphur oxygen base, isobutyl-sulphur oxygen base, sec-butyl sulphur oxygen base, tertiary butyl sulphur oxygen base, amyl group sulphur oxygen base, isopentyl sulphur oxygen base, hexyl sulphur oxygen base, heptyl sulphur oxygen base, octyl group sulphur oxygen base, 2-ethylhexyl sulphur oxygen base, decyl sulphur oxygen base, dodecyl sulphur oxygen base, octadecyl sulphur oxygen base, dibenzylsulfide oxygen base etc.
As thering is substituent aryl sulphur oxygen base, be preferably the aryl sulphur oxygen base of carbonatoms 6～30, can list for example thiophenyl oxygen base, 1-naphthyl sulphur oxygen base, 2-naphthyl sulphur oxygen base, 2-chlorobenzene sulfenyl oxygen base, 2-methylbenzene sulfenyl oxygen base, 2-anisole sulfenyl oxygen base, 2-butyl phenyl ether sulfenyl oxygen base, 3-chlorobenzene sulfenyl oxygen base, 3-trifluoromethyl thiophenyl oxygen base, 3-cyano group thiophenyl oxygen base, 3-nitrophenylsulfenyl oxygen base, 4-fluorobenzene sulfenyl oxygen base, 4-cyano group thiophenyl oxygen base, 4-anisole sulfenyl oxygen base, 4-dimethylamino thiophenyl oxygen base, 4-methyl sulfanyl thiophenyl oxygen base, 4-phenyl sulfanyl thiophenyl oxygen base etc.
As halogen atom, there are fluorine atom, chlorine atom, bromine atoms, iodine atom etc.
As thering is substituent haloalkyl, can list single methyl fluoride, difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl, single brooethyl, two brooethyls, trisbromomethyl etc.
As can there is substituent amide group on N, can list N, N-dimethylformamide base, N, N-diethylamide base etc.
Wherein, as X 22, from solvent solubility and the aspect that improves the assimilated efficiency in long wavelength region, be preferably and can there is substituent alkyl, can there is substituent aryl, can there is substituent thiazolinyl, can there is substituent alkynyl, can there is substituent alkoxyl group, can there is substituent aryloxy, can there is substituent alkyl sulfide oxygen base, can there is substituent aryl sulphur oxygen base, can there is substituent haloalkyl, can there is substituent amino, or can there is substituent amide group on N, wherein, more preferably can there is substituent alkyl.
In addition, the n in general formula (B) represents 0～5 integer, from the viewpoint of synthetic easiness, is preferably 0～3 integer, 0～2 integer more preferably.
In general formula (B), there are a plurality of X 22time, a plurality of X 22can be identical, also can be different.
The concrete example of the oxime Photoepolymerizationinitiater initiater that above-mentioned general formula (B) is represented is as follows.
[changing 47]
[changing 48]
The represented compound of general formula used in the present invention (B) is in the wavelength region may of 250nm～500nm, to have the compound of absorbing wavelength.More preferably in the wavelength region may of 300nm～380nm, there is the compound of absorbing wavelength.The high compound of the absorbancy of 308nm and 355nm particularly preferably.
Example as halogenated organic compound, specifically, if can list woods etc., " Bull Chem.Soc.Japan " 42, 2924 (1969), United States Patent (USP) the 3rd, 905, No. 815 specification sheetss, Japanese Patent Publication 46-4605 communique, Japanese kokai publication sho 48-36281 communique, Japanese kokai publication sho 55-32070 communique, Japanese kokai publication sho 60-239736 communique, Japanese kokai publication sho 61-169835 communique, Japanese kokai publication sho 61-169837 communique, Japanese kokai publication sho 62-58241 communique, Japanese kokai publication sho 62-212401 communique, Japanese kokai publication sho 63-70243 communique, Japanese kokai publication sho 63-298339 communique, M.P.Hutt " Journal of Heterocyclic Chemistry " 1 (No.3), etc. (1970) compound of recording in, can list especially trihalogenmethyl and replace Hou oxazole compounds, s-triazine.
Example as Hexaarylbiimidazole compound, can list for example Japanese Patent Publication 6-29285 communique, United States Patent (USP) the 3rd, 479, No. 185, United States Patent (USP) the 4th, 311, No. 783, United States Patent (USP) the 4th, 622, the various compounds of recording in each specification sheets of No. 286 grades, specifically, can list 2, 2 '-bis-(Chloro-O-Phenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(o-bromophenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(o, p-dichlorophenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(Chloro-O-Phenyl)-4, 4 ', 5, 5 '-tetra-(m-p-methoxy-phenyl) diimidazole, 2, 2 '-bis-(o, o '-dichlorophenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(O-Nitrophenylfluorone)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(o-methyl-phenyl-)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(adjacent trifluorophenyls)-4, 4 ', 5, 5 '-tetraphenyl diimidazole etc.
Photoepolymerizationinitiater initiater can be used in combination one kind or two or more.Using in situation of more than two kinds, can use the represented compound of multiple general formula (B), also can use the represented compound of multiple general formula (II).In addition, can use general formula (II) and (III) in represented compound at least a kind separately.In addition, can use general formula (II) and (III) represented compound separately at least one and except general formula (II) and (III) oxime compound represented compound or the Photoepolymerizationinitiater initiater except oxime compound.In addition, can be used together sensitizing agent.
The total content of Photoepolymerizationinitiater initiater is with respect to the total solids composition in coloring photosensitive combination, be preferably 0.1 quality %～20 quality %, more preferably 0.5 quality %～10 quality %, most preferably be 1 quality %～10 quality %.If within the scope of this, highly sensitive, in addition while exposing, look characteristic is also good.
< (E) alkali-soluble tackiness agent >
In coloring photosensitive combination of the present invention, in order to improve tunicle formative and from the viewpoint of pattern formative, preferably to use alkali-soluble tackiness agent.
Alkali-soluble tackiness agent has alkali-soluble, in addition, is not particularly limited, preferably can be from thermotolerance, developability, enter the viewpoints such as chirality and selected.
As alkali-soluble tackiness agent, be wire organic high molecular polymer, and be preferably alkali-soluble tackiness agent solvable at organic solvent and that the enough weak alkaline aqueous solutions of energy develop.As such wire organic high molecular polymer, can list the polymkeric substance at side chain with carboxylic acid, for example can list Japanese kokai publication sho No. 59-44615, No. 54-34327, Japanese Patent Publication, No. 58-12577, Japanese Patent Publication, No. 54-25957, Japanese Patent Publication, No. 59-53836, Japanese kokai publication sho, in each communique that No. 59-71048, Japanese kokai publication sho, record, Sipacril 2739OF, acrylic copolymer, itaconic acid copolymer, β-crotonic acid multipolymer, maleic acid, partial esterification maleic acid etc., the acid cellulose derivative that equally has a carboxylic acid at side chain is useful.
Except above-mentioned alkali-soluble tackiness agent, as alkali-soluble tackiness agent, make to have the polymkeric substance of hydroxyl and acid anhydrides addition and material etc., polycarboxylated styrene be that resin, polysiloxane series resin, poly-((methyl) vinylformic acid 2-hydroxyl ethyl ester), Polyvinylpyrolidone (PVP), polyoxyethylene, polyvinyl alcohol etc. are also useful.In addition, wire organic high molecular polymer can be to have the hydrophilic monomer polymkeric substance that copolymerization forms in addition.As its example, can list alkoxyalkyl (methyl) acrylate, (methyl) hydroxyalkyl acrylate, (methyl) vinylformic acid glyceryl ester, (methyl) acrylamide, N hydroxymethyl acrylamide, the second month in a season or tertiary alkyl acrylamide, dialkyl aminoalkyl (methyl) acrylate, (methyl) vinylformic acid morpholine ester, NVP, N-caprolactam, vinyl imidazole, vinyl triazole, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate of side chain or straight chain, (methyl) butyl acrylate of side chain or straight chain, or, phenoxy group hydroxypropyl (methyl) acrylate etc.In addition, as thering is hydrophilic monomer, contain tetrahydrofurfuryl, phosphate, phosphate-based, quaternary ammonium salt base, vinyloxy group chain, propenyloxy group chain, sulfonic group and the monomer that forms from the group of its salt, morpholino ethyl etc. etc. is useful.
In addition, in order to improve cross-linking efficiency, alkali-soluble tackiness agent can have polymerizable group at side chain, such as polymkeric substance at side chain with allyl group, (methyl) acryl, allyloxy alkyl etc. etc., is also useful.Example as the above-mentioned polymkeric substance that contains polymerizable group, can list Dianal NR series (Mitsubishi Rayon Co., Ltd system), Photomer6173 (the polyurethane acroleic acid oligopolymer that contains COOH (polyurethane acrylic oligomer) .Diamond Shamrock Co., Ltd system), Biscoat R-264, KS Resist106 (being Osaka Organic Chemical Industry Co., Ltd.'s system), CYCLOMER P series, PLACCEL CF200 series (being Daicel Chemical Industries Ltd. system), Ebecryl3800 (Daicel-Cytec Company Ltd. system) etc.In addition, in order to improve the intensity of cured film, alcohol soluble nylon, 2, the polyethers of 2-pair-(4-hydroxy phenyl)-propane and Epicholorohydrin etc. is also useful.
In these various alkali-soluble tackiness agents, from stable on heating viewpoint, being preferably polycarboxylated styrene is resin, polysiloxane series resin, acrylic resin, acrylamide resin, acrylic acid or the like/acrylamide copolymer resin, the viewpoint of controlling from developability, is preferably acrylic resin, acrylamide resin, acrylic acid or the like/acrylamide copolymer resin.
