CN108475012A - Photosensitive coloring composition, solidfied material, coloring spacer, image display device - Google Patents

Photosensitive coloring composition, solidfied material, coloring spacer, image display device Download PDF

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Publication number
CN108475012A
CN108475012A CN201680075723.5A CN201680075723A CN108475012A CN 108475012 A CN108475012 A CN 108475012A CN 201680075723 A CN201680075723 A CN 201680075723A CN 108475012 A CN108475012 A CN 108475012A
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methyl
ring
group
less
acid
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CN201680075723.5A
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CN108475012B (en
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伊藤敦哉
小川善秀
裴丽华
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Mitsubishi Kasei Corp
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Mitsubishi Kasei Corp
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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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • 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
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • 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
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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 issue of the present invention is to provide a kind of photosensitive coloring composition, the pattern that light-proofness is high, high reliability and surface smoothness are excellent can be formed, and spacer is coloured particularly preferred for being formed.The photosensitive coloring composition of the present invention contains：(a) colorant, (b) alkali soluble resin, (c) Photoepolymerizationinitiater initiater, (d) olefinic unsaturated compound, (e) solvent, and (f) dispersant, wherein, (a) colorant includes organic pigment and carbon black, (b) alkali soluble resin includes (b I) epoxy (methyl) acrylate, (b II) (methyl) acrylic copolymeric resins, (b II) (methyl) acrylic copolymeric resins contain side chain the repetitive unit α with ethylenic unsaturated bond and the repetitive unit β from unsaturated carboxylic acid, and, the content ratio of the repetitive unit α in (b II) (methyl) acrylic copolymeric resins is 12 moles of % or more.

Description

Photosensitive coloring composition, solidfied material, coloring spacer, image display device
Technical field
The present invention relates to photosensitive coloring compositions etc..Specifically, it is related to the colour filter in such as liquid crystal display etc. In be preferably used to form coloring spacer etc. photosensitive coloring composition, will be obtained from photosensitive coloring composition solidification Coloring spacer, the image display device for having the coloring spacer.
Background technology
Liquid crystal display (LCD) is utilized under the action 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 constituting the unit of LCD is by using photoetching process as the profit of representative mostly It is formed with the method for photosensitive composite.For the photosensitive composite, since it is easy to be formed fine structure, also It is easy to carry out the such reason of the processing for big picture substrate, from now on, the scope of application has further widened trend.
But for use photosensitive composite manufacture LCD for, due to the electrical characteristics of photosensitive composite itself, The influence of impurity contained in photosensitive composite cannot keep the voltage applied to liquid crystal, exist and generate display therefrom Display it is uneven the problems such as the case where.In particular, in colour liquid crystal display close to the component of liquid crystal layer, for example in liquid For so-called column spacer, light spacer used in crystal panel in order to which the interval holding of 2 substrates is constant etc., It influences notable.
In the past, it was used for TFT (thin film transistor (TFT), Thin Film Transistor) in the spacer that will do not have light-proofness In the case of type LCD, sometimes due to through spacer the light that comes and so that the TFT as switch element is malfunctioned.In order to It prevents from having recorded the method using the spacer (coloring spacer) with light-proofness in the situation, such as patent document 1.
On the other hand, in recent years, along with the variation of panel construction, it is proposed that disposably form height by photoetching process The method of different coloring spacers.For example, Patent Document 2 discloses the following contents：It is special by combining a variety of light absorptions Property different specific pigment kind ensures the balance of the light absorption 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.
On the other hand, disclosed in patent document 3 using the alkali soluble resin of specific structure can also realize light-proofness, The control of difference of height, the adaptation with substrate.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 8-234212 bulletins
Patent document 2：International Publication No. 2013/115268
Patent document 3：Japanese Unexamined Patent Publication 2013-134263 bulletins
Invention content
The subject that the invention solves
In recent years, along with the variation of panel construction, it is desirable that further increase the light-proofness of coloring spacer.As raising The method of light-proofness can enumerate the method using the high pigment of light-proofness and improve the face in photosensitive coloring composition Expect the method etc. of content ratio.It is that the inventors of the present invention are studied as a result, it has been found that, in photosensitive color group described in Patent Document 2 Close object in, high pigment of light-proofness etc. is applied in combination further increase coloring spacer light-proofness when, it is attached in film surface Crosslink density difference near close and film bottom increases, and fold, table are generated in film coated surface due to the thermal contraction of curing process Face flatness becomes inadequate.
In addition, foring the high coloring spacer of light-proofness using the photosensitive coloring composition described in patent document 3 In the case of, it is found that there are following this problems：It is dissolved out to formation taking as its upper layer film from the impurity of colorant In solvent when to film, further, since cure component is few and keep the dissolution of impurity also more under high pigment levels, as a result, making The display less reliable of LCD.
Present invention is made in view of the above circumstances, and the purpose of the present invention is to provide one kind capable of forming light-proofness High, high reliability and the excellent pattern of surface smoothness photosensitive coloring composition.
The method to solve the problem
It is that the inventors of the present invention have made intensive studies in order to solve the above problems as a result, it has been found that, by photosensitive color group Epoxy (methyl) acrylate is applied in combination in conjunction object and specific (methyl) acrylic copolymeric resins are solvable as alkali Property resin, can solve the above subject, so as to complete the present invention.
That is, the present invention has the composition of [1] below~[9].
[1] a kind of photosensitive coloring composition, contains：(a) colorant, (b) alkali soluble resin, (c) photopolymerization are drawn Send out agent, (d) olefinic unsaturated compound, (e) solvent and (f) dispersant, wherein
(a) colorant includes organic pigment and carbon black,
(b) alkali soluble resin includes (b-I) epoxy (methyl) acrylate and (b-II) (methyl) propylene Acids copolymer resins, (b-II) (methyl) acrylic copolymeric resins contain the repetition list that side chain has ethylenic unsaturated bond First α and repetitive unit β from unsaturated carboxylic acid, also,
The content ratio of the repetitive unit α in (b-II) (methyl) acrylic copolymeric resins is 12 moles of % More than.
[2] photosensitive coloring composition described in above-mentioned [1], wherein the organic pigment includes to be selected from the following general formula (1) Compound represented, the geometric isomer of the compound, the salt of the compound and the compound geometric isomer salt in At least one organic black pigments,
[chemical formula 1]
(in formula (1), R11And R16Independently of one another hydrogen atom, CH3、CF3, fluorine atom or chlorine atom；
R12、R13、R14、R15、R17、R18、R19And R20It is independently of one another hydrogen atom, halogen atom, R to each other21、COOH、 COOR21、COO-、CONH2、CONHR21、CONR21R22、CN、OH、OR21、COCR21、OCONH2、OCONHR21、OCONR21R22、 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 R20At least one of group Direct Bonding or pass through oxygen atom, sulphur atom, NH or NR between closing optionally mutually21Bridging and be mutually bonded；
R21And R22The independently of one another alkyl of carbon atom number 1~12, the naphthenic base of carbon atom number 3~12, carbon atom number The alkynyl of 2~12 alkenyl, the cycloalkenyl group of carbon atom number 3~12 or carbon atom number 2~12.)
