CN107407881A - Sept is coloured to be formed with photosensitive coloring composition, solidfied material, coloring sept, image display device - Google Patents

Sept is coloured to be formed with photosensitive coloring composition, solidfied material, coloring sept, image display device Download PDF

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Publication number
CN107407881A
CN107407881A CN201680014325.2A CN201680014325A CN107407881A CN 107407881 A CN107407881 A CN 107407881A CN 201680014325 A CN201680014325 A CN 201680014325A CN 107407881 A CN107407881 A CN 107407881A
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CN
China
Prior art keywords
pigment
methyl
sept
coloring
acid
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Pending
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CN201680014325.2A
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Chinese (zh)
Inventor
伊藤敦哉
小川善秀
大津猛
裴丽华
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Mitsubishi Chemical Corp
Mitsubishi Kasei Corp
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Mitsubishi Kasei Corp
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Application filed by Mitsubishi Kasei Corp filed Critical Mitsubishi Kasei Corp
Priority to CN202110817357.9A priority Critical patent/CN113608408A/en
Publication of CN107407881A publication Critical patent/CN107407881A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—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
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of 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
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G02F1/13398—Spacer materials; Spacer properties
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

Abstract

The problem of the present invention is to provide a kind of photosensitive coloring composition, and it can form the pattern that light-proofness is high, surface smoothness is excellent, and colour sept particularly preferred for being formed.The coloring sept formation photosensitive coloring composition of the present invention contains：(a) colouring agent, (b) alkali soluble resin, (c) Photoepolymerizationinitiater initiater, (d) alefinically unsaturated compounds, (e) solvent and (f) dispersant, wherein, (c) Photoepolymerizationinitiater initiater includes the oxime ester compound shown in following formula (I)s.

Description

Colour sept formed with photosensitive coloring composition, solidfied material, coloring sept, Image display device
Technical field
The present invention relates to photosensitive coloring composition etc..Specifically, it is related in the colour filter such as liquid crystal display In be preferably used to form the photosensitive coloring composition of coloring sept etc., solidify the photosensitive coloring composition obtained from Coloring sept, the image display device for possessing the coloring sept.
Background technology
Liquid crystal display (LCD) make use of in the presence of the ON/OFF of the voltage applied to liquid crystal, the arrangement of liquid crystal molecule The property that mode changes.On the other hand, each component for forming LCD unit is by the profit using photoetching process as representative mostly Formed with the method for photosensitive composite.For the photosensitive composite, fine structure is formed because it is easy, is gone back The reasons why easily processing of the progress for big picture substrate is such, from now on, its scope of application has the trend further expanded.
But for using photosensitive composite manufacture LCD for, due to the electrical characteristics of photosensitive composite itself, The influence of contained impurity in photosensitive composite, the voltage applied to liquid crystal can not be kept, exists and produces display therefrom Display it is uneven the problems such as situation.Particularly, for the component in colour liquid crystal display device close to liquid crystal layer, for example in liquid For the so-called column spacer that is used in crystal panel in order to which the interval holding of 2 substrates is constant, light spacer etc., its Influence notable.
In the past, in the case where the sept without light-proofness is used for into TFT types LCD, sometimes because through sept And come light and make to malfunction as the TFT of switch element.In order to prevent being recorded in the situation, such as patent document 1 Use the method for the sept (coloring sept) with light-proofness.
On the other hand, in recent years, along with the change of panel construction, it is proposed that disposably form height by photoetching process The method of different coloring septs.For example, Patent Document 2 discloses herein below：It is special by combining a variety of light absorbs Property different specific pigment kind ensures the balance of the light absorbs of ultraviolet region and visibility region, can keep light-proofness and liquid crystal Voltage retention, and shape, difference of height are controlled, so as to realize the adaptation with substrate.It is in addition, public in patent document 3 The technology for having used a variety of organic coloring pigments as pigment is opened, patent document 4 discloses that the skill using organic black pigments Art.
On the other hand, herein below has been recorded in patent document 5：In order to improve solidification in colour filter resist purposes Property, it is used as highly sensitive Photoepolymerizationinitiater initiater using specific oxime ester compound.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 8-234212 publications
Patent document 2：International Publication No. 2013/115268
Patent document 3：Korean granted patent 10-1266295 publications
Patent document 4：Japanese Unexamined Patent Application Publication 2014-529652 publications
Patent document 5：Japanese Unexamined Patent Application Publication 2014-500852 publications
The content of the invention
Invent problem to be solved
In recent years, along with the change of panel construction, it is desirable to further improve the light-proofness of coloring sept.As raising The method of light-proofness, the face in the method and raising photosensitive coloring composition using the high pigment of light-proofness can be enumerated Expect method of content ratio etc..The result that the present inventor etc. is studied is found, in the photonasty described in patent document 2~4 In coloured composition, when high pigment of light-proofness etc. is applied in combination further to improve the light-proofness of coloring sept, in film Crosslink density difference increase near near surface and film bottom, pleat is produced due to the thermal contraction of curing process in film coated surface Wrinkle, surface smoothness become insufficient.
On the other hand, recorded in patent document 5 and used specific oxime ester compound as color resist (colour Resist Photoepolymerizationinitiater initiater).But do not record and imply in patent document 5 and the oxime ester compound is used for shape Into the Photoepolymerizationinitiater initiater of the photosensitive coloring composition of coloring sept.Therefore, it is spaced the oxime ester compound as coloring Can be produced during the Photoepolymerizationinitiater initiater use of thing formation photosensitive coloring composition which type of effect and it is indefinite.
The present invention is to carry out in view of the foregoing, and it is an object of the invention to provide one kind can form light-proofness The photosensitive coloring composition of pattern high, surface smoothness is excellent.
The method for solving problem
The present inventor etc. have found to solve the result that above-mentioned problem has made intensive studies, by photosensitive color group Specific oxime ester compound is used to solve above-mentioned problem, as Photoepolymerizationinitiater initiater so as to complete this hair in compound It is bright.
That is, the present invention has the composition of following [1]~[14].
[1] a kind of coloring sept formation photosensitive coloring composition, it contains：(a) colouring agent, (b) alkali-soluble Resin, (c) Photoepolymerizationinitiater initiater, (d) alefinically unsaturated compounds, (e) solvent and (f) dispersant, wherein,
(c) Photoepolymerizationinitiater initiater includes the oxime ester compound shown in following formula (I)s,
[chemical formula 1]
(in above-mentioned logical formula (I),
R1Represent that optionally there is the aromatic ring yl of substituent,
R2The alkanoyl optionally with substituent or the optional aroyl with substituent are represented,
R3Represent hydrogen atom or optionally there is the alkyl of substituent,
R4Represent that optionally there is the aromatic ring yl of substituent,
R5And R6The phenyl ring optionally with substituent or the optional naphthalene nucleus with substituent are represented independently of one another, wherein, R5And R6In at least any one for optionally have substituent naphthalene nucleus,
R1And R4In at least any one there is-OR7Base is as substituent, wherein R7Represent alkylhalide group,
X represents direct key or carbonyl,
Z represents direct key or carbonyl.)
[2] the coloring sept formation photosensitive coloring composition described in above-mentioned [1], wherein, (a) colouring agent contains Have selected from least one of red pigment and orange pigment and selected from least one of blue pigment and violet pigment.
[3] the coloring sept formation photosensitive coloring composition described in above-mentioned [2], wherein, the red pigment is Following (1), the orange pigment are following (2), the blue pigment is following (3), the violet pigment is following (4),
(1) C.I. paratoneres 177, at least one of 254 are selected from
(2) C.I. pigment oranges 43, at least one of 64 are selected from
(3) C.I. pigment blue 15s are selected from:6th, at least one of 60
(4) selected from C.I. pigment Violet 23s, at least one of 29
[4] the coloring sept formation photosensitive coloring composition described in above-mentioned [2] or [3], wherein, relative to described (a) mass parts of colouring agent 100, the content ratio selected from least one of red pigment and orange pigment pigment are 1 mass parts Above and below 30 mass parts.
[5] the coloring sept formation photosensitive coloring composition any one of above-mentioned [2]~[4], wherein, phase For the mass parts of (a) colouring agent 100, the content ratio selected from least one of blue pigment and violet pigment pigment is More than 20 mass parts and below 90 mass parts.
[6] the coloring sept formation photosensitive coloring composition any one of above-mentioned [1]~[5], wherein, institute State (a) colouring agent and contain organic black pigments.
[7] the coloring sept formation photosensitive coloring composition described in above-mentioned [6], wherein, organic black face Salt of the material containing the compound shown in following formula (1), its geometric isomer, its salt or its geometric isomer,
[chemical formula 2]
(in above-mentioned formula (1), R11And R16Independently of one another hydrogen atom, CH3、CF3, fluorine atom or chlorine atom；
R12、R13、R14、R15、R17、R18、R19And R20Hydrogen atom, halogen atom, R are independently of one another to each other21、COOH、 COOR21、COO-、CONH2、CONHR21、CONR21R22、CN、OH、OR21、COCR21、OOCNH2、OOCNHR21、OOCNR21R22、 NO2、NH2、NHR21、NR21R22、NHCOR22、NR21COR22, N=CH2, N=CHR21, N=CR21R22、SH、SR21、SOR21、 SO2R21、SO3R21、SO3H、SO3 -、SO2NH2、SO2NHR21Or SO2NR21R22；
Also, it is selected from R12With R13、R13With R14、R14With R15、R17With R18、R18With R19And R19With R20In at least one group Close mutual Direct Bonding or by oxygen atom, sulphur atom, NH or NR11Bridging and be mutually bonded；
R21And R22The independently of one another alkyl of carbon number 1~12, the cycloalkyl of carbon number 3~12, carbon number The alkynyl of 2~12 alkenyl, the cycloalkenyl group of carbon number 3~12 or carbon number 2~12.)
[8] the coloring sept formation photosensitive coloring composition any one of above-mentioned [1]~[7], wherein, institute State (a) colouring agent and contain carbon black.
[9] the coloring sept formation photosensitive coloring composition described in above-mentioned [1], wherein, (a) colouring agent contains There are organic pigment and carbon black.
[10] the coloring sept formation photosensitive coloring composition described in above-mentioned [9], wherein, above-mentioned organic face Material contains selected from least one of red pigment, orange pigment, blue pigment and violet pigment.
[11] the coloring sept formation photosensitive coloring composition described in above-mentioned [9] or [10], wherein, it is described organic Pigment contains selected from least one of following (1)~(4),
(1) C.I. paratoneres 177, at least one of 254 are selected from
(2) C.I. pigment oranges 43, at least one of 64 are selected from
(3) C.I. pigment blue 15s are selected from:6th, at least one of 60
(4) selected from C.I. pigment Violet 23s, at least one of 29
[12] the coloring sept formation photosensitive coloring composition any one of above-mentioned [9]~[11], wherein, The organic pigment contains blue pigment and violet pigment.
[13] the coloring sept formation photosensitive coloring composition any one of above-mentioned [9]~[12], wherein, Relative to the mass parts of (a) colouring agent 100, the content ratio of carbon black is more than 5 mass parts and below 50 mass parts.
[14] the coloring sept formation photosensitive coloring composition any one of above-mentioned [1]~[13], it is solid The optical density of average every 1 μm of thickness of film after change is more than 1.0.
[15] the coloring sept formation photosensitive coloring composition any one of above-mentioned [1]~[14], it is used In disposably forming highly different coloring septs by photoetching process.
[16] a kind of solidfied material, it is to form the coloring sept any one of above-mentioned [1]~[15] with photosensitive Property coloured composition solidification obtained from.
[17] a kind of coloring sept, it is formed as the solidfied material described in above-mentioned [16].
[18] a kind of image display device, it possesses the coloring sept described in above-mentioned [17].
The effect of invention
According to the present invention it is possible to provide the photosensitive color that can form the pattern that light-proofness is high, surface smoothness is excellent Composition.Furthermore it is possible to provide, light-proofness is excellent, surface smoothness also excellent solidfied material and coloring sept, furthermore, it is possible to The image display device for possessing such coloring sept is provided.
Embodiment
Hereinafter, embodiments of the present invention are specifically described, but the present invention is not limited to following embodiment, can To implement after carrying out various changes in the range of its main points.
It should be noted that in the present invention, " (methyl) acrylic " refers to " acrylic and/or methylpropenyl ", " (methyl) acrylate ", " (methyl) acryloyl group " also illustrate that same implication.
The implication of " (co) polymer " include homopolymer (homopolymer) and copolymer (copolymer) this two Person, the implication of " sour (acid anhydrides) ", " ... sour (acid anhydride) " include both acid and its acid anhydrides.In addition, in the present invention, it is described " acrylic resin " refers to the (co) polymer comprising (methyl) acrylic acid, comprising (methyl) acrylate with carboxyl (co) polymer.
In addition, in the present invention, " monomer " is the term relative with so-called polymer substance (polymer), except Beyond the monomer (monomer) of narrow sense, in addition to the implication such as dimer, trimer, oligomer.
In the present invention, described " total solid content " refer in photosensitive coloring composition or the ink that describes below in institute Whole compositions beyond the solvent contained.
In the present invention, " weight average molecular weight " refers to polyphenyl second is determined and be converted into using GPC (gel permeation chromatography) The weight average molecular weight (Mw) of alkene.
In addition, in the present invention, unless otherwise specified, " amine value " represents to be converted into the amine of effective solid constituent Value, it is the value with the KOH quality representations of equivalent for the alkali number of every 1g solid constituents equivalent to dispersant.It should be noted that On its assay method, it is described below.On the other hand, unless otherwise specified, described " acid number " represents to be converted into effectively The acid number of solid constituent, it is calculated by acid-base titration.
In addition, in this manual, the percentage represented with " quality " and part and the percentage represented with " weight " and part Represent identical meanings.
[photosensitive coloring composition]
The photosensitive coloring composition of the present invention contains following component as essential component：
(a) colouring agent
(b) alkali soluble resin
(c) Photoepolymerizationinitiater initiater
(d) alefinically unsaturated compounds
(e) solvent
(f) dispersant.
In addition, the photosensitive coloring composition of the present invention further improves containing adaptations such as silane couplers as needed Agent, coating enhancer, development modifying agent, ultra-violet absorber, antioxidant, surfactant, pigment derivative etc. are other to match somebody with somebody Synthesis point, each gradation composition are generally used with the state being dissolved or dispersed in solvent.
The photosensitive coloring composition of the present invention pattern excellent due to light-proofness height, surface smoothness can be formed, because This can be preferably used to form coloring sept, i.e. can be preferably used as colouring sept formation photosensitive coloring composition.
On the other hand, the characteristic such as light-proofness, surface smoothness is due to being the illuminating part in such as organic EL display The characteristic also required in interlayer, the purposes particularly beyond the coloring such as coloring interlayer (coloring バ Application Network) sept, therefore can be with It is not limited in using in sept is coloured.The photosensitive coloring composition of the present invention is described in detail below, as long as It is not particularly illustrated, both the purposes that will be coloured sept purposes and colour beyond sept illustrates together.
In the photosensitive coloring composition of 1st mode of the invention, (a) colouring agent contains selected from red pigment and orange pigment At least one of and selected from least one of blue pigment and violet pigment, also, (c) Photoepolymerizationinitiater initiater includes The oxime ester compound shown in formula (I) described below.
In addition, in the photosensitive coloring composition of 2nd mode of the invention, (a) colouring agent include organic black pigments (with Under, sometimes referred to simply as " organic black pigments shown in formula (1) "), the organic black pigments are the formulas (1) described below Shown compound, its geometric isomer, the salt of its salt or its geometric isomer.
In addition, in the photosensitive coloring composition of the 3rd mode of the invention, (a) colouring agent contains organic pigment and carbon black, and And (c) Photoepolymerizationinitiater initiater includes the oxime ester compound shown in the formula (I) described below.
On the other hand, the photosensitive coloring composition of the 4th mode of the invention is coloring sept formation photosensitive color Composition, also, (c) Photoepolymerizationinitiater initiater includes the oxime ester compound shown in the formula (I) described below.
Hereinafter, unless otherwise specified, " photosensitive coloring composition of the invention " refers in above-mentioned 1st~4 mode All photosensitive coloring compositions.
＜ (a) colouring agents ＞
(a) colouring agent used in the photosensitive coloring composition of 1st mode of the invention contains selected from red pigment and orange At least one of color pigment and selected from least one of blue pigment and violet pigment.So, the present invention the 1st The photosensitive coloring composition of mode can be by realizing high light-proofness containing specific organic coloring pigments.
As (a) colouring agent, preferably using pigment, as pigment, inorganic pigment can be used, organic face can also be used Material.The absorption of ultraviolet is reduced and suppress from the voltage retention for suppressing liquid crystal and is easily controlled shape, the viewpoint of difference of height Consider, preferably using organic pigment.
The chemical constitution of these pigment is not particularly limited, except such as azo, phthalocyanines, quinoline azone class, benzo miaow Oxazolone class, isoindoline ketone, twoBeyond the organic pigments such as piperazine class, indanthrone kinds, class, it can also utilize various inorganic Pigment etc..Hereinafter, the concrete example of pigment that can be used in the present invention is shown with pigment sequence number." the C.I. face being exemplified below Expect that the terms such as red 2 " refer to pigment call number (C.I.).
As red pigment, can enumerate C.I. paratoneres 1,2,3,4,5,6,7,8,9,12,14,15,16,17,21, 22、23、31、32、37、38、41、47、48、48:1、48:2、48:3、48:4、49、49:1、49:2、50:1、52:1、52:2、 53、53:1、53:2、53:3、57、57:1、57:2、58:4、60、63、63:1、63:2、64、64:1、68、69、81、81:1、81: 2、81:3、81:4、83、88、90:1、101、101:1、104、108、108:1、109、112、113、114、122、123、144、 146、147、149、151、166、168、169、170、172、173、174、175、176、177、178、179、181、184、185、 187、188、190、193、194、200、202、206、207、208、209、210、214、216、220、221、224、230、231、 232、233、235、236、237、238、239、242、243、245、247、249、250、251、253、254、255、256、257、 258、259、260、262、263、264、265、266、267、268、269、270、271、272、273、274、275、276。
Wherein it is possible to it is preferred that enumerate C.I. pigment red 4s 8：1、122、168、177、202、206、207、209、224、242、 254, more preferably enumerate C.I. paratoneres 177,209,224,254.
It should be noted that from the aspect of dispersiveness, light-proofness, preferably using C.I. paratoneres 177,254,272.Profit It is preferably low using absorption of UV in the case of the photosensitive coloring composition solidification for making the 1st mode of the invention with ultraviolet Pigment as red pigment.From the viewpoint, more preferably using C.I. paratoneres 254,272.
As orange (orange) pigment, can enumerate C.I. pigment oranges 1,2,5,13,16,17,19,20,21,22,23, 24、34、36、38、39、43、46、48、49、61、62、64、65、67、68、69、70、71、72、73、74、75、77、78、79。
Wherein it is possible to it is preferred that enumerate C.I. pigment oranges 38,71.It should be noted that examined in terms of dispersiveness, light-proofness Consider, preferably using C.I. pigment oranges 43,64,72.The photosensitive coloring composition for making the 1st mode of the invention using ultraviolet solidifies In the case of, preferably it is used as orange pigment using the low pigment of absorption of UV.From the viewpoint, more preferably use C.I. pigment orange 64,72.
As blue pigment, C.I. pigment blue 1s, 1 can be enumerated:2、9、14、15、15:1、15:2、15:3、15:4、15: 6、16、17、19、25、27、28、29、33、35、36、56、56:1、60、61、61:1、62、63、66、67、68、71、72、73、 74、75、76、78、79。
Wherein it is possible to it is preferred that enumerate C.I. pigment blue 15s, 15:1、15:2、15:3、15:4、15:6, more preferably enumerate C.I. Pigment blue 15:6.
It should be noted that from the aspect of dispersiveness, light-proofness, preferably using C.I. pigment blue 15s:6、16、60.Profit It is preferably low using absorption of UV in the case of the photosensitive coloring composition solidification for making the 1st mode of the invention with ultraviolet Pigment as blue pigment.From the viewpoint, more preferably using C.I. pigment blue 60s.
As violet pigment, C.I. pigment violet 1s, 1 can be enumerated:1、2、2:2、3、3:1、3:3、5、5:1、14、15、16、 19、23、25、27、29、31、32、37、39、42、44、47、49、50。
Wherein it is possible to it is preferred that enumerate C.I. pigment violet 1s 9,23, C.I. pigment Violet 23s are more preferably enumerated.
It should be noted that from the aspect of dispersiveness, light-proofness, preferably using C.I. pigment Violet 23s, 29.Using ultraviolet In the case that line makes the photosensitive coloring composition solidification of the 1st mode of the invention, preferably using the low pigment of absorption of UV As violet pigment.From the viewpoint, more preferably using C.I. pigment violets 29.
, can as the organic coloring pigments that can be used beyond red pigment, orange pigment, blue pigment, violet pigment To enumerate such as viridine green, yellow uitramarine.
As viridine green, can enumerate C.I. naphthol greens 1,2,4,7,8,10,13,14,15,17,18,19,26,36, 45、48、50、51、54、55.Wherein it is possible to it is preferred that enumerate C.I. pigment Green 7s, 36.
As yellow uitramarine, C.I. pigment yellows 1,1 can be enumerated:1、2、3、4、5、6、9、10、12、13、14、16、17、 24、31、32、34、35、35:1、36、36:1、37、37:1、40、41、42、43、48、53、55、61、62、62:1、63、65、73、 74、75、81、83、87、93、94、95、97、100、101、104、105、108、109、110、111、116、117、119、120、 126、127、127:1、128、129、133、134、136、138、139、142、147、148、150、151、153、154、155、 157、158、159、160、161、162、163、164、165、166、167、168、169、170、172、173、174、175、176、 180、181、182、183、184、185、188、189、190、191、191:1、192、193、194、195、196、197、198、 199、200、202、203、204、205、206、207、208。
Wherein it is possible to it is preferred that C.I. pigment yellow 83s, 117,129,138,139,150,154,155,180,185 are enumerated, more It is preferred that enumerate C.I. pigment yellow 83s, 138,139,150,180.
Among these, from the viewpoint of the control of light-proofness, shape and difference of height, preferably comprise in following pigment extremely Lack more than one.
Red pigment：C.I. paratonere 177,254,272
Orange pigment：C.I. pigment orange 43,64,72
Blue pigment：C.I. pigment blue 15:6、60
Violet pigment：C.I. pigment Violet 23,29
In addition, from the viewpoint of the control of light-proofness, shape and difference of height, red pigment preferably following (1) is orange Pigment preferably following (2), blue pigment preferably following (3), violet pigment preferably following (4).
(1) C.I. paratoneres 177, at least one of 254 are selected from
(2) C.I. pigment oranges 43, at least one of 64 are selected from
(3) C.I. pigment blue 15s are selected from:6th, at least one of 60
(4) selected from C.I. pigment Violet 23s, at least one of 29
It should be noted that the combination for color is not particularly limited, from the viewpoint of light-proofness, example can be enumerated Such as the combination of the combination of red pigment and blue pigment, blue pigment and orange pigment, blue pigment and orange pigment and purple Combination of pigment etc..
In addition, in addition to above-mentioned coloring pigment, black color material can also be used.