As aforesaid propylene, acid is resin, is preferably the multipolymer that formed by the monomer being selected from (methyl) vinylformic acid benzyl ester, (methyl) vinylformic acid, (methyl) Hydroxyethyl acrylate, (methyl) acrylamide etc., above-mentioned Photomer6173, KS resist-106, CYCLOMER P series etc.
From viewpoints such as developability, liquid viscosities, it is 1000～2 * 10 that alkali-soluble tackiness agent is preferably weight-average molecular weight (the polystyrene conversion value of utilizing GPC method to record) 5polymkeric substance, more preferably 2000～1 * 10 5polymkeric substance, be particularly preferably 5000～5 * 10 4polymkeric substance.Can use separately, also two or more kinds may be used.
Other compositions of < >
For coloring photosensitive combination of the present invention, further as required, only otherwise damage effect of the present invention, just can contain known additive, for example multi-functional thiol compound, chain-transfer agent, stopper, organic solvent, tensio-active agent, adhesion modifying agent, linking agent, development accelerant and other additives.
Below, for these compositions, describe.
(multi-functional thiol's compound)
Coloring photosensitive combination of the present invention can contain multi-functional thiol's compound.
Coloring photosensitive combination of the present invention is by comprising multi-functional thiol's compound, can improve sensitivity, suppress the ion stripping that causes because of dyestuff isochrome material etc., while using coloring photosensitive combination of the present invention in the colour filter of liquid crystal indicator is made, the deteriorated of the image quality such as cross-talk (crosstalk) can be prevented, the demonstration of bright-coloured high image quality can be realized.
In the present invention, " multi-functional thiol's compound " refers to the compound in molecule with more than 2 thiol group.As above-mentioned multi-functional thiol's compound, be preferably more than 100 low molecular compound of molecular weight, specifically, be preferably molecular weight 100～1500, more preferably 150～1000.Above-mentioned multi-functional thiol's compound preferably has 2～10 thiol groups in molecule, further preferably has 2～6.In addition, these compounds preferably become the system that plays booster action when above-mentioned free radical polymerization monomer carries out polymerization.Specifically, the addition that preferably makes multi-functional thiol's compound is 1～20 quality % with respect to total total solids composition of composition, or becomes the addition fewer more simultaneously than the addition of the above-mentioned free radical polymerization monomer containing.
As the concrete example that can be used for multi-functional thiol's compound of the present invention, can list for example trimethylolpropane tris (3-mercaptopropionic acid ester), tetramethylolmethane four (3-mercaptopropionic acid ester), Tetraglycol 99 two (3-mercaptopropionic acid ester), Dipentaerythritol six (3-mercaptopropionic acid ester), tetramethylolmethane four (thioglycol acid esters), tetramethylolmethane four (3-sulfydryl butyric ester), butyleneglycol two (3-sulfydryl butyric ester), 1, two (the 3-sulfydryl butyl oxygen base) butane of 4-, 1, 3, 5-tri-(3-sulfydryl butyl oxygen base ethyl)-1, 3, 5-triazine-2, 4, 6 (1H, 3H, 5H)-triketones etc. are as preferred multi-functional thiol's compound.
The content of multi-functional thiol's compound is preferably 0.01～20 quality % with respect to the total solids composition in coloring photosensitive combination, more preferably 0.1～10 quality %.If the content of multi-functional thiol's compound, within the scope of this, can provide: the sensitivity of coloring photosensitive combination is good and storage stability good, the good adhesion of the pixel of the colour filter of gained, do not have pattern damaged, when for liquid crystal indicator the good coloring photosensitive combination of electrical characteristic.
(sensitizing agent)
In coloring photosensitive combination of the present invention, also can add sensitizing agent.As the typical sensitizing agent using in the present invention, can list Crivello (J.V.Crivello, Adv.in Polymer Sci, 62,1 (1984)) disclosed sensitizing agent in, specifically, can list Bi, perylene, acridine, thioxanthone, CTX, benzoflavine, N-vinylcarbazole, 9,10-dibutoxy anthracene, anthraquinone, benzophenone, tonka bean camphor, coumarin ketone (ketocourmarin), phenanthrene, camphorquinone, phenothiazine derivative etc.Preferably with respect to Photoepolymerizationinitiater initiater, with the ratio of 50～200 quality %, add sensitizing agent.
(chain-transfer agent)
In coloring photosensitive combination of the present invention, can also add chain-transfer agent.As for chain-transfer agent of the present invention, can list for example N, the N such as N-dimethylamino M-nitro benzoic acid ethyl ester, N-dialkyl amido M-nitro benzoic acid alkyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, N-phenyl mercaptobenzimidazole etc. have the sulfhydryl compound of heterocycle etc.
Chain-transfer agent can be used alone or two or more kinds may be used.
The addition of chain-transfer agent is the scope of 0.01～15 quality % with respect to the total solids composition of coloring photosensitive combination of the present invention, this viewpoint from desensitization deviation is preferred, more preferably 0.1～10 quality %, be particularly preferably 0.5～5 quality %.
(stopper)
Coloring photosensitive combination of the present invention can contain stopper.
Stopper refers to the material of having given play to following effects,, the polymerizations such as the free radical producing in coloring photosensitive combination by light, heat are caused kind, implement to supply with hydrogen (or authorizing hydrogen), supply with energy (or authorizing energy), supply with electronics (or authorizing electronics) etc., make polymerization cause kind of an inactivation, suppress to cause unwanted polymerization.Can use the stopper recorded in 0154th～0173 section, TOHKEMY 2007-334322 communique etc.
Wherein, as stopper, preferably can list p methoxy phenol.
The content of the stopper in coloring photosensitive combination of the present invention with respect to the total mass of polymerizable compound be preferably 0.0001～5 quality %, more preferably 0.001～5 quality %, be particularly preferably 0.001～1 quality %.
((F) organic solvent)
Coloring photosensitive combination of the present invention preferably contains (F) organic solvent.
In addition, the dispersive composition in the present invention preferably contains (F) organic solvent.
The contained organic solvent of the organic solvent that dispersive composition is contained and coloring photosensitive combination can be identical type, also can be different sorts, the contained organic solvent of the organic solvent that dispersive composition is contained and coloring photosensitive combination can be a kind, can be also two or more.
(F) organic solvent is so long as the organic solvent of the solvability of each composition that can meet and deposit, the coating while making coloring photosensitive combination, just substantially be not particularly limited, particularly preferably from the viewpoint of the solvability of solids component, coating, security, selected.
As (F) organic solvent, as ester class, can list for example ethyl acetate, acetic acid-positive butyl ester, isobutyl acetate, pentyl formate, Isoamyl Acetate FCC, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ethoxyacetic acid alkyl esters (example: ethoxyacetic acid methyl esters, ethoxyacetic acid ethyl ester, ethoxyacetic acid butyl ester (can list methoxy menthyl acetate, methoxyacetic acid ethyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate etc. specifically.)), 3-oxygen base alkyl propionates class, 2-oxygen base alkyl propionates class, 2-oxygen base-2 Methylpropionic acid methyl esters, 2-oxygen base-2 Methylpropionic acid ethyl ester, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, Propyl pyruvate, methyl acetoacetate, methyl aceto acetate, 2-oxo-butanes acid methyl esters, 2-oxo-butanes acetoacetic ester etc.
In addition, as ethers, can list such as diethylene glycol dimethyl ether, tetrahydrofuran (THF), ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, acetic acid methyl cellosolve, acetic acid ethyl cellosolve, diglycol monotertiary methyl ether, carbiphene, diglycol monotertiary butyl ether, glycol ether ethyl-methyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol list ethyl ether acetic ester, propylene glycol list propyl ether acetic ester etc.
As ketone, can list such as methylethylketone, pimelinketone, 2-heptanone, 3-heptanone etc.
As aromatic hydrocarbon based, can preferably list such as toluene, dimethylbenzene etc.
Its solvability from the solvability of aforementioned each composition and while comprising alkali-soluble tackiness agent, be coated with the planar viewpoints such as improvement, these organic solvents preferably mix two or more.Now, the mixing solutions particularly preferably being formed by two or more material being selected from 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, acetic acid ethyl cellosolve, ethyl lactate, diethylene glycol dimethyl ether, glycol ether ethyl-methyl ether, butylacetate, 3-methoxy methyl propionate, 2-heptanone, pimelinketone, ethyl carbitol acetic ester, acetate of butyl carbitol, methyl proxitol and methyl proxitol acetate.
Content as organic solvent in coloring photosensitive combination, is preferably the amount that total solids constituent concentration in coloring photosensitive combination reaches 10 quality %～80 quality %, more preferably reaches the amount of 15 quality %～60 quality %.
(tensio-active agent)
Coloring photosensitive combination of the present invention can contain tensio-active agent.
As tensio-active agent, can use any in negatively charged ion system, positively charged ion system, nonionic system or both sexes, preferred surfactant is that nonionic is tensio-active agent.Specifically, can list the nonionic of recording in the 0058th section, TOHKEMY 2009-098616 communique is tensio-active agent, and wherein, being preferably fluorine is tensio-active agent.
As can be used for other tensio-active agents of the present invention, for example can list as commercially available product, MEGA FAC F142D, MEGA FAC F172, MEGA FAC F173, MEGA FAC F176, MEGA FAC F177, MEGA FAC F183, MEGA FAC F479, MEGA FAC F482, MEGA FAC F554, MEGA FAC F780, MEGA FAC F781, MEGA FAC F781-F, MEGA FAC R30, MEGA FAC R08, MEGA FAC F-472SF, MEGAFAC BL20, MEGA FAC R-61, MEGA FAC R-90 (more than, DIC (strain) system), FLUORAD FC-135, FLUORAD FC-170C, FLUORAD FC-430, FLUORAD FC-431, Novec FC-4430 (more than, Sumitomo 3M (strain) system), Asahi Guard AG7105,7000,950,7600, SURFLON S-112, SURFLON S-113, SURFLON S-131, SURFLON S-141, SURFLON S-145, SURFLON S-382, SURFLON SC-101, SURFLON SC-102, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC-106 (more than, Asahi Glass (strain) system), EFTOP EF351, EFTOP EF352, EFTOP EF801, EFTOP EF802 (more than, Mitsubishi Materials electronics changes into company's (the マ テ リ ア of Mitsubishi Le Electricity changes into (strain)) system), Ftergent250 (NEOS (strain) system).