[3] a kind of photosensitive coloring composition, contains：(a) colorant, (b) alkali soluble resin, (c) photopolymerization are drawn Send out agent, (d) olefinic unsaturated compound, (e) solvent and (f) dispersant, wherein
(a) colorant includes selected from least one of red pigment and orange pigment and to be selected from blue pigment And at least one of violet pigment,
(b) alkali soluble resin includes (b-I) epoxy (methyl) acrylate and (b-II) (methyl) propylene Acids copolymer resins, (b-II) (methyl) acrylic copolymeric resins contain the repetition list that side chain has ethylenic unsaturated bond First α and repetitive unit β from unsaturated carboxylic acid, also,
The content ratio of the repetitive unit α in (b-II) (methyl) acrylic copolymeric resins is 12 moles of % More than.
[4] photosensitive coloring composition described in any one of above-mentioned [1]~[3], wherein the repetitive unit α has Chemical constitution shown in the following general formula (I),
[chemical formula 2]
(in formula (I), R1And R2Each independently represent hydrogen atom or methyl, R3Indicate the connection group of divalent).
[5] photosensitive coloring composition described in any one of above-mentioned [1]~[4], wherein relative to photosensitive color group The all solids ingredient in object is closed, the content ratio of (b-II) (methyl) acrylic copolymeric resins is 1 mass % or more.
[6] photosensitive coloring composition described in any one of above-mentioned [1]~[5], average every 1 of film after solidification The optical density of μm film thickness is 1.0 or more.
[7] a kind of solidfied material, be by described in any one of above-mentioned [1]~[6] photosensitive coloring composition solidification and It obtains.
[8] a kind of coloring spacer is formed by the solidfied material described in above-mentioned [7].
[9] a kind of image display device has the coloring spacer described in above-mentioned [8].
The effect of invention
According to the present invention it is possible to which high light-proofness, high reliability and the excellent pattern of surface smoothness can be formed by providing Photosensitive coloring composition.Furthermore it is possible to the solidfied material and coloring spacer that light-proofness is excellent, surface smoothness is excellent are provided, The image display device for having such coloring spacer can also be provided.
Specific implementation mode
Hereinafter, embodiments of the present invention are specifically described, but the present invention is not limited to the following embodiments and the accompanying drawings, and it can To implement after being made 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 meaning.
In the present invention, the meaning of described " (co) polymer " includes homopolymer (homopolymer) and copolymer Both (copolymer) meaning of, described " sour (acid anhydrides) ", " ... sour (acid anhydride) " includes both acid and its acid anhydrides.In addition, In the present invention, " acrylic resin " refers to the (co) polymer comprising (methyl) acrylic acid, comprising the (first with carboxyl Base) acrylate (co) polymer.
In addition, in the present invention, " monomer " is the term opposite with so-called polymer substance (polymer), in addition to Further include the meanings such as dimer, trimer, oligomer other than the monomer (monomer) of narrow sense.
In the present invention, described " total solid content " refers to institute in the ink described in photosensitive coloring composition or below Whole components other than the solvent contained.
In the present invention, " weight average molecular weight " refers to being measured using GPC (gel permeation chromatography) and being converted into polyphenyl second The weight average molecular weight (Mw) of alkene.
In addition, in the present invention, unless otherwise specified, " amine value " indicates the amine for being converted into effective solid constituent Value, is with the value for the alkali number that the KOH quality representations of equivalent are the every 1g solid constituents for being equivalent to dispersant.It should be noted that About its assay method, it is described below.On the other hand, unless otherwise specified, described " acid value " expression is converted into effectively The acid value of solid constituent, is calculated by acid-base titration.
In addition, in the present specification, the percentage indicated with the percentage of " quality " expression and part and with " weight " and part Indicate identical meanings.
[photosensitive coloring composition]
The photosensitive coloring composition of the present invention contains following component as essential component：
(a) colorant
(b) alkali soluble resin
(c) Photoepolymerizationinitiater initiater
(d) olefinic unsaturated compound
(e) solvent
(f) dispersant,
Further contain the adaptations enhancers such as silane coupling agent, coating enhancer, development modifying agent, purple as needed Other gradation compositions such as ultraviolet absorbers, antioxidant, surfactant, pigment derivative, each gradation composition usually with dissolving or The state being scattered in solvent uses.
In the photosensitive coloring composition of the 1st mode of the present invention, (a) colorant contains organic pigment and carbon black.In addition, In the photosensitive coloring composition of the 2nd mode of the present invention, (a) colorant contains in red pigment and orange pigment extremely Lack one kind and is selected from least one of blue pigment and violet pigment.In addition, the photonasty of the 3rd mode of the present invention Color composition is used to form coloring spacer.
Hereinafter, unless otherwise specified, " photosensitive coloring composition of the invention " refers to the photosensitive of above-mentioned 1st mode The photosensitive coloring composition of property coloured composition, the photosensitive coloring composition of the 2nd mode and the 3rd mode it is all photosensitive Property coloured composition.
＜ (a) colorants ＞
As long as (a) colorant used in the photosensitive coloring composition of the present invention can be such that photosensitive color combines Object and by the photosensitive coloring composition cure obtained from solidfied material colour color material, be not particularly limited, can lift Go out such as pigment, dyestuff, it is preferable to use pigment from the viewpoint of durability.
As pigment, organic pigment, inorganic pigment can be enumerated, from the voltage retention reduction for inhibiting liquid crystal and is inhibited The absorption of ultraviolet light and be easy to control from the viewpoint of shape, difference of height, it is preferable to use organic pigment.
(a) colorant used in the photosensitive coloring composition of the 1st mode of the present invention contains organic pigment and carbon black. So, it is easy to carry out the control of shape, difference of height, surface smoothness by using the few organic pigment of ultraviolet radiation absorption Also it is easy to become good, in addition, by also using carbon black other than using organic pigment, high light-proofness may be implemented.
The type 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 organic coloring pigments.In addition, from the viewpoint of light-proofness, it is excellent Choosing contains organic black pigments.
The chemical constitution of these pigment is not particularly limited, in addition to azo, phthalocyanines, quinoline azone class, benzimidazolone Class, isoindoline ketone, twoOther than the organic pigments such as piperazine class, indanthrone kinds, class, various inorganic pigments can also be utilized Deng.Hereinafter, the concrete example for the pigment for showing to be used in the present invention with pigment serial number." the C.I. paratoneres being exemplified below The terms such as 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, C.I. pigment red 4s 8 can preferably be enumerated:1、122、149、168、177、179、194、202、206、207、209、224、242、 254,272, more preferably enumerate C.I. pigment red 149s, 177,179,194,209,224,254.It should be noted that from dispersion Property, from the aspect of light-proofness, it is preferable to use C.I. paratoneres 177,254,272, using ultraviolet curing, as Red pigment considers, it is preferable to use the low red pigment of absorption of UV from the viewpoint, more preferably uses 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.Its In, it can preferably enumerate C.I. pigment oranges 38,43,64,71,72.It should be noted that from the aspect of dispersibility, light-proofness, It is preferable to use C.I. pigment oranges 43,64,72, as orange pigment, it is preferable to use ultraviolet using ultraviolet curing The low orange pigment of line absorption rate considers from the viewpoint, more preferably uses C.I. pigment oranges 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、15:6,16,60, More preferably enumerate C.I. pigment blue 15s:6.