In black color material, reduce and suppress the absorption of ultraviolet from the voltage retention for suppressing liquid crystal and be easily controlled From the viewpoint of shape, difference of height, preferably using organic black pigments, particularly from the viewpoint of light-proofness, preferably use Organic black pigments, the organic black pigments are compound, its geometric isomer, its salt or its geometry shown in following formula (1) The salt of isomers.
[chemical formula 3]
In formula (1), R11And R16Independently of one another hydrogen atom, CH3、CF3, fluorine atom or chlorine atom；
R12、R13、R14、R15、R17、R18、R19And R20Hydrogen atom, halogen atom, R are independently of one another to each other21、COOH、 COOR21、COO-、CONH2、CONHR21、CONR21R22、CN、OH、OR21、COCR21、OOCNH2、OOCNHR21、OOCNR21R22、 NO2、NH2、NHR21、NR21R22、NHCOR22、NR21COR22, N=CH2, N=CHR21, N=CR21R22、SH、SR21、SOR21、 SO2R21、SO3R21、SO3H、SO3 -、SO2NH2、SO2NHR21Or SO2NR21R22；
Also, it is selected from R12With R13、R13With R14、R14With R15、R17With R18、R18With R19And R19With R20In at least one group Close mutual Direct Bonding or by oxygen atom, sulphur atom, NH or NR11Bridging and be mutually bonded；
R21And R22The independently of one another alkyl of carbon number 1~12, the cycloalkyl of carbon number 3~12, carbon number The alkynyl of 2~12 alkenyl, the cycloalkenyl group of carbon number 3~12 or carbon number 2~12.
There is the geometric isomer of compound shown in formula (1) following core texture (wherein, to eliminate in structural formula Substituent), trans- trans isomer is probably most stable of.
[chemical formula 4]
In the case that the compound that formula (1) represents is anionic property, preferably using any known suitable sun from Son, such as metal, organic and inorganic or metal organic cation, be specially alkali metal, alkaline-earth metal, transition metal, primary amine, secondary Obtained from the quaternary ammoniums such as the tertiary amines such as amine, trialkylamine, tetra-allkylammonium or Organometallic complexes compensate to its electric charge Salt.In addition, in the case that the geometric isomer for the compound that formula (1) represents is anionic property, preferably same salt.
In the substituent of formula (1) and their definition, consider from the tendency for improving screening rate, it is preferably following Substituent.This is because, it is considered that following substituent without absorption, on the form and aspect of pigment without influence.
R12、R14、R15、R17、R19And R20It is preferably hydrogen atom, fluorine atom or chlorine atom, more preferably hydrogen independently of each other Atom.
R13And R18It is preferably hydrogen atom, NO independently of each other2、OCH3、OC2H5, bromine atoms, chlorine atom, CH3、C2H5、N (CH3)2、N(CH3)(C2H5)、N(C2H5)2, Alpha-Naphthyl, betanaphthyl, SO3H or SO3 -, more preferably hydrogen atom or SO3H。
R11And R16It is preferably hydrogen atom, CH independently of each other3Or CF3, more preferably hydrogen atom.
It is preferably selected from R11With R16、R12With R17、R13With R18、R14With R19And R15With R20In at least one combination it is identical, More preferably R11With R16Identical, R12With R17Identical, R13With R18Identical, R14With R19Identical and R15With R20It is identical.
The alkyl of carbon number 1~12 is, for example, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl Base, the tert-butyl group, 2- methyl butyls, n-pentyl, 2- amyl groups, 3- amyl groups, 2,2- dimethyl propyls, n-hexyl, heptyl, n-octyl, 1,1,3,3- tetramethyl butyls, 2- ethylhexyls, nonyl, decyl, undecyl or dodecyl.
The cycloalkyl of carbon number 3~12 is, for example, cyclopropyl, Cvclopropvlmethvl, cyclobutyl, cyclopenta, cyclohexyl, ring Hexyl methyl, trimethylcyclohexyl, thujyl (thujyl), norbornene, bornyl, norcarane alkyl, caryl,Alkyl, Norpinane base, pinane base, 1- adamantyls or 2- adamantyls.
The alkenyl of carbon number 2~12 is, for example, vinyl, pi-allyl, 2- propylene -2- bases, 2- butene-1s-base, 3- fourths Alkene -1- bases, 1,3- butadiene -2- bases, 2- amylene -1- bases, 3- 2-pentenyls, 2-Base -1- butylene -3- bases, 2- methyl -3- Butene-2-base, 3- methyl-2-butene-1- bases, 1,4- pentadiene-3- bases, hexenyl, octenyl, nonenyl, decene base or ten Dialkylene.
The cycloalkenyl group of carbon number 3~12 be, for example, 2- cyclobutane -1- bases, 2- cyclopentene -1- bases, 2- cyclohexene -1- bases, 3- cyclohexene -1- bases, 2,4- cyclohexadiene -1- bases, 1- pairsAlkene -8- bases, 4 (10)-limonene -10- bases, 2- ENBs -1- Base, 2,5- norbornadiene -1- bases, 7,7- dimethyl -2,4- norcaranes diene -3- bases or camphyl.
The alkynyl of carbon number 2~12 be, for example, 1- propine -3- bases, 1- butine -4- bases, 1- pentyne -5- bases, 2- methyl - 3- crotonylenes-base, 1,4- pentadiine -3- bases, 1,3- pentadiine -5- bases, 1- hexin -6- bases, cis- 3- methyl -2- amylenes -4- Alkynes -1- bases, trans- 3- methyl -2- amylenes -4- alkynes -1- bases, 1,3- hexadiine -5- bases, 1- octyne -8- bases, 1- n-heptylacetylene -9- bases, 1- Decine -10- bases or 1- dodecyne -12- bases.
Halogen atom is, for example, fluorine atom, chlorine atom, bromine atoms or iodine atom.
Organic black pigments shown in above-mentioned formula (1) are preferably the compound shown in following formulas (2).
[chemical formula 5]
As the concrete example of such organic black pigments, trade name Irgaphor (registration mark) can be enumerated Black S 0100CF (BASF AG's manufacture) organic black pigments.
The organic black pigments are preferably dispersed in dispersant, solvent by method described later and used.In addition, if dividing The sulfonic acid of above-mentioned formula (2) when scattered be present, then dispersiveness, keeping quality improve sometimes.
As the black color material beyond the organic black pigments shown in above-mentioned formula (1), can enumerate carbon black, acetylene black, Lampblack, bone black, graphite, iron oxide black, nigrosine, match it is peaceful it is black, titanium is black, black etc..Among these, from light-proofness, picture characteristics Viewpoint considers that it is preferable to use carbon black.As the example of carbon black, following carbon black can be enumerated.
Mitsubishi chemical Co., Ltd's system：MA7、MA8、MA11、MA77、MA100、MA100R、MA100S、MA220、MA230、 MA600、MCF88、#5、#10、#20、#25、#30、#32、#33、#40、#44、#45、#47、#50、#52、#55、#650、# 750、#850、#900、#950、#960、#970、#980、#990、#1000、#2200、#2300、#2350、#2400、#2600、# 2650、#3030、#3050、#3150、#3250、#3400、#3600、#3750、#3950、#4000、#4010、OIL7B、OIL9B、 OIL11B、OIL30B、OIL31B
Degussa company systems：Printex (registration mark, same as below) 3, Printex3OP, Printex30, Printex30OP、Printex40、Printex45、Printex55、Printex60、Printex75、Printex80、 Printex85、Printex90、Printex A、Printex L、Printex G、Printex P、Printex U、Printex V、SpecialBlack550、SpecialBlack350、SpecialBlack250、
SpecialBlack100、SpecialBlack6、SpecialBlack5、SpecialBlack4、Color Black FW1、Color Black FW2、Color Black FW2V、Color Black FW18、Color Black FW200、Color Black S160、Color Black S170
Cabot company systems：Monarch (registration mark, same as below) 120, Monarch280, Monarch460, Monarch800、Monarch880、Monarch900、Monarch1000、Monarch1100、Monarch1300、 Monarch1400, Monarch4630, REGAL (registration mark, same as below) 99, REGAL99R, REGAL415, REGAL415R、REGAL250、REGAL250R、REGAL330、REGAL400R、REGAL55R0、REGAL660R、BLACK PEARLS480, PEARLS130, VULCAN (registration mark, same as below) XC72R, ELFTEX (registration mark) -8
Columbian Carbon company systems：RAVEN (registration mark, same as below) 11, RAVEN14, RAVEN15, RAVEN16、RAVEN22、RAVEN30、RAVEN35、RAVEN40、RAVEN410、RAVEN420、RAVEN450、RAVEN500、 RAVEN780、RAVEN850、RAVEN890H、RAVEN1000、RAVEN1020、RAVEN1040、RAVEN1060U、 RAVEN1080U、RAVEN1170、RAVEN1190U、RAVEN1250、RAVEN1500、RAVEN2000、RAVEN2500U、 RAVEN3500、RAVEN5000、RAVEN5250、RAVEN5750、RAVEN7000
Carbon black can also use the carbon black obtained from resin-coating.Use the carbon black obtained from resin-coating When, there is adaptation, the effect of volumetric resistivity value improved to glass substrate.As the carbon black obtained from resin-coating, Preferably it can use such as the carbon black described in Japanese Unexamined Patent Publication 09-71733 publications.From volume resistance, dielectric constant side Face considers, preferably using resin-coating carbon black.
The carbon black handled as the cladding for being carried out using resin, preferably Na and Ca total content are below 100ppm. Carbon black usually contains the ash content of a few percent, and the composition of the ash content is whole from feedstock oil during manufacture, fuel oil (or gas), reaction The mixed Na and Ca, K, Mg, Al, Fe such as sealing and the stove material of granulation water and reacting furnace etc..Wherein, Na and Ca are usual Contain hundreds of more than ppm respectively, by reducing Na and Ca, being impregnated with to transparency electrode (ITO) and other electrodes can be suppressed, existed The tendency of electric short circuit can be prevented.
As the method for the content for reducing these ash contents for containing Na, Ca, the strict content pole for selecting Na, Ca can be used Few material is as feedstock oil, fuel oil (or gas) and the reaction terminating water when manufacturing carbon black and strongly reduces for adjusting knot The method of the addition of the alkaloid substance of structure.As other methods, it can enumerate and the carbon black made from stove is entered with water, hydrochloric acid etc. Row washs and dissolved the method for removing Na, Ca.
Specifically, carbon black mixing is made to be scattered in water, hydrochloric acid or aquae hydrogenii dioxidi, then addition is insoluble in the solvent of water, Now, carbon black is transferred to solvent side, and while being completely separated from the water, the nearly all Na and Ca that are present in carbon black are dissolved in water Or it is removed in acid.In order to which Na and Ca total amount are reduced into below 100ppm, although also having only by individually strict choosing Select the carbon black manufacturing process of raw material or be individually dissolved in the situation that the mode that water or acid dissolve can be realized as, but it is logical It is below 100ppm to cross and two ways is applied in combination to the total amount for being easier to make Na and Ca.
In addition, preferred below the pH6 of resin-coating carbon black so-called acidic black.Due to the scattered footpath (agglomerate in water Size, agglomerate size) diminish, or even the cladding under fine unit can be carried out, therefore it is preferred that.More preferably average grain diameter Below 40nm, dibatyl phithalate (DBP) below uptake 140ml/100g carbon black.By in above range, to exist Obtain the tendency of the good film of light-proofness.Average grain diameter refers to number average bead diameter, refer to by particle picture parsing obtain etc. Circular diameter is imitated, the particle picture parsing is to be shot using electron microscope observation with tens thousand of times, and what is shot is several The photo in the visual field, the particle of 2000~3000 or so these photos is measured by image processing apparatus.
Preparation is not particularly limited with the method for the carbon black of resin-coating, such as the use level of carbon black and resin is suitable , can be with the following method after adjustment：
1. resin and cyclohexanone, toluene, dimethylbenzene equal solvent are mixed and heated dissolving and resin solution is made, by carbon black And water mixes and suspension is made, above-mentioned resin solution and above-mentioned suspension are mixed, after being separated from water carbon black, removed Water simultaneously carries out heating mixing, obtains composition, is sheet by obtained composition molding, its drying is made after being crushed；
2. the resin solution prepared as described above and suspension are mixed, will after carbon black and resin spheroidizing Obtained shot-like particle separation, heating, remove the solvent and water of remaining；
3. making the carboxylic acids such as maleic acid, fumaric acid in the solvent of above-mentioned example, add carbon black and mixed, make it Solvent is removed after drying, having obtained addition attachment (adding) has the carbon black of carboxylic acid, then adds resin wherein and carries out dry-mixed；
4. the monomer component containing reactive group for forming resin to be covered is subjected to high-speed stirred with water and prepared Suspension, cooled down after polymerization, the resin containing reactive group is obtained from polymer suspension, is then added thereto Carbon black is simultaneously kneaded, and makes carbon black and reaction-ity group reaction (being grafted carbon black), then cooled down and crushed；Etc..
The species of resin for coat processing is also not particularly limited, usually synthetic resin, from dispersed and scattered From the aspect of stability, preferably further there is the resin of benzene nucleus in the structure, this is due to it as amphoteric surfactant It is with better function.
As specific synthetic resin, phenolic resin, melmac, xylene resin, phthalic acid can be used The thermosetting resins such as diallyl phthalate resin, glyptal resin, epoxy resin, alkylbenzene resin and polystyrene, makrolon, Polyethylene terephthalate, polybutylene terephthalate (PBT), Noryl, polysulfones, poly- paraphenylene terephthalamide are to benzene two The heat such as amine, polyamidoimide, polyimides, PABM, polyether sulfone PPSU, polyarylate, polyether-ether-ketone Plastic resin.
Resin is 1~30 mass % preferably with respect to the total amount of carbon black and resin to the covering amount of carbon black, by being More than above-mentioned lower limit, the tendency that can form the carbon black fully coated be present.On the other hand, by making bag of the resin to carbon black The amount of covering is below above-mentioned higher limit, and resin adhesion to each other can be prevented and make the tendency of favorable dispersibility by existing.
Coloring interval can be made in the carbon black for using resin coat processing and formed in this wise according to usual way The light screening material of thing is used, and the colour filter using the coloring sept as inscape can be made by usual way.If Using such carbon black, then existing can be to be realized with a low cost inclining for high shading rate and the low coloring sept of surface reflectivity To.In addition, carbon blacksurface is coated by using resin, thus it is speculated that also have the function that Ca, Na being sealing into carbon black.
In addition, in addition to above-mentioned organic coloring pigments, black color material, dyestuff can also be used.As can act as The dyestuff of color material, can enumerate azo dyes, anthraquinone dyes, phthalocyanines dye, quinone imides dyestuff, quinolines dyestuff, Nitro class dyestuff, carbonyl class dyestuff, methine class dyestuff etc..
As azo dyes, for example,：C.I. acid yellow 11, C.I. acid orange 7s, C.I. acid reds 37, C.I. acid red 18 0, C.I. acid blues 29, C.I. directly red 28, C.I. directly red 83, C.I. directly Huang 12, C.I. direct oranges 26th, C.I. direct greens 28, C.I. direct greens 59, C.I. active yellows 2, C.I. active reds 17, C.I. active reds 120, C.I. activity Black 5, C.I. disperse oranges 5, C.I. disperse reds 58, C.I. disperse blues 165, C.I. alkali blues 41, C.I. Basic Red 18s, C.I. media Red 7, C.I. media Huang 5, C.I. Mordant Blacks 7 etc..
As anthraquinone dyes, for example,：C.I. Vat blue 4, C.I. Acid Blue 40s, C.I. ACID GREEN 25s, C.I. active blue 19, C.I. reactive blue 4s 9, C.I. disperse red 60s, C.I. Disperse Blue-56s, C.I. disperse blue 60s etc..
In addition, as phthalocyanines dye, for example, C.I. vat blues 5 etc., as quinone imides dyestuff, Ke Yiju Go out such as C.I. alkali blue 3s, C.I. alkali blues 9, as quinolines dyestuff, for example, C.I. solvent yellow 33s, C.I. Quinoline yellow, C.I. dispersion yellow 64s etc., as nitro class dyestuff, for example, C.I. Indian yellows 1, C.I. acid oranges 3, C.I. Disperse Yellow 42 etc..
These pigment are preferably dispersed into average grain diameter and are usually less than 1 μm, are preferably less than 0.5 μm, more preferably 0.25 μ Below m and use.Here, the benchmark of average grain diameter is the number of pigment particles.
It should be noted that in the photosensitive coloring composition of the 1st mode of the invention, the average grain diameter of pigment is to pass through The value that dynamic light scattering (DLS) is determined and obtained by pigment particle size.Particle size determination is that the photosensitive color fully diluted is combined Thing (is generally diluted and mass % of pigment concentration 0.005~0.2 or so is made, but have what is recommended according to determining instrument During concentration, by the concentration) carry out, and determined at 25 DEG C.
On the other hand, (a) colouring agent used in the photosensitive coloring composition of the 2nd mode of the invention includes organic black Pigment, the organic black pigments are compound, its geometric isomer, its salt or its geometric isomer shown in above-mentioned formula (1) Salt.So, it is believed that by including specific organic black pigments, it is possible to achieve low-k and high shading rate.
(a) colouring agent used in 2nd mode of the invention can also contain other in addition to above-mentioned organic black pigments Colouring agent.As other colouring agents, preferably using pigment, pigment can be that organic pigment can also be inorganic pigment, but from suppression The voltage retention of liquid crystal processed reduces and suppressed the absorption of ultraviolet and is easily controlled from the viewpoint of shape, difference of height, more It is preferred that use organic pigment.As organic pigment, the organic pigment enumerated in the 1st mode can be used.
In addition, in addition to above-mentioned pigment, other black color materials can also be used.
It is easy from the voltage retention reduction for suppressing liquid crystal and the absorption for suppressing ultraviolet in other black color materials Shape is controlled, from the viewpoint of difference of height, preferably using other organic black pigments beyond above-mentioned formula (1) Suo Shi.As Other organic black pigments, it is peaceful black etc. that nigrosine, black, match can be enumerated.
In addition, in the 2nd mode of the invention, inorganic black pigments can be used.As inorganic black pigments, can enumerate Carbon black, acetylene black, lampblack, bone black, graphite, iron oxide black, titanium are black etc..Among these, from the viewpoint of light-proofness, picture characteristics, Carbon black can preferably be used.As the example of carbon black, carbon black cited in the 1st mode can be used.Furthermore it is also possible to use Other color materials such as the dyestuff enumerated in the 1st mode.
In addition, (a) colouring agent used in the photosensitive coloring composition of the 3rd mode of the invention contains organic pigment and charcoal It is black.So, by using the few organic pigment of ultraviolet radiation absorption, the control of shape, difference of height is easily carried out, in addition, logical Cross except organic pigment also uses carbon black, it is possible to achieve high light-proofness.
The species of organic pigment is not particularly limited, and from the viewpoint of adaptation, preferably comprises selected from red pigment, orange At least one of color pigment, blue pigment and violet pigment.As red pigment, orange pigment, blue pigment and purple face Material, pigment cited in the 1st mode can be used.
Among these, from the viewpoint of the control of light-proofness and shape and difference of height, preferably comprise following (1)~ At least one of (4) more than.
(1) C.I. paratoneres 177, at least one of 254 are selected from
(2) C.I. pigment oranges 43, at least one of 64 are selected from
(3) C.I. pigment blue 15s are selected from:6th, at least one of 60
(4) selected from C.I. pigment Violet 23s, at least one of 29
Among these, from the viewpoint of the light-proofness in the particularly long wavelength region of visibility region, preferably using indigo plant Color pigment and/or violet pigment.Particularly, the absorption spectrum of carbon black due to from short wavelength to long wavelength side its absorbance decline, It is excellent and the dulling luminosity ratio organic pigment of ultraviolet region increases, therefore from the viewpoint of light-proofness and plate-making property is realized simultaneously Blue pigment and/or violet pigment are applied in combination with carbon black for choosing, more preferably combine blue pigment and violet pigment with carbon black Use.
In addition, from the viewpoint of light-proofness, organic pigment preferably comprises organic black pigments.As organic black face Material, the organic black pigments cited by the 1st mode can be used.Furthermore it is also possible to using other organic cited by the 1st mode Coloring pigment, other black color materials, dyestuff etc..
In addition, the coloring sept formation of 4th mode of the invention is with (a) colouring agent used in photosensitive coloring composition As long as desired coloring sept can be formed just to be not particularly limited.For example, easily controlled from the absorption for suppressing ultraviolet From the viewpoint of shape processed, difference of height, above described preferably as the 1st mode containing being selected from red pigment and orange face Material at least one of and selected from least one of blue pigment and violet pigment.
So, the coloring sept formation as the 4th mode is coloured with (a) used in photosensitive coloring composition Agent, those described in (a) colouring agent used in the photosensitive coloring composition as the 1st mode can be applied, in addition, Those described in (a) colouring agent used in the photosensitive coloring composition as the 2nd or the 3rd mode can be applied.
On the other hand, in the coloring sept formation photosensitive coloring composition of the 4th mode, from the viewpoint of light-proofness Consider, preferably at least containing black color material, more preferably at least contain carbon black.In addition, reduced from the voltage retention for suppressing liquid crystal, And suppress the absorption of ultraviolet and be easily controlled from the viewpoint of shape, difference of height, more preferably at least comprising above-mentioned Organic Black Color pigment.From the voltage retention reduction and shape, the sight of the controlling of difference of height for realizing light-proofness and suppression liquid crystal simultaneously Point considers, carbon black and organic black pigments can also be applied in combination.
In the coloring sept formation photosensitive coloring composition of the 4th mode, as the use level of above-mentioned colouring agent, The preferable value in the photosensitive coloring composition of the invention described below can be used.Alternatively, it is also possible to required by Optical density come suitably adjust, can also using International Publication No. 2013/062011, International Publication No. 2013/115268, Japanese Unexamined Patent Application Publication 2014-534460 publications, Japanese Unexamined Patent Application Publication 2014-529652 publications, Japanese Unexamined Patent Publication 2014-146029 public affairs Value described in report, International Publication No. 2013/179237, Japanese Unexamined Patent Publication 2011-107707 publications etc..
＜ (b) alkali soluble resins ＞
As (b) alkali soluble resin used in the present invention, as long as the resin containing carboxyl or hydroxyl is just without spy Do not limit, for example,：Epoxy (methyl) acrylic resin, acrylic resin, the epoxy resin containing carboxyl, Carbamate resins containing carboxyl, novolaks resinoid, polyvinylphenol resinoid etc., wherein, preferred epoxy (first Base) acrylic resin, acrylic resin.These resins can be used alone, or a variety of uses of mixing.
As (b) alkali soluble resin used in the present invention, from the viewpoint of excellent plate-making, particularly preferably make (" the epoxy containing carboxyl below, is sometimes referred to as with following alkali soluble resins (b1) and/or alkali soluble resin (b2) (methyl) acrylate ").
＜ alkali soluble resins (b1) ＞
It is the alkali soluble resin being obtained as below：Make α, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturation are single Carboxylate and epoxy resin addition, then make itself and polyacid and/or its anhydride reaction.
＜ alkali soluble resins (b2) ＞
It is the alkali soluble resin being obtained as below：Make α, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturation are single Carboxylate and epoxy resin addition, then make itself and polyalcohol and polyacid and/or its anhydride reaction.