In addition, as tensio-active agent, can list that to comprise the represented Component units A of following formula (W) and Component units B and utilize the weight-average molecular weight (Mw) of the polystyrene conversion that the gel permeation chromatography using tetrahydrofuran (THF) as solvent records be 1, multipolymer more than 000 and below 10,000 is as preference.
[changing 49]
(in formula (W), R 1and R 3independently represent separately hydrogen atom or methyl, R 2represent straight-chain alkyl-sub-, the R of carbonatoms more than 1 and below 4 4represent that hydrogen atom or alkyl, the L of carbonatoms more than 1 and below 4 represent that alkylidene group, p and the q of carbonatoms more than 3 and below 6 means that quality percentage, the p of polymerization ratio represent 10 quality % above and numerical value, q below 80 quality % represent 20 quality % above and numerical value, r below 90 quality % represent that integer, n more than 1 and below 18 represent the integer more than 1 and below 10.)
Above-mentioned L is preferably the represented branched alkylidene of following formula (W-2).R in formula (W-2) 5represent the alkyl of carbonatoms more than 1 and below 4, from the aspect of consistency and the wettability with respect to applied, be preferably the alkyl of carbonatoms more than 1 and below 3, more preferably carbonatoms 2 or 3 alkyl.
P in formula (W) and q sum (p+q) are preferably p+q=100, that is, be 100 quality %.
The weight-average molecular weight of above-mentioned multipolymer (Mw) is more preferably more than 1,500 and below 5,000.
[changing 50]
These tensio-active agents can be used separately a kind, or can use two or more.
The addition of the tensio-active agent in coloring photosensitive combination of the present invention is preferably 0.01～2.0 quality %, is particularly preferably 0.02～1.0 quality % with respect to the total solids composition of coloring photosensitive combination.If in this scope, coating and cured film has good uniformity.
(adhesion modifying agent)
Coloring photosensitive combination of the present invention can contain adhere to modifying agent,
Adherence modifying agent is the compound making as the adhesivity raising of the inorganics of supporter and the cured film of coloring photosensitive combination layer, and described inorganics is silicon compounds such as glass, silicon, silicon oxide, silicon nitride, gold, copper, aluminium etc.Specifically, can list silane coupling agent etc.As the silane coupling agent that adheres to modifying agent, be to take the silane coupling agent that the upgrading at interface is object, can be not particularly limited and use known silane coupling agent.
As silane coupling agent, be preferably the silane coupling agent of the 0048th section of record of TOHKEMY 2009-98616 communique, wherein, more preferably γ-glycidoxy propyl trialkoxy silane, γ-methacryloxypropyl trialkoxy silane.They can use separately a kind or and use two or more.
The content of the adhesion modifying agent in coloring photosensitive combination of the present invention becomes component to be preferably 0.1～20 quality %, 0.2～5 quality % more preferably with respect to the total solids of coloring photosensitive combination.
(linking agent)
In coloring photosensitive combination of the present invention, use linking agent can be assisted, thereby the hardness that makes coloring photosensitive combination solidify the pigmented layer forming can also be further improved.
As linking agent, so long as can carry out the curing linking agent of film by crosslinking reaction, just be not particularly limited, for example can list that (a) epoxy resin, (b) are that at least a kind of substituting group in methylol, alkoxy methyl and acyloxy methyl replaces with being selected from, melamine compound, guanidine amine compound, glycoluril (Glycoluril) compound or carbamide compound, (c) are that at least a kind of substituting group in methylol, alkoxy methyl and acyloxy methyl replaces with being selected from, oxybenzene compound, naphthol compound or hydroxyl anthracene compound.Wherein, be preferably polyfunctional epoxy resin.
For the detailed content of the concrete example of linking agent etc., can be with reference to the record of TOHKEMY 2004-295116 communique (0134)～(0147) section.
(development accelerant)
In the situation that the alkali dissolution in the territory, non-exposed area while wanting to promote coloring photosensitive combination layer to expose, further improve the developability of coloring photosensitive combination, can also add development accelerant.Development accelerant is preferably lower molecular weight organic carboxyl acid compound, the molecular weight lower molecular weight phenolic compound 1000 below of molecular weight below 1000.
Specifically, can list such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, diethylacetic acid, enanthic acid (enanthic acid), the aliphatic monocarboxylic acid such as sad; The aliphatic dicarboxylic acids such as oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid (suberic acid), nonane diacid (azelaic acid), sebacic acid (sebacic acid), undecane dicarboxylic acid (brassylic acid), Methylpropanedioic acid (methylmalonic acid), ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl-succsinic acid, citraconic acid; The aliphatic tricarboxylic acids such as tricarballylic acid (tricarballylic acid), equisetic acid (aconitic acid), camphoronic acid (camphoronic acid); M-nitro benzoic acid, toluic acid (toluic acid), cuminic acid (cuminic acid), mesitylenic acid (hemellitic acid), the aromatic series monocarboxylic acids such as woods acid (Mesitylenic Acid); The aromatic polycarboxylic acids such as phthalic acid, m-phthalic acid, terephthalic acid, trihemellitic acid, trimesic acid, the inclined to one side tetracid of benzene (mellophanic acid), pyromellitic acid (pyromellitic acid); Other carboxylic acids such as phenylacetic acid, hydratropic acid (hydratropic acid), phenylpropionic acid, amygdalic acid (mandelic acid), phenylsuccinic acid, atropic acid (atropic acid), styracin, methyl cinnamate, cinnamein, cinnamylidene acetic acid, coumalic acid, umbellic acid (umbellic acid).
(other additives)
In coloring photosensitive combination of the present invention, can further coordinate as required various additives, such as weighting agent, macromolecular compound beyond above-mentioned, UV light absorber, oxidation inhibitor etc.As these additives, can list the material of recording in the section of TOHKEMY 2004-295116 communique (0155)～(0156).
The hot stopper that can contain record in (0081) section, photostabilizer, the TOHKEMY 2004-295116 communique recorded in (0078) section, TOHKEMY 2004-295116 communique in coloring photosensitive combination of the present invention.
(preparation method of coloring photosensitive combination)
Coloring photosensitive combination of the present invention by by aforementioned each composition and as required any composition of use mixed to prepare.Preferably use above-mentioned dispersive composition as coloring agent component, and aforementioned each composition is mixed and prepared with any composition of use as required.
It should be noted that, when preparing coloring photosensitive combination, can be disposable cooperation form each composition of coloring photosensitive combination, also can successively coordinate.In addition, ordering in launching, operating condition during cooperation is not subject to special restriction.
For by above-mentioned prepared coloring photosensitive combination, after preferably can utilizing the strainer etc. of 0.01 μ m～3.0 μ m left and right, aperture to filter, then in.
Coloring photosensitive combination of the present invention can form the color solidification film of excellent heat resistance, contrast gradient excellence, the colored pixels of the colour filter that therefore, can be suitable for using in liquid crystal indicator etc. forms purposes and printing ink liquid, inkjet ink and coating etc. and makes purposes.
< < colour filter and manufacture method > > thereof
Colour filter of the present invention arranges supporter and consists of the formed painted areas of coloring photosensitive combination of the present invention at this supporter.Painted areas on supporter consists of the pigmented layer such as red (R), green (G), blue (B) etc. that forms each pixel of colour filter.
The manufacture method of colour filter of the present invention comprises: above-mentioned coloring photosensitive combination is given on supporter and the pigmented layer that forms pigmented layer (coloring photosensitive combination layer) forms operation (A), the pigmented layer being formed by operation (A) is carried out the exposure process (B) of the exposure of pattern-like and the pigmented layer after above-mentioned exposure is developed and forms the developing procedure (C) of colored pattern.
In addition, in the manufacture method of colour filter of the present invention, be particularly preferably the operation (D) that the colored pattern further arranging obtaining carries out heat treated in operation (C).
Below, the manufacture method for colour filter of the present invention more specifically describes.
-operation (A)-
With regard to the manufacture method of colour filter of the present invention, first by coating processes such as rotary coating, slot coated, curtain coating coating, roller coat cloth, rod coating, ink-jets, on supporter, give above-mentioned coloring photosensitive combination of the present invention, thereby formation pigmented layer, then makes this pigmented layer dry by heating (prebake) or vacuum-drying etc.
As supporter, can list such as the soda glass for liquid crystal indicator, non-alkali glass, pyrex, silica glass, silicon substrate, resin substrate etc.In addition, in order to improve with the adhesion of the layer on top, to prevent material diffusion or make the smooth of surface, lower coating can be set on these supporters as required.
As the condition of prebake, can list and use hot plate or baking oven in 70 ℃～130 ℃ heating condition of about 0.5 minute～15 minutes.
The thickness of the pigmented layer being formed by coloring photosensitive combination in addition, can suitably be selected according to object.In color filter for liquid crystal display, be preferably the scope of 0.2 μ m～5.0 μ m, the scope of 1.0 μ m～4.0 μ m more preferably.It should be noted that, the thickness of pigmented layer is dried thickness.