It should be noted that, it is preferable to use C.I. pigment blue 15s from the aspect of dispersibility, light-proofness:6,16,60, In the case of using ultraviolet curing, as blue pigment, it is preferable to use the low blue pigment of absorption of UV, from the viewpoint Consider, more preferably uses 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, 29, more preferably enumerate C.I. pigment Violet 23s.
It should be noted that, it is preferable to use C.I. pigment Violet 23s, 29, are utilizing purple from the aspect of dispersibility, light-proofness In the case of outside line is cured, as violet pigment, it is preferable to use the low violet pigment of absorption of UV, considers from the viewpoint, More preferably use C.I. pigment violets 29.
As the organic coloring face that can be used other than red pigment, orange pigment, blue pigment, violet pigment Material, it can be cited for example that viridine green, yellow uitramarine etc..
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 enumerate C.I. pigment yellow 83s, 117,129, 138,139,150,154,155,180,185, more preferably enumerate C.I. pigment yellow 83s, 138,139,150,180.
In these, from the viewpoint of the control of light-proofness and shape and difference of height, preferably comprise in following pigment At least one more than.
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 is preferably (1) below, orange Preferably (2) below, preferably (3) below, violet pigment is preferably (4) below for blue pigment for pigment.
(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:6, at least one of 60
(4) C.I. pigment Violet 23s, at least one of 29 are selected from
It should be noted that in the photosensitive coloring composition of the 1st mode, when for a variety of organic pigments are applied in combination A combination thereof is not particularly limited, from visible light region especially long wavelength region light-proofness from the viewpoint of, it is preferable to use Blue pigment and/or violet pigment.In particular, the absorption spectrum of carbon black is due under from short wavelength to long wavelength side its absorbance It drops and the dulling luminosity ratio organic pigment of ultraviolet region increases, therefore from the viewpoint of realizing light-proofness and plate-making property simultaneously, It is preferred that blue pigment and/or violet pigment are applied in combination with carbon black, more preferably by blue pigment and violet pigment and carbon black group It closes and uses.
On the other hand, it using a small amount of carbon black, from the viewpoint of light-proofness, preferably comprises selected from red face Material and at least one of orange pigment and it is selected from least one of blue pigment and violet pigment, as its specific group The example of conjunction, can enumerate the combination of red pigment and blue pigment, the combination of blue pigment and orange pigment, blue pigment and The combination etc. of orange pigment and violet pigment.
Furthermore, it is possible to further use black color material other than these organic coloring pigments.It, can be with as black color material Enumerate the inorganic black pigments such as carbon black, organic black pigments.
On the other hand, organic coloring pigments can also be replaced using organic black pigments.
The photosensitive coloring composition of 1st mode contains the carbon black as black color material.So, by having in use Carbon black is also used other than machine pigment, and high light-proofness may be implemented.In the case of using carbon black, due to being especially in the presence of smooth surface Property the tendency that is deteriorated, therefore, by using the present invention, the tendency that above-mentioned surface smoothness is deteriorated can be improved by existing.As charcoal Black example can enumerate following such carbon black.
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 corporations：Printex (registered trademark, 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、PrintexG、SpecialBlack550、SpecialBlack350、SpecialBlack250、SpecialBlack100、 SpecialBlack6、SpecialBlack5、SpecialBlack4、Color Black FW1、Color Black FW2、 Color Black FW2V、Color Black FW18、Color Black FW18、Color Black FW200、Color Black S160、Color Black S170
Cabot corporations：Monarch (registered trademark, same as below) 120, Monarch280, Monarch460, Monarch800、Monarch880、Monarch900、Monarch1000、Monarch1100、Monarch1300、 Monarch1400, Monarch4630, REGAL (registered trademark, same as below) 99, REGAL99R, REGAL415, REGAL415R、REGAL250、REGAL250R、REGAL330、REGAL400R、REGAL55R0、REGAL660R、BLACK PEARLS480, PEARLS130, VULCAN (registered trademark) XC72R, ELFTEX (registered trademark) -8
Columbian Carbon corporations：RAVEN (registered trademark, same as below) 11, RAVEN14, RAVEN15, RAVEN16、RAVEN22RAVEN30、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 cladding.Use the carbon black obtained from resin cladding When, have the effect of improving adaptation to glass substrate, volumetric resistivity value.As using resin cladding obtained from carbon black, It can it is preferable to use the carbon blacks etc. described in such as Japanese Unexamined Patent Publication 09-71733 bulletins.From volume resistance, dielectric constant side Face considers, it is preferable to use resin coats carbon black.
As the carbon black for the cladding processing carried out using resin, the total content of preferably Na and Ca are 100ppm or less. Carbon black usually contains the ash content of a few percent, and the composition of the ash content is whole from feedstock oil when manufacture, fuel oil (or gas), reaction The mixed Na and Ca, K, Mg, Al, Fe etc. such as sealing and the stove material of granulation water and reacting furnace.Wherein, Na and Ca are usual Contain hundreds of ppm or more respectively, by reducing Na and Ca, can inhibit being impregnated with to transparent electrode (ITO) and other electrodes, exist It can prevent the tendency of electric short circuit.
As the method for the content for reducing the ash content that these contain Na, Ca, the content pole of stringent selection Na, Ca may be used Few substance as manufacture carbon black when feedstock oil, fuel oil (or gas) and reaction terminating water and strongly reduce for adjust knot The method of the additive amount of the alkaloid substance of structure.As other methods, can enumerate with water, hydrochloric acid etc. to the carbon black made from stove into Row washs and dissolves 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, At this point, carbon black is transferred to solvent side, 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 although the total amount of Na and Ca are reduced to 100ppm hereinafter, also having only through individually stringent choosing It has selected the carbon black manufacturing process of raw material or has individually been dissolved in the case where mode that water or acid dissolve can be realized as, but is logical Crossing two ways being applied in combination is easier to make the total amount of Na and Ca for 100ppm or less.
In addition, resin coats the preferred pH6 of carbon black so-called acidic blacks below.Due to dispersion diameter (agglomerate in water Size, agglomerate size) become smaller, or even the cladding under fine unit can be carried out, therefore it is preferred that.More preferable average grain diameter 40nm or less, dibatyl phithalate (DBP) uptake 140ml/100g carbon blacks below.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 find out etc. Circular diameter is imitated, the particle picture parsing is shot with tens thousand of times using electron microscope observation, and what is shot is several The photo in the visual field measures the particle of 2000~3000 or so these photos by image processing apparatus.