As the epoxy resin of raw material, it is preferable to use (such as the Mitsubishi Chemical's strain formula meeting of such as bisphenol A type epoxy resin Society's manufacture " Epikote (registration mark, same as below) 828 ", " Epikote 1001 ", " Epikote 1002 ", " Epikote 1004 " etc.), the alcoholic extract hydroxyl group as bisphenol A type epoxy resin and epichlorohydrin reaction obtained from epoxides (example As Nippon Kayaku K. K manufacture " NER-1302 " (76 DEG C of epoxide equivalent 323, softening point)), bisphenol F type resin (such as Mitsubishi chemical Co., Ltd manufacture " Epikote 807 ", " EP-4001 ", " EP-4002 ", " EP-4004 etc. "), pass through bis-phenol Epoxy resin obtained from the alcoholic extract hydroxyl group of F type epoxy resin reacts with epichlorohydrin (such as Nippon Kayaku K. K's manufacture " NER-7406 " (66 DEG C of epoxide equivalent 350, softening point)), bisphenol-s epoxy resin, biphenyl glycidol ether (such as Mitsubishi Learn Co., Ltd. manufacture " YX-4000 "), phenol novolak type epoxy resin (such as Nippon Kayaku K. K manufacture " EP-152 " of the manufacture of " EPPN-201 ", Mitsubishi chemical Co., Ltd, " EP-154 ", Dow chemical companies manufacture " DEN-438 "), (o-, m-, p-) cresol novolak type epoxy resin (such as Nippon Kayaku K. K manufacture " EOCN (registration mark, same as below) -102S ", " EOCN-1020 ", " EOCN-104S "), isocyanuric acid three-glycidyl ester (such as " TEPIC (registration mark) " of Misao Kusano's manufacture), (such as the Japanese chemical drug strain of triphenol methylmethane type epoxy resin Formula commercial firm manufacture " EPPN (registration mark, same as below) -501 ", " EPN-502 ", " EPPN-503 "), ester ring type asphalt mixtures modified by epoxy resin Fat (" Celloxide 2021P ", " Celloxide (registration mark, the following phase of Daisel chemical industry Co., Ltd's manufacture EHPE " together)), the phenolic resin that generates the reaction of bicyclopentadiene and phenol carry out it is glycidated obtained from epoxy Resin (such as " EXA-7200 " of the manufacture of DIC companies, " NC-7300 " of Nippon Kayaku K. K's manufacture), following formulas (C1) epoxy resin~(C4) represented etc..
Specifically, it can enumerate what the Nippon Kayaku K. K as epoxy resin shown in following formulas (B1) manufactured Shown in " XD-1000 ", following formulas (B2) as epoxy resin Nippon Kayaku K. K manufacture " NC-3000 ", under State " ESF-300 " that Nippon Steel ＆ Sumitomo Metal Corporation as epoxy resin shown in formula (C4) manufactures etc..
[chemical formula 6]
In above-mentioned formula (B1), a represents average value, represents 0~10 number, R111Represent hydrogen atom, halogen atom, carbon atom Any group in the alkyl of number 1~8, the cycloalkyl of carbon number 3~10, phenyl, naphthyl or xenyl.Need what is illustrated It is multiple R present in 1 molecule111It can be the same or different.
[chemical formula 7]
In above-mentioned formula (B2), b represents average value, represents 0~10 number, R121Represent hydrogen atom, halogen atom, carbon atom Any group in the alkyl of number 1~8, the cycloalkyl of carbon number 3~10, phenyl, naphthyl or xenyl.Need what is illustrated It is multiple R present in 1 molecule121It can be the same or different.
[chemical formula 8]
In above-mentioned formula (B3), X represents following formulas (B3-1) or the link group shown in (B3-2).But in molecular structure Include more than 1 adamantane structure.C represents 2 or 3 integer.
[chemical formula 9]
[chemical formula 10]
In above-mentioned formula (B3-1) and (B3-2), R131~R134And R135~R137Separately represent that optionally there is substitution Adamantyl, optionally hydrogen atom, the alkyl of the carbon number 1~12 with substituent or the optional benzene with substituent of base Base.* bonding position is represented.
[chemical formula 11]
In above-mentioned formula (B4), p and q separately represent 0~4 integer, R141And R142Separately represent carbon The alkyl or halogen atom of atomicity 1~4, R143And R144Separately represent the alkylidene of carbon number 1~4, x and y difference Independently represent more than 0 integer.
Among these, the epoxy resin represented by preferably using any one in formula (B1)~(B4).
As α, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester, (methyl) propylene can be enumerated Acid, butenoic acid, o-, m- or p- vinyl benzoic acid, the α positions haloalkyl, alkoxy, halogen atom, nitre of (methyl) acrylic acid The monocarboxylic acids such as base, cyano group substituent, 2- (methyl) acrylyl oxy-ethyls butanedioic acid, 2- (methyl) acrylyl oxy-ethyls adipic acid, 2- (methyl) acrylyl oxy-ethyls phthalic acid, 2- (methyl) acrylyl oxy-ethyl hexahydro phthalic acid, 2- (methyl) acryloyl Oxygen ethyl maleic acid, 2- (methyl) acryloxypropyls butanedioic acid, 2- (methyl) acryloxypropyls adipic acid, 2- (methyl) third The hydrogen phthalate of alkene monomethacryloxypropyl four, 2- (methyl) acryloxypropyls phthalic acid, 2- (methyl) acryloxypropyls Malaysia Acid, 2- (methyl) acryloyl-oxy butyl butanedioic acid, 2- (methyl) acryloyl-oxy butyl adipic acid, 2- (methyl) acryloyl-oxy butyl Four hydrogen phthalates, 2- (methyl) acryloyl-oxy butyl phthalic acid, 2- (methyl) acryloyl-oxy butyl maleic acid, at (methyl) On acrylic acid monomer obtained from the lactone such as addition 6-caprolactone, beta-propiolactone, gamma-butyrolacton, δ-valerolactone or Addition butanedioic acid (acid anhydride) on (methyl) hydroxyalkyl acrylates, pentaerythrite three (methyl) acrylate, phthalic acid (acid anhydride), Monomer, (methyl) acrylic acid dimer etc. obtained from the acid such as maleic acid (acid anhydride) (acid anhydrides).
Among these, from the aspect of sensitivity, (methyl) acrylic acid is particularly preferably.
As the addition α on epoxy resin, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester Method, known method can be used.For example, can in the presence of esterification catalyst, make α at a temperature of 50~150 DEG C, β- Unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester react with epoxy resin.
As esterification catalyst used herein, triethylamine, trimethylamine, benzyldimethylamine, 2,4, benzyl diethyl can be used Quaternary ammonium salts such as the tertiary amines such as base amine, tetramethyl ammonium chloride, etamon chloride, DTAC etc..
It should be noted that epoxy resin, α, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester, And esterification catalyst may be used alone, can also be used in combination of two or more kinds.
α, β-unsaturated monocarboxylic or the α with carboxyl, the usage amount of β-unsaturated monocarboxylic ester are as follows：Relative to epoxy The equivalent of epoxy radicals 1 of resin, the preferably scope of the scope of 0.5~1.2 equivalent, more preferably 0.7~1.1 equivalent.
If α, β-unsaturated monocarboxylic or the α with carboxyl, the usage amount of β-unsaturated monocarboxylic ester is less, then insatiable hunger It is ensuing also to become insufficient with the reaction of polyacid and/or its acid anhydrides with the import volume deficiency of group.In addition, residual is big The epoxy radicals of amount is also unfavorable.On the other hand, if the usage amount is more, α, β-unsaturated monocarboxylic or with carboxyl α, β-unsaturated monocarboxylic ester left behind as unreacted reactant.Curing characteristics deterioration is confirmed in the case of any one Tendency.
As polyacid and/or its acid anhydrides, can enumerate selected from maleic acid, butanedioic acid, itaconic acid, phthalic acid, four Hydrogen phthalic acid, hexahydrophthalic acid, Pyromellitic Acid, trimellitic acid, benzophenone tetrabasic carboxylic acid, hexahydrophthalic acid Methyl esters, endo-methylene group tetrahydrophthalic acid, chlorendic acid, methyl tetrahydrophthalic acid, biphenyltetracarboxyacid acid, with And one kind in these sour acid anhydrides etc. or two or more.
It is preferred that maleic acid, butanedioic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, Benzene tetracarboxylic acid, trimellitic acid, biphenyltetracarboxyacid acid or these sour acid anhydrides.Particularly preferred tetrahydrophthalic acid, biphenyltetracarboxyacid acid, Tetrabydrophthalic anhydride or biphenyl tetracarboxylic dianhydride.
On the addition reaction of polyacid and/or its acid anhydrides, known method can be used, can with α, β-unsaturation Monocarboxylic acid or the α with carboxyl, under conditions of β-addition reaction of the unsaturated monocarboxylic ester to epoxy resin is same, are continued to React and obtain object.
The addition amount of polyacid and/or its acid anhydrides composition preferably makes carboxylic epoxy (methyl) acrylate tree of generation The acid number of fat is more than 10mgKOH/g, more preferably more than 20mgKOH/g, more preferably 50mgKOH/g range above The addition amount of degree, and preferably make the acid number of carboxylic epoxy (methyl) acrylate of generation be 150mgKOH/g Below, be more preferably below 140mgKOH/g, more preferably 120mgKOH/g scopes degree addition amount.It is more by making The addition amount of first acid and/or its acid anhydrides composition is more than above-mentioned lower limit, the tendency that alkali-developable becomes good be present, in addition, Become good below above-mentioned higher limit, curing performance to be present by making the addition amount of polyacid and/or its acid anhydrides composition to incline To.
It should be noted that in the addition reaction of the polyacid and/or its acid anhydrides, can add trimethylolpropane, The polyfunctional alcohols such as pentaerythrite, dipentaerythritol import multiple-branching construction.
Carboxylic epoxy (methyl) acrylate is generally as follows acquisition：Single to epoxy resin and α, β-unsaturation Carboxylic acid or the α with carboxyl, mix in the reactant of β-unsaturated monocarboxylic ester after polyacid and/or its acid anhydrides or To epoxy resin and α, β-unsaturated monocarboxylic or the α with carboxyl, mix in the reactant of β-unsaturated monocarboxylic ester polynary Acid and/or its acid anhydrides and polyfunctional alcohol are heated afterwards.
In this case, the order by merging of polyacid and/or its acid anhydrides and polyfunctional alcohol are not particularly limited.By heating, Polyacid and/or its acid anhydrides and it is present in epoxy resin and α, β-unsaturated monocarboxylic or the α with carboxyl, the single carboxylic of β-unsaturation Any hydroxyl in the reactant of acid esters and the mixture of polyfunctional alcohol carries out addition reaction.
Being converted into for carboxylic epoxy (methyl) acrylate determined by gel permeation chromatography (GPC) is poly- The weight average molecular weight (Mw) of styrene is usually more than 1000, is preferably more than 1500, is more preferably more than 2000, is further excellent Elect more than 3000 as, particularly preferably more than 4000, and usually less than 10000, be preferably less than 8000, more preferably Less than 6000.It is high to the dissolubility of developer solution when the weight average molecular weight is smaller, when the weight average molecular weight is excessive, to developer solution Dissolubility is low.
Carboxylic epoxy (methyl) acrylate can be used alone, and can also mix two or more resin Use.
Alternatively, it is also possible to which a part for above-mentioned carboxylic epoxy (methyl) acrylate is replaced into adhesive tree Used after fat.I.e., it is possible to carboxylic epoxy (methyl) acrylate is applied in combination with other adhesive resins.The feelings Under condition, the ratio of carboxylic epoxy (methyl) acrylate in (b) alkali soluble resin is preferably set to 50 matter Amount more than %, particularly preferably it is set to more than 80 mass %.
The other adhesive resins that can be applied in combination with carboxylic epoxy (methyl) acrylate do not limit, Selected from photosensitive coloring composition institute commonly used resin.For example, Japanese Unexamined Patent Publication 2007-271727 Adhesive tree described in number publication, Japanese Unexamined Patent Publication 2007-316620 publications, Japanese Unexamined Patent Publication 2007-334290 publications etc. Fat etc..It should be noted that other adhesive resins may be used alone, can also be used in combination of two or more kinds.
In addition, as (b) alkali soluble resin, from from the viewpoint of the compatibility of pigment, dispersant etc., preferably using Acrylic resin, the acrylic resin described in preferably using Japanese Unexamined Patent Publication 2014-137466 publications.
As acrylic resin, for example, (following, the title of the ethylenically unsaturated monomer with more than 1 carboxyl For " unsaturated monomer (b1) ") and other ethylenically unsaturated monomers (hereinafter referred to as " unsaturated monomer (b2) ") that can be copolymerized Copolymer.
As unsaturated monomer (b1), for example,：(methyl) acrylic acid, butenoic acid, α-chloroacrylic acid, cinnamic acid Such unsaturated monocarboxylic；Maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, in Unsaturated dicarboxylic as health acid or its acid anhydrides；Mono succinate [2- (methyl) acryloyloxyethyl ester], phthalic acid list [2- (methyl) acryloyloxyethyl ester] as more than 2 yuan polyacid list [(methyl) acryloxyalkyl] ester；ω-carboxylic Two ends as base polycaprolactone list (methyl) acrylate have list (methyl) acrylic acid of the polymer of carboxyl and hydroxyl Ester；To vinyl benzoic acid acid etc..
These unsaturated monomers (b1) can be used alone or mix two or more use.
In addition, as unsaturated monomer (b2), for example,：N-phenylmaleimide, N- cyclohexyl Malaysia acyl N- positions substituted maleimide amine as imines；Styrene, α-methylstyrene, 4-Vinyl phenol, to hydroxy-alpha-methyl benzene Ethene, to aromatic ethenyl compound as vinylbenzyl glycidyl base ether, acenaphthylene；
(methyl) methyl acrylate, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) propylene Sour 2- hydroxy methacrylates, (methyl) allyl acrylate, (methyl) benzyl acrylate, polyethylene glycol (degree of polymerization 2~10) methyl ether (methyl) acrylate, polypropylene glycol (degree of polymerization 2~10) methyl ether (methyl) acrylate, polyethylene glycol (degree of polymerization 2~ 10) single (methyl) acrylate of single (methyl) acrylate, polypropylene glycol (degree of polymerization 2~10), (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, three ring [5.2.1.02,6] decane -8- bases (methyl) acrylate, the ring of (methyl) acrylic acid two Amylene ester, glycerine list (methyl) acrylate, (methyl) acrylic acid 4- hydroxylphenyl esters, p -cumylphenol it is ethylene-oxide-modified (methyl) acrylate, (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates, 3- [(first Base) acryloyloxymethyl] oxetanes, as 3- [(methyl) acryloyloxymethyl] -3- Ethyloxetanes (methyl) acrylate；
Cyclohexyl vinyl ether, isobornyl vinyl ethers, three ring [5.2.1.02,6] decane -8- bases vinyl ethers, five rings Pentadecyl vinyl ethers, 3- (ethyleneoxy methyl) vinyl ethers as -3- Ethyloxetanes；Polystyrene, gather (methyl) methyl acrylate, poly- (methyl) n-butyl acrylate, the end of polymer molecular chain as polysiloxanes have single Polymeric monomer of (methyl) acryloyl group etc..
These unsaturated monomers (b2) can be used alone or mix two or more use.
In the copolymer of unsaturated monomer (b1) and unsaturated monomer (b2), the unsaturated monomer (b1) in the copolymer Copolymerization ratios be preferably 5~50 mass %, more preferably 10~40 mass %.By making unsaturated monomer with such scope (b1) it is copolymerized, the tendency for the photosensitive coloring composition that can obtain alkali-developable and excellent storage stability is present.
As unsaturated monomer (b1) and the specific example of the copolymer of unsaturated monomer (b2), for example, Japan Unexamined Patent 7-140654 publications, Japanese Unexamined Patent Publication 8-259876 publications, Japanese Unexamined Patent Publication 10-31308 publications, Japan are special Open flat 10-300922 publications, Japanese Unexamined Patent Publication 11-174224 publications, Japanese Unexamined Patent Publication 11-258415 publications, Japan Copolymer disclosed in JP 2000-56118 publications, Japanese Unexamined Patent Publication 2004-101728 publications etc..
The copolymer of unsaturated monomer (b1) and unsaturated monomer (b2) can be manufactured by known method, can be with For example, by Japanese Unexamined Patent Publication 2003-222717 publications, Japanese Unexamined Patent Publication 2006-259680 publications, International Publication No. 2007/ Method disclosed in No. 029871 grade controls its structure and Mw, Mw/Mn.
＜ (c) Photoepolymerizationinitiater initiaters ＞
(c) Photoepolymerizationinitiater initiater is directly to absorb light and cause decomposition reaction or hydrogen abstraction reaction, so as to polymerize with generation The composition of the function of living radical.It is additional that polymerization accelerant (chain-transferring agent), sensitizing dyestuff etc. can also be added as needed on Agent uses.
(c) Photoepolymerizationinitiater initiater in the photosensitive coloring composition of the present invention includes the oxime esters shown in following formula (I)s Compound.So, it is believed that by the oxime ester compound shown in comprising following formula (I)s, by institute in its carbazole skelton The naphthalene nucleus that contains and increase the light absorptive for long wavelength light, the crosslink density inside film can be improved, further, since structure In there is halogen atom, the compound is easily distributed in film coated surface, can suppress because oxygen hinder influence cause film surface Crosslink density excessively increases.
[chemical formula 12]
In above-mentioned logical formula (I),
R1Represent that optionally there is the aromatic ring yl of substituent,
R2The alkanoyl optionally with substituent or the optional aroyl with substituent are represented,
R3Represent hydrogen atom or optionally there is the alkyl of substituent,
R4Represent that optionally there is the aromatic ring yl of substituent,
R5And R6The phenyl ring optionally with substituent or the optional naphthalene nucleus with substituent are represented independently of one another, wherein, R5And R6In at least any one for optionally have substituent naphthalene nucleus,
R1And R4In at least any one there is-OR7Base is as substituent, wherein R7Represent alkylhalide group,
X represents direct key or carbonyl,
Z represents direct key or carbonyl.
As R1In aromatic ring yl, aromatic cyclic hydrocarbon group and aromatic heterocycle can be enumerated, its carbon number is preferably Less than 30, be more preferably less than 12, more preferably less than 8, and usually more than 4, be preferably more than 6.By to be upper State below higher limit, the tendency that dissolubility becomes good be present, by being set to more than above-mentioned lower limit, exist easily while realize Sensitivity and deliquescent tendency.
Aromatic cyclic hydrocarbon group refers to the aromatic series hydrocarbon ring with 1 free valency.Aromatic hydrocarbon as aromatic cyclic hydrocarbon group Ring, can be it is monocyclic can also be condensed ring, for example,：Phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, ring, aphthacene ring, pyrene Ring, BaP ring,Ring, benzo phenanthrene ring, acenaphthene ring, fluoranthene ring, fluorenes ring etc..
In addition, aromatic heterocycle refers to the heteroaromatic with 1 free valency.Fragrance as aromatic heterocycle Race's heterocycle, can be it is monocyclic can also be condensed ring, for example,：Furan nucleus, benzofuran ring, thiphene ring, benzothiophene Ring, pyrrole ring, pyrazole ring, imidazole ring,Diazole ring, indole ring, carbazole ring, pyrrolo- imidazole ring, pyrrolo-pyrazole ring, pyrroles And pyrrole ring, Thienopyrroles ring, thienothiophene ring, furans and pyrrole ring, furans and furan nucleus, thienofuran ring, benzene It is and differentAzoles ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, Isoquinolin ring, cinnolines (cinnoline) ring, quinoxaline ring, phenanthridines ring, benzimidazole ring,Pyridine ring, quinazoline ring, quinazoline Ketone ring, Azulene ring etc..
The substituent optionally having as aromatic ring yl, alkyl, hydroxyl, alkoxy, halogen atom, alkylhalide group can be enumerated (alkyl obtained from part or all of hydrogen atom is substituted by halogen atom), alkyl groups in the halogenalkoxy (part or all of hydrogen atom Alkoxy obtained from being substituted by halogen atom) etc., from the viewpoint of surface cure, preferably halogen atom, alkylhalide group or alkyl halide Epoxide, in addition, from the viewpoint of synthesis easiness, it is preferably unsubstituted.
Among these, from the viewpoint of sensitivity, preferably optionally there is the aromatic cyclic hydrocarbon group of substituent, more preferably appoint Phenyl ring base of the choosing with substituent.
R2In the carbon number of alkanoyl be not particularly limited, from the viewpoint of sensitivity, preferably more than 2, separately Outside, from the viewpoint of sensitivity, preferably less than 20, more preferably less than 12, more preferably less than 7, further Preferably less than 5, less than 3 are particularly preferably.
As the specific example of alkanoyl, acetyl group, propiono, bytyry etc. can be enumerated, among these, from sensitivity From the viewpoint of, preferably acetyl group or propiono, more preferably acetyl group.
The substituent optionally having as alkanoyl, hydroxyl, alkoxy, halogen atom etc. can be enumerated, from sensitivity Viewpoint considers, preferably unsubstituted.
R2In the carbon number of aroyl be not particularly limited, from the viewpoint of sensitivity, preferably more than 7, separately Outside, from the viewpoint of sensitivity, preferably less than 20, more preferably less than 12, more preferably less than 10, particularly preferably For less than 8.
As the specific example of aroyl, benzoyl, methyl benzoyl, naphthoyl etc. can be enumerated, these are worked as In, from the viewpoint of sensitivity, more preferably benzoyl.
The substituent optionally having as aroyl, hydroxyl, alkoxy, halogen atom etc. can be enumerated, from sensitivity Viewpoint considers, preferably unsubstituted.
Among these, from the viewpoint of sensitivity, preferably make R2Optionally to have the alkanoyl of substituent, more preferably Unsubstituted alkanoyl, more preferably acetyl group.
R3In the carbon number of alkyl be not particularly limited, from the viewpoint of dissolubility, preferably more than 1, more excellent Elect more than 2, more preferably more than 5, particularly preferably more than 7 as, in addition, from the viewpoint of compatibility, preferably 20 Below, less than 15, more preferably less than 10 are more preferably.
As the specific example of alkyl, methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, 2- can be enumerated Ethylhexyl etc., among these, from the viewpoint of dissolubility, preferably octyl group or 2- ethylhexyls, more preferably 2- ethylhexyls.
The substituent optionally having as alkyl, hydroxyl, alkoxy, halogen atom, phosphate etc. can be enumerated, from synthesis It is more preferably unsubstituted from the viewpoint of easiness.
Among these, from the viewpoint of dissolubility, preferably make R3Optionally to have the alkyl of substituent, more preferably not Substituted alkyl, more preferably 2- ethylhexyls.
As R4In aromatic ring yl, aromatic cyclic hydrocarbon group and aromatic heterocycle can be enumerated, its carbon number is preferably Less than 30, be more preferably less than 12, more preferably less than 8, and usually more than 4, be preferably more than 6.By being set to Below above-mentioned higher limit, the tendency that dissolubility becomes good be present, by being set to more than above-mentioned lower limit, it is easy while real to exist Existing sensitivity and deliquescent tendency.
Aromatic cyclic hydrocarbon group refers to the aromatic series hydrocarbon ring with 1 free valency.Aromatic hydrocarbon as aromatic cyclic hydrocarbon group Ring, can be it is monocyclic can also be condensed ring, for example,：Phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, ring, aphthacene ring, pyrene Ring, BaP ring,Ring, benzo phenanthrene ring, acenaphthene ring, fluoranthene ring, fluorenes ring etc..