-operation (B)-
Then,, with regard to the manufacture method of colour filter of the present invention, the pigmented layer being formed on supporter is carried out to the exposure of pattern-like.Light or radioactive rays as applicable to exposure, be preferably g ray, h ray, i ray, various laser, is particularly preferably i ray.When irradiating light use high voltage mercury lamp, preferably with 5mJ/cm 2～500mJ/cm 2exposure irradiate.
In addition, as other exposure light sources, can use each mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, various LASER Light Source of ultra-high voltage, high pressure, middle pressure, low pressure etc.
～used the exposure process of LASER Light Source～
In having used the Exposure mode of LASER Light Source, irradiate light and be preferably ultraviolet laser, the wavelength of the scope of 300nm～360nm more preferably of scope of wavelength that wavelength is the scope of 300nm～410nm.Specifically, particularly preferably use the third high harmonic wave (355nm) of the Nd:YAG laser of the large and less expensive Solid State Laser of output rating, the XeCl (308nm) of excimer laser, XeF (353nm).As pattern exposure amount, from productive viewpoint, be preferably 1mJ/cm 2～100mJ/cm 2scope, 1mJ/cm more preferably 2～50mJ/cm 2scope.
As exposure apparatus, be not particularly limited, as commercially available device, can use Callisto (V-TECHNOLOGY Co., Ltd. system), EGIS (V-TECHNOLOGY Co., Ltd. system), DF2200G (large Japanese SCREEN Co., Ltd. system) etc.In addition, also preferably use above-mentioned device in addition.
-operation (C)-
Then, the pigmented layer for after exposure, utilizes developing solution to develop.Thus, can form colored pattern.Developing solution so long as the uncured portion of pigmented layer is dissolved and do not dissolved the material of cured portion, can be used combination, the alkaline aqueous solution of various organic solvents.When developing solution is alkaline aqueous solution, alkali concn is preferably adjusted according to the mode that reaches pH10～13.As above-mentioned alkaline aqueous solution, can list for example sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, water glass, sodium metasilicate, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrroles, piperidines, 1,8-diazabicyclo-[5,4,0]-alkaline aqueous solutions such as 7-undecylene.
Development time is preferably 30 seconds～and 300 seconds, more preferably 30 seconds～120 seconds.Development temperature is preferably 20 ℃～40 ℃, more preferably 23 ℃.
Development can utilize alr mode, spray mode, spray pattern etc. to carry out.
In addition, after using alkaline aqueous solution to develop, preferably utilize water to clean.
In the manufacture method of colour filter of the present invention, also particularly preferably the colored pattern (pixel) that uses coloring photosensitive combination to form is utilized the post-exposure of uviolizing.
-operation (D)-
Preferably to the colored pattern after developing or further carry out heat treated to having carried out the colored pattern of the post-exposure based on uviolizing as above.By formed colored pattern being carried out to heat treated (curing processing after so-called), thereby can further make colored pattern solidify.This heat treated can utilize such as hot plate, various well heater, baking oven etc. to carry out.
Temperature during as heat treated, is preferably 100 ℃～300 ℃, more preferably 150 ℃～250 ℃.In addition, be preferably heat-up time about 10 minutes～120 minutes.
The colored pattern obtaining therefrom forms the green pixel in colour filter.When making has the colour filter of pixel of multiple color tones, according to required number of colours, repeatedly carry out above-mentioned operation (A), operation (B), operation (C) and operation (D).
It should be noted that, can finish whenever formation, exposure, the development of monochromatic pigmented layer to carry out above-mentioned operation (D) after (each color) the disposable above-mentioned operation (D) of carrying out after also can finishing in formation, exposure, the development of whole pigmented layer of required color number.
In addition, coloring photosensitive combination of the present invention can form green pigmented layer, and green pixel is arranged on supporter, and when colored pixels consists of the blue green of redness, the order that pigmented layer is set can be arbitrary order.
< < display unit > >
The colour filter (colour filter of the present invention) that manufacture method by colour filter of the present invention obtains has used coloring photosensitive combination of the present invention, thus thermotolerance and contrast gradient excellent.
Display unit of the present invention possesses colour filter of the present invention.
As display unit of the present invention, specifically, be preferably liquid-crystal display (liquid crystal indicator; LCD), the display unit for portable terminal device such as OLED display (organic EL display), liquid crystal projection apparatus, display device for game computer, portable phone, display unit for digital camera, the display unit of display unit etc. for auto navigation, be especially preferably photographic camera display unit.
By colour filter of the present invention, during for organic EL display, liquid crystal indicator etc., when realizing good tone, the image that can realize dichroism and contrast gradient excellence shows.
< liquid crystal indicator >
For having used the liquid crystal indicator of colour filter of the present invention to describe.For the definition of organic EL display, liquid crystal indicator, the detailed content of each display unit, be described in such as in " electronic console device (Electricity デ ィ ス プ レ イ デ バ イ ス) (the clear husband's work of assistant 々 wood, (strain) census of manufacturing can be issued nineteen ninety) ", " display devices (デ ィ ス プ レ イ デ バ イ ス) (she blows along chapter work, industry books (strain) and puts down into distribution in the first year) " etc.In addition, for liquid crystal indicator, be for example described in " LCD Technology of new generation (inferior generation liquid crystal デ ィ ス プ レ イ Ji Intraoperative) (Uchida Tatsuo compiles, (strain) census of manufacturing can 1994 distribution) ".The present invention's liquid crystal indicator applicatory is not particularly limited, in the liquid crystal indicator applicable to the variety of way of recording in example " LCD Technology of new generation " described above.
For colour filter of the present invention, for the liquid crystal indicator of colored TFT mode, be particularly effective.Liquid crystal indicator for colored TFT mode, for example, record " color TFT-LCD indicating meter (vertical publication (strain) distribution in 1996 altogether) ".And then, the present invention also applicable to the visual angles such as pixel partitioning scheme such as transverse electric field type of drive, MVA such as IPS extended liquid crystal indicator, STN, TN, VA, OCS, FFS and R-OCB etc.In addition, colour filter of the present invention is also available for COA (Color-filter On Array; Color filter array) mode.
If colour filter of the present invention is used for to liquid crystal indicator, when the three-wavelength pipe combination with known cold-cathode tube in the past, can realize high-contrast, and then, by using the LED light source of red, green, blue (RGB-LED) as backlight, thereby can provide brightness colorrendering quality high and that purity of color is high good liquid crystal indicator.
Embodiment
Below, further by embodiment, the present invention is specifically described, but the present invention is not limited to following embodiment.It should be noted that, unless otherwise specified, " % ", " part " are quality criterias.
(embodiment 1-1)
-preparation of green dispersive composition 1-
The preparation > of < look material composition
By commercially available C.I. Pigment green 58 (goods name: 140 parts of the FASTGENGREEN A110 processed of Dainippon Ink Chemicals) 100 parts, 50 parts of dyestuff Y1 (following structure), 400 parts, sodium-chlor and water-miscible organic solvent glycol ethers are put in desk-top kneader ((strain) Ru Jiang chamber of commerce system) mixing 10 hours.Then, this is mixing after for thing, dissolver ((strain) Japanese smart mechanism is done made) stirs, mixes with water, repeatedly filter, wash, remove sodium-chlor and solvent, obtain the moisture filter cake of look material.Then, this moisture filter cake is dried to 6 hours in the baking oven of 80 ℃, obtains the look material composition of C.I. Pigment green 58 and dyestuff Y1.
[changing 51]
Dyestuff Y1
The < rough segmentation > that falls apart
Use above-mentioned look material composition, after allocating according to following composition, utilize Eiger mill (Eiger mill) (EigerJapan (strain) system) with the zirconium oxide bead of diameter 0.8mm, mixture to be disperseed.
Look material composition: 150 parts
Dispersion agent: SOLSPERSE 22000 (Japanese Lubrizol (strain) system)
10 parts
Dispersion agent: SOLSPERSE 24000 (Japanese Lubrizol (strain) system)
80 parts
Organic solvent: 220 parts of propylene glycol methyl ether acetates
The accurate > that disperses of <
Dispersion after above-mentioned rough segmentation is loose takes out, and adds 30 parts of propylene glycol methyl ether acetates, and mix in 100 parts of dispersions.Then, use Eiger mill (EigerJapan (strain) system) and the zirconium oxide bead of diameter 0.1mm to be disperseed.
< concentration is adjusted >
Dispersion after precision is disperseed takes out, and adding propylene glycol methyl ether acetate to be diluted to pigment concentration is 10%, makes green dispersive composition 1.
-preparation of coloring photosensitive combination-
Following each composition is mixed, dissolved, prepare coloring photosensitive combination 1-1.
Organic solvent 1: 29 parts of propylene glycol methyl ether acetates
Organic solvent 2: 26 parts, glycol ether ethyl-methyl ether
Alkali-soluble tackiness agent 1: cyclohexyl methacrylate/methacrylic acid/glycidyl methacrylate (=mol ratio: 7 parts of the affixtures of methacrylic acid 30/30/40) (45% propylene glycol monomethyl ether solution)
Alkali-soluble tackiness agent 2: 6 parts of allyl methacrylate(AMA)/Sipacril 2739OF=mol ratios 70/30 (weight-average molecular weight 26800)
Polymerizable compound 1: 4 parts of Japanese chemical drug (strain) system, KAYARAD DPHA
Polymerizable compound 2: 4 parts of East Asia synthetic (strain) system, ARONIX TO-2349
Stopper: 0.003 part of p methoxy phenol
Photoepolymerizationinitiater initiater 1:1-(O-acetyl oxime)-1-[9-ethyl-6-(Thenoyl (thiophenoyl))-9H-carbazole-3-yl] 0.3 part, acetone
Photoepolymerizationinitiater initiater 2:1,3-dihydro-1-phenyl-2H-benzimidazolyl-2 radicals-thioketones (thione)
0.2 part
Multi-functional thiol's compound: Isosorbide-5-Nitrae-bis-(3-sulfydryl butyryl acyloxy) butane
0.1 part
Adhere to modifying agent: 0.2 part of 3-methacryloxypropyl trimethoxy silane
Fluorine is tensio-active agent: 5 parts of the MEGA FAC processed F-554 of DIC company (0.2% propylene glycol methyl ether acetate solution)
1 30 parts of green dispersive compositions
(embodiment 1-2～1-6)
In embodiment 1-1, except by the content change of recording according to table 1 for the preparation of the dyestuff of look material composition, carry out the operation identical with embodiment 1-1, produce coloring photosensitive combination 1-2～1-6.