The method of the carbon black of spare resin cladding processed is not particularly limited, such as the use level of carbon black and resin is suitable After adjustment, following method can be used：
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, and above-mentioned resin solution and above-mentioned suspension are mixed, and after so that carbon black is separated from water, removes Water simultaneously carries out heating mixing, obtains composition, is sheet by obtained composition molding, is made it dry after crushing；
2. the resin solution prepared as described above and suspension are mixed, it, will after carbon black and resin spheroidizing Obtained shot-like particle separation, heating, removes the solvent and water of remaining；
3. making the carboxylic acids such as maleic acid, fumaric acid in the solvent of above-mentioned example, adding carbon black and being 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 constituting resin to be covered is carried out high-speed stirred with water and is prepared Suspension is cooled down after polymerization, and 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 (carbon black is made to be grafted), then cooled down and crushed；Etc..
The type for carrying out the resin of cladding processing is also not particularly limited, usually synthetic resin, from dispersibility and dispersion From the aspect of stability, preferably further there is the resin of benzene nucleus in the structure, this is because it is 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, polyaminobismaleimide, polyether sulfone polyphenylsulfone, 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 making it be More than above-mentioned lower limiting value, there is the tendency that can form the carbon black fully coated.On the other hand, by making packet of the resin to carbon black The amount of covering is for above-mentioned upper limit value hereinafter, in the presence of the tendency that can prevent the adhesion of resin to each other from making favorable dispersibility.
Coloring interval can be made in the carbon black for carrying out cladding processing using resin in this wise and being formed according to usual way The light screening material of object uses, and can be made by usual way using the coloring spacer as the colour filter of inscape.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 spacer of surface reflectivity To.In addition, by being coated to carbon blacksurface with resin, thus it is speculated that also have the function of Ca, Na being sealing into carbon black.
As the black color material other than carbon black, the suction of ultraviolet light is reduced and inhibits from the voltage retention of liquid crystal is inhibited It receives and is easy to control from the viewpoint of shape, difference of height, it is preferable to use organic black pigments, are especially examined from the viewpoint of light-proofness Consider, it is preferable to use selected from the following general formula (1) compound represented, the geometric isomer of the compound, the compound salt and should At least one of salt of geometric isomer of compound organic black pigments are (hereinafter, sometimes referred to simply as " above-mentioned general formula (1) institute The organic black pigments shown ").
[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 R20It is independently of one another hydrogen atom, halogen atom, R to each other21、COOH、 COOR21、COO-、CONH2、CONHR21、CONR21R22、CN、OH、OR21、COCR21、OCONH2、OCONHR21、OCONR21R22、 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 R20At least one of group Direct Bonding or pass through oxygen atom, sulphur atom, NH or NR between closing optionally mutually21Bridging and be mutually bonded；
R21And R22The independently of one another alkyl of carbon atom number 1~12, the naphthenic base of carbon atom number 3~12, carbon atom number The alkynyl of 2~12 alkenyl, the cycloalkenyl group of carbon atom number 3~12 or carbon atom number 2~12.
There is the geometric isomer of general formula (1) compound represented nuclear structure below (wherein, to be omitted in structural formula Substituent group), trans- trans isomer may be most stable of.
[chemical formula 4]
In the case that the compound that general formula (1) indicates is anionic property, preferably utilize 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 its charge Salt.In addition, in the case that the geometric isomer for the compound that general formula (1) indicates is anionic property, preferably same salt.
In the substituent group of general formula (1) and their definition, consider from the tendency for improving screening rate, it is preferably below Substituent group.This is because, it is believed that substituent group below is 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 atom, 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 R20At least one of combination it is identical, More preferable R11With R16Identical, R12With R17Identical, R13With R18Identical, R14With R19Identical and R15With R20It is identical.
The alkyl of carbon atom number 1~12 is, for example, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl Base, tertiary butyl, 2- methyl butyls, n-pentyl, 2- amyls, 3- amyls, 2,2- dimethyl propyls, n-hexyl, heptyl, n-octyl, 1,1,3,3- tetramethyl butyls, 2- ethylhexyls, nonyl, decyl, undecyl or dodecyl.
The naphthenic base of carbon atom 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 atom number 2~12 is, for example, vinyl, 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 atom 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- norbornene -1- Base, 2,5- norbornadiene -1- bases, 7,7- dimethyl -2,4- norcaranes diene -3- bases or camphyl.
The alkynyl of carbon atom number 2~12 is, 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 atom or iodine atom.
Organic black pigments shown in above-mentioned general formula (1) are preferably the following general formula (2) compound represented.
[chemical formula 5]
As the concrete example of such organic black pigments, trade name Irgaphor (registered trademark) can be enumerated The organic black pigments of Black S 0100CF (BASF AG's manufacture).
The organic black pigments are preferably dispersed in dispersant, solvent by aftermentioned method and are used.In addition, if dividing There are the sulfonic acids of above-mentioned general formula (2) when scattered, then dispersibility, keeping quality improve sometimes.
As the black color material other than organic black pigments shown in above-mentioned general formula (1), can enumerate acetylene black, lampblack, Bone black, graphite, iron oxide black, nigrosine, match it is peaceful it is black, titanium is black, black etc..
In addition, other than above-mentioned pigment, dyestuff can also be used.It, can as the dyestuff that color material can be used as to use To enumerate azo dyes, anthraquinone dyes, phthalocyanines dye, quinone imides dyestuff, quinolines dyestuff, nitro class dyestuff, carbonyl Base class dyestuff, methchlorenes dyes etc..
As azo dyes, it can be cited for example that：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 26, 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, it can be cited for example that：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, it can be cited for example that 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, it can be cited for example that C.I. solvent yellow 33s, C.I. Quinoline yellow, C.I. dispersion yellow 64s etc., as nitro class dyestuff, it can be cited for example that C.I. Indian yellows 1, C.I. acid oranges 3, C.I. Disperse Yellow 42 etc..
It is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μ that these pigment, which are preferably dispersed into average grain diameter, M or less and use.Here, the benchmark of average grain diameter is the number of pigment particles.
It should be noted that the average grain diameter of pigment is to be measured by dynamic light scattering (DLS) and found out by pigment particle size Value.Particle size determination is (to be usually diluted to the photosensitive coloring composition after fully diluting and pigment concentration 0.005 is made ~0.2 mass % or so, but according to determining instrument and when there is the concentration recommended, by the concentration) it carries out, and surveyed at 25 DEG C It is fixed.
(a) colorant used in the photosensitive coloring composition of 2nd mode contains selected from red pigment and orange pigment At least one of and be selected from least one of blue pigment and violet pigment.So, the 2nd mode of the invention Photosensitive coloring composition by the combination containing specific organic coloring pigments, high light-proofness may be implemented.
As red pigment, orange pigment, blue pigment and violet pigment, can be remembered with the 1st mode suitable for use The same pigment carried.The combination of color is not particularly limited, but from the viewpoint of light-proofness, it can be cited for example that red The combination of color pigment and blue pigment, the combination of orange pigment and blue pigment, orange pigment and blue pigment and violet pigment Combination etc..
In addition, the photosensitive coloring composition of the 2nd mode can also contain red pigment, orange pigment, blue pigment and Pigment other than violet pigment preferably comprises black color material from the viewpoint of light-proofness.It, can be suitable as black color material Using with same black color material recorded in the 1st mode.