In addition, aromatic heterocycle refers to the heteroaromatic with 1 free valency.Fragrance as aromatic heterocycle Race's heterocycle, can be it is monocyclic can also be condensed ring, for example,：Furan nucleus, benzofuran ring, thiphene ring, benzothiophene Ring, pyrrole ring, pyrazole ring, imidazole ring,Diazole ring, indole ring, carbazole ring, pyrrolo- imidazole ring, pyrrolo-pyrazole ring, pyrroles And pyrrole ring, Thienopyrroles ring, thienothiophene ring, furans and pyrrole ring, furans and furan nucleus, thienofuran ring, benzene It is and differentAzoles ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, Isoquinolin ring, cinnolines (cinnoline) ring, quinoxaline ring, phenanthridines ring, benzimidazole ring,Pyridine ring, quinazoline ring, quinazoline Ketone ring, Azulene ring etc..
The substituent optionally having as aromatic ring yl, alkyl, hydroxyl, alkoxy, halogen atom etc. can be enumerated, from dissolving From the viewpoint of property, preferably alkyl or alkoxy, more preferably alkyl, further preferred methyl.
The number of substituent is not particularly limited, from the viewpoint of dissolubility, preferably more than 1, more preferably 2 with It is upper, more preferably more than 3, in addition, from the viewpoint of compatibility, preferably less than 10, more preferably less than 5, enter one Step is preferably less than 4.
Among these, from the viewpoint of dissolubility, preferably make R4Optionally to have the aromatic cyclic hydrocarbon group of substituent, more Preferably there is the aromatic cyclic hydrocarbon group of more than 2 methyl, more preferablyBase.
R5And R6Represent that optionally there is the phenyl ring or naphthalene nucleus of substituent independently of one another, wherein, R5And R6In it is at least any Individual is the naphthalene nucleus for optionally having substituent.As specific combination, can enumerate：R5Optionally to have phenyl ring, the R of substituent6For The optionally combination of the naphthalene nucleus with substituent；R5Optionally to have naphthalene nucleus, the R of substituent6For the optionally phenyl ring with substituent Combination；R5Optionally to have naphthalene nucleus, the R of substituent6For the combination of the optionally naphthalene nucleus with substituent.
Among these, from the viewpoint of light absorptive, R can be enumerated5Optionally to have the naphthalene nucleus and R of substituent6To appoint The combination of phenyl ring of the choosing with substituent.
R5In the case of for the optionally phenyl ring with substituent, 1, R of the N atomistic bindings in phenyl ring can be enumerated6It is bonded in 2, X be bonded in the mode of 4.Similarly, R6In the case of for the optionally phenyl ring with substituent, N atom keys can be enumerated Close 1, R in phenyl ring5Be bonded in 2, Z be bonded in the mode of 4.
On the other hand, R5In the case of for the optionally naphthalene nucleus with substituent, in formula (I), R is bonded to5On X, N it is former Son, R6The optional position of the naphthalene nucleus can be bonded in.For example,：1, R of the N atomistic bindings in naphthalene nucleus6Be bonded in 2, X is bonded in the mode of 4；And R6Be bonded in 1 of naphthalene nucleus, N atomistic bindings the mode of 6 is bonded in 2, X.
Similarly, R6In the case of for the optionally naphthalene nucleus with substituent, in formula (I), R is bonded to6On Z, N atom, R5The optional position of the naphthalene nucleus can be bonded in.For example,：1, R of the N atomistic bindings in naphthalene nucleus5It is bonded in 2, Z keys Close the mode at 4；And R5Be bonded in 1 of naphthalene nucleus, N atomistic bindings the mode of 6 is bonded in 2, Z.
As R5And R6In phenyl ring, the substituent that optionally has of naphthalene nucleus, hydroxyl, alkoxy, halogen atom can be enumerated Deng preferably unsubstituted from the viewpoint of sensitivity.
R1And R4In at least any one there is-OR7Base is as substituent.Can be R1With-OR7Base or R4 With-OR7Base, it can also be R1And R4There is-OR independently of one another7Base.Among these, from the viewpoint of sensitivity, preferably R1With-OR7Base.
R7Represent alkylhalide group, R7In the carbon number of alkylhalide group be not particularly limited, it is excellent from the viewpoint of dissolubility Elect more than 1 as, more preferably more than 2, more preferably more than 3, in addition, from the viewpoint of compatibility, preferably 10 with Under, more preferably less than 7, more preferably less than 5.
Carbochain in alkylhalide group can be straight chain, or side chain, can also be ring-type, from the viewpoint of ease of manufacturing Consider, preferably straight chain.
The number of halogen atom possessed by alkylhalide group is not particularly limited, from the viewpoint of dissolubility, preferably 1 with It is upper, more preferably more than 2, more preferably more than 3, in addition, from the viewpoint of compatibility, preferably less than 7, more preferably For less than 6, more preferably less than 5.
As the specific example of alkylhalide group, 2,2,3,3- tetra- fluoropropyls, 2,2,2- trifluoroethyls, 2 can be enumerated, 2,3,3, 4,4,5,5- octafluoro amyl groups etc., among these, from the viewpoint of ease of manufacturing, more preferably 2,2,3,3- tetra- fluoropropyls.
The substituent optionally having as alkylhalide group, hydroxyl, alkoxy etc. can be enumerated, from the viewpoint of ease of manufacturing Consider, it is preferably unsubstituted.
X represents direct key or carbonyl, from the viewpoint of adaptation, preferably direct key, and from the viewpoint of sensitivity, Preferably carbonyl.
In addition, Z represents direct key or carbonyl, from the viewpoint of adaptation, preferably direct key, from the viewpoint of sensitivity Consider, preferably carbonyl.
As the specific example of the oxime ester compound shown in above-mentioned logical formula (I), following compound can be enumerated.
[chemical formula 13]
[chemical formula 14]
[chemical formula 15]
[chemical formula 16]
[chemical formula 17]
[chemical formula 18]
[chemical formula 19]
[chemical formula 20]
(c) Photoepolymerizationinitiater initiater in the photosensitive coloring composition of the present invention includes the oxime ester shown in above-mentioned logical formula (I) Class compound, but can also further contain other Photoepolymerizationinitiater initiaters.
As other Photoepolymerizationinitiater initiaters, for example, Japanese Unexamined Patent Application 59-152396 publications, Japanese Unexamined Patent Application The Metallocenic compound for including cyclopentadiene titanium compound described in 61-151197 publications；Japanese Unexamined Patent Publication 2000-56118 publications Described in Hexaarylbiimidazole derivative；Halomethylation described in Japanese Unexamined Patent Publication 10-39503 publicationsDiazole derives The N- such as thing, halomethyl Striazine derivative, N- phenylglycines aryl-alpha-amido acids, N- aryl-a-amino acid salt, The free radical activators such as N- aryl-a-amino acid esters, alpha-aminoalkyl benzophenone derivatives；Japanese Unexamined Patent Publication 2000-80068 public affairs Report, Japanese Unexamined Patent Publication 2006-36750 publications, International Publication No. 2008/075564, International Publication No. 2009/131189 etc. Described in oxime ester derivative etc..
Photoepolymerizationinitiater initiater may be used alone, can also be used in combination of two or more kinds.
In order to improve induction sensitivity, it can coordinate as needed in Photoepolymerizationinitiater initiater and correspond to image exposure light source Wavelength sensitizing dyestuff, polymerization accelerant.As sensitizing dyestuff, can enumerate：Japanese Unexamined Patent Publication 4-221958 publications, day Xanthene pigment, Japanese Unexamined Patent Publication 3-239703 publications, Japanese Unexamined Patent Publication 5- described in this Unexamined Patent 4-219756 publications The cumarin pigment with heterocycle, Japanese Unexamined Patent Publication 3-239703 publications, the Japanese Unexamined Patent Publication 5- that No. 289335 publications are recorded The methylene pyrrole described in 3- oxos coumarin compound, Japanese Unexamined Patent Publication 6-19240 publications described in No. 289335 publications Cough up pigment and Japanese Unexamined Patent Application 47-2528 publications, Japanese Unexamined Patent Application 54-155292 publications, Japanese Patent Publication 45- No. 37377 publications, Japanese Unexamined Patent Application 48-84183 publications, Japanese Unexamined Patent Application 52-112681 publications, Japanese Unexamined Patent Application 58- No. 15503 publications, Japanese Unexamined Patent Application 60-88005 publications, Japanese Unexamined Patent Application 59-56403 publications, Japanese Unexamined Patent Publication 2-69 Number publication, Japanese Unexamined Patent Application 57-168088 publications, Japanese Unexamined Patent Publication 5-107761 publications, Japanese Unexamined Patent Publication 5-210240 Pigment with dialkyl amido benzene skeleton described in number publication, Japanese Unexamined Patent Publication 4-288818 publications etc..
In these sensitizing dyestufves, the preferably sensitizing dyestuff containing amino more preferably has ammonia in same intramolecular The compound of base and phenyl.Particularly preferred such as 4,4 '-dimethylamino benzophenone, 4,4 '-diethylamino benzophenone, 2- aminobenzophenones, 4- aminobenzophenones, 4,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, 3,4- bis- The benzophenone compounds such as aminobenzophenone；2- (to dimethylaminophenyl) benzoAzoles, 2- are (to diethylamino benzene Base) benzoAzoles, 2- (p- dimethylaminophenyls) benzo [4,5] benzoAzoles, 2- (to dimethylaminophenyl) benzo [6,7] benzoDouble (to diethylamino the phenyl) -1,3,4- of azoles, 2,5-Azoles, 2- (to dimethylaminophenyl) benzo thiophene Azoles, 2- (to diethylamino phenyl) benzothiazole, 2- (to dimethylaminophenyl) benzimidazole, 2- are (to diethylamino Phenyl) benzimidazole, double (p- diethylamino the phenyl) -1,3,4- thiadiazoles of 2,5-, (to dimethylaminophenyl) pyridine, (to diethylamino phenyl) pyridine, (to dimethylaminophenyl) quinoline, (to diethylamino phenyl) quinoline, (to diformazan Base aminophenyl) pyrimidine, (to diethylamino phenyl) pyrimidine etc. contain to compound of dialkylaminophenyl etc..Wherein, Most preferably 4,4 '-dialkyl amido benzophenone.
One kind can also be used alone in sensitizing dyestuff, or combines two or more use.
As polymerization accelerant, such as ESCAROL 507 ethyl ester, benzoic acid 2- dimethylaminoethyls can be used The aliphatic amines such as the aromatic amines such as ester, n-butylamine, N methyldiethanol amine, the sulfhydryl compound described below etc..Polymerization promotes Agent may be used alone, can also be used in combination of two or more kinds.
＜ (d) alefinically unsaturated compounds ＞
The photosensitive coloring composition of the present invention includes (d) alefinically unsaturated compounds.By unsaturated comprising (d) olefinic Compound, sensitivity improve.
The alefinically unsaturated compounds used in the present invention are the chemical combination that intramolecular has at least one ethylenically unsaturated group Thing.Specifically, for example, (methyl) acrylic acid, (methyl) alkyl acrylate, acrylonitrile, styrene and with 1 Monoesters that the carboxylic acid of ethylenic unsaturated bond is formed with polyalcohol or monohydric alcohol etc..
In the present invention, particularly preferably using the multifunctional olefinic in 1 molecule with more than 2 ethylenically unsaturated groups Monomer.The number of ethylenically unsaturated group is not particularly limited possessed by multifunctional olefinic type monomers, usually more than 2, excellent Elect more than 4, more preferably more than 5, and preferably less than 8, more preferably less than 7 as.Under being set to above-mentioned More than limit value, exist with highly sensitive tendency, by being set to below above-mentioned higher limit, the dissolubility existed in a solvent carries High tendency.
As the example of multifunctional olefinic type monomers, for example,：Aliphatic polyhydroxy compound and unsaturated carboxylic acid The ester of formation；The ester that aromatic polyhydroxy compounds are formed with unsaturated carboxylic acid；Pass through aliphatic polyhydroxy compound, aromatic series Ester etc. obtained from the esterification of the polyols such as polyol and unsaturated carboxylic acid and polybasic carboxylic acid.
The ester formed as above-mentioned aliphatic polyhydroxy compound and unsaturated carboxylic acid, can enumerate ethylene glycol diacrylate Ester, triethylene glycol diacrylate, trimethylolpropane trimethacrylate, methylolethane triacrylate, pentaerythrite Diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol tetraacrylate, two seasons penta The acrylic acid of the aliphatic polyhydroxy compounds such as the acrylate of tetrol five, dipentaerythritol acrylate, glyceryl acrylate Ester, the acrylate of these example compounds is replaced with into methacrylate obtained from methacrylate, similarly replace Itaconate obtained from being changed to itaconate, butenoate or replace with maleate obtained from replacing with butenoate Obtained from maleate etc..
The ester formed as aromatic polyhydroxy compounds and unsaturated carboxylic acid, can enumerate hydroquinones diacrylate Ester, hydroquinones dimethylacrylate, resorcinol diacrylate, resorcinol dimethylacrylate, 1,2,3- benzene Acrylate and methacrylate of the aromatic polyhydroxy compounds such as triphenol triacrylate etc..
As the ester as obtained from the esterification of polybasic carboxylic acid and unsaturated carboxylic acid and polyol, it is not necessary to be Single substance, if enumerating its representational specific example, the condensation of acrylic acid, phthalic acid and ethylene glycol can be enumerated Thing；The condensation product of acrylic acid, maleic acid and diethylene glycol；The condensation product of methacrylic acid, terephthalic acid (TPA) and pentaerythrite；Third Olefin(e) acid, adipic acid, the condensation product etc. of butanediol and glycerine.
In addition, the example as the multifunctional olefinic type monomers used in the present invention, polyisocyanate compound and hydroxyl (methyl) acrylate or (methyl) acrylate reactions of polyisocyanate compound and polyalcohol and hydroxyl and obtain Carbamate (methyl) esters of acrylic acid arrived；Polynary epoxide and hydroxyl (methyl) acrylate or (methyl) propylene Epoxy Acrylates as the addition reaction of acid；The acrylic amides such as ethylenebisacrylamide；Phthalic acid two The pi-allyl esters such as allyl ester；Compounds containing vinyl such as phthalic acid divinyl base ester etc..
As above-mentioned carbamate (methyl) esters of acrylic acid, for example,：DPHA-40H、UX-5000、UX- 5002D-P20, UX-5003D, UX-5005 (Nippon Kayaku K. K's manufacture), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufacture of chemical industry Co., Ltd. of Xin Zhong villages), UA-306H, UA-510H, UF-8001G (manufacture of KCC of Xie Rong societies), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (Japan's synthesis KCC manufactures) etc..
Among these, from the viewpoint of curability, as (d) alefinically unsaturated compounds, (methyl) third is preferably used Olefin(e) acid Arrcostab, more preferably using dipentaerythritol acrylate.
They may be used alone, can also be used in combination of two or more kinds.
＜ (e) solvents ＞
The photosensitive coloring composition of the present invention includes (e) solvent.By the way that comprising (e) solvent, pigment can be scattered in In solvent, and coating becomes easy.
The photosensitive coloring composition of the present invention is generally so that (a) colouring agent, (b) alkali soluble resin, (c) photopolymerization to be drawn Hair agent, (d) alefinically unsaturated compounds, (f) dispersant and other various materials for using as needed are dissolved or dispersed in molten State in agent uses.Among solvent, from the viewpoint of dispersiveness, coating, preferable organic solvent.
Among organic solvent, from the viewpoint of coating, solvent of the boiling point for 100~300 DEG C of scopes is preferably selected, More preferably select solvent of the boiling point for 120~280 DEG C of scopes.It should be noted that boiling point mentioned here refers in pressure Boiling point under 1013.25hPa.
As such organic solvent, such as following solvent can be enumerated.
Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, the third two Alcohol list ether, propane diols mono-n-butyl ether, glycol tertiary butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list N-butyl ether, methoxy amylalcohol, DPE, dipropylene glycol monomethyl ether, 3- methyl -3- methoxybutanols, three second Glycol monomethyl ether, Triethylene glycol ethyl ether, glycol monoalkyl ethers as tripropylene glycol methyl ether；
Glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl Ether, dibutyl ethylene glycol ether, glycol dialkyl ether class as dimethyl ether；
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, ethylene glycol mono-n-butyl ether acetic acid esters, propane diols list first Ether acetic acid ester, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, propylene glycol monobutyl ether acetic acid esters, methoxybutyl Acetic acid esters, 3- methoxybutyls acetic acid esters, methoxypentyl acetic acid esters, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol list second Ether acetic acid ester, diethylene glycol mono-n-butyl ether acetic acid esters, dipropylene glycol monomethyl ether acetic acid esters, triethylene glycol monomethyl ether acetic acid esters, three Glycol alkyl ether acetate esters as ethylene glycol monoethylether acetate, 3- methyl -3- methoxybutyl acetic acid esters；
The glycol diacetate classes such as ethylene acetate, 1,3 butylene glycol diacetate esters, 1,6-HD diacetate esters；
The alkyl acetate class such as cyclohexyl acetate；
Amyl ether, ether, dipropyl ether, Di Iso Propyl Ether, dibutyl ethers, diamyl ether, ethyl isobutyl ether, hexyl ether Such ethers；
Acetone, MEK, methyl amyl ketone, methyl isopropyl Ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl Ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, ethyl pentyl group ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxy Ketone as pentanone；
Ethanol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, propane diols, butanediol, diethylene glycol, DPG, three Ethylene glycol, methoxy amylalcohol, glycerine, monohydric alcohol or polyalcohols as benzylalcohol；
Pentane, normal octane, diisobutylene, n-hexane, hexene, isoprene, cinene, aliphatic as dodecane Hydro carbons；
Hexamethylene, hexahydrotoluene, methylcyclohexene, ester ring type hydro carbons as bicyclohexyl；
It is aromatic hydrocarbon as benzene,toluene,xylene, isopropylbenzene；
Amyl formate, Ethyl formate, ethyl acetate, butyl acetate, propyl acetate, pentyl acetate, methyl isobutyrate, second two Alcohol acetic ester, ethyl propionate, propyl propionate, butyl butyrate, isobutyl isobutyrate (IBIB), methyl isobutyrate, ethyl caprate, stearic acid fourth Ester, ethyl benzoate, 3- ethoxypropanoates, 3- ethoxyl ethyl propionates, 3- methoxy methyl propionates, 3- methoxypropionic acids Ethyl ester, 3- methoxy propyls propyl propionate, 3- methoxy propyls acid butyl ester, chain or ring-type esters as gamma-butyrolacton；
Alkoxy carboxylic acids as 3- methoxypropionic acids, 3- ethoxy-propionic acids；
Halogenated hydrocarbon as chlorobutane, chloropentane；
Ether ketone as methoxy pentanone；
Nitrile etc. as acetonitrile, benzonitrile.
As equivalent to above-mentioned commercially available organic solvent, can enumerate：Mineral spirits (Mineral spirit), Varsol#2, Apco#18solvent, Apco thinner, Socal solvent No.1 and No.2, Solvesso#150, Shell TS28solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve (" cellosolve (cellosolve) it is be " registration mark, same as below), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetic acid Ester, diethylene glycol dimethyl ether (diglyme) (above-mentioned is trade name) etc..
These organic solvents can be used alone, and can also combine two or more use.
In the case of forming coloring sept with photoetching process, as organic solvent, boiling point is preferably selected as 100~200 DEG C The organic solvent of (under the conditions of pressure 1013.25hPa, below, on boiling point all same) scope.More preferably there are 120~170 DEG C Boiling point organic solvent.
In above-mentioned organic solvent, from the molten of the constituent in the harmonious good, composition of coating, surface tension etc. From the aspect of Xie Du is higher, preferred diol alkylether acetates class.
In addition, glycol alkyl ether acetate esters can be used alone, can also be used with other organic solvent combinations.As The organic solvent being applied in combination, particularly preferably glycol monoalkyl ethers.
Wherein, consider from the dissolubility of the constituent in composition, particularly preferred propylene glycol monomethyl ether.Need what is illustrated That the polarity of glycol monoalkyl ethers is high, if its addition is excessive, exist pigment easily cohesion and making obtain thereafter The tendency that the storage stabilities such as the viscosity rising of chromoresin composition decline, therefore, the ratio of the glycol monoalkyl ethers in solvent Example is preferably the mass % of 5 mass %~30 mass %, more preferably 5 mass %~20.
It is also preferable to organic solvent (following, sometimes referred to as " high boiling solvent ") group with more than 150 DEG C boiling points Close and use.By being applied in combination with such high boiling solvent, although photosensitive coloring composition becomes to be difficult to drying, have Prevent the destroyed effect of the uniform dispersity of the pigment in composition in the case of drastically drying.
That is, there is the precipitation such as preventing from slit spray nozzle front end because of color material, the effect of foreign matter defect is produced solidification. From the aspect of such effect height, in above-mentioned various solvents, particularly preferred diethylene glycol mono-n-butyl ether, diethylene glycol Dan Zhengding Ether acetic acid ester and diethylene glycol monoethyl ether acetic acid esters.
The content ratio of high boiling solvent is preferably 3 mass %~50 mass %, more preferably 5 mass % in organic solvent The mass % of~40 mass %, particularly preferably 5 mass %~30.More than for above-mentioned lower limit, existing can suppress for example In tendency of the slit spray nozzle front end because producing foreign matter defect the precipitation, solidification of color material etc., in addition, by for above-mentioned higher limit with Under, can be slack-off with the drying temperature of composite inhibiting, the productive temp that can suppress to be dried under reduced pressure technique so as to presence is bad, pre- The tendency for the problem of pin hole of baking (pre-bake) is such.
It should be noted that the high boiling solvent of more than 150 DEG C of boiling point can be glycol alkyl ether acetate esters, in addition Can be glycol alkyl ether class, in this case, can not also the high boiling solvent containing more than 150 DEG C of boiling point in addition.
As preferable high boiling solvent, for example, the diethylene glycol mono-n-butyl ether acetic acid in above-mentioned various solvents Ester, diethylene glycol monoethyl ether acetic acid esters, dipropylene glycol methyl ether acetic acid esters, 1,3 butylene glycol diacetate esters, 1,6-HD two Acetic acid esters, glycerol triacetate etc..
＜ (f) dispersants ＞
In the photosensitive coloring composition of the present invention, due to making (a) colouring agent imperceptibly disperse and making its dispersity Stabilize for ensuring that quality stability is important, therefore contain (f) dispersant.
As (f) dispersant, the preferably macromolecule dispersing agent with functional group, in addition, from the aspect of dispersion stabilization, It is preferred that there is carboxyl；Phosphate；Sulfonic group；Or their alkali；Primary amino radical, secondary amino group or tertiary amino；Quaternary ammonium salt base；From pyrrole The macromolecule dispersing agent of the functional groups such as the nitrogenous heterocyclic group such as pyridine, pyrimidine, pyrazine.
Wherein, particularly from can be carried out when pigment is disperseed with a small amount of dispersant it is scattered from the viewpoint of, it is especially excellent Choosing has primary amino radical, secondary amino group or tertiary amino；Quaternary ammonium salt base；From alkali such as the nitrogenous heterocyclic groups such as pyridine, pyrimidine, pyrazine The macromolecule dispersing agent of property functional group.