It should be noted that, the dyestuff using in embodiment 1-2～1-24 is as described below.
[changing 52]
Dyestuff Y2
[changing 53]
Dyestuff Y3
[changing 54]
Dyestuff Y4
[changing 55]
Dyestuff Y5
[changing 56]
Dyestuff Y6
(embodiment 1-7)
-preparation of green dispersive composition 7-
The miniaturization > of < pigment
140 parts of 58100 parts of the C.I. Pigment greens using, 400 parts, sodium-chlor and glycol ethers are put in desk-top kneader ((strain) Ru Jiang chamber of commerce system) to mixing 10 hours in embodiment 1-1.Then, this mixing thing is stirred, mixed with dissolver for water ((strain) Japanese smart mechanism is done made), then repeatedly filter, wash, thereby sodium-chlor and solvent are removed, obtain the moisture filter cake of look material.Then, this moisture filter cake is dried to 6 hours in the baking oven of 80 ℃, obtains the miniaturization pigment of C.I. Pigment green 58.
The < rough segmentation > that falls apart
Use above-mentioned miniaturization pigment, after following composition allotment, use Eiger mill (EigerJapan (strain) system) and the zirconium oxide bead of diameter 0.8mm to disperse mixture.
100 parts of miniaturization pigment
667 parts of the 7.5% propylene glycol methyl ether acetate solution of dyestuff Y1 (above-claimed cpd)
Dispersion agent: SOLSPERSE22000 (Japanese Lubrizol (strain) system)
10 parts
Dispersion agent: SOLSPERSE24000 (Japanese Lubrizol (strain) system)
80 parts
The accurate > that disperses of <
Dispersion after above-mentioned rough segmentation is loose takes out, and then uses Eiger mill (EigerJapan (strain) system) and the zirconium oxide bead of diameter 0.1mm to disperse.
< concentration is adjusted >
Dispersion after above-mentioned accurate dispersion is taken out, add propylene glycol methyl ether acetate to dilute so that pigment concentration reaches 10%, make green dispersive composition 7.
-preparation of coloring photosensitive combination 1-7-
In embodiment 1-1, except green dispersive composition 1 being replaced by green dispersive composition 7, carry out the operation identical with embodiment 1-1, produce coloring photosensitive combination 1-7.
(embodiment 1-8～1-12)
In embodiment 1-7, the content of recording according to table 1 changes the dyestuff adding in rough segmentation is loose, in addition, carries out the operation identical with embodiment 1-7, produces coloring photosensitive combination 1-8～1-12.
(embodiment 1-13)
-preparation of green dispersive composition 13-
The miniaturization > of < pigment
140 parts of 58100 parts of the C.I. Pigment greens using, 400 parts, sodium-chlor and glycol ethers are put in desk-top kneader ((strain) Ru Jiang chamber of commerce system) to mixing 10 hours in embodiment 1-1.Then, by this mixing thing and for water dissolver ((strain) Japanese smart mechanism is done made) stir, mix, then repeatedly filter, wash, thereby sodium-chlor and solvent are removed, obtain the moisture filter cake of look material.Then, this moisture filter cake is dried to 6 hours in the baking oven of 80 ℃, obtains the miniaturization pigment of C.I. Pigment green 58.
The < rough segmentation > that falls apart
Use above-mentioned miniaturization pigment, after following composition allotment, utilize Eiger mill (EigerJapan (strain) system) and the zirconium oxide bead of diameter 0.8mm to be disperseed in mixture.Now, under pulverulence, miniaturization pigment and dyestuff are mixed at first, then add other materials and disperse.
Miniaturization pigment: 100 parts
Dyestuff Y1:50 part
10 parts of dispersion agent: SOLSPERSE 22000 (Japanese Lubrizol (strain) system)
80 parts of dispersion agent: SOLSPERSE 24000 (Japanese Lubrizol (strain) system)
Organic solvent: 220 parts of propylene glycol methyl ether acetates
The accurate > that disperses of <
Dispersion after above-mentioned rough segmentation is loose takes out, and with respect to 100 parts of dispersions, adds 30 parts of propylene glycol methyl ether acetates, and mixes.Then, use Eiger mill (EigerJapan (strain) system) and the zirconium oxide bead of diameter 0.1mm to disperse.
< concentration is adjusted >
Dispersive composition after above-mentioned accurate dispersion is taken out, add propylene glycol methyl ether acetate to dilute so that pigment concentration reaches 10%, thereby make green dispersive composition 13.
-preparation of cured composition for color 1-13-
In embodiment 1-1, except using the alternative green dispersive composition 1 of green dispersive composition 13, carry out the operation identical with embodiment 1-1, produce coloring photosensitive combination 1-13.
(embodiment 1-14～1-18)
In embodiment 1-13, except the content of recording according to table 1 changes the dyestuff adding in rough segmentation is loose, carry out the operation identical with embodiment 1-13, produce coloring photosensitive combination 1-14～1-18.
(embodiment 1-19)
-preparation of green dispersive composition 19-
The miniaturization > of < pigment
140 parts of 58 100 parts of the C.I. Pigment greens using, 400 parts, sodium-chlor and glycol ethers are put in desk-top kneader ((strain) Ru Jiang chamber of commerce system) to mixing 10 hours in embodiment 1-1.Then, after this mixing thing is stirred, mixed with dissolver for water ((strain) Japanese smart mechanism is done made), repeatedly filter, wash, thereby sodium-chlor and solvent are removed, obtain the moisture filter cake of look material.Then, this moisture filter cake is dried to 6 hours in the baking oven of 80 ℃, obtains the miniaturization pigment of C.I. Pigment green 58.
The < rough segmentation > that falls apart
Use above-mentioned miniaturization pigment, after following composition allotment, use Eiger mill (EigerJapan (strain) system) and the zirconium oxide bead of diameter 0.8mm to be disperseed in mixture.
Miniaturization pigment: 100 parts
10 parts of dispersion agent: SOLSPERSE 22000 (Japanese Lubrizol (strain) system)
80 parts of dispersion agent: SOLSPERSE 24000 (Japanese Lubrizol (strain) system)
260 parts of propylene glycol methyl ether acetates
The accurate > that disperses of <
Dispersion after above-mentioned rough segmentation is loose takes out, and adds 100 parts of dispersions and 11 parts of dyestuff Y1 and mixes.Then, add 30 parts of propylene glycol methyl ether acetates, use Eiger mill (EigerJapan (strain) system) and the zirconium oxide bead of diameter 0.1mm to disperse.
< concentration is adjusted >
Dispersive composition after above-mentioned accurate dispersion is taken out, add propylene glycol methyl ether acetate to dilute so that pigment concentration reaches 10%, thereby make green dispersive composition 19.
-preparation of coloring photosensitive combination 1-19-
In embodiment 1-1, green dispersive composition 1 is replaced by green dispersive composition 19, in addition, carry out the operation identical with embodiment 1-1, produce coloring photosensitive combination 1-19.
(embodiment 1-20～1-24)
In embodiment 1-19, the dyestuff adding while changing accurate dispersion except the content of recording according to table 1, carry out the operation identical with embodiment 1-19, produce coloring photosensitive combination 1-20～1-24.
(comparative example 1-1)
-preparation of green dispersive composition A-
The miniaturization > of < pigment
140 parts of 58 100 parts of the C.I. Pigment greens using, 400 parts, sodium-chlor and glycol ethers are put in desk-top kneader ((strain) Ru Jiang chamber of commerce system) to mixing 10 hours in embodiment 1-1.Then, after this mixing thing is stirred, mixed with dissolver for water ((strain) Japanese smart mechanism is done made), repeatedly filter, wash and sodium-chlor and solvent are removed, obtain the moisture filter cake of look material.Then, this moisture filter cake is dried to 6 hours in the baking oven of 80 ℃, obtains the miniaturization pigment of C.I. Pigment green 58.
The < rough segmentation > that falls apart
Use above-mentioned miniaturization pigment, after following composition allotment, utilize Eiger mill (EigerJapan (strain) system) and the zirconium oxide bead of diameter 0.8mm to be disperseed in mixture.
Miniaturization pigment: 100 parts
10 parts of dispersion agent: SOLSPERSE 22000 (Japanese Lubrizol (strain) system)
80 parts of dispersion agent: SOLSPERSE 24000 (Japanese Lubrizol (strain) system)
260 parts of propylene glycol methyl ether acetates
The accurate > that disperses of <
After above-mentioned rough segmentation is loose, dispersion takes out, and with respect to 100 parts of dispersions, adds 19 parts of 11 parts of dyestuff Y1 and propylene glycol methyl ether acetates, and mixes.Then, utilize Eiger mill (EigerJapan (strain) system) and the zirconium oxide bead of diameter 0.1mm to be disperseed, obtain the green dispersive composition A of pigment concentration 10%.
-preparation of coloring photosensitive combination A-
In embodiment 1-1, except green dispersive composition 1 being changed into green dispersive composition A, carry out the operation identical with embodiment 1-1, produce coloring photosensitive combination A.