The photosensitive coloring composition of 3rd mode is coloring spacer formation photosensitive coloring composition, (a) colorant It is not particularly limited.It can be cited for example that comprising at least arbitrary in foregoing organic coloring pigments, black color material, dyestuff A kind of colorant.In addition, as (a) colorant, can use with it is recorded same in the 1st mode and the 2nd mode Toner, in addition, from the viewpoint of light-proofness, can also use comprising organic black pigments shown in above-mentioned general formula (1) Toner.
＜ (b) alkali soluble resins ＞
(b) alkali soluble resin used in the present invention is the resin comprising carboxyl or hydroxyl, especially includes (b-I) ring Oxygen (methyl) acrylate and (b-II) (methyl) acrylic copolymeric resins, (b-II) (methyl) acrylic compounds are total Poly resin contains side chain the repetitive unit α with ethylenic unsaturated bond and the repetitive unit β from unsaturated carboxylic acid, and (b- II) content ratio of the repetitive unit α in (methyl) acrylic copolymeric resins is 10 moles of % or more, preferably 12 moles of % More than.
(b-I) epoxy (methyl) acrylate is used alone as in the case of (b) alkali soluble resin, generally comes It says, the main chain of the resin has the structure of aromatic series etc., and heat flow is easy tod produce due to the structure, generates fold and makes surface Flatness is easy to be deteriorated.Since fold light-proofness also declines, easy tos produce and be unable to get desired light-proofness and light leakage The problems such as.
In addition, for colouring spacer, used mostly with the film thickness higher than black matrix".In addition, in order to be arranged Desired difference of height, it is desirable to the coating characteristic of thermal deformation is not susceptible to photosensitive coloring composition, in order to ensure compression Pigment concentration is preferably set as lower compared with black matrix" by characteristic or reliability.As a result, in colouring spacer, in film table Nearby and near film bottom the difference of crosslink density further increases in face, easy tos produce fold.In addition, due to such thermal deformation, In the presence of the tendency for being unable to ensure enough difference of height formatives.
In order to have both such various performances, it is believed that by being applied in combination in main chain without aromatic rings etc. and being heat-shrinked few Acrylic resin, particularly glass transition temperature are high, are not susceptible to the weight of heat flow contained from unsaturated carboxylic acid Specific (methyl) acrylic copolymeric resins of multiple unit can reduce heat flow and inhibit the generation of fold, so as to Keep surface smoothness good.But in the case where low (methyl) acrylic copolymeric resins of sensitivity are applied in combination, exist The tendency of less reliable, it is therefore contemplated that by importing the olefinic of specified rate in (methyl) acrylic copolymeric resins not Saturated bond can substantially ensure sensitivity and keep reliability good, as a result, may be implemented to have both surface smoothness and reliable Property.
＜ (b-I) epoxy (methyl) acrylate ＞
(b-I) epoxy (methyl) acrylate is epoxide and α, β-unsaturated monocarboxylic and/or ester moiety The reactant of α with carboxyl, β-unsaturated monocarboxylic ester and the hydroxyl that is generated by the reaction further with polyacid And/or its acid anhydrides etc. have 2 or more can be reacted with the compound of the substituent group of hydroxyl reaction obtained from resin.
(b-I) epoxy (methyl) acrylate used in the present invention, from the viewpoint of reliability, especially It is preferable to use following epoxies (methyl) acrylates (b1) and/or epoxy (methyl) acrylate (b2) (hereinafter, having When be known as " epoxy (methyl) acrylate containing carboxyl ").
＜ epoxies (methyl) acrylate (b1) ＞
Make α, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester and epoxy resin addition, then makes it With alkali soluble resin obtained from polyacid and/or its anhydride reaction.
＜ epoxies (methyl) acrylate (b2) ＞
Make α, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester and epoxy resin addition, then makes it With alkali soluble resin obtained from polyalcohol and polyacid and/or its anhydride reaction.
Here, so-called epoxy resin refers to, also including the raw material compound before heat cure forms resin Substance can be used suitable for selection from well known epoxy resin as the epoxy resin.In addition, epoxy resin can make Compound obtained from being reacted with epichlorohydrin with phenolic compounds.As phenolic compounds, there is phenol hydroxyl preferably more than divalent or divalent It can also be polymer that the compound of base, which can be monomer,.
As the type of raw material epoxy resin, it is preferable to use cresol novolak type epoxy resin, phenol novolac are clear Paint shaped epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, triphenol methylmethane type epoxy resin, biphenyl phenolic aldehyde are clear Paint shaped epoxy resin, naphthol novolak type epoxy resin, as the sudden reaction object of bicyclopentadiene and phenol or cresols into one Epoxy resin, the epoxy resin containing adamantyl, the fluorenes type epoxy resin of reaction product etc. reacted with epichlorohydrin is walked, it can With suitable for using in this wise in epoxy resin of the main chain with aromatic rings.
In addition, as the concrete example of epoxy resin, it is preferable to use such as bisphenol A type epoxy resin (such as Mitsubishis Learn " Epikote (registered trademark, same as below) 828 ", " Epikote 1001 ", " Epikote of Co., Ltd.'s manufacture 1002 ", " Epikote 1004 " etc.), reacted with epichlorohydrin as the alcoholic extract hydroxyl group of bisphenol A type epoxy resin obtained from epoxidation Object (such as " NER-1302 " (76 DEG C of epoxide equivalent 323, softening point) of Nippon Kayaku K. K's manufacture), bisphenol F type resin It is (such as " Epikote 807 ", " EP-4001 ", " EP-4002 ", " EP-4004 etc. " of Mitsubishi chemical Co., Ltd's manufacture), logical Cross bisphenol f type epoxy resin alcoholic extract hydroxyl group reacted with epichlorohydrin obtained from epoxy resin (such as Nippon Kayaku K. K's system " NER-7406 " (66 DEG C of epoxide equivalent 350, the softening point) made), bisphenol-s epoxy resin, biphenyl glycidol ether (such as three " YX-4000 " of water chestnut Chemical Co., Ltd. manufacture), phenol novolak type epoxy resin (such as Nippon Kayaku K. K's system " EP-152 " of the manufacture of " EPPN-201 " that makes, Mitsubishi chemical Co., Ltd, " EP-154 ", the manufacture of Dow chemical companies " DEN-438 "), (o-, m-, p-) cresol novolak type epoxy resin (such as Nippon Kayaku K. K manufacture " EOCN (registered trademark, same as below) -102S ", " EOCN-1020 ", " EOCN-104S "), isocyanuric acid three-glycidyl ester (such as " TEPIC (registered trademark) " of Misao Kusano's manufacture), (such as the Japanese chemical drug strain of triphenol methylmethane type epoxy resin Formula commercial firm manufacture " EPPN (registered trademark, same as below) -501 ", " EPN-502 ", " EPPN-503 "), ester ring type asphalt mixtures modified by epoxy resin Fat (" Celloxide 2021P ", " Celloxide (registered trademark, the following phase of Daisel chemical industry Co., Ltd's manufacture EHPE " together)), the phenolic resin that generates bicyclopentadiene and reacting for phenol carry out it is glycidated obtained from epoxy Resin (such as " NC-7300 " of " EXA-7200 " of the manufacture of DIC companies, Nippon Kayaku K. K's manufacture), the following general formula (B1)~(B4) epoxy resin etc. indicated.Specifically, the day as epoxy resin shown in the following general formula (B1) can be enumerated " XD-1000 ", the Japanese chemical drug strain formula meeting shown in the following general formula (B2) as epoxy resin of this chemical drug Co., Ltd. manufacture " NC-3000 " of society's manufacture, shown in the following general formula (B4) as the manufacture of Nippon Steel ＆ Sumitomo Metal Corporation of epoxy resin " ESF-300 " etc..