In addition, as macromolecule dispersing agent, for example,：Carbamates dispersant, acrylic dispersants, Polyethyleneimine amine dispersant, polyallyl amine dispersant, the monomer and dispersant, the polyoxy of polymeric monomer formation with amino Vinyl alkyl ethers dispersant, the esters dispersant of polyoxyethylene two, polyethers phosphoric acid class dispersant, polyester phosphoric acid class dispersant, mountain Pears sugar alcohol acid anhydride aliphatic ester dispersant, aliphatic modified polyesters dispersant etc..
As the specific example of such dispersant, trade name EFKA (registration mark, BASF AG's system can be enumerated Make), DISPERBYK (registration mark, BYK-Chemie companies manufacture), Disparlon (registration mark, nanmu this chemical conversion strain formula meeting Society manufactures), SOLSPERSE (registration mark, Lubrizol companies manufacture), KP (Shin-Etsu Chemial Co., Ltd's manufacture), Polyflow (Kyoeisha Chemical Co., Ltd.'s manufacture), Ajisper (registration mark, Ajincomoto Co., Inc's manufacture) etc..
These macromolecule dispersing agents can be used alone, or combine two or more use.
The weight average molecular weight (Mw) of macromolecule dispersing agent is usually more than 700, is preferably more than 1000, and is usually Less than 100,000, preferably 50, less than 000.
Among these, from the viewpoint of pigment-dispersing, (f) dispersant preferably comprises the carbamic acid with functional group Esters macromolecule dispersing agent and/or acrylic polymer dispersant, particularly preferably include acrylic polymer dispersant.
In addition, from the aspect of dispersiveness, keeping quality, preferably with basic functionality and with polyester key and/or polyethers The macromolecule dispersing agent of key.
As carbamates and acrylic polymer dispersant, for example, DISPERBYK 160~ 166th, 182 serial (they being carbamates), DISPERBYK2000,2001, LPN21116 etc. (being acrylic compounds) (with On be BYK-Chemie companies manufacture).
If specifically preferred chemical constitution of the example as carbamates macromolecule dispersing agent, can enumerate example Chemical combination such as by making the number-average molecular weight 300~10,000 of polyisocyanate compound, intramolecular with 1 or 2 hydroxyl Thing and same intramolecular have weight average molecular weight 1,000~200,000 obtained from the reaction of the compound of active hydrogen and tertiary amino Dispersion resin etc..Above-mentioned dispersion resin is handled by using the level Four such as benzyl chloride agent, the whole of tertiary amino can be made Or a part is changed into quaternary ammonium salt base.
As the example of above-mentioned polyisocyanate compound, can enumerate：PPDI, Toluene-2,4-diisocyanate, 4- bis- are different Cyanate, Toluene-2,4-diisocyanate, 6- diisocyanate, 4,4 '-methyl diphenylene diisocyanate, naphthalene -1,5- diisocyanate, ditolyl The aromatic diisocyanates such as amine diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4- The aliphatic diisocyanates such as trimethyl hexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate Alicyclic two isocyanides such as ester, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), ω, ω '-diisocyanate dimethyl cyclohexane Acid esters, xylylene diisocyanate, α, α, α ', α '-tetramethyl xylylene diisocyanate etc. have the fat of aromatic rings (cyclo) aliphatic diisocyanates, lysine ester triisocyanate, hendecane -1,6,11- triisocyanates, 1,8- diisocyanate -4- Isocyanatomethyl octane, hexa-methylene -1,3,6- triisocyanates, bicycloheptane triisocyanate, triphenyl methane three are different The triisocyanates such as cyanate, D2EHDTPA triphenyl triisocyanate and their tripolymer, hydride and they Polyalcohol addition product etc..
As the tripolymer of polyisocyanates, preferably organic diisocyanate, most preferably toluene diisocynate The tripolymer of ester and the tripolymer of IPDI.They can be used alone, and can also combine two or more Use.
As the manufacture method of the tripolymer of isocyanates, following method can be enumerated：Use appropriate trimerization catalyst Agent, isocyanide is carried out to above-mentioned polyisocyanates such as tertiary amines, phosphine, alkoxide species, metal oxide, metal carboxylate The trimerizing of the part of perester radical, trimerizing is terminated by adding catalyst poison, is then removed with solvent extraction, thin-film distillation Unreacted polyisocyanates is removed, so as to obtain the polyisocyanates containing cyamelide ester group of target.
, can be with as the compound of the number-average molecular weight 300~10,000 in same intramolecular with 1 or 2 hydroxyl Enumerate polyether Glycols, polyester diol, PCDL, polyolefin dihydric alcohol etc. and the side of these compounds Terminal hydroxyl material and mixture of more than two kinds in them obtained from the alkyl alkoxide of carbon number 1~25.
As polyether Glycols, PTMEG, polyethers esterdiol and their mixture of more than two kinds can be enumerated. As PTMEG, can enumerate will material obtained from oxidation polyamino alkenyl or copolymerization, it is such as polyethylene glycol, polypropylene glycol, poly- Ethylene glycol propane diols, polyoxy butylen glycol, polyoxy hexylidene glycol, polyoxy octamethylene glycol and the of more than two kinds of theirs mix Compound.
As polyethers esterdiol, can enumerate by making the glycol containing ether or mixture and dicarboxyl with other glycol Acid or their anhydride reaction or make oxyalkylene and polyester-diol react obtained from material, such as poly- (polyoxy butylidene) Adipate ester etc..
As PTMEG, most preferably polyethylene glycol, polypropylene glycol, polyoxy butylen glycol or these compounds The compound that side end hydroxyl is formed by the alkyl alkoxide of carbon number 1~25.
As polyester-diol, can enumerate：Dicarboxylic acids (butanedioic acid, glutaric acid, adipic acid, decanedioic acid, fumaric acid, Malaysia Acid, phthalic acid etc.) or their acid anhydrides and glycol (ethylene glycol, diethylene glycol, triethylene glycol, propane diols, DPG, three Propane diols, 1,2- butanediols, 1,3 butylene glycol, 1,4- butanediols, 2,3- butanediols, 3- methyl isophthalic acids, 5- pentanediols, new penta 2 Alcohol, 2- methyl-1,3-propanediols, 2- methyl-2-propyl -1,3- propane diols, 2-butyl-2-ethyl-1,3-propanediol, 1,5- penta Glycol, 1,6-HD, 2- methyl -2,4-PD, 2,2,4- trimethyl -1,3- pentanediols, 2- ethyl -1,3- hexylene glycols, It is the aliphatic diol such as 2,5- dimethyl -2,5-HD, 1,8- ethohexadiols, 2- methyl isophthalic acids, 8- ethohexadiols, 1,9- nonanediols, double Aromatic diol, the N- methyl diethanols such as the alicyclic diols such as (methylol) hexamethylene, benzene dimethanol, double (hydroxyl-oxethyl) benzene N- alkyl dialkanol amines such as amine etc.) material obtained from polycondensation, such as polyethylene glycol adipate, poly adipate succinic acid ester, Polyadipate 1,6- hexylene glycols ester, polyadipate ethylene glycol propylene glycol ester etc., or using above-mentioned glycols or carbon number 1~ 25 monohydric alcohol is as polylactone diol obtained from initiator or polylactone monohydric alcohol, such as polycaprolactone glycol, poly- methyl Valerolactone and their mixture of more than two kinds.As polyester-diol, most preferably polycaprolactone glycol or with carbon number 1~25 alcohol is the polycaprolactone that initiator obtains.
As PCDL, poly- carbonic acid (1,6- hexylene glycol) ester, poly- carbonic acid (3- methyl isophthalic acids, 5- penta 2 can be enumerated Alcohol) ester etc., as polyolefin diols, the poly- isoamyl two of polybutadiene diol, hydrogenation type polybutadiene diol, hydrogenation type can be enumerated Enediol etc..
They may be used alone, can also be used in combination of two or more kinds.
It is usually 300~10,000 that same intramolecular, which has the number-average molecular weight of the compound of 1 or 2 hydroxyl, preferably For 500~6,000, more preferably 1,000~4,000.
The compound for having active hydrogen and tertiary amino in same intramolecular used in the present invention is illustrated.
As hydrogen atom of active hydrogen, the i.e. Direct Bonding on oxygen atom, nitrogen-atoms or sulphur atom, can enumerate hydroxyl, Hydrogen atom in the functional groups such as amino, sulfydryl, wherein, preferably amino, particularly primary amino radical hydrogen atom.
Tertiary amino is not particularly limited, and for example, the amino of the alkyl with carbon number 1~4, or heterocycle Structure, more specifically imidazole ring or triazole ring etc..
If the such compound in same intramolecular with active hydrogen and tertiary amino of example, can enumerate N, N- bis- Methyl isophthalic acid, 3- propane diamine, N, N- diethyl -1,3- propane diamine, N, N- dipropyl -1,3- propane diamine, N, N- dibutyl -1,3- third Diamines, N, N- dimethyl-ethylenediamines, N, N- diethyl ethylenediamines, N, N- dipropyl ethylenediamine, N, N- dibutyl ethylenediamine, N, N- Dimethyl -1,4- butanediamine, N, N- diethyl -1,4- butanediamine, N, N- dipropyl -1,4- butanediamine, N, N- dibutyl -1,4- Butanediamine etc..
In addition, the nitrogen heterocyclic ring in the case of being nitrogen heterocyclic ring structure as tertiary amino, can be enumerated：Pyrazole ring, miaow Azoles ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, BTA ring, benzoAzoles ring, benzo Nitrogenous 5 circle heterocycles such as thiazole ring, diazosulfide ring, it is pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, different Nitrogenous 6 circle heterocycles such as quinoline ring.In these nitrogen heterocyclic rings, preferably imidazole ring or triazole ring.
If these have the compound of imidazole ring and amino to specific example, 1- (3- aminopropyls) miaow can be enumerated Azoles, histidine, 2- aminooimidazoles, 1- (2- amino-ethyls) imidazoles etc..
In addition, if specific example these there is triazole ring and the compound of amino, then can enumerate 3- amino -1,2,4- Triazole, 5- (2- amino -5- chlorphenyls) -3- phenyl -1H-1,2,4- triazoles, 4- amino -4H-1,2,4- triazole -3,5- glycol, 3- amino-5-phenyl -1H-1,3,4- triazoles, 5- amino -1,4- diphenyl -1,2,3- triazoles, 3- amino -1- benzyl -1H-2, 4- triazoles etc..
Wherein, preferably N, N- dimethyl -1,3- propane diamine, N, N- diethyl -1,3- propane diamine, 1- (3- aminopropyls) miaow Azoles, 3- amino -1,2,4- triazoles.
They can be used alone, or combine two or more use.
The optimizing mixing proporiton rate of raw material is as follows when manufacturing carbamates macromolecule dispersing agent：Relative to polyisocyanates The mass parts of compound 100, the compound in same intramolecular with the number-average molecular weight 300~10,000 of 1 or 2 hydroxyl are 10~200 mass parts, it is preferably 20~190 mass parts, more preferably 30~180 mass parts, has in same intramolecular active The compound of hydrogen and tertiary amino is 0.2~25 mass parts, is preferably 0.3~24 mass parts.
The known method that the manufacture of carbamates macromolecule dispersing agent manufactures according to polyurethane resin is carried out.As Solvent during manufacture, usually using ketones such as acetone, MEK, methyl iso-butyl ketone (MIBK), cyclopentanone, cyclohexanone, isophorones；Second The esters such as acetoacetic ester, butyl acetate, cellosolve acetate；The hydro carbons such as benzene,toluene,xylene, hexane；It is DAA, isopropanol, secondary The chloro things such as the part such as butanol, tert-butyl alcohol alcohols, dichloromethane, chloroform；The ethers such as tetrahydrofuran, ether；Dimethylformamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide polar aprotic solvent etc..They can be used alone, or combination 2 kinds with Upper use.
In above-mentioned manufacture, usually using urethane catalysts.As the catalyst, for example, Tin system, the acetylacetone,2,4-pentanediones such as dibutyltin dilaurate, dioctyl tin dilaurate, dibutyl tin dicaprylate, tin octoate Tertiary amines such as the iron such as iron, iron chloride system, triethylamine, triethylenediamine etc..They can be used alone, or combination 2 kinds with Upper use.
It is preferably to control reacted amine value that same intramolecular, which has the import volume of the compound of active hydrogen and tertiary amino, In the amount of 1~100mgKOH/g scopes, the amount in 5~95mgKOH/g scopes is more preferably controlled.Amine value is to basic amine group with acid Carry out acid-base titration, the value corresponding with acid number represented with KOH mg numbers.When amine value is less than above range, scattered energy be present The tendency that power declines, in addition, if exceeding above range, then developability is easily reduced.
It should be noted that in the reaction of the above in macromolecule dispersing agent in the case of remaining NCO, if Further destroying NCO with alcohol, amino-compound, then the ageing stability of product uprises, therefore preferably.
The weight average molecular weight (Mw) of carbamates macromolecule dispersing agent is usually 1,000~200,000, preferably 2, 000~100,000, more preferably 3,000~50,000 scope.When the molecular weight is less than 1,000, dispersiveness and stably dispersing Property it is poor, if it exceeds 200,000, then decreased solubility, bad dispersibility, the control of simultaneous reactions becomes difficult.
As acrylic polymer dispersant, preferably use that (functional group mentioned here is as height with functional group Contained functional group is in the functional group above described in dispersal agent molecule) and monomer containing unsaturated group and do not have function Random copolymer, graft copolymer, the block copolymer that group but monomer containing unsaturated group are formed.These copolymers can be with Manufactured with known method.
As the monomer with functional group and containing unsaturated group, (methyl) acrylic acid, 2- (methyl) third can be enumerated Alkene acyloxyethyl butanedioic acid, 2- (methyl) acrylyl oxy-ethyls phthalic acid, 2- (methyl) acrylyl oxy-ethyl hexahydrobenzene diformazan Acid, acrylic acid dimer etc. have unsaturated monomer, dimethyl aminoethyl (methyl) acrylate, the diethylamino of carboxyl Ethyl (methyl) acrylate and their quaternaries etc. have tertiary amino, the unsaturated monomer of quaternary ammonium salt base as concrete example. They can be used alone, or combine two or more use.
As the monomer without functional group but containing unsaturated group, (methyl) methyl acrylate, (first can be enumerated Base) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) third Olefin(e) acid isobutyl ester, (methyl) tert-butyl acrylate, (methyl) benzyl acrylate, (methyl) phenyl acrylate, (methyl) acrylic acid Cyclohexyl, (methyl) acrylate, (methyl) acrylic acid phenoxy group methyl esters, (methyl) 2-EHA, (methyl) isobornyl acrylate, (methyl) acrylic acid tricyclodecyl, (methyl) tetrahydrofurfuryl acrylate, N- ethenyl pyrrolidones Ketone, Styrene and its derivatives, α-methylstyrene, N- N-cyclohexylmaleimides, N-phenylmaleimide, N- benzyl horses Come the N- substituted maleimides such as acid imide amine, acrylonitrile, vinyl acetate and poly- (methyl) methyl acrylate polymeric monomer, polyphenyl second Alkene polymeric monomer, poly- (methyl) acrylic acid 2- hydroxy methacrylates polymeric monomer, polyethylene glycol polymeric monomer, polypropylene glycol polymeric monomer, gather oneself in Polymeric monomers such as ester polymeric monomer etc..They can be used alone, or combine two or more use.
Acrylic polymer dispersant is particularly preferably by the A blocks with functional group and the B block without functional group A-B the or B-A-B block copolymers of composition, now, except comprising functional group and containing unsaturated group from above-mentioned in A blocks Beyond the part-structure of the monomer of group, it can also contain and not include functional group but the monomer containing unsaturated group from above-mentioned Part-structure, these structures in the A blocks can by random copolymerization or block copolymerization it is arbitrary in the form of contain.In addition, Content of the part-structure without functional group in A blocks is usually below 80 mass %, more excellent preferably below 50 mass % Elect as below 30 mass %.
B block is included from the above-mentioned part-structure without functional group but the monomer containing unsaturated group, in 1 B Can contain the part-structure from two or more monomer in block, these structures in the B block can with random copolymerization or Any form of block copolymerization contains.
A-B the or B-A-B block copolymers can for example be prepared using living polymerization as shown below.
Living polymerization includes living anion polymerization method, anion living polymerization method, radical living polymerization method, its In, the polymerization activity kind of living anion polymerization method is anion, such as is represented by following synthetic routes.
[chemical formula 21]
(living anion polymerization method)
In the case of
In said synthesis route, Ar1For 1 valency organic group, Ar2For different from Ar11 valency organic group, M is metal raw Son, s and t are respectively more than 1 integer.
The polymerization activity kind of radical living polymerization method is free radical, such as is represented by following synthetic routes.
[chemical formula 22]
(radical living polymerization method)
(nitryl method)
In the case of
(ATRP method)
In the case of
In said synthesis route, Ar1For 1 valency organic group, Ar2For different from Ar11 valency organic group, j and k are respectively More than 1 integer, RaFor hydrogen atom or 1 valency organic group, RbWith RaDifference, it is hydrogen atom or 1 valency organic group.
When synthesizing the acrylic polymer dispersant, can use Japanese Unexamined Patent Publication 9-62002 publications, P.Lutz,P.Masson et al,Polym.Bull.12,79(1984),B.C.Anderson,G.D.Andrews et al, Macromolecules,14,1601(1981),K.Hatada,K.Ute,et al,Polym.J.17,977(1985),18, 1037 (1986), the great Yi, field Tagayasu Den one of the right hand, Process Technology of Polymer, 36,366 (1987), East Village is quick to be prolonged, damp this light man, macromolecule Collection of thesis, 46,189 (1989), M.Kuroki, T.Aida, J.Am.Chem.Sic, 109,4737 (1987), phase Tian Zhuosan, well Upper auspicious flat, Synthetic Organic Chemistry, 43,300 (1985), D.Y.Sogoh, W.R.Hertler et al, Macromolecules, Known method described in 20,1473 (1987) etc..
The acrylic polymer dispersant that can be used in the present invention can be A-B block copolymers, or B-A-B block copolymers, form A blocks/B block ratio preferably 1/99~80/20 of its copolymer, particularly preferably 5/95~ 60/40 (mass ratio), by being in the range of this, exist and be able to ensure that dispersiveness and the balanced of storage stability incline To.
In addition, in A-B block copolymers that 1g can be used in the present invention, B-A-B block copolymers, quaternary ammonium salt base The amount of group is preferably generally 0.1~10mmol, by being in the range of this, exists and is able to ensure that and good dispersed inclines To.
It should be noted that in such block copolymer, caused ammonia in the fabrication process would generally be contained sometimes Base, its amine value is 1~100mgKOH/g or so, from the viewpoint of dispersiveness, preferably more than 10mgKOH/g, is more preferably More than 30mgKOH/g, more preferably more than 50mgKOH/g, and preferably below 90mgKOH/g, more preferably Below 80mgKOH/g, more preferably below 75mgKOH/g.
Here, the amine value of the dispersant of these block copolymers etc. with equivalent in dispersant sample in addition to solvent Solid constituent 1g alkali number suitable KOH mass represents, is determined by following method.
Accurate weighing dispersant 0.5~1.5g of sample in 100mL beaker, with 50mL acetic acid, using possessing The automatic titration device of pH electrodes, with 0.1mol/L HClO4Acetic acid solution carries out acid-base titration to the solution, and titration pH is bent The flex point of line obtains amine value according to the following formula as titration end-point.
Amine value [mgKOH/g]=(561 × V)/(W × S)
[wherein, W：Represent the dispersant sample amount of weighing [g], V：Represent titer [mL], the S in titration end-point：Represent to divide The solid component concentration [quality %] of powder sample.]
In addition, the amine value of the block copolymer depends on the presence or absence of acidic-group as acid number basis and its species, Generally preferable acid number junior, usually below 10mgKOH/g, its weight average molecular weight (Mw) is preferably 1000~100,000 Scope.By being in above range, exist and be able to ensure that good dispersed tendency.
For being not particularly limited with concrete structure of the quaternary ammonium salt group as the macromolecule dispersing agent of functional group, but from From the viewpoint of dispersiveness, the repeat unit (following, sometimes referred to as " repeat unit (i) ") preferably with following formula (i) expression.
[chemical formula 23]
In above-mentioned formula (i), R31~R33It is each independently hydrogen atom, the optionally alkyl with substituent, optional with taking Dai Ji aryl or the aralkyl optionally with substituent, R31~R33In more than 2 can be mutually bonded and form ring-type knot Structure.R34For hydrogen atom or methyl, X is the link group of divalent, Y-For counter anion.
The R of above-mentioned formula (i)31~R33In the optionally carbon number of alkyl with substituent be not particularly limited, be usually More than 1, and preferably less than 10, more preferably less than 6.
As the specific example of alkyl, methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group etc. can be enumerated, Among these, preferably methyl, ethyl, propyl group, butyl, amyl group or hexyl, more preferably methyl, ethyl, propyl group or butyl.Separately Outside, can be the arbitrary form in straight-chain, branched.Furthermore it is also possible to contain the ring-type knots such as cyclohexyl, cyclohexyl methyl Structure.
The R of above-mentioned formula (i)31~R33In the optionally carbon number of aryl with substituent be not particularly limited, be usually More than 6, and preferably less than 16, more preferably less than 12.
As the specific example of aryl, phenyl, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl, diethylbenzene can be enumerated Base, naphthyl, anthryl etc., among these, preferably phenyl, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl or diethyl phenyl, More preferably phenyl, aminomethyl phenyl or ethylphenyl.
The R of above-mentioned formula (i)31~R33In the optionally carbon number of aralkyl with substituent be not particularly limited, generally For more than 7, and preferably less than 16, more preferably less than 12.
As the specific example of aralkyl, it is sub- that phenylmethylene, phenyl-ethylene, phenylpropylene, phenyl can be enumerated Butyl, phenyl isopropylidene etc., among these, preferably phenylmethylene, phenyl-ethylene, phenylpropylene or phenyl Aden Base, more preferably phenylmethylene or phenyl-ethylene.
Among these, from the viewpoint of dispersiveness, preferably R31~R33Alkyl or aralkyl are each independently, specifically Ground, preferably R31And R33It is each independently methyl or ethyl and R32For phenylmethylene or phenyl-ethylene, more preferably R31And R33For methyl and R32For phenylmethylene.
In addition, in the case that above-mentioned macromolecule dispersing agent has tertiary amine as functional group, it is excellent from the viewpoint of dispersiveness The repeat unit (following, sometimes referred to as " repeat unit (ii) ") that choosing represents with following formula (ii).
[chemical formula 24]
In above-mentioned formula (ii), R35And R36Be each independently hydrogen atom, optionally the alkyl with substituent, it is optional with The aryl of substituent or the aralkyl optionally with substituent, R35And R36It can be mutually bonded and form cyclic structure, R37For hydrogen Atom or methyl, Z are the link group of divalent.
In addition, the R as above-mentioned formula (ii)35And R36In optionally have substituent alkyl, can preferably be employed as State the R of formula (i)31~R33And the group of example.
Similarly, the R as above-mentioned formula (ii)35And R36In optionally have substituent aryl, can preferably be employed as The R of above-mentioned formula (i)31~R33And the group of example.In addition, the R as above-mentioned formula (ii)35And R36In optionally with substituent Aralkyl, it can preferably be employed as the R of above-mentioned formula (i)31~R33And the group of example.