(comparative example 1-2)
The miniaturization > of < pigment
140 parts of 58100 parts of the C.I. Pigment greens using, 400 parts, sodium-chlor and glycol ethers are put in desk-top kneader ((strain) Ru Jiang chamber of commerce system) to mixing 10 hours in embodiment 1-1.Then, after this mixing thing is stirred, mixed with dissolver for water conservancy ((strain) Japanese smart mechanism is done made), repeatedly filter, wash and sodium-chlor and solvent are removed, obtain the moisture filter cake of look material.Then, this moisture filter cake is dried to 6 hours in the baking oven of 80 ℃, obtains the miniaturization pigment of C.I. Pigment green 58.
The < rough segmentation > that falls apart
Use above-mentioned miniaturization pigment, after following composition allotment, utilize Eiger mill (EigerJapan (strain) system) and the zirconium oxide bead of diameter 0.8mm to be disperseed in mixture.
Miniaturization pigment: 100 parts
10 parts of dispersion agent: SOLSPERSE 22000 (Japanese Lubrizol (strain) system)
80 parts of dispersion agent: SOLSPERSE 24000 (Japanese Lubrizol (strain) system)
Propylene glycol methyl ether acetate: 260 parts
The accurate > that disperses of <
Dispersion after above-mentioned rough segmentation is loose takes out, and with respect to 100 parts of dispersions, adds 19 parts of propylene glycol methyl ether acetates and mixes.Then, utilize Eiger mill (EigerJapan (strain) system) and the zirconium oxide bead of diameter 0.1mm to disperse.After dispersion, add 11 parts of dyestuff Y1, utilize three-in-one motor (three one motor) to mix, obtain green dispersive composition B.
-preparation of cured composition for color B-
In embodiment 1-1, green dispersive composition 1 is changed to green dispersive composition B, in addition, carry out the operation identical with embodiment 1-1, produce coloring photosensitive combination B.
(comparative example 1-3)
-preparation of green dispersive composition C-
After following composition allotment, PAINT SHAKER for mixture (development of Seiwa skill) and the zirconium oxide bead of diameter 0.1mm are disperseed, obtain green dispersive composition C.
The C.I. Pigment green 58:100 part of using in embodiment 1-1
Dyestuff Y1:50 part
10 parts of dispersion agent: SOLSPERSE 22000 (Japanese Lubrizol (strain) system)
80 parts of dispersion agent: SOLSPERSE 24000 (Japanese Lubrizol (strain) system)
Propylene glycol methyl ether acetate: 760 parts
-preparation of coloring photosensitive combination C-
In embodiment 1-1, green dispersive composition 1 is changed to green dispersive composition C, in addition, carry out the operation identical with embodiment 1-1, produce coloring photosensitive combination C.
Ci, the Cf of the coloring photosensitive combination of producing are thus as follows.
The concentration of the particular dye of the Ci in embodiment 1-1～embodiment 1-6 during by ready-mixed and calculating, be 33.3%, the dyestuff of Cf in the dispersive composition after the concentration adjustment after disperseing to finish dense and calculating is 5.0% in embodiment 1-1～embodiment 1-6.
What in addition, the Ci in embodiment 1-7～embodiment 1-18 was fallen apart by rough segmentation forms and calculates.The Ci of embodiment 1-7～embodiment 1-12 is 5.8%, the Ci of embodiment 1-13～embodiment 1-18 is 7.8%.The densitometer of the dyestuff of Cf in the dispersive composition after the concentration adjustment after dispersion finishes is calculated, and in embodiment 1-7～embodiment 1-18, is 5.0%.
In embodiment 1-19～embodiment 1-24, Ci is disperseed by precision forms and calculates, and is 7.8%, and the concentration of the dyestuff of Cf in the dispersive composition after the concentration adjustment after disperseing to finish and calculating is 5.0%.
In addition, comparative example 1-1～comparative example 1-3 is Ci=Cf and is 5.0%.
-evaluate-
As the coloring photosensitive combination 1-1～1-24 obtaining in above-mentioned and the performance evaluation of A～C, for dichroism, contrast gradient, thermotolerance, according to the method illustrating below, evaluate.In addition, for the dye adsorption rate to pigment in each green dispersive composition, also evaluate simultaneously.Evaluation result is shown in table 1.
-formation of coloring photosensitive combination layer (pigmented layer)-
At glass (#1737; Corning Incorporated's system) on substrate, utilize spin-coating method to be coated on after the coloring photosensitive combination of preparing in above-mentioned, in drying at room temperature 30 minutes, make volatile component volatilization, thereby formed pigmented layer.For this pigmented layer, across the mask of thread pattern, irradiate i ray (wavelength 365nm), form sub-image.Light source for i ray, forms directional light with ultrahigh pressure mercury lamp, then irradiates.Now, irradiation light quantity is made as to 40mJ/cm 2.Then, for the pigmented layer that is formed with this sub-image, use the aqueous solution (concentration 2.4%) of sodium carbonate/bicarbonate in 26 ℃ of developments 45 seconds, then, with flowing water, rinse after 20 seconds, spray dry, obtain thread pattern image.To the thread pattern image of gained in 230 ℃ carry out 20 minutes after cure processing, obtain the pigmented layer of the viridescent thread pattern of tool of thickness 2 μ m.
(contrast gradient evaluation)
The substrate of the rewarding pigmented layer of tool is clipped between 2 polarizing coatings, use chroma-luminance meter (TOPCON (strain) system, model: BM-5A) brightness value in the brightness value in the parallel situation of the polarization axle of 2 polarizing coatings and vertical situation is measured, brightness in the parallel situation of the polarization axle of 2 polarizing coatings, divided by the brightness in vertical situation, is obtained the value of gained and is spent as a comparison.Contrast gradient is higher, and the colour filter of using as liquid crystal indicator demonstrates better performance.
(dichroism)
Use micro-spectral determinator (Olympus (strain) system, model OSP-SP200) to measure the transmitted spectrum of the pigmented layer obtaining in above-mentioned.According to the transmitted spectrum of gained, obtain tristimulus coordinates x value, y value, Y value in CIE1931 coloring system.
For dichroism, in the situation that the Y value in (x, y)=(0.300,0.600) is high, can thinks and there is excellent dichroism.Y value is larger, can think that dichroism is more excellent.
(thermotolerance)
After using micro-spectral determinator (Olympus (strain) system, model OSP-SP200) to measure the transmitted spectrum of the pigmented layer obtaining in above-mentioned, in 230 ℃, carry out 60 minutes append and cure, again evaluate transmitted spectrum.Calculate the Y value poor (Δ Y) of appending before and after curing, using it as stable on heating index.Δ Y is less, can think that thermotolerance is more excellent.
(dye adsorption rate)
Utilize ultracentrifugation separating machine (Hitachi's work machine (strain) system) to carry out centrifugal treating in 50000rpm each green dispersive composition, obtain the supernatant liquor that comprises free composition.Utilize HPLC to evaluate the amount of dye in supernatant liquor, utilize following formula to define adsorption rate.
[several 2]
[table 1]
Content as shown in Table 1.Coloring photosensitive combination 1-1～1-24 of the present invention has excellent thermotolerance with respect to the coloring photosensitive combination A～C of comparative example.Thermotolerance is relevant to dye adsorption rate, thus, can infer by dye adsorption in pigment, thereby make thermal discoloration obtain inhibition.The dye adsorption rate of colo(u)rant dispersion thing of the present invention uprises, and is therefore easy to obtain high heat resistance.
Dye strength Ci when its reason can be thought because drop into dyestuff during the dispersive composition in making the present invention causes higher than the dye strength Cf in final dispersive composition.That is, can think: for example, by drop into dyestuff (that is recorded in embodiment 1-1 drops into dyestuff with solid state when the pigment miniaturization) with greater concn, thereby be easy to cause the absorption to pigment.
As described in comparative example, even drop in dispersion step, the in the situation that of being only uniformly mixed in the situation that dyestuff is lower concentration and after dispersion step, dye adsorption rate is also low, thereby also step-down of thermotolerance.
In addition, surprisingly, coloring photosensitive combination 1-1～1-24 of the present invention has excellent contrast gradient for the coloring photosensitive combination A～C of comparative example.Its reason is still not clear, but can infer, is due to following reason, that is, dye adsorption in surface of pigments, the free amount of dye in dispersion is few, therefore, has suppressed the dyestuff cohesion in film-forming process.Can infer: by suppressing the cohesion of dyestuff, thereby can reduce as the particle in the pigmented layer of the reason of scattering of light, so contrast gradient improves.
(embodiment 1-25)
The making > of < liquid crystal indicator
By following method, make colour filter, make and used the liquid crystal indicator of this colour filter, and display characteristic is evaluated.
The making > of the red colored photosensitive composite R of <
Following red pigment dispersion is formed and mixed, use clarifixator at rotating speed 3, under 000rpm, stir 3 hours.By therefrom mixing solutions further utilize the dispersion treatment of having used the pearl dispersion machine DISPERMAT (GETZMANN company system) of 0.3mm φ zirconium oxide bead to carry out 12 hours, then, further use the high pressure dispersion machine NANO-3000-10 (Japanese ビ ー イ ー イ ー (strain) system) with the mechanism of decompressor, at 2000kg/cm 3pressure under, with flow 500g/min, carry out dispersion treatment.Repeat this dispersion treatment 10 times, obtain pigment dispensing composition.
(red pigment dispersion composition)
C.I. Pigment red is 254 75 parts
C.I. Pigment red is 177 50 parts
70 parts of benzyl methacrylate/Sipacril 2739OFs
(copolymerization ratio of components 70/30 weight-average molecular weight 30000, acid number 40)
800 parts of propylene glycol methyl ether acetates
In the pigment dispensing composition of gained, further add the composition of following composition, produce red photosensitive composite R.