[chemical formula 6]
In above-mentioned general formula (B1), a indicates average value, indicates 0~10 number, R111Indicate hydrogen atom, halogen atom, carbon atom Arbitrary group in the alkyl of number 1~8, the naphthenic base of carbon atom number 3~10, phenyl, naphthalene or xenyl.It needs to illustrate It is multiple R present in 1 molecule111It can be the same or different.
[chemical formula 7]
In above-mentioned general formula (B2), b indicates average value, indicates 0~10 number, R121Indicate hydrogen atom, halogen atom, carbon atom Arbitrary group in the alkyl of number 1~8, the naphthenic base of carbon atom number 3~10, phenyl, naphthalene or xenyl.It needs to illustrate It is multiple R present in 1 molecule121It can be the same or different.
[chemical formula 8]
In above-mentioned general formula (B3), X indicates to link group shown in the following general formula (B3-1) or (B3-2), wherein molecule knot Include 1 or more adamantane structure in structure, c indicates 2 or 3 integer.
[chemical formula 9]
[chemical formula 10]
In above-mentioned general formula (B3-1) and (B3-2), R131~R134And R135~R137Separately indicate that optionally there is substitution Adamantyl, hydrogen atom, the optionally alkyl of the carbon atom number 1~12 with substituent group or the optional benzene with substituent group of base Base, * indicate bonding position.
[chemical formula 11]
In above-mentioned general formula (B4), p and q separately indicate 0~4 integer, R141And R142Separately indicate carbon The alkyl or halogen atom of atomicity 1~4, R143And R144Separately indicate the alkylidene of carbon atom number 1~4, x and y difference Independently indicate 0 or more integer.
In these, from the viewpoint of reliability, it is preferable to use represented by any of general formula (B1)~(B4) Epoxy resin.
As α, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester can enumerate (methyl) propylene The positions α halogenated alkyl, alkoxy, halogen atom, the nitre of acid, butenoic acid, o-, m- or p- vinyl benzoic acid, (methyl) acrylic acid The monocarboxylic acids such as base, cyano substituent, 2- (methyl) acrylyl oxy-ethyls succinic 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 succinic acid, 2- (methyl) acryloxypropyls adipic acid, 2- (methyl) third Four hydrogen phthalate of alkene monomethacryloxypropyl, 2- (methyl) acryloxypropyls phthalic acid, 2- (methyl) acryloxypropyls Malaysia Acid, 2- (methyl) acryloyl-oxy butyl succinic 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 lactones such as addition 6-caprolactone, beta-propiolactone, gamma-butyrolacton, δ-valerolactone or Addition succinic 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).
In these, from the aspect of sensitivity, particularly preferably (methyl) acrylic acid.
As the addition α on epoxy resin, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester Method can use well known method.For example, can in the presence of esterification catalyst, at 50~150 DEG C at a temperature of make α, β- Unsaturated monocarboxylic or α with carboxyl, β-unsaturated monocarboxylic ester are reacted with epoxy resin.It is urged as esterification used herein Agent can use tertiary amines, tetramethyl ammonium chloride, the tetrems such as triethylamine, trimethylamine, benzyldimethylamine, 2,4, benzyldiethylamine Quaternary ammonium salts such as ammonium chloride, dodecyl trimethyl ammonium chloride 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.
The usage amount of α, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester are as follows：Relative to epoxy 1 equivalent of epoxy group of resin, the preferably range of 0.5~1.2 equivalent, the more preferably range of 0.7~1.1 equivalent.By setting More than above-mentioned lower limiting value, the import volume of unsaturated group can be made abundant, existed in next and polyacid and/or its acid The reaction of acid anhydride also becomes adequately to be inclined to.In addition, by being set as above-mentioned upper limit value hereinafter, in the presence of α, β-unsaturation can be inhibited single Carboxylic acid or α with carboxyl, the tendency that β-unsaturated monocarboxylic ester left behind as unreacted reactant.
As polyacid and/or its acid anhydrides, can enumerate selected from maleic acid, succinic 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 more than one kind or two kinds of acid anhydrides of these acid etc..
It is preferred that maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, The acid anhydrides of benzene tetracarboxylic acid, trimellitic acid, biphenyltetracarboxyacid acid or these acid.Particularly preferred tetrahydrophthalic acid, biphenyltetracarboxyacid acid, Tetrabydrophthalic anhydride or biphenyltetracarboxylic dianhydride.
About the addition reaction of polyacid and/or its acid anhydrides, well known method can be used, can with α, β-unsaturation Monocarboxylic acid or α with carboxyl are continued under the conditions of β-unsaturated monocarboxylic ester is same to the addition reaction of epoxy resin It reacts and obtains object.The addition amount of polyacid and/or its acid anhydrides ingredient preferably makes the carboxylic epoxy (methyl) of generation The acid value of acrylate is degree, further preferably 20~140mgKOH/ as the range of 10~150mg KOH/g The addition amount of degree as the range of g.By make polyacid and/or its acid anhydrides ingredient addition amount be above-mentioned lower limiting value with On, there are alkali-developables to become good tendency, in addition, by making the addition amount of polyacid and/or its acid anhydrides ingredient be above-mentioned Upper limit value is hereinafter, there are curing performances to become good tendency.
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：To epoxy resin and α, β-unsaturation is single Carboxylic acid or α with carboxyl, in the reactant of β-unsaturated monocarboxylic ester after mixing polyacid and/or its acid anhydrides or To epoxy resin and α, β-unsaturated monocarboxylic or the α with carboxyl are mixed in the reactant of β-unsaturated monocarboxylic ester polynary Acid and/or its acid anhydrides and polyfunctional alcohol heat later.In this case, polyacid and/or its acid anhydrides and polyfunctional alcohol's is mixed Conjunction sequence is not particularly limited.By heating, polyacid and/or its acid anhydrides and it is present in epoxy resin and α, β-unsaturation list carboxylic Arbitrary hydroxyl in acid or the α with carboxyl, β-reactant of unsaturated monocarboxylic ester and the mixture of polyfunctional alcohol adds At reaction.
The chemical constitution of repetitive unit contained in epoxy (methyl) acrylate containing carboxyl does not limit especially It is fixed, it can be cited for example that chemical constitution as shown below.
[chemical formula 12]
[chemical formula 13]
[chemical formula 14]
[chemical formula 15]
It should be noted that in above-mentioned formula (C-1)~(C-15), X indicates structure below.
[chemical formula 16]
(in above structure X, R11Indicate hydrogen atom or methyl, Y indicates the residue of hydrogen atom or polyacid, in addition, polyacid It can also be cross-linked with each other.)