Among these, R35And R36It is preferred that it is each independently the alkyl optionally with substituent, more preferably methyl or second Base.
R as above-mentioned formula (i)31~R33And the R of above-mentioned formula (ii)35And R36In alkyl, aralkyl or aryl institute optionally The substituent having, halogen atom, alkoxy, benzoyl, hydroxyl etc. can be enumerated.
In above-mentioned formula (i) and (ii), as link the group X and Z of divalent, for example,：Carbon number 1~10 Alkylidene, the arlydene ,-CONH-R of carbon number 6~1243- base ,-COOR44- base [wherein, R43And R44It is former for singly-bound, carbon The alkylidene of subnumber 1~10 or the ether (alkyl oxyalkyl) of carbon number 2~10] etc., it is preferably-COO-R44- base.
In addition, in above-mentioned formula (i), the Y as counter anion-, Cl can be enumerated-、Br-、I-、ClO4 -、BF4 -、 CH3COO-、PF6 -Deng.
The content ratio for the repeat unit that above-mentioned formula (i) represents is not particularly limited, from the viewpoint of dispersiveness, relatively In above-mentioned formula (i) represent repeat unit content ratio and above-mentioned formula (ii) represent repeat unit content ratio it is total Meter, preferably 60 moles of below %, more preferably 50 moles of below %, it is more preferably 40 moles of below %, particularly preferred For 35 moles of below %, and preferably 5 moles of more than %, more preferably 10 moles of more than %, more preferably 20 rub You are more than %, particularly preferably 30 moles of more than %.
In addition, repeat unit the containing shared by whole repeat units of macromolecule dispersing agent that above-mentioned formula (i) represents Ratio is not particularly limited, and from the viewpoint of dispersiveness, preferably 1 mole of more than %, more preferably 5 moles of more than %, enters One step is preferably 10 moles of more than %, and preferably 50 moles of below %, be preferably 30 moles of below %, more preferably 20 rub You are below %, particularly preferably 15 moles of below %.
In addition, repeat unit the containing shared by whole repeat units of macromolecule dispersing agent that above-mentioned formula (ii) represents Ratio is not particularly limited, and from the viewpoint of dispersiveness, preferably 5 moles of more than %, more preferably 10 moles of more than %, enters One step be preferably 15 moles of more than %, particularly preferably 20 moles of more than %, and preferably 60 moles of below %, more preferably 40 moles of below %, more preferably 30 moles of below %, particularly preferably 25 moles of below %.
In addition, from improve with the compatibility of the adhesive ingredients such as solvent, make from the viewpoint of dispersion stabilization improves, high score Sub- dispersant preferably has the repeat unit (following, sometimes referred to as " repeat unit (iii) ") that following formula (iii) represents.
[chemical formula 25]
In above-mentioned formula (iii), R40For ethylidene or propylidene, R41Optionally to have the alkyl of substituent, R42For hydrogen atom Or methyl, n are 1~20 integer.
The R of above-mentioned formula (iii)41In the optionally carbon number of alkyl with substituent be not particularly limited, usually 1 with Above, it is preferably more than 2, and preferably less than 10, more preferably less than 6.
As the specific example of alkyl, methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group etc. can be enumerated, Among these, preferably methyl, ethyl, propyl group, butyl, amyl group or hexyl, more preferably methyl, ethyl, propyl group or butyl.Separately Outside, it can be in straight-chain, branched any form.Alternatively, it is also possible to contain the ring-type knot such as cyclohexyl, cyclohexyl methyl Structure.
In addition, from the viewpoint of the compatibility relative to adhesive ingredients such as solvents and dispersiveness, in above-mentioned formula (iii) N be preferably more than 1, more preferably more than 2, and preferably less than 10, more preferably less than 5.
Containing in addition, the repeat unit of above-mentioned formula (iii) expression is shared in whole repeat units of macromolecule dispersing agent It is proportional to be not particularly limited, preferably 1 mole of more than %, more preferably 2 moles of more than %, more preferably 4 moles of % More than, and preferably 30 moles of below %, more preferably 20 moles of below %, more preferably 10 moles of below %. In the case of in above range, the compatibility and dispersion stabilization that can be realized simultaneously relative to adhesive ingredients such as solvents be present Tendency.
In addition, from improve dispersant relative to the adhesive ingredients such as solvent compatibility, make dispersion stabilization improve sight Point considers, macromolecule dispersing agent preferably has repeat unit that following formula (iv) represents (following, sometimes referred to as " repeat unit (iv)”)。
[chemical formula 26]
In above-mentioned formula (iv), R38For the optional alkyl with substituent, the aryl optionally with substituent or it is optional with The aralkyl of substituent.R39For hydrogen atom or methyl.
The R of above-mentioned formula (iv)38In the optionally carbon number of alkyl with substituent be not particularly limited, usually 1 with Above, it is preferably more than 2, more preferably more than 4, and preferably less than 10, more preferably less than 8.
As the specific example of alkyl, methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group etc. can be enumerated, Among these, preferably methyl, ethyl, propyl group, butyl, amyl group or hexyl, more preferably methyl, ethyl, propyl group or butyl.Separately Outside, it can be in straight-chain, branched any form.Alternatively, it is also possible to contain the ring-type knot such as cyclohexyl, cyclohexyl methyl Structure.
The R of above-mentioned formula (iv)38In the optionally carbon number of aryl with substituent be not particularly limited, usually 6 with On, and preferably less than 16, more preferably less than 12, more preferably less than 8.
As the specific example of aryl, phenyl, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl, diethylbenzene can be enumerated Base, naphthyl, anthryl etc., among these, preferably phenyl, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl or diethyl phenyl, More preferably phenyl, aminomethyl phenyl or ethylphenyl.
The R of above-mentioned formula (iv)38In the optionally carbon number of aralkyl with substituent be not particularly limited, usually 7 More than, and preferably less than 16, more preferably less than 12, more preferably less than 10.
As the specific example of aralkyl, it is sub- that phenylmethylene, phenyl-ethylene, phenylpropylene, phenyl can be enumerated Butyl, phenyl isopropylidene etc., among these, preferably phenylmethylene, phenyl-ethylene, phenylpropylene or phenyl Aden Base, more preferably phenylmethylene or phenyl-ethylene.
Among these, from the viewpoint of solvent compatibility and dispersion stabilization, R38Preferably alkyl or aralkyl, it is more excellent Elect methyl, ethyl or phenylmethylene as.
As R38In the substituent that optionally has of alkyl, halogen atom, alkoxy etc. can be enumerated.In addition, as virtue The substituent that base or aralkyl optionally have, alkyl, halogen atom, alkoxy of chain etc. can be enumerated.In addition, R38Shown The alkyl of chain includes any of straight-chain and branched.
In addition, from the viewpoint of dispersiveness, the whole of repeat unit that above-mentioned formula (iv) represents in macromolecule dispersing agent Shared content ratio is preferably 30 moles of more than %, more preferably 40 moles of more than %, is more preferably in repeat unit 50 moles of more than %, and preferably 80 moles of below %, more preferably 70 moles of below %.
Macromolecule dispersing agent can also have repeat unit (i), repeat unit (ii), repeat unit (iii) and repeat single Repeat unit beyond first (iv).As the example of such repeat unit, can enumerate from styrene, Alpha-Methyl benzene second The styrene monomers such as alkene；(methyl) acryloyl chloride etc. (methyl) acryloyl chloride class monomer；(methyl) acrylamide, N- methylols Acrylamide etc. (methyl) acrylamide monomers；Vinyl acetate；Acrylonitrile；Allyl glycidyl ether, butenoic acid contracting Water glycerin ether；The repeat unit of the monomers such as N- metering system morpholides.
From the viewpoint of further raising dispersiveness, macromolecule dispersing agent is preferably the block with A blocks and B block Copolymer, the A blocks have repeat unit (i) and repeat unit (ii), and the B block is without repeat unit (i) and again Multiple unit (ii).
The block copolymer is preferably A-B block copolymers or B-A-B block copolymers.By importing season in A blocks Ammonium salt groups and tertiary amino, unexpectedly there is the tendency for the dispersibility for significantly improving dispersant.In addition, B block preferably has Repeat unit (iii), in addition, more preferably having repeat unit (iv).
In A blocks, repeat unit (i) and repeat unit can be contained with any form of random copolymerization, block copolymerization (ii).Furthermore it is possible to contain two or more repeat unit (i) and repeat unit (ii) respectively in 1 A block, in this case, Each repeat unit can be contained with any form of random copolymerization, block copolymerization in the A blocks.
Furthermore it is also possible to contain the repeat unit beyond repeat unit (i) and repeat unit (ii) in A blocks, as The example of such repeat unit, it can enumerate from above-mentioned repeat unit of (methyl) acrylic ester monomer etc..Weight Content of the repeat unit in A blocks beyond multiple unit (i) and repeat unit (ii) is preferably 0~50 mole of %, more preferably For 0~20 mole of %, the repeat unit is free of most preferably in A blocks.
The repeat unit beyond repeat unit (iii) and (iv) can be contained in B block, as such repeat unit Example, can enumerate from styrene monomers such as styrene, α-methylstyrenes；(methyl) such as (methyl) acryloyl chlorides Acryloyl chloride class monomer；(methyl) acrylamide, N hydroxymethyl acrylamide etc. (methyl) acrylamide monomers；Vinyl acetate Ester；Acrylonitrile；Allyl glycidyl ether, butenoic acid glycidol ether；The repetition list of the monomers such as N- metering system morpholides Member.
Content of the repeat unit in B block beyond repeat unit (iii) and repeat unit (iv) is preferably 0~50 to rub You are %, more preferably 0~20 mole of %, the repeat unit is free of most preferably in B block.
In addition, from the aspect of dispersion stabilization is improved, preferably (f) dispersant combines with the pigment derivative described below Use.
Other gradation composition ＞ of ＜ photosensitive coloring compositions
In the photosensitive coloring composition of the present invention, in addition to mentioned component, it can suitably coordinate silane coupler etc. Closely sealed enhancer, coating enhancer, development modifying agent, ultra-violet absorber, antioxidant, surfactant, pigment derivative Deng.
(1) closely sealed enhancer
In order to improve the adaptation with substrate, closely sealed raising can be contained in the photosensitive coloring composition of the present invention Agent.As closely sealed enhancer, preferably compound of silane coupler, phosphorous acidic group etc..
, can be various silane coupled by epoxies, (methyl) acrylic compounds, amino etc. as the species of silane coupler 1 kind of exclusive use in agent, or two or more is used in mixed way.
As preferable silane coupler, for example,：3- methacryloxypropyls methyl dimethoxysilane, (methyl) acryloxy silane such as 3- methyl allyl acyloxypropyl trimethoxysilanes class, 2- (3,4- epoxycyclohexyls) ethyl Trimethoxy silane, 3- glycidoxy-propyltrimethoxy silanes, 3- glycidoxypropyls diethoxy silane, 3- epoxies Ureido silane class, the 3- isocyanic acids third such as the epoxy silane classes such as the third oxygen propyl-triethoxysilicane, 3- urea propyl-triethoxysilicanes The isocynate silane class such as ethyl triethoxy silicane alkane, the particularly preferably silane coupler of epoxy silane class.
As the compound of phosphorous acidic group, the phosphoric acid ester of (methyl) acryloyl group, more preferably following formulas are preferably comprised (g1), the compound that (g2) or (g3) is represented.
[chemical formula 27]
In above-mentioned formula (g1), (g2) and (g3), R51Represent hydrogen atom or methyl, l and the integer that l ' is 1~10, m 1, 2 or 3.
The compound of these phosphorous acidic groups may be used alone, can also be used in combination of two or more kinds.
(2) surfactant
In order to improve coating, surfactant can also be contained in the photosensitive coloring composition of the present invention.
As surfactant, can use for example anionic surfactant, cationic surface active agent, it is non-from The various surfactants such as subtype surfactant, amphoteric surfactant.Wherein, it is dysgenic from being brought to various characteristics The low this respect of possibility considers, preferably using nonionic surface active agent, wherein, from the aspect of coating, fluorine class, silicon class Surfactant is effective.
As such surfactant, for example,：TSF4460 (manufacture of organosilicon Co., Ltd. of GE Toshiba), DFX-18 (manufacture of NEOS companies), BYK-300, BYK-325, BYK-330 (manufacture of BYK Chemie companies), (SHIN-ETSU HANTOTAI has KP340 Ji Gui Co., Ltd. manufacture), F-470, F-475, F-478, F-559 (manufacture of DIC companies), SH7PA (Toray Silicone public affairs Department manufacture), DS-401 (Daikin Co., Ltd's manufacture), L-77 (Nippon Unicar Co. Ltd.'s manufacture), FC4430 (Sumitomo 3M public affairs Department's manufacture) etc..
It should be noted that surfactant can use one kind, can also in any combination with 2 kinds of ratio combine with Upper use.
(3) pigment derivative
In order to improve dispersiveness, keeping quality, it can also contain in photosensitive coloring composition of the invention and be helped as scattered The pigment derivative of agent.
As pigment derivative, can enumerate azo, phthalocyanines, quinoline azone class, benzimidazole ketone, quinophthalone class, Isoindoline ketone, twoPiperazine class, Anthraquinones, indanthrone kinds, perylene kinds, pyrene ketone, diketopyrrolo-pyrrole class, twoThe derivative of piperazine class etc., wherein, preferably phthalocyanines, quinophthalone class.
As the substituent of pigment derivative, sulfonic group, sulfoamido and its quaternary salt, phthalimide first can be enumerated Base, dialkyl aminoalkyl, hydroxyl, carboxyl, amide groups etc., they can be bonded in directly or across alkyl, aryl, heterocyclic radical etc. On pigment skeleton, in the substituent of above-mentioned pigment derivative, preferred sulfonic group.In addition, it can substitute on a pigment skeleton These multiple substituents.
As the concrete example of pigment derivative, the sulfonic acid of phthalocyanine, the sulfonic acid of quinophthalone, anthraquinone can be enumerated Sulfonic acid, the sulfonic acid of quinoline azone, the sulfonic acid of diketopyrrolo-pyrrole, twoThe sulfonic acid of piperazine Deng.These pigment derivatives can be used alone, or combine two or more use.
(4) photoacid generator
The photoacid generator is the compound for referring to produce acid by ultraviolet, and it when being exposed by being produced Raw sour effect, enables cross-linking reaction carry out in the presence of the crosslinking agent such as melamine compound.
In such photoacid generator, dissolubility preferably in a solvent, particularly for photosensitive color group The high material of dissolubility in the solvent of compound, such as can enumerate：Diphenyl iodineXylyl iodinePhenyl is (to methoxy benzene Methyl) iodineDouble (m-nitro base) iodineDouble (to tert-butyl-phenyl) iodineDouble (rubigan) iodineDouble (positive 12 Alkyl) iodineTo isobutyl phenenyl (p-methylphenyl) iodineP-isopropyl phenyl (p-methylphenyl) iodineEtc. Diaryl iodonium Or chloride, bromide or boron fluoride salt, hexafluorophosphate, hexafluoro arsenite, the aromatic series of the triaryl matte such as triphenylsulfonium The sulfonium organic boron network such as sulfonate, four (pentafluorophenyl group) borates etc., diphenyl phenacyl sulfonium (normal-butyl) triph-enylborate Compound class or double (trichloromethyl) triazines of 2- methyl -4,6-, double (trichloromethyl) triazines of 2- (4- methoxyphenyls) -4,6- Deng triaizine compounds etc., but it is not limited to this.
(5) crosslinking agent
The present invention photosensitive coloring composition in can further add crosslinking agent, for example, can be used melamine or Guanidine aminated compounds.As these crosslinking agents, the chemical combination of the melamine or guanamines class shown in for example following formulas (6) can be enumerated Thing.
[chemical formula 28]
In formula (6), R61Expression-NR66R67The aryl of base or carbon number 6~12, R61For-NR66R67In the case of base, R62、R63、R64、R65、R66And R67In an expression-CH2OR68Base, R61In the case of aryl for carbon number 6~12, R62、R63、R64And R65In an expression-CH2OR68Base, remaining R62、R63、R64、R65、R66And R67Table independently from each other Show hydrogen or-CH2OR68Base, wherein, R68Represent the alkyl of hydrogen atom or carbon number 1~4.
Here, the aryl of typical carbon number 6~12 is phenyl, 1- naphthyls or 2- naphthyls, is gone back on these phenyl, naphthyl The substituents such as alkyl, alkoxy, halogen atom can be bonded.The carbon number of alkyl and alkoxy is respectively 1~6 or so.It is above-mentioned In, R68The alkyl of expression is methyl or ethyl, is particularly preferably methyl.
The melamine class compound corresponding with formula (6), the compound of i.e. following formulas (6-1) include：Six hydroxyl first Base melamine, pentamethylol melamine, tetra methylol melamine, HMMM, pentamethoxyl first Base melamine, tetramethoxymethyl melamine, six ethoxyl methyl melamines etc..
[chemical formula 29]
In formula (6-1), R62、R63、R64、R65、R66And R67In one be aryl in the case of, R62、R63、R64And R65In An expression-CH2OR68Base, remaining R62、R63、R64、R65、R66And R67Hydrogen atom or-CH are represented independently of one another2OR68 Base, here, R68Represent hydrogen atom or alkyl.
In addition, the R in guanidine aminated compounds, the i.e. formula (6) corresponding with formula (6)61Include for the compound of aryl： Tetra methylol benzoguanamine, tetramethoxymethyl benzoguanamine, trimethoxy methyl benzoguanamine, tetraethoxy methyl benzocarbamidine Amine etc..
Furthermore it is also possible to use the crosslinking agent with methylol or hydroxymethyl alkyl ether.It is exemplified below the example.
Double (the hydroxymethyl) -4- methylphenols of 2,6-, the 4- tert-butyl groups -2,6- double (hydroxymethyl) phenol, 5- ethyls -1,3- Double (hydroxymethyl) perhydro -1,3,5- triazine -2- ketone (common name N- ethyl dihydroxymethyls triazinone) or its dimethyl ether body, dihydroxy Methyl trimethylene urea or double (hydroxymethyl) perhydro -1,3,5- of its dimethyl ether body, 3,5-(the common name two of diazine -4- ketone Hydroxymethylfurfural) or its dimethyl ether body, the urea of tetra methylol glyoxal two (tetramethyrol glyoxal diureine) Or its tetramethyl ether body.
It should be noted that these crosslinking agents can be used alone, can also be applied in combination two or more.Use friendship Join agent when, its amount relative to all solids composition of photosensitive coloring composition be preferably 0.1~15 weight %, particularly preferably 0.5~10 weight %.
(6) sulfhydryl compound
In addition, in order to improve the adaptation to substrate, the sulfhydryl compound as polymerization accelerant can also be added.
As the species of sulfhydryl compound, 2-mercaptobenzothiazole, 2- sulfydryl benzos can be enumeratedAzoles, 2- sulfydryl benzos Imidazoles, ethanthiol, the mercaptan of the last of the ten Heavenly stems two, 1,4- dimethyl sulfydryls benzene, dimercapto propionic acid butanediol ester, dimercapto acetic acid butanediol Ester, glycol dimercaptosuccinate, trimethylolpropane tris mercaptoacetate, dimercapto propionic acid butanediol ester, trihydroxy methyl third Alkane tri-thiol propionic ester, trimethylolpropane tris mercaptoacetate, the mercaptopropionic acid ester of pentaerythrite four, the sulfydryl second of pentaerythrite four Acid esters, tri-thiol propionic acid trihydroxy ethyl ester, ethylene glycol double (3- mercaptobutylates), butanediol double (3- mercaptobutylates), 1,4- Double (3- sulfydryls butyryl acyloxy) butane, trimethylolpropane tris (3- mercaptobutylates), pentaerythrite four (3- mercaptobutylates), Pentaerythrite three (3- mercaptobutylates), ethylene glycol double (3- mercaptoisobutanoics acid esters), butanediol double (3- mercaptoisobutanoics acid esters), three Hydroxymethyl-propane three (3- mercaptoisobutanoics acid esters), 1,3,5- tri- (3- sulfydryls butoxyethyl group) -1,3,5- triazines -2,4,6 (1H, 3H, 5H)-triketone etc. has sulfhydryl compound or the multifunctional sulfhydryl compound of aliphatic of heterocycle etc..These sulfhydryl compounds can So that one kind is used alone, or two or more can also be used in mixed way.
Components matching amount ＞ in ＜ photosensitive coloring compositions
In the photosensitive coloring composition of the present invention, the content of (a) colouring agent is relative in photosensitive coloring composition Total solid content amount be usually more than 10 mass %, be preferably more than 20 mass %, more preferably more than 30 mass %, and Preferably generally below 60 mass %, it is more preferably below 50 mass %.
By making the content of (a) colouring agent be more than above-mentioned lower limit, exist to obtain enough optical density (OD) tendency, In addition, by being set to below above-mentioned higher limit, the tendency for being readily available sufficiently plate-making characteristic be present.
In addition, in the 1st mode and the 4th mode, it is relative selected from least one of red pigment and orange pigment pigment It is preferably more than 1 mass parts, more preferably more than 2 mass parts, is more preferably 3 mass parts in the mass parts of (a) colouring agent 100 More than, and preferably below 30 mass parts, more preferably below 20 mass parts, more preferably below 15 mass parts, more More preferably below 10 mass parts, particularly preferably below 7 mass parts.By being set to more than above-mentioned lower limit, exist To the tendency of enough optical density (OD), by being set to below above-mentioned higher limit, the tendency for being able to ensure that plate-making characteristic be present.
In addition, in the 1st mode and the 4th mode, it is relative selected from least one of blue pigment and violet pigment pigment It is preferably more than 20 mass parts, more preferably more than 30 mass parts, is more preferably 40 matter in the mass parts of (a) colouring agent 100 Measure more than part, still more preferably for more than 50 mass parts, particularly preferably more than 60 mass parts, be most preferably 65 mass parts with On, additionally, it is preferred that being below 90 mass parts, more preferably below 80 mass parts, more preferably below 75 mass parts, especially Preferably below 70 mass parts.By being set to more than above-mentioned lower limit, the tendency for being able to ensure that light-proofness be present, on being set to State below higher limit, the tendency for being able to ensure that plate-making characteristic be present.
In addition, in the 2nd mode, relative to the mass parts of (a) colouring agent 100, organic black face shown in above-mentioned formula (1) The content of material is preferably more than 5 mass parts, more preferably more than 10 mass parts, more preferably more than 20 mass parts, more entered One step is preferably more than 40 mass parts, particularly preferably more than 60 mass parts, be most preferably more than 70 mass parts, additionally, it is preferred that For below 95 mass parts, more preferably below 90 mass parts, more preferably below 85 mass parts, particularly preferably 80 mass Below part.By being set to more than above-mentioned lower limit, the tendency that can improve light-proofness be present, by be set to above-mentioned higher limit with Under, the tendency that can suppress reliability reduction be present.
In addition, in the 3rd mode, relative to the mass parts of (a) colouring agent 100, organic pigment is preferably more than 30 mass parts, More preferably more than 50 mass parts, more preferably more than 60 mass parts, particularly preferably more than 70 mass parts, in addition, excellent Elect as below 99 mass parts, more preferably below 95 mass parts, more preferably below 90 mass parts, particularly preferably 85 matter Measure below part, be most preferably below 80 mass parts.By being set to more than above-mentioned lower limit, exist and be able to ensure that inclining for plate-making characteristic To by being set to below above-mentioned higher limit, the tendency that can obtain enough optical density (OD) being present.