(red photosensitive composite R forms)
100 parts of above-mentioned red pigment dispersions
12 parts of the propylene glycol methyl ether acetate solution (solids component 50%) of benzyl methacrylate/methacrylic acid (=70/30[mol ratio]) multipolymer (Mw:30,000)
Polymerizable compound 1: 12.1 parts of Japanese chemical drug (strain) system, KAYARAD DPHA
Photoepolymerizationinitiater initiater: 2-(Chloro-O-Phenyl)-4,3.1 parts of 5-diphenyl-imidazole base dipolymers
Sensitization pigment: 4,4 '-bis-(diethylamino) 4.2 parts of benzophenone
Supply with hydrogen compound: 2.1 parts of 2-mercaptobenzothiazoles
Stopper: 0.001 part of p methoxy phenol
Fluorine is 0.5 part, tensio-active agent (trade(brand)name: Megafac R08 DIC (strain) system)
60 parts of propylene glycol methyl ether acetates
The making > of the blue photosensitive composite B of <
In the making of red colored photosensitive composite R, use 100 parts of C.I. pigment Blue 15s: 6 substitute C.I. Pigment red 254, with 23 parts of C.I. pigment Violet 23s, substitute C.I. Pigment red 177, in addition, carry out identical operation, produce blue photosensitive composite B.
The making > of < black photosensitive composition K
The colo(u)rant dispersion thing of allocating following composition forms, and similarly carries out dispersion treatment, thereby produce black pigment dispersion during with making red pigment dispersion.
(black pigment dispersion composition)
Carbon black (trade(brand)name: Nipex35, Degussa Japan Co., Ltd. system)
13.1 parts
6.7 parts, polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, molecular weight 3.7 ten thousand)
79.1 parts of propylene glycol methyl ether acetates
0.65 part of dispersion agent (following compound)
[changing 57]
Use the black pigment dispersion of gained, according to following composition, prepare black photosensitive composition K.
(black photosensitive composition K composition)
25 parts of above-mentioned black pigment dispersions
8.5 parts of propylene glycol methyl ether acetates
53 parts of methylethylketones
Tackiness agent: 9.1 parts, the mixture of 27 parts of random copolymerss of benzyl methacrylate/methacrylic acid=78/22 mol ratio (molecular weight 3.8 ten thousand) and 73 parts of propylene glycol methyl ether acetates
0.002 part of Hydroquinone monomethylether
12 parts of polymerizable compound: DPHA (Japanese chemical drug company system)
Amino-the 3 '-bromophenyl of two (three chloroethyls)-6-[4 ' of polymerization starter: 2,4-(N, the two ethoxy carbonyl methyl of N-)] 0.16 part of-s-triazine
0.042 part of methylethylketone 30% solution of tensio-active agent (following compound)
[changing 58]
The making > of < colour filter
The formation > of the black matrix of <
After utilizing UV washing unit to clean alkali-free glass substrate, with clean-out system, scrub, and then carry out ultrasonic cleaning with ultrapure water.In 120 ℃, this substrate heat is processed 3 minutes, after making condition of surface stable, this substrate is carried out cooling, temperature adjustment to 23 ℃.
Utilization has spreader for glass substrate (FIS Asia company system, the trade(brand)name: MH-1600) be coated with above-mentioned black photosensitive composition K on this substrate of slit-shaped nozzle.Then, at VCD (Minton dryer; Chemical industry (strain) society system is answered in Tokyo) in 30 seconds, a part for solvent is dried, the mobility of coating layer is disappeared, then in 120 ℃ of prebake 3 minutes, obtain the black photosensitive composition layer of thickness 2.4 μ m.
Utilization has the PROXIMITY type exposure machine (high-tech electronic engineering corporation of Hitachi (the Ha イ テ Network Electricity エ Application ジ ニ ア リ Application グ of Hitachi (strain) society) system) of ultrahigh pressure mercury lamp, make under the state of substrate and the vertical placement of mask (the quartzy exposed mask with picture pattern), distance between exposed mask face and this photosensitive composite layer is set as to 200 μ m, with exposure 300mJ/cm 2carry out pattern exposure.
Then, utilize spray spout to spray with pure water, after making the surface uniform of this black photosensitive composition layer wetting, to utilize KOH be developing solution (KOH, contain nonionogenic tenside, trade(brand)name: CDK-1, Fujiphoto electronic material company (the Off ィ of Fuji Le system エ レ Network ト ロ ニ Network ス マ テリアル ズ society) system) develops in 23 ℃, the spray that carries out under flat burner pressure 0.04MPa 80 seconds, obtains the image of patterning.Then, utilize ultra-high voltage washing nozzle, with the pressure injection ultrapure water of 9.8MPa, residue is removed.Finally, in 220 ℃ of thermal treatments of carrying out 30 minutes, formed black matrix.
The formation > of < rgb pixel
Be formed with on the glass substrate of above-mentioned black matrix, when the green coloring photosensitive composite of making in red photosensitive composite R, blue photosensitive composite B, embodiment 1-1 is utilized respectively with black matrix formation successively, identical operation is carried out stacked and patterning, obtains the colour filter of RGB3 color pixel.Now, RGB painted portion thickness of all kinds is 1.6 μ m.
The formation > of < ITO electrode
The glass substrate that is formed with colour filter is put into sputter equipment, in 100 ℃ of whole vacuum evaporations thick ITO, has then carried out annealing for 90 minutes in 240 ℃, makes ITO crystallization, has formed ito transparent electrode.
The formation > of < distance piece
The identical method of distance piece shape method of utilizing record in the embodiment 1 with TOHKEMY 2004-240335 communique forms distance piece on the ito transparent electrode of above-mentioned made.
< liquid crystal aligning is controlled the formation > by projection
Use following positive-working photosensitive resin layer coating fluid, on the ito transparent electrode of above-mentioned distance piece, form liquid crystal aligning control projection being formed with.
Wherein, expose, develop and cure operation and use following method.
The mode that photomask is according to the rules the distance of 100 μ m apart from the surface of photo-sensitive resin configures PROXIMITY type exposure machine (high-tech electronic engineering corporation of Hitachi (the Ha イ テ Network Electricity エ Application ジ ニ ア リ Application グ of Hitachi (strain) society) system), across this photomask, utilizes ultrahigh pressure mercury lamp with irradiation energy 150mJ/cm 2carry out PROXIMITY exposure.
Then, utilize spray-type developing apparatus, 2.38% tetramethylammonium hydroxide aqueous solution is sprayed 30 seconds to substrate in 33 ℃, develop simultaneously.Like this, by the unwanted part of photo-sensitive resin (exposure portion) is developed and to be removed, thereby obtained being formed with by pattern the base plate for liquid crystal display device that liquid crystal aligning that the photo-sensitive resin that is desired shape forms is controlled use projection on colour filter side group plate.
Then,, by curing 30 minutes with the base plate for liquid crystal display device of projection being formed with this liquid crystal aligning control, thereby formed, on base plate for liquid crystal display device, there is curing liquid crystal aligning control projection at 230 ℃.
(positive-working photosensitive resin layer is write out a prescription with coating fluid)
53.0 parts of eurymeric resist liquid (FH-2413F processed of Fujiphoto electronic material company)
46.5 parts of methylethylketones
0.05 part of MEGA FAC F-780F (DIC (strain) company system)
The making > of < liquid crystal indicator
The alignment films being formed by polyimide is further set on the base plate for liquid crystal display device obtaining in above-mentioned.Then, in the mode with according to surrounding the pixel groups of colour filter, be arranged at the sealing agent of the position printing epoxy resin that black matrix housing is around suitable, and drip MVA pattern liquid crystal, after counter substrate laminating, fitted substrate is heat-treated, make sealant cures.
On the two sides of the liquid crystal cells obtaining therefrom, attach the polarization plates HLC2-2518 of (strain) SANRITSU company system.Then, the LED light source as light source (back light of Sony Corporation's LCD TV processed, KDL-40ZX1) is disposed to the back side of the liquid crystal cells that is provided with above-mentioned polarization plates, makes liquid crystal indicator (LCD).
By above-mentioned made liquid crystal indicator there is high-contrast and brightness, be suitable as display unit.It should be noted that, in the present embodiment, carry out utilizing the evaluation of MVA mode LCD, but can think in colour filter by the liquid crystal indicator in other patterns, OLED display and use coloring photosensitive combination of the present invention, also can similarly obtain good image quality.
(embodiment 2-1)
Following each composition is mixed, dissolved, prepare coloring photosensitive combination 2-1, evaluate.
Organic solvent: 21 parts of propylene glycol methyl ether acetates
Organic solvent: 25 parts, glycol ether ethyl-methyl ether
Alkali soluble resin 1: 1 part of allyl methacrylate(AMA)/Sipacril 2739OF=mol ratio 70/30 (weight-average molecular weight 26800)
2.2 parts of blocked isocyanate B1
Polymerizable compound: 3.3 parts of monomer M 1 ((strain) M215 processed, following structure are synthesized in East Asia)
Polymerizable compound: 3.2 parts of Japanese chemical drug (strain) system, KAYARAD DPHA
Stopper: 0.003 part of p methoxy phenol
Photoepolymerizationinitiater initiater 1:1-(O-acetyl oxime)-1-[9-ethyl-6-(Thenoyl)-9H-carbazole-3-yl] 0.4 part, acetone
Multi-functional thiol's compound: 0.4 part of clear and electrician's (strain) KARENZ MTBD1 processed
Adhere to modifying agent: 0.15 part of 3-methacryloxypropyl trimethoxy silane
Fluorine is tensio-active agent: 5.5 parts of the MEGA FAC processed F-554 of DIC company (0.2% propylene glycol methyl ether acetate solution)
1 30 parts of green dispersive compositions
[changing 59]
(embodiment 2-2～2-6)
In the preparation of coloring photosensitive combination 2-1, the dyestuff Y1 that green dispersive composition 1 is contained changes into dyestuff Y2～Y6, in addition, carry out the operation identical with the preparation of coloring photosensitive combination 2-1, produce coloring photosensitive combination 2-2～2-6.