It can also be enumerated other than front is described as epoxy (methyl) acrylate containing carboxyl Recorded epoxy (methyl) acrylate containing carboxyl in KR published patent 10-2013-0022955 bulletins Deng.
The weight of the polystyrene conversion measured by gel permeation chromatography (GPC) of epoxy (methyl) acrylate Average molecular weight (Mw) is usually 1000 or more, preferably 2000 or more, more preferably 3000 or more, further preferably 4000 with It is upper, particularly preferably 5000 or more, and usually 10000 or less, preferably 8000 or less, more preferably 7000 or less.Pass through Be set as above-mentioned lower limiting value or more, there are reliabilities to become good tendency, in addition, by be set as above-mentioned upper limit value hereinafter, in the presence of Dissolubility becomes good tendency.
The acid value of epoxy (methyl) acrylate is not particularly limited, preferably 10mgKOH/g or more, more preferably For 20mgKOH/g or more, further preferably 40mgKOH/g or more, be still more preferably 60mgKOH/g or more, Particularly preferably 80mgKOH/g or more, and preferably 200mgKOH/g or less, more preferably 150mgKOH/g with Under, further preferably 120mgKOH/g or less, particularly preferably 100mgKOH/g or less.By being set as above-mentioned lower limiting value More than, exist and the deliquescent tendency of appropriate development can be obtained, in addition, by being set as above-mentioned upper limit value hereinafter, in the presence of will not mistake Degree develops so as to the tendency for inhibiting film to dissolve.
The chemical constitution of epoxy (methyl) acrylate is not particularly limited, from the viewpoint of reliability, preferably Containing epoxy (methyl) acrylate with repeat unit structure shown in the following general formula (b-I-I) (hereinafter, sometimes simple Referred to as " (b-I-I) epoxy (methyl) acrylate ") and/or with part-structure shown in the following general formula (b-I-II) Epoxy (methyl) acrylate (hereinafter, sometimes referred to simply as " (b-I-II) epoxy (methyl) acrylate ").
[chemical formula 17]
In formula (b-I-I), R11Indicate hydrogen atom or methyl, R12Indicate the optionally divalent alkyl with substituent group.Formula (b-I- I the phenyl ring in) can further be replaced by arbitrary substituent group, and * indicates bonding position.
[chemical formula 18]
In formula (b-I-II), R13Each independently represent hydrogen atom or methyl, R14Indicate have cyclic hydrocarbon group as side chain Divalent alkyl, R15And R16The aliphatic group of the optionally divalent with substituent group is each independently represented, m and n are each independently Indicate that 0~2 integer, * indicate bonding position.
＜ (b-I-I) epoxy (methyl) acrylate ＞
First, to epoxy (methyl) acrylate with repeat unit structure shown in above-mentioned general formula (b-I-I) It is described in detail.
[chemical formula 19]
In formula (b-I-I), R11Indicate hydrogen atom or methyl, R12Indicate the optionally divalent alkyl with substituent group.Formula (b-I- I the phenyl ring in) can further be replaced by arbitrary substituent group, and * indicates bonding position.
(R12)
In above-mentioned formula (b-I-I), R12Indicate the optionally divalent alkyl with substituent group.
As divalent alkyl, the aliphatic group of divalent, the aromatic group of divalent, 1 or more divalent fat can be enumerated The group that the aromatic group of the divalent of race's group and 1 or more links.
As the aliphatic group of divalent, straight-chain, branched, cricoid divalent aliphatic group can be enumerated.These are worked as In, from the viewpoint of development dissolubility, the preferred divalent aliphatic group of straight-chain, on the other hand, from developer solution is reduced to exposing From the viewpoint of being impregnated with of light portion, preferably cricoid divalent aliphatic group.Its carbon atom number is usually 1 or more, preferably 3 with Above, more preferably 6 or more, additionally, it is preferred that for 20 or less, more preferably 15 or less, further preferably 10 or less.By being set as More than above-mentioned lower limiting value, exist and be easy to get strong film, be not susceptible to rough surface, to become good to the adaptation of substrate Good tendency, in addition, by being set as above-mentioned upper limit value hereinafter, film when there is the deterioration for being easy to inhibit sensitivity, development is reduced, To the tendency for making image resolution ratio improve.
The concrete example of straight-chain aliphatic group as divalent can enumerate methylene, ethylidene, n-propylene, positive Asia Butyl, positive pentylidene, positive hexylidene, positive heptamethylene etc..In these, from the viewpoint of the outspoken nature of skeleton, preferred methylene Base.
As the branched aliphatic group of divalent, in the straight-chain aliphatic group that the divalent described in front can be enumerated Structure with methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl etc. as side chain.
The quantity of the ring of cyclic aliphatic group with divalent is not particularly limited, usually 1 or more, preferably 2 More than, and usually 12 or less, preferably 10 or less.By being set as above-mentioned lower limiting value or more, exist to be formed it is strong Film, substrate adaptation become good tendency, in addition, being easy to inhibit sensitivity hereinafter, existing by being set as above-mentioned upper limit value Film when deteriorating, developing is reduced, to the tendency for making image resolution ratio improve.Cyclic aliphatic group as divalent it is specific Example, can enumerate from cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isoborneol alkane ring, Buddha's warrior attendant Group obtained from 2 hydrogen atoms is eliminated on the rings such as alkane ring, cyclododecane ring, dicyclopentadiene.In these, from skeleton From the viewpoint of outspoken nature, group obtained from 2 hydrogen atoms is preferably eliminated from dicyclopentadiene ring, adamantane ring.
The substituent group that aliphatic group as divalent optionally has, can enumerate hydroxyl, methyl, ethyl, n-propyl, The alkyl of the carbon atom numbers such as isopropyl, normal-butyl, sec-butyl, tertiary butyl, amyl, isopentyl 1~5；The carbon such as methoxyl group, ethyoxyl The alkoxy of atomicity 1~5；Hydroxyl；Nitro；Cyano；Carboxyl etc..In these, from the viewpoint of synthesis easiness, preferably It is unsubstituted.
In addition, the aromatic group as divalent, can enumerate aromatic cyclic hydrocarbon group group and the heteroaromatic of divalent of divalent Group.Its carbon atom number is usually 4 or more, is preferably 5 or more, is more preferably 6 or more, and preferably 20 or less, more preferably It is 15 or less, further preferably 10 or less.By being set as above-mentioned lower limiting value or more, exists and be easy to get strong film, be not easy Rough surface occurs, to become good tendency to the adaptation of substrate, in addition, by being set as above-mentioned upper limit value hereinafter, depositing It is being easy that film when deterioration, the development of sensitivity is inhibited to reduce, to the tendency for making image resolution ratio improve.
As the aromatic series hydrocarbon ring in the aromatic cyclic hydrocarbon group group of divalent, it can be monocycle can also be condensed ring, can enumerate Such as phenyl ring with 1 free valency, naphthalene nucleus, anthracene nucleus, phenanthrene ring, ring, aphthacene ring, pyrene ring, BaP ring,Ring, benzo The groups such as phenanthrene ring, acenaphthene ring, fluoranthene ring, fluorenes ring.Can be monocycle in addition, as the heteroaromatic in aromatic heterocyclic group Can also be condensed ring, it can be cited for example that furan nucleus, benzofuran ring, thiphene ring, benzothiophene ring with 1 free valency, Pyrrole ring, pyrazole ring, imidazole ring,Diazole ring, indole ring, carbazole ring, pyrrolo- imidazole ring, pyrrolo-pyrazole ring, pyrrolo- Pyrrole ring, Thienopyrroles ring, thienothiophene ring, furans and pyrrole ring, furans and furan nucleus, thienofuran ring, benzo It is differentIt is azoles ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, different Quinoline ring, cinnolines (cinnoline) ring, quinoxaline ring, phenanthridines ring, benzimidazole ring,Phenazine ring, quinazoline ring, quinazolinone Ring,The groups such as ring.In these, from the viewpoint of patterned property, preferably phenyl ring or naphthalene nucleus, more preferable phenyl ring.
The substituent group that aromatic group as divalent optionally has, can enumerate hydroxyl, methyl, methoxyl group, ethyl, Ethyoxyl, propyl, propoxyl group etc..It is preferably unsubstituted from the viewpoint of development dissolubility, resistance to hygroscopicity in these.
In addition, the base that the aromatic group of the divalent as 1 or more divalent aliphatic group and 1 or more links Group can enumerate the aromatic group of the aliphatic group and 1 or more foregoing divalent of 1 or more foregoing divalent The group to link.
The quantity of the aliphatic group of divalent is not particularly limited, usually 1 or more, preferably 2 or more, and leads to Often it is 10 or less, preferably 5 or less, more preferably 3 or less.By being set as above-mentioned lower limiting value or more, there are easy To strong film, it is not likely to produce rough surface, to become good tendency to the adaptation of substrate, in addition, on by being set as Upper limit value is stated hereinafter, in the presence of being easy that film when deterioration, the development of sensitivity is inhibited to reduce, to make inclining for image resolution ratio raising To.
The quantity of the aromatic group of divalent is not particularly limited, usually 1 or more, preferably 2 or more, and leads to Often it is 10 or less, preferably 5 or less, more preferably 3 or less.By being set as above-mentioned lower limiting value or more, there are easy To strong film, it is not likely to produce rough surface, to become good tendency to the adaptation of substrate, in addition, on by being set as Upper limit value is stated hereinafter, in the presence of being easy that film when deterioration, the development of sensitivity is inhibited to reduce, to make inclining for image resolution ratio raising To.
The group that the aromatic group of divalent as 1 or more divalent aliphatic group and 1 or more links Concrete example can enumerate group etc. shown in following formula (b-I-I-A)~(b-I-I-F).In these, from the outspoken nature of skeleton From the viewpoint of the hydrophobization of film, preferred group shown in following formula (b-I-I-A).
[chemical formula 20]
As described above, the phenyl ring in formula (b-I-I) can further be replaced by arbitrary substituent group.As the substituent, It can be cited for example that hydroxyl, methyl, methoxyl group, ethyl, ethyoxyl, propyl, propoxyl group etc..The quantity of substituent group does not limit especially It is fixed, can be 1, or 2 or more.
It is preferably unsubstituted from the viewpoint of patterned property in these.
In addition, from the viewpoint of convieniently synthesized property, repeat unit structure is preferably following shown in above-mentioned formula (b-I-I) Repeat unit structure shown in formula (b-I-I-1).
[chemical formula 21]
In formula (b-I-I-1), R11And R12With the R in above-mentioned formula (b-I-I)11And R12Meaning is identical, RXIndicate hydrogen atom or Polyacid residue, * indicate bonding position.Phenyl ring in formula (b-I-I-1) can further be replaced by arbitrary substituent group.
So-called polyacid residue refers to the 1 valence group that 1 OH base is eliminated by polyacid or its acid anhydrides.As polyacid, It can enumerate selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, equal benzene Tetracarboxylic acid, trimellitic acid, benzophenone tetrabasic carboxylic acid, methylhexahydrophthaacid acid, endo-methylene group tetrahydrophthalic acid, hexahydro It is more than one kind or two kinds of carbic acid, methyl tetrahydrophthalic acid, bibenzene tetracarboxylic.
In these, from the viewpoint of patterned property, preferably maleic acid, succinic acid, itaconic acid, phthalic acid, Tetrahydrophthalic acid, hexahydrophthalic acid, Pyromellitic Acid, trimellitic acid, bibenzene tetracarboxylic, more preferably tetrahydrochysene neighbour benzene Dioctyl phthalate, bibenzene tetracarboxylic, tetrahydrophthalic acid, bibenzene tetracarboxylic.
(b-I-I) it is repeated shown in above-mentioned formula (b-I-I-1) contained in 1 molecule of epoxy (methyl) acrylate single Meta structure can be a kind of or two or more, such as can be mixed RXFor the structure and R of hydrogen atomXFor polyacid The structure of residue.
In addition, weight shown in above-mentioned formula (b-I-I) contained in 1 molecule of (b-I-I) epoxy (methyl) acrylate The quantity of multiple cellular construction is not particularly limited, preferably 1 or more, be more preferably 3 or more, and preferably 20 with Under, more preferably 15 or less.By being set as above-mentioned lower limiting value or more, exists and be easy to get strong film, be not likely to produce surface Coarse tendency, in addition, by being set as above-mentioned upper limit value hereinafter, film when there is the deterioration for being easy to inhibit sensitivity, development subtracts It is few, to the tendency for making image resolution ratio improve.
Pass through the polystyrene of (b-I-I) epoxy (methyl) acrylate that gel permeation chromatography (GPC) measures The weight average molecular weight (Mw) of conversion is not particularly limited, preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, still more preferably it is 3000 or more, particularly preferably 4000 or more, most preferably 5000 or more, and preferably It is 30000 or less, more preferably 20000 or less, further preferably 10000 or less, particularly preferably 8000 or less.By setting More than above-mentioned lower limiting value, existing can make the residual film ratio of photosensitive coloring composition become good tendency, in addition, by being set as Above-mentioned upper limit value is hereinafter, there are image resolution ratios to become good tendency.
(b-I-I) acid value of epoxy (methyl) acrylate is not particularly limited, preferably 10mgKOH/g or more, More preferably 20mgKOH/g or more, further preferably 40mgKOH/g or more, still more preferably be 50mgKOH/g or more, Particularly preferably 80mgKOH/g or more, and preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, into one Step is preferably 130mgKOH/g or less, particularly preferably 100mgKOH/g or less.By being set as above-mentioned lower limiting value or more, there are aobvious Shadow dissolubility improves, image resolution ratio becomes good tendency, in addition, by being set as above-mentioned upper limit value hereinafter, there are photonasty The residual film ratio of coloured composition becomes good tendency.
It is exemplified below the concrete example of (b-I-I) epoxy (methyl) acrylate.It should be noted that the * tables in example Show bonding position.
[chemical formula 22]
[chemical formula 23]
[chemical formula 24]
[chemical formula 25]
＜ (b-I-II) epoxy (methyl) acrylate ＞
Then, epoxy (methyl) acrylate with part-structure shown in above-mentioned