In addition, in the 3rd mode, relative to the mass parts of (a) colouring agent 100, in red pigment and orange pigment At least one pigment is preferably more than 0 mass parts, more preferably more than 1 mass parts, more preferably more than 2 mass parts, separately Outside, preferably below 30 mass parts, more preferably below 20 mass parts, more preferably below 15 mass parts, particularly preferably For below 10 mass parts, be most preferably 0 mass parts.By being set to more than above-mentioned lower limit, enough optical density can be obtained by existing (OD) tendency, by being set to below above-mentioned higher limit, the tendency for being able to ensure that plate-making characteristic be present.
In addition, in the 3rd mode, relative to the mass parts of (a) colouring agent 100, in blue pigment and violet pigment At least one pigment is preferably more than 20 mass parts, more preferably more than 30 mass parts, more preferably more than 40 mass parts, Still more preferably for more than 50 mass parts, particularly preferably more than 60 mass parts, be most preferably more than 65 mass parts, in addition, Preferably below 90 mass parts, more preferably below 85 mass parts, more preferably below 80 mass parts.By being set to above-mentioned More than lower limit, the tendency for being able to ensure that light-proofness be present, by being set to below above-mentioned higher limit, exist and be able to ensure that plate-making is special The tendency of property.
(a) in the case that colouring agent contains organic black pigments, relative to the mass parts of (a) colouring agent 100, organic black face Material is preferably more than 5 mass parts, more preferably more than 10 mass parts, more preferably more than 20 mass parts, additionally, it is preferred that being Below 50 mass parts, more preferably below 40 mass parts, more preferably below 30 mass parts, it is particularly preferably 20 mass parts Below.By being set to more than above-mentioned lower limit, the tendency that can obtain enough optical density (OD) be present, by being set to the above-mentioned upper limit Value is following, the tendency for being able to ensure that plate-making characteristic be present.
(a) in the case that colouring agent contains carbon black, relative to the mass parts of (a) colouring agent 100, carbon black is preferably 5 mass parts Above, more preferably more than 10 mass parts, more preferably more than 15 mass parts, particularly preferably more than 20 mass parts, separately Outside, preferably below 50 mass parts, more preferably below 40 mass parts, more preferably below 35 mass parts, particularly preferably Below 30 mass parts.By being set to more than above-mentioned lower limit, the tendency that can obtain enough optical density (OD) be present, by setting Below above-mentioned higher limit, the tendency for being able to ensure that plate-making characteristic be present.
For the content ratio of (b) alkali soluble resin, relative to the total of photosensitive coloring composition of the invention Solid constituent, usually more than 5 mass %, be preferably more than 10 mass %, more preferably more than 20 mass %, further preferably For more than 25 mass %, particularly preferably more than 30 mass %, and usually below 85 mass %, be preferably 80 mass % with Under, more preferably below 70 mass %, more preferably below 60 mass %, still more preferably for below 50 mass %, Particularly preferably below 40 mass %.
By the way that the content of (b) alkali soluble resin is set as more than above-mentioned lower limit, it is relative unexposed portion can be suppressed In the deliquescent reduction of developer solution, the tendency that can suppress poor visualization be present.In addition, by be set to above-mentioned higher limit with Under, developer solution can be suppressed the impregnability of exposure portion is increased, so as to which presence can suppress sharp (sharp) property, close of pixel The tendency that conjunction property declines.
For the content ratio of (c) Photoepolymerizationinitiater initiater, relative to the total of photosensitive coloring composition of the invention Solid constituent, usually more than 0.1 mass %, be preferably more than 0.5 mass %, more preferably more than 1 mass %, further excellent Elect as more than 2 mass %, be still more preferably more than 3 mass %, particularly preferably more than 4 mass %, and usually 15 Below quality %, it is preferably below 10 mass %, more preferably below 8 mass %, more preferably below 7 mass %.
By making the content ratio of (c) Photoepolymerizationinitiater initiater be that more than above-mentioned lower limit existing to suppress under sensitivity The tendency of drop, by being set to below above-mentioned higher limit, deliquescent reduction of the unexposed portion relative to developer solution can be suppressed, deposited The tendency of poor visualization can suppressed.
(c) content ratio of the oxime ester compound shown in above-mentioned logical formula (I) contained in Photoepolymerizationinitiater initiater is without spy Do not limit, usually more than 10 mass %, be preferably more than 30 mass %, more preferably more than 50 mass %, further preferably For more than 70 mass %, particularly preferably more than 90 mass %, and usually below 100 mass %.Under being set to above-mentioned More than limit value, the surface smoothness of the solidfied material obtained by existing becomes good tendency.
In the case of using (c) Photoepolymerizationinitiater initiater and polymerization accelerant simultaneously, relative to the photosensitive color of the present invention The total solid content of composition, the content ratio of polymerization accelerant are preferably more than 0.05 mass %, and usually 10 mass % Below, it is preferably below 5 mass %, relative to the mass parts of (c) Photoepolymerizationinitiater initiater 100, generally with the ratio of 0.1~50 mass parts Example uses polymerization accelerant, particularly preferably uses polymerization accelerant with the ratio of 0.1~20 mass parts.
By making the content ratio of polymerization accelerant be that more than above-mentioned lower limit existing can suppress for exposure light The tendency that sensitivity declines, by being set to below above-mentioned higher limit, can suppress dissolubility of the unexposed portion relative to developer solution Decline, the tendency that can suppress poor visualization be present.
In addition, for mixing ratio shared in photosensitive coloring composition of the sensitizing dyestuff in the present invention, from spirit It is usually below 20 mass % from the viewpoint of sensitivity, in the total solid content in photosensitive coloring composition, is preferably 15 Below quality %, more preferably below 10 mass %.
For the content ratio of (d) alefinically unsaturated compounds, relative to the photosensitive coloring composition of the present invention Total solid content, usually below 30 mass %, be preferably below 20 mass %, more preferably below 15 mass %.Pass through The content ratio for making (d) alefinically unsaturated compounds is below above-mentioned higher limit, can suppress developer solution and exposure portion is impregnated with Property increase, be readily available the tendency of good image so as to exist.It should be noted that (d) alefinically unsaturated compounds contain Proportional lower limit is usually more than 1 mass %, is preferably more than 5 mass %.
It should be noted that the photosensitive coloring composition of the present invention is adjusted by using (e) solvent so that it is solid Body constituent concentration is usually more than 5 mass %, is preferably more than 10 mass %, and usually below 50 mass %, be preferably 30 Below quality %.
It is usually 1 matter in the solid constituent of photosensitive coloring composition for the content ratio of (f) dispersant Measure more than %, be preferably more than 3 mass %, more preferably more than 5 mass %, and usually below 30 mass %, be preferably Below 20 mass %, more preferably below 15 mass %, more preferably below 10 mass %.
In addition, relative to the mass parts of (a) colouring agent 100, the content ratio of (f) dispersant is usually more than 5 mass parts, more Preferably more than 10 mass parts, more preferably more than 15 mass parts, and usually below 50 mass parts, particularly preferably 30 Below mass parts.
By make the content ratio of (f) dispersant for more than above-mentioned lower limit, exist be readily available it is enough dispersed Tendency, by being set to below above-mentioned higher limit, exist can be by suppressing sensitivity, system with respect to the ratio for reducing other compositions The tendency of the declines such as version property.
Using in the case of closely sealed enhancer, its content ratio relative to the total solid in photosensitive coloring composition into Divide is usually 0.1~5 mass %, preferably 0.2~3 mass %, more preferably 0.4~2 mass %.By making closely sealed carry The content ratio of high agent is more than above-mentioned lower limit, the tendency for the raising effect that can fully obtain adaptation be present, passes through It is set to below above-mentioned higher limit, the tendency that sensitivity declines, remains residue after development and turn into defect can be suppressed by existing.
In addition, in the case of using surfactant, its content ratio is relative to total in photosensitive coloring composition Solid constituent is usually 0.001~10 mass %, is preferably 0.005~1 mass %, more preferably 0.01~0.5 matter Measure %, be most preferably 0.03~0.3 mass %.By making the content of surfactant be more than above-mentioned lower limit, exist easily Flatness, the tendency of uniformity of film are shown, by being set to below above-mentioned higher limit, exists and easily shows the flat of film Slip, uniformity, and the tendency of the deterioration of other characteristics can be suppressed.
The physical property ＞ of ＜ photosensitive coloring compositions
The photosensitive coloring composition of the present invention can be suitable for colouring sept formation purposes, be spaced from as coloring From the viewpoint of thing, black is preferably presented.In addition, equivalent to 1 μm of the thickness of its film optical density (OD) be preferably 1.0 with It is upper, more preferably more than 1.2, more preferably more than 1.5, particularly preferably more than 1.8, and usually less than 4.0, it is excellent Elect less than 3.0, more preferably less than 2.5 as.
The manufacture method ＞ of ＜ photosensitive coloring compositions
The photosensitive coloring composition (following, sometimes referred to as " resist ") of the present invention can be made according to usual way It is standby.
Generally, (a) colouring agent is preferably in advance using paint shaker, sand mill, ball mill, roller mill, burrstone mill, air-flow Mill, homogenizer etc. carry out decentralized processing.By decentralized processing, (a) colouring agent is by micronized, therefore, the coating characteristics of resist It is improved.
Decentralized processing is generally preferably with by (a) colouring agent, (e) solvent, (f) dispersant and (b) alkali soluble resin Part or all of system being applied in combination carry out (it is following, manage sometimes by the mixture for supplying decentralized processing and in this place In obtained composition be referred to as " ink " or " dispersible pigment dispersion ").Particularly, if divided using macromolecule dispersing agent as (f) Powder, then resulting ink and resist through when thickening be inhibited (dispersion stabilization is excellent), therefore preferably.
Therefore, it is preferably fabricated at least to disperse containing (a) colouring agent, (e) solvent and (f) in the process of manufacture resist The dispersible pigment dispersion of agent.As (a) colouring agent, (e) organic solvent and (f) dispersant that can be used in dispersible pigment dispersion, Those that can be used in photosensitive coloring composition can be preferably employed as respectively.
It should be noted that carry out scattered place for the liquid containing the whole compositions coordinated in colored resin composition In the case of reason, caused heat release during due to decentralized processing, high response composition is likely to occur modification.It is therefore preferable that with System containing macromolecule dispersing agent carries out decentralized processing.
In the case of making (a) colouring agent scattered with sand mill, preferably using 0.1~8mm of particle diameter or so bead or oxygen Change zirconium pearl.For decentralized processing condition, temperature is usually 0 DEG C to 100 DEG C, is preferably room temperature to 80 DEG C of scope, according to The difference of the composition of liquid and the size of decentralized processing device etc., the suitable time of jitter time simultaneously differ, therefore can be appropriate Regulation.Scattered standard substantially is：The gloss of ink is controlled so that 20 degree of mirror surface luster (JIS of resist Z8741 50~300 scope) is reached.
In the case that the glossiness of resist is relatively low, decentralized processing is insufficient, coarse pigment (color material) particle of residual More, developability, adaptation, distinguishing etc. may become insufficient.In addition, if decentralized processing is carried out to gloss number more than above-mentioned Scope, then pigment crushes and produces a large amount of ultramicrons, therefore the impaired tendency of dispersion stabilization on the contrary be present.
In addition, the dispersion particle diameter for the pigment being dispersed in ink is usually 0.03~0.3 μm, dynamic light scattering method can be passed through Etc. determining.
Then, will be mixed by the ink that above-mentioned decentralized processing obtains with above-mentioned other compositions included in resist, Uniform solution is made.In the manufacturing process of resist, situation about being mixed into due to fine dust in liquid is more, because This, obtained resist wishes to carry out filtration treatment by filter etc..
[solidfied material]
Can be by making the photosensitive coloring composition of the present invention solidify to obtain solidfied material.Photosensitive coloring composition is consolidated Solidfied material obtained from change can be preferably used as colouring sept.
[coloring sept]
Then, sept is coloured obtained from the photosensitive coloring composition for having used the present invention, according to its manufacture Method illustrates.
(1) supporter
As the supporter for forming coloring sept, as long as there is the intensity of appropriateness, to its material without spy Do not limit.Transparency carrier mainly is used, as its material, for example, the polyesters tree such as polyethylene terephthalate The thermoplastic resin film-making such as the polyolefin resins such as fat, polypropylene, polyethylene, makrolon, polymethyl methacrylate, polysulfones The thermosetting resin pieces or various glass etc. such as material, epoxy resin, unsaturated polyester resin, poly- (methyl) acrylic resin.
Wherein, from the viewpoint of heat resistance, preferably glass, heat-resistant resin.In addition, also have in substrate surface film forming The situation of ITO, IZO etc. transparency electrode.In addition to transparency carrier, it can also be formed on tft array.
In order to improve the surface physical properties such as cementability, Corona discharge Treatment, ozone can also be carried out to supporter as needed Film formation processing of the various resins such as processing, silane coupler, urethane based resin etc..
The thickness of transparency carrier is usually 0.05~10mm, is preferably 0.1~7mm scope.In addition, carrying out various trees In the case of the film formation processing of fat, its thickness is usually 0.01~10 μm, preferably 0.05~5 μm of scope.
(2) sept is coloured
The photosensitive coloring composition of the present invention is used for same with known colour filter photosensitive coloring composition Purposes.Hereinafter, for situation about being used as coloring sept (black light spacer), according to the photonasty for having used the present invention The specific example of the forming method of the black light spacer of coloured composition illustrates.
Generally, on the substrate of black light spacer to be set, the methods of passing through coating, is with the supply sense of membranaceous or pattern-like Photosensitiveness coloured composition, and make solvent seasoning.Then, formed by carrying out pattern the methods of the photoetching process that is exposed-develops. Then, carry out adding exposure, heat cure processing as needed, thus form black light spacer on the substrate.
(3) formation of sept is coloured
[1] to the supply method of substrate
The photosensitive coloring composition of the present invention is generally with the state that is dissolved or dispersed in solvent to supplying on substrate.Make For its supply method, known method, such as spin-coating method, bar (Wire bar) method, flow coat method, die coating can be passed through Method, rolling method, spraying process etc. are carried out.Furthermore it is possible to supplied by ink-jet method, print process etc. to form pattern-like.
When wherein, using die coating method, the usage amount of coating fluid can be significantly cut down, and do not use spin-coating method when institute completely The influence of the fog of attachment etc., foreign matter generation etc. can be suppressed, be preferable from the viewpoint of synthesis.
Coating weight is different according to purposes, such as in the case of black light spacer, is usually in terms of dry film thickness 0.5 μm~10 μm, preferably 1 μm~9 μm, particularly preferably 1 μm~7 μm of scope.In addition, it is important that dry film thickness or most End form into sept height on whole substrate uniformly.In the case where inequality is big, it can produce striped in liquid crystal panel and lack Fall into.
Wherein, highly different black is disposably formed by photoetching process using the photosensitive coloring composition of the present invention In the case of light spacer, the height of the black light spacer ultimately formed can be different.
It should be noted that as substrate, substrate known to glass substrate etc. can be used.In addition, substrate surface is preferred For plane.
[2] drying means
On to substrate supply photosensitive coloring composition after film drying preferably by using hot plate, IR baking ovens, The seasoning of convection oven is carried out.Done alternatively, it is also possible to combine the decompression for not improving temperature and being dried in pressure-reducing chamber Dry method.
Dry condition suitably selects according to the species of solvent composition, the performance for the drying machine to be used etc..Dry Time according to the temperature generally at 40 DEG C~130 DEG C such as the species of solvent composition, the performance for the drying machine to be used, 15 seconds The scope of~5 minutes is selected, and the temperature, the scope of 30 seconds~3 minutes preferably at 50 DEG C~110 DEG C are selected.
[3] exposure method
Exposure is that the mask pattern of minus is overlapped on the film of photosensitive coloring composition, and is shone across the mask pattern The light source of ultraviolet or luminous ray is penetrated to carry out.In the case of being exposed using exposed mask, can use makes exposure Method of the mask close to the film of photosensitive coloring composition；Exposed mask is disposed substantially away to the painting of photosensitive coloring composition The position of film, across the method for the exposed mask projection exposure light.Swash alternatively, it is also possible to use without using the utilization of mask pattern The scan exposure mode of light.
Now, as needed, can be in deoxidation gas in order to prevent the sensitivity of the optical polymerism layer caused by oxygen from declining It is exposed under atmosphere or is exposed on optical polymerism layer after the oxygen barrier layer such as formation polyvinyl alcohol layer.
As the preferred embodiment of the present invention, the situation of highly different black light spacer is formed simultaneously by photoetching process Under, for example, using with light shielding part (light transmittance 0%) and as the average transmittance of multiple opening portions relative to average transmittance The exposed mask of the highest opening portion opening portion small (completely through opening portion) (centre passes through opening portion).With it, Residual film ratio is produced through opening portion and completely through the difference of average transmittance, the i.e. difference of light exposure of opening portion by middle Difference.
It is known that middle transmission is for example made by the rectangular light-shielding pattern of the lightproof unit with small polygon Method of opening portion etc..Additionally, it is known that controlled by being used as the film of the materials such as the chromium system of absorber, molybdenum system, tungsten system, silicon systems Light rate and method for making etc..
Light source used in above-mentioned exposure is not particularly limited.As light source, can enumerate for example：Xenon lamp, Halogen lamp LED, tungsten The lamps such as lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, metal halide lamp, middle medium pressure mercury lamp, Cooper-Hewitt lamp, carbon arc, fluorescent lamp Light source；Argon laser, YAG laser, PRK, N_2 laser, helium cadmium laser, blue or green violet semiconductor laser, near-infrared half LASER Light Sources such as conductor Laser etc..When being irradiated using the light of specific wavelength, optical filter can also be utilized.
As optical filter, can for example use the type of the light transmittance of film control exposure wavelength, be used as this In the case of material, for example, Cr compounds (Cr oxide, nitride, oxynitride, fluoride etc.), MoSi, Si, W, Al etc..
As light exposure, usually 1mJ/cm2Above, it is preferably 5mJ/cm2Above, more preferably 10mJ/cm2More than, and Usually 300mJ/cm2Below, it is preferably 200mJ/cm2Below, it is more preferably 150mJ/cm2Below.
In addition, close in the case of Exposure mode, as exposure object and the distance of mask pattern, usually 10 μm with It is upper, be preferably more than 50 μm, more preferably more than 75 μm, in addition, usually less than 500 μm, preferably less than 400 μm, it is more excellent Elect less than 300 μm as.
[4] developing method
After having carried out above-mentioned exposure, by using the development of the aqueous solution or organic solvent of alkali compounds, Ke Yi Picture pattern is formed on substrate.In the aqueous solution, it can further contain surfactant, organic solvent, buffer, complexing Agent, dyestuff or pigment.
As alkali compounds, can enumerate：Sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, carbonic acid Hydrogen sodium, saleratus, sodium metasilicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, dibastic sodium phosphate, potassium hydrogen phosphate, biphosphate The inorganic alkaline compounds such as sodium, potassium dihydrogen phosphate, ammonium hydroxide, or MEA, diethanol amine or triethanolamine, monomethyl Amine, dimethyl amine or Trimethylamine, MEA, diethylamide or triethylamine, single isopropylamine or diisopropylamine, positive fourth Base amine, monoisopropanolamine, diisopropanolamine (DIPA) or triisopropanolamine, aziridine, ethene diimine, TMAH (TMAH), the organic basic compound such as choline.These alkali compounds can be mixture of more than two kinds.
As above-mentioned surfactant, can enumerate for example：Polyoxyethylene alkyl ether class, polyoxyethylene alkylaryl ether class, The nonionic surface active agent such as polyxyethylated ester class, sorbitan alkyl esters, monoglyceride alkyl esters；Alkyl The anion such as benzenesulfonates, alkyl naphthalene sulfonic acid salt, alkylsurfuric acid salt, alkyl sulfonates, sulfosuccinate ester salt class Type surfactant；The amphoteric surfactantes such as alkyl betaines bases, amino acids.
As organic solvent, can enumerate for example：Isopropanol, benzylalcohol, ethyl cellosolve, butyl cellosolve, ethylene glycol monophenyl ether, Propane diols, DAA etc..Organic solvent can be used alone, and can also be applied in combination with the aqueous solution.
The condition of development treatment is not particularly limited, generally can be in the scope, preferably that development temperature is 10 DEG C~50 DEG C At 15 DEG C~45 DEG C, particularly preferably at 20~40 DEG C using immersion development method, spray development method, fur brush development method, ultrasonic wave Any means in the developing methods such as development method are carried out.
[5] additional exposure and heat cure processing
For the substrate after development, can carry out adding exposure as needed according to the method same with above-mentioned exposure method Light, alternatively, it is also possible to carry out heat cure processing.Heat cure treatment conditions now are as follows：Model of the temperature at 100 DEG C~280 DEG C Enclose, the scope preferably at 150 DEG C~250 DEG C selects, scope selection of the time at 5 minutes~60 minutes.
The size of coloring sept of the present invention, shape etc. can be according to specification of the colour filter using it etc. with Adjustment, photosensitive coloring composition of the invention especially for by photoetching process simultaneously formed sept and auxiliary sept this The black light spacer that the height of sample is different is useful, in this case, the height of sept is usually 2~7 μm or so, auxiliary Sept generally has the height less than sept, is 0.2~1.5 μm or so.
In addition, from the viewpoint of light-proofness, the optical density (OD) of the coloring sept of the invention equivalent to 1 μm is preferred For more than 1.2, more preferably more than 1.5, more preferably more than 1.8, in addition, usually less than 4.0, be preferably 3.0 with Under.Optical density (OD) mentioned here is the value determined by the method described below.
[colour filter]
The colour filter of the present invention possesses the coloring sept of above-mentioned such present invention, such as can manufacture as follows：In conduct Glass substrate superimposed layer black matrix", red, green, pixel shader layer, the face coat of blueness of transparency carrier, form coloring After sept, alignment films are formed.
Such colour filter with coloring sept of the invention and liquid crystal drive side base plate are bonded and form liquid crystal Box, liquid crystal is injected in the liquid crystal cell formed, it is possible thereby to manufacture the liquid crystal display dress for possessing the coloring sept of the present invention The image display device such as put.
Embodiment
Then, enumerating embodiment and comparative example, more specifically the present invention will be described, but as long as without departing from the present invention's Purport, the present invention are not limited to following embodiment.
The constituent of the photosensitive coloring composition used in following embodiment and comparative example is as follows.
＜ organic black pigments ＞
BASF AG manufactures, and Irgaphor (registration mark) Black S 0100CF (have the chemistry shown in following formula (2) Structure)
[chemical formula 30]
＜ alkali soluble resin-I ＞
The mass parts of propylene glycol methyl ether acetate 145 are subjected to nitrogen displacement while being stirred, are warming up to 120 ℃.The mass parts of styrene 10, the mass parts of GMA 85.2 are added dropwise thereto and there is tricyclodecane skeleton Mono acrylic ester the FA-513M of manufacture (Hitachi Chemical Co., Ltd.) 66 mass parts, and with dropwise addition 2 in 3 hours, 2 '-azo Double mass parts of -2- methylbutyronitriles 8.47, then continue to have stirred 2 hours at 90 DEG C.Then, air will be changed into reaction vessel Displacement, the mass parts of three (dimethylaminomethyl) phenol 0.7 and the matter of hydroquinones 0.12 are put into the mass parts of acrylic acid 43.2 Part is measured, continues reaction 12 hours at 100 DEG C.Then, tetrabydrophthalic anhydride (THPA) 56.2 mass parts, triethylamine are added 0.7 mass parts, reacted 3.5 hours at 100 DEG C.Weight by the alkaline bleach liquor soluble resin-I obtained above of GPC measure is equal Molecular weight Mw is about 8400, acid number 80mgKOH/g.