Use coloring photosensitive combination 2-1～2-6, evaluate as described below.The results are shown in table 2.
< specific inductivity >
Specific inductivity utilize following a)～i) method carry out.
A) chromium glass substrate (the thickness 0.3 μ m of 1 limit 75mm, chromium film) is upper so that the mode that after solidifying, the thickness of (after curing afterwards) becomes 3.2 μ m is adjusted rotating speed covering, and utilizes spin coater coating coloring photosensitive combination.
B) then, the chromium glass substrate that covers that is formed with coloring film is carried out to prebake on hot plate under the condition of 100 ℃, 120 seconds, make solvent seasoning.
C), after prebake, use the ultrahigh pressure mercury lamp of 2.5kw, with 50mJ/cm 2exposure coloring film is carried out to rayed.
D) then, utilize hot air circulation type drying machine, the chromium glass substrate that covers that is formed with coloring film is heating and curing (curing afterwards) under the condition of 220 ℃, 60 minutes, produce test film.
E) after curing after, cut the coloring film at the place, an angle of getting test film, chromium surface is exposed.
F) then, at the back side of test film spin coating silver thickener, carry out air-dry.Then, utilize above-mentioned silver-colored thickener surperficial chromium to be exposed to the silver-colored thickener conducting (connection) at face and the back side.
G) after dry; use vacuum deposition apparatus (trade(brand)name: ion sputtering E1030, Hitachi's (strain) system); at the table coated surface of test film, utilize PtPd target material as illustrated in fig. 1 in upper main electrode 2 (inner circle) and the guard electrode 3 (cylindrical) of making the about 50nm of evaporation thickness of test film 1 (substrate 1).It should be noted that, on test film 1, by above-mentioned e) in cut to get chromium surface 4 exposed.
H) after electrode fabrication, utilize contact pin type surface shape measuring device (trade(brand)name: DEKTAK3, (strain) ULVAC system), the thickness of filming of the part that there is no electrode of test film is measured.
I) then, electrostatic capacity tester (accurate Impedance Analyzers 4294A, AGILENT TECHNOLOGIES (strain) system) is installed to dielectric Test fixture (Lure Electricity テ ス ト Off ィ Network ス チ ャ ー) 16451B and electrode, the above-mentioned g of further arrangement) test film in, the DIELECTRIC CONSTANT ε while measuring the voltage of alternating current that applies 1kHz, 0.5V '.Measurement result is evaluated according to following determinating reference.
(determinating reference)
A: DIELECTRIC CONSTANT ε ' is lower than 3.0
B: DIELECTRIC CONSTANT ε ' is more than 3.0～lower than 5.0
C: DIELECTRIC CONSTANT ε ' is more than 5.0
The resistance to fluidity > that peels off of <
According to following step a)～e) thickness of determination test sheet, calculate swelling ratio, using this value of calculating as for evaluating the resistance to index of peeling off fluidity.Wherein, when the resistance to poor test film of peeling off fluidity is immersed in stripping liquid, films and in stripping liquid, dissolve or peel off from substrate, thereby cannot measure thickness.Such test film is evaluated as to " * ".
A) measure the d by above-mentioned (mensuration of specific inductivity)) thickness (FT0) of the test film of gained.
B) after measuring, as stripping liquid, use the mixture (MEA/DMSO=7/3 mass ratio) of monoethanolamine (MEA) and dimethyl sulfoxide (DMSO) (DMSO), above-mentioned test film is flooded 120 seconds in 80 ℃ in stripping liquid.
C) in groove (vat), be full of the liquid of MEA/DMSO=7/3, the above-mentioned b of further dipping) test film after dipping, then on the test film brace table of contact pin type surface shape measuring device (trade(brand)name: DEKTAK3, (strain) ULVAC system), load the test film that stripping liquid has covered surperficial state, measure coating thickness (FT1) (determining film thickness of the solvent swelling state based on stripping liquid).
D) in other grooves, be full of pure water, be immersed in above-mentioned c) in there is the test film of swelling, standing 1 Dinner, replaces and films after contained stripping liquid and water, by test film in 200 ℃ dry 30 minutes, again measure and be coated with thickness (FT2).
E) utilize FT0, FT1, the FT2 obtaining by said determination, by following formula, calculated swelling ratio and the film decrement of test film, based on following benchmark, evaluate the resistance to fluidity of peeling off.It should be noted that, for (FT1-FT0), be the apparent swelling being caused by stripping liquid due to what measure, and therefore, utilization is stripped from liquid erosion caudacoria minimizing part (FT2-FT0) and proofreaies and correct, and has calculated true swelling ratio.Measurement result is evaluated according to following determinating reference.
True swelling ratio (%)=100 * (FT1-FT2)/FT0
Film decrement (%)=100 * (FT2-FT0)/FT0
(determinating reference)
A: true swelling ratio≤40% and film decrement≤5%, resistance to peel off fluidity good.
B: true swelling ratio≤40% and film decrement > 5%, the resistance to fluidity of peeling off is in the scope of allowing.
C: film and occur to dissolve or peel off, resistance to peel off fluidity poor.
[table 2]
Known, in the colour filter that is used in COA purposes by the formed coloring photosensitive combination of combination of particular dye of the present invention, also demonstrate good performance.

Claims (12)

1. a coloring photosensitive combination, it comprises (A) veridian, (B) and has the dyestuff of the female skeleton different from described veridian and (C) polymerizable compound, and the 15 quality % of described (B) dyestuff are adsorbed in the surface of described (A) veridian above.
2. coloring photosensitive combination according to claim 1, its be included in same system to described (A) veridian and described (B) dyestuff carry out dispersion treatment and dispersive composition.
3. coloring photosensitive combination according to claim 2, wherein,
Described dispersive composition is when the concentration of disperseing described (B) dyestuff in the dispersive composition at initial stage being made as to Ci, the concentration of described (B) dyestuff in the dispersive composition after disperseing to finish is made as to Cf, meets the dispersive composition of the relation of Ci > Cf.
4. according to the coloring photosensitive combination described in any one in claim 1～3, wherein,
Described (B) dyestuff be by be selected from following general formula (a-1), (a-2), (b) and (c) in the represented compound of at least one general formula,
General formula (a-1) and (a-2) in, R 1～R 5represent independently of one another hydrogen atom or monovalence substituting group,
In general formula (b), R 6and R 7represent independently of one another hydrogen atom or monovalence substituting group, R 8represent hydrogen atom, fatty group, aryl, heterocyclic radical, formamyl, carbalkoxy, aryloxy carbonyl, acyl group, alkyl sulphonyl, aryl sulfonyl or sulfamyl, Q represents diazonium composition residue,
The represented pigment of general formula (b) can form polymer more than dipolymer in position arbitrarily,
In general formula (c), R 9and R 10represent independently of one another hydrogen atom or monovalence substituting group, R 11represent hydrogen atom, fatty group, aryl, heterocyclic radical, formamyl, carbalkoxy, aryloxy carbonyl, acyl group, alkyl sulphonyl, aryl sulfonyl or sulfamyl, A represents diazonium composition residue.
5. according to the coloring photosensitive combination described in any one in claim 1～4, it comprises the dispersive composition that will after described (A) veridian and described (B) dyestuff ready-mixed, the look material mixture of gained be disperseed and obtain.
6. according to the coloring photosensitive combination described in any one in claim 1～5, it also contains (D) Photoepolymerizationinitiater initiater.
7. according to the coloring photosensitive combination described in any one in claim 1～6, it also contains (E) alkali-soluble tackiness agent.
8. a colour filter, its right to use requires the coloring photosensitive combination described in any one in 1～7 to make.
9. a manufacture method for colour filter, it has following operation:
Pigmented layer forms operation, the coloring photosensitive combination described in any one in claim 1～7 is imparted on supporter and forms pigmented layer;
Exposure process is pattern-like by formed pigmented layer exposure; With
Developing procedure, develops and forms colored pattern the pigmented layer after exposure.
10. a display unit, the colour filter that it possesses colour filter claimed in claim 8 or obtains by manufacture method claimed in claim 9.
The manufacture method of 11. 1 kinds of coloring photosensitive combinations, the dyestuff that makes (A) veridian and (B) have the female skeleton different from described veridian disperses and prepares dispersive composition, with described dispersive composition, prepares coloring photosensitive combination.
The manufacture method of 12. 1 kinds of coloring photosensitive combinations, make (A) veridian and (B) there is the dyestuff mixing of the female skeleton different from described veridian and prepare look material composition, described look material composition disperseed and prepare dispersive composition, with described dispersive composition, preparing coloring photosensitive combination.
CN201280062389.1A 2012-03-30 2012-12-14 Colored photosensitive composition, color filter and method for producing same, and display device Pending CN103998532A (en)

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CN106918996A (en) * 2015-12-28 2017-07-04 住友化学株式会社 Photosensitive composition, colour filter and the display device comprising the colour filter
CN107256881A (en) * 2017-06-28 2017-10-17 京东方科技集团股份有限公司 Display panel and preparation method thereof, display device

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CN106918996A (en) * 2015-12-28 2017-07-04 住友化学株式会社 Photosensitive composition, colour filter and the display device comprising the colour filter
CN107256881A (en) * 2017-06-28 2017-10-17 京东方科技集团股份有限公司 Display panel and preparation method thereof, display device

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