＜ alkali soluble resin-II ＞
" ZCR-1642H " (MW=6500, the acid number=98mg-KOH/g) of Nippon Kayaku K. K's manufacture
＜ dispersant-I ＞
" DISPERBYK-LPN21116 " of BYK-Chemie companies manufacture (has quaternary ammonium salt base and tertiary amino by side chain A blocks and the acrylic A-B block copolymer formed without the B block of quaternary ammonium salt base and amino, its amine value are 70mgKOH/g, acid number are below 1mgKOH/g)
Following formula (1a) and the repeat unit of (2a) are included in dispersant-I A blocks, following formula (3a) is included in B block Repeat unit.The repeat unit of following formula (1a), (2a) and (3a) is shared in dispersant-I whole repeat units to be contained Proportional is respectively 11.1 moles of %, 22.2 moles of %, 6.7 moles of %.
[chemical formula 31]
＜ dispersant-II ＞
" DISPERBYK-167 " (the carbamates macromolecule dispersing agent) of BYK-Chemie companies manufacture
＜ pigment derivatives ＞
" Solsperse12000 " of Lubrizol companies manufacture
＜ solvent-I ＞
PGMEA：Propylene glycol methyl ether acetate
＜ solvent-II ＞
MB：3- methoxybutanols
＜ Photoepolymerizationinitiater initiater-I ＞
Irgacure OXE03 (BASF AG's manufacture)
[chemical formula 32]
＜ Photoepolymerizationinitiater initiater-II ＞
[chemical formula 33]
＜ Photoepolymerizationinitiater initiater-III ＞
[chemical formula 34]
＜ photopolymerization monomers ＞
DPHA：The dipentaerythritol acrylate of Nippon Kayaku K. K's manufacture
＜ additives ＞
Nippon Kayaku K. K's manufacture, KAYAMER PM-21 (phosphate containing methylacryloyl)
＜ surfactants ＞
The Megafac F-559 of DIC companies manufacture
The evaluation ＞ of ＜ optical density (OD)
Optical density (OD) is determined using transmission-type densimeter (" D200-II " of the manufacture of Gretag Macbeth companies). In addition, being also determined to the thickness of measurement site, the optical density (unit OD) of per unit thickness (1 μm) is calculated.
The evaluation ＞ of ＜ substrate adaptations
It is for the pattern as object, resolution ratio is good, pattern is remained on substrate sample split shed diameter is minimum The value of the opening diameter (μm) of person is as minimum closely sealed.The value is smaller, and substrate adaptation is more excellent.
The evaluation ＞ of ＜ surface smoothnesss
For the pattern as object, have using light microscope in the visual field of 70 μm of 70 μ m to the surface after heating Observed without fold is produced.It should be noted that metewand is as follows.
○：Micron-sized fold is not observed on the surface of pattern
×：It is obvious in the fold of the surface micrometre-grade of pattern
The evaluation ＞ of ＜ surface roughnesses
For the pattern as object, the three-dimensional non-planar contact surfaces shape measure system of Ling Hua systems Co., Ltd. is utilized Micromap, using 50 times of optical lenses, with Focus patterns determine surface roughness Sa in the visual field of 70 μm of 70 μ m (arithmetic average roughness, nm).
The preparation ＞ of ＜ dispersible pigment dispersions 1
Quality of pigment, dispersant, dispersing aid, alkali soluble resin and the solvent that table 1 is recorded described according to table 1 Than being mixed.The solution has been carried out with paint shaker to the decentralized processing of 3 hours in 25~45 DEG C of scope.As Pearl, 0.5mm φ zirconium oxide bead is used, add 2.5 times of quality of dispersion liquid.After scattered end, filter is utilized Pearl is separated with dispersion liquid, is prepared for dispersible pigment dispersion 1.
The preparation ＞ of ＜ dispersible pigment dispersions 2 and 3
Except pigment, dispersant, dispersing aid, alkali soluble resin and the solvent for recording table 1 are according to described in table 1 Beyond mass ratio is mixed, equally operated with dispersible pigment dispersion 1, be prepared for dispersible pigment dispersion 2 and 3.
＜ dispersible pigment dispersions 4 (cladding carbon black dispersion liquid) ＞
Carbon black is manufactured using common Audit For Process.Wherein, as feedstock oil, the poor ethene of Na, Ca, S is used Residue oil, and used coke oven gas to be used for being burnt.In addition, as reaction terminating water, use and use ion exchange The pure water that resin is handled.Using homogenizer with 5,000~6,000rpm to obtained carbon black 540g and pure water 14500g It is stirred together 30 minutes, has obtained slurry.The slurry is transferred in the container with screw type mixer, while with big About 1,000rpm is mixed, and marginally with the addition of respectively dissolved with epoxy resin " Epikote828 " (Mitsubishi Chemical's strain on one side Formula commercial firm manufactures) 60g toluene 600g.About 15 minutes, the carbon black being dispersed in water was fully transferred to toluene side, forms about 1mm particle.
Then, carried out removing moisture with the wire netting of 60 mesh, be then placed in vacuum drier, 7 are dried at 70 DEG C Hour, toluene and water are removed completely.
Resulting cladding carbon black, dispersant, pigment derivative and solvent are carried out according to the mass ratio described in table 2 Mixing.
It is sufficiently stirred, is pre-mixed using agitator.Then, model of the paint shaker at 25~45 DEG C is utilized Enclose and carry out 6 hours decentralized processings, as pearl, use 0.5mm φ zirconium oxide bead, and add and dispersion liquid identical matter Amount, disperse after terminating, separated pearl with dispersion liquid using filter, so as to be prepared for (the cladding carbon black dispersion of dispersible pigment dispersion 4 Liquid).
[embodiment 1 and 2, comparative example 1~3]
Using the dispersible pigment dispersion 1~4 of above-mentioned preparation, each composition is added according to the mixing ratio of table 2, and further add PGMEA causes solid constituent to reach 22 mass %, and being stirred makes its dissolving, is prepared for photosensitive coloring composition.Using institute Obtained photosensitive coloring composition, evaluated according to the method described below.It should be noted that the top in table 2 Value represent be each composition usage amount, on the other hand, what the value of bottom represented be each composition solid constituent amount relative to The content ratio of the total solid content amount of photosensitive coloring composition.
The disposable forming method ＞ of solidfied materials highly different ＜
Using circulator each coloring photosensitive combination is coated with glass substrate (" AN100 " that AGC companies manufacture).Connect , on hot plate at 110 DEG C heat drying 70 seconds, form film.
Using with 5~50 μm (5~20 μm of diameter：1 μm, 25 μm~50 μm of interval：Interval 5 μm) various diameters circle Shape pattern completely through 5~50 μm (5~20 μm of opening portion and diameter：1 μm, 25 μm~50 μm of interval：Interval 5 μm) it is various The centre of the circular pattern of diameter passes through the exposed mask of opening portion and the straight line opening portion (completely through) of 100 μm of width, Exposure-processed has been carried out to resulting film.Centre is through the Cr that opening portion is that the light transmittance under wavelength 365nm is 10 ± 2% The film of oxide.It is 220 μm to expose spacing (distance between mask and coated face).As irradiation light, use in wavelength Intensity under 365nm is 32mW/cm2Ultraviolet, light exposure 100mJ/cm2.In addition, ultraviolet irradiation is carried out in atmosphere.
Then, using the nonionic surface active agent by the potassium hydroxide containing 0.05 weight % and 0.08 weight % Developer solution made of the aqueous solution of (" A-60 " of Kao Corp's manufacture), implements hydraulic pressure 0.15MPa spraying at 25 DEG C After development, terminated and developed with pure water, spraying is washed with water and is cleaned.The spray development time was adjusted between 10~120 seconds It is whole, it is set to 1.5 times that dissolving removes the time of unexposed film.
By aforesaid operations, the pattern of unnecessary portion is obtained eliminating.By the substrate formed with the pattern in baking oven In, heated 20 minutes at 230 DEG C and solidify pattern, obtained generally cylindrical spacer patterns.
Method according to above describing determines the unit thickness (1 μm) of the pattern corresponding with above-mentioned straight line opening portion Optical density (OD).In addition, for the circular pattern with 5~50 μm completely through in 5~50 μm of opening portion and identical Between pass through pattern corresponding to opening portion, the evaluation of substrate adaptation has been carried out according to the method above described.In addition, for it is upper Pattern corresponding to straight line opening portion is stated, the evaluation of surface smoothness has been carried out according to the method above described.In addition, for it is upper Pattern corresponding to straight line opening portion is stated, the evaluation of surface roughness has been carried out according to the method above described.Each result is shown in table 2 In.
Confirm that the unit OD of the coated substrates for the photosensitive coloring composition for having used embodiment 1 and 2 is high, and light-proofness is excellent Different, surface smoothness is excellent.In addition, the middle substrate adaptation through opening portion is also good.
On the other hand, although comparative example 1~3 is identical with the unit OD of embodiment 1 and 2 value, smooth surface is confirmed Property it is poor, and the middle substrate adaptation through opening portion is poor.
In general, in order to improve coloring sept light-proofness, it is known that improve pigment concentration method and combination make With the method for the high pigment of light-proofness.But during using such method, it is believed that ultraviolet transmission rate declines, in film thickness direction Generation crosslink density is poor, and compared with the bottom of film, the crosslink density on film surface increases, in the effect of the thermal contraction of curing process Under, film surface produces fold, and surface smoothness is deteriorated.
For the photosensitive coloring composition of the present invention, it is believed that due to having used the oxime ester shown in above-mentioned formula (I) Class compound is as Photoepolymerizationinitiater initiater, and in the presence of the halogen atom in the chemical constitution of the compound, the compound is in film Surface vicinity is easily distributed initiator and influenceed by oxygen obstruction, and the crosslink density for thus suppressing film surface excessively increases, from And the fold on film surface caused by can reducing the thermal contraction of curing process produces.
In addition, it is believed that in the carbazole skelton of the compound, increase the absorbability of long wavelength light due to naphthalene nucleus, it is also sharp The crosslink density near the bottom of film can be improved with the long wavelength light contained by ultraviolet lamp, therefore, even with middle saturating The pattern that the low opening portion of transmitance as crossing opening portion is formed, substrate adaptation also become good.
[embodiment 3 and comparative example 4]
Using the dispersible pigment dispersion 3 and 4 of above-mentioned preparation, the side according to the ratio in solid constituent for the mixing ratio of table 3 Formula adds each composition, adds PGMEA so that solid constituent reaches 22 mass %, being stirred makes its dissolving, is prepared for photosensitive Property coloured composition.Using resulting photosensitive coloring composition, the light exposure in exposure-processed is set to 40mJ/cm2, remove Evaluated beyond this according to order similarly to Example 1.It should be noted that the value on top in table 3 represent be The usage amount of each composition, on the other hand, what the value of bottom represented is the solid constituent amount of each composition relative to photosensitive color group The content ratio of the total solid content amount of compound.In addition, the evaluation visual field of surface smoothness is 5cm × 5cm.
[table 3]
The unit OD that confirms the coated substrates for the photosensitive coloring composition for having used embodiment 3 is high, light-proofness is excellent, Surface smoothness is excellent.In addition, the middle substrate adaptation through opening portion is also good.
On the other hand, although comparative example 4 is identical with the unit OD of embodiment 3 value, surface smoothness is poor, rough surface The value of degree is also big, additionally confirms, and centre is poor through the substrate adaptation of opening portion.
Using specific mode, the present invention is described in detail, but those skilled in the art it should be clear that In the case of without prejudice to the intent and scope of the present invention, various changes, deformation can be carried out.It should be noted that the application The Japan that Japanese patent application (Patent 2015-048577), on March 11st, 2015 based on proposition on March 11st, 2015 propose Patent application (Patent 2015-048578) and August in 2015 Japanese patent applications (Patent 2015-157456) proposed on the 7th and Complete, its content is used as reference to be introduced in the application.
Industrial applicibility
According to the photosensitive coloring composition of the present invention, the solidfied material that light-proofness is high, surface smoothness is excellent can be provided And coloring sept, it is furthermore possible to also provide possessing the image display device of such coloring sept.Therefore, the present invention is feeling Photosensitiveness coloured composition, solidfied material, coloring sept and image display device each field in industrial practicality it is high.

Claims (18)

1. one kind coloring sept formation photosensitive coloring composition, it contains：(a) colouring agent, (b) alkali soluble resin, (c) Photoepolymerizationinitiater initiater, (d) alefinically unsaturated compounds, (e) solvent and (f) dispersant, wherein,
(c) Photoepolymerizationinitiater initiater includes the oxime ester compound shown in following formula (I)s,
In above-mentioned logical formula (I),
R1Represent that optionally there is the aromatic ring yl of substituent,
R2The alkanoyl optionally with substituent or the optional aroyl with substituent are represented,
R3Represent hydrogen atom or optionally there is the alkyl of substituent,
R4Represent that optionally there is the aromatic ring yl of substituent,
R5And R6The phenyl ring optionally with substituent or the optional naphthalene nucleus with substituent are represented independently of one another, wherein, R5And R6 In at least any one for optionally have substituent naphthalene nucleus,
R1And R4In at least any one there is-OR7Base is as substituent, wherein R7Represent alkylhalide group,
X represents direct key or carbonyl,
Z represents direct key or carbonyl.
2. coloring sept formation photosensitive coloring composition according to claim 1, wherein, (a) colouring agent Contain at least one selected from least one of red pigment and orange pigment and in blue pigment and violet pigment Kind.
3. coloring sept formation photosensitive coloring composition according to claim 2, wherein, the red pigment is Following (1), the orange pigment are following (2), the blue pigment is following (3), the violet pigment is following (4),
(1) C.I. paratoneres 177, at least one of 254 are selected from,
(2) C.I. pigment oranges 43, at least one of 64 are selected from,
(3) C.I. pigment blue 15s are selected from:6th, at least one of 60,
(4) selected from C.I. pigment Violet 23s, at least one of 29.
4. the coloring sept formation photosensitive coloring composition according to Claims 2 or 3, wherein, relative to described (a) mass parts of colouring agent 100, the content ratio selected from least one of red pigment and orange pigment pigment are 1 mass parts Above and below 30 mass parts.
5. the coloring sept formation photosensitive coloring composition according to any one of claim 2~4, wherein, phase For the mass parts of (a) colouring agent 100, the content ratio selected from least one of blue pigment and violet pigment pigment is More than 20 mass parts and below 90 mass parts.
6. according to coloring sept formation photosensitive coloring composition according to any one of claims 1 to 5, wherein, institute State (a) colouring agent and contain organic black pigments.
7. coloring sept formation photosensitive coloring composition according to claim 6, wherein, organic black face Salt of the material containing the compound shown in following formula (1), its geometric isomer, its salt or its geometric isomer,
In above-mentioned formula (1), R11And R16Independently of one another hydrogen atom, CH3、CF3, fluorine atom or chlorine atom；
R12、R13、R14、R15、R17、R18、R19And R20Hydrogen atom, halogen atom, R are independently of one another to each other21、COOH、COOR21、 COO-、CONH2、CONHR21、CONR21R22、CN、OH、OR21、COCR21、OOCNH2、OOCNHR21、OOCNR21R22、NO2、NH2、 NHR21、NR21R22、NHCOR22、NR21COR22, N=CH2, N=CHR21, N=CR21R22、SH、SR21、SOR21、SO2R21、SO3R21、 SO3H、SO3 -、SO2NH2、SO2NHR21Or SO2NR21R22；
Also, it is selected from R12With R13、R13With R14、R14With R15、R17With R18、R18With R19And R19With R20In at least one combination phase Direct Bonding or pass through oxygen atom, sulphur atom, NH or NR between mutually11Bridging and be mutually bonded；
R21And R22The independently of one another alkyl of carbon number 1~12, the cycloalkyl of carbon number 3~12, carbon number 2~12 Alkenyl, the cycloalkenyl group of carbon number 3~12 or the alkynyl of carbon number 2~12.
8. according to coloring sept formation photosensitive coloring composition according to any one of claims 1 to 7, wherein, institute State (a) colouring agent and contain carbon black.
9. coloring sept formation photosensitive coloring composition according to claim 1, wherein, (a) colouring agent Contain organic pigment and carbon black.
10. coloring sept formation photosensitive coloring composition according to claim 9, wherein, the organic pigment Containing selected from least one of red pigment, orange pigment, blue pigment and violet pigment.
11. the coloring sept formation photosensitive coloring composition according to claim 9 or 10, wherein, it is described organic Pigment contains selected from least one of following (1)~(4),
(1) C.I. paratoneres 177, at least one of 254 are selected from,
(2) C.I. pigment oranges 43, at least one of 64 are selected from,
(3) C.I. pigment blue 15s are selected from:6th, at least one of 60,
(4) selected from C.I. pigment Violet 23s, at least one of 29.
12. the coloring sept formation photosensitive coloring composition according to any one of claim 9~11, wherein, The organic pigment contains blue pigment and violet pigment.
13. the coloring sept formation photosensitive coloring composition according to any one of claim 9~12, wherein, Relative to the mass parts of (a) colouring agent 100, the content ratio of carbon black is more than 5 mass parts and below 50 mass parts.
14. the coloring sept formation photosensitive coloring composition according to any one of claim 1~13, it solidifies The optical density of average every 1 μm of thickness of film afterwards is more than 1.0.
15. the coloring sept formation photosensitive coloring composition according to any one of claim 1~14, it is used for Highly different coloring septs is disposably formed by photoetching process.
16. a kind of solidfied material, it is by the coloring sept formation photosensitive color any one of claim 1~15 Obtained from composition solidification.
17. one kind coloring sept, it is formed as the solidfied material described in claim 16.
18. a kind of image display device, it possesses the coloring sept described in claim 17.
CN201680014325.2A 2015-03-11 2016-03-10 Sept is coloured to be formed with photosensitive coloring composition, solidfied material, coloring sept, image display device Pending CN107407881A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006162784A (en) * 2004-12-03 2006-06-22 Toppan Printing Co Ltd Photosensitive colored composition and color filter using the same
WO2011152066A1 (en) * 2010-06-04 2011-12-08 ダイトーケミックス株式会社 Oxime ester compound, process for producing oxime ester compound, photopolymerization initiator, and photosensitive composition
CN103153952A (en) * 2010-10-05 2013-06-12 巴斯夫欧洲公司 Oxime ester derivatives of benzocarbazole compounds and their use as photoinitiators in photopolymerizable compositions
JP2013147483A (en) * 2012-01-20 2013-08-01 Hunet Plus Co Ltd New high sensitive alpha-keto oxime ester photopolymerization initiator and photopolymerization composition containing the compound
JP2014009325A (en) * 2012-07-02 2014-01-20 Nippon Kagaku Kogyosho:Kk Novel photopolymerization initiator and photosensitive resin composition using the same
JP2014139668A (en) * 2012-12-20 2014-07-31 Mitsubishi Chemicals Corp Colored cured object and its manufacturing method, color filter, and liquid crystal display device
TW201432323A (en) * 2012-12-27 2014-08-16 Fujifilm Corp Composition for color filter, infrared ray transmitting filter and fabricating method thereof, and infrared ray sensor

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08234212A (en) 1995-02-28 1996-09-13 Casio Comput Co Ltd Liquid crystal display element
JP2006162874A (en) * 2004-12-06 2006-06-22 Fujikura Ltd Optical fiber cable with connector
KR101266295B1 (en) 2009-09-09 2013-05-23 제일모직주식회사 Black photosensitive resin composition and black matrix manufactured by using the same
JP2012181509A (en) * 2011-02-08 2012-09-20 Mitsubishi Chemicals Corp Photosensitive coloring composition, colored spacer, color filter and liquid crystal display device
KR101349622B1 (en) 2011-08-26 2014-01-10 롬엔드하스전자재료코리아유한회사 Photopolymerizable unsaturated resin, photosensitive resin composition comprising the same, and light shielding spacer and liquid crystal display device formed therefrom
CN103890660B (en) * 2011-10-25 2019-05-31 三菱化学株式会社 Coloring photosensitive combination, coloring spacer, colour filter and liquid crystal display device
KR102006041B1 (en) * 2011-12-07 2019-07-31 바스프 에스이 Oxime ester photoinitiators
JP6036708B2 (en) 2012-01-31 2016-11-30 三菱化学株式会社 Colored photosensitive composition, black photo spacer, and color filter
KR102112041B1 (en) 2012-06-01 2020-05-18 바스프 에스이 Black colorant mixture
JP6031901B2 (en) * 2012-09-06 2016-11-24 東洋インキＳｃホールディングス株式会社 Photosensitive coloring composition, colored film and color filter
KR101658374B1 (en) 2013-01-25 2016-09-22 롬엔드하스전자재료코리아유한회사 Colored photosensitive resin composition with dual property for column spacer and black matrix
JP6096146B2 (en) * 2013-05-10 2017-03-15 富士フイルム株式会社 Colored composition, colored cured film, color filter, solid-state imaging device, and image display device
WO2014208348A1 (en) 2013-06-24 2014-12-31 東レ株式会社 Black resin composition for touch panels
KR20190021493A (en) * 2014-05-01 2019-03-05 후지필름 가부시키가이샤 Coloring composition, film, color filter, method for forming pattern, method for producing color filter, solid-state imaging device, and infrared sensor

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006162784A (en) * 2004-12-03 2006-06-22 Toppan Printing Co Ltd Photosensitive colored composition and color filter using the same
WO2011152066A1 (en) * 2010-06-04 2011-12-08 ダイトーケミックス株式会社 Oxime ester compound, process for producing oxime ester compound, photopolymerization initiator, and photosensitive composition
CN103153952A (en) * 2010-10-05 2013-06-12 巴斯夫欧洲公司 Oxime ester derivatives of benzocarbazole compounds and their use as photoinitiators in photopolymerizable compositions
JP2013147483A (en) * 2012-01-20 2013-08-01 Hunet Plus Co Ltd New high sensitive alpha-keto oxime ester photopolymerization initiator and photopolymerization composition containing the compound
JP2014009325A (en) * 2012-07-02 2014-01-20 Nippon Kagaku Kogyosho:Kk Novel photopolymerization initiator and photosensitive resin composition using the same
JP2014139668A (en) * 2012-12-20 2014-07-31 Mitsubishi Chemicals Corp Colored cured object and its manufacturing method, color filter, and liquid crystal display device
TW201432323A (en) * 2012-12-27 2014-08-16 Fujifilm Corp Composition for color filter, infrared ray transmitting filter and fabricating method thereof, and infrared ray sensor

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110178083A (en) * 2017-02-15 2019-08-27 三菱化学株式会社 Photosensitive coloring composition, solidfied material, coloring spacer, image display device
CN113372757A (en) * 2021-07-29 2021-09-10 业成科技（成都）有限公司 Ultraviolet light curing printing ink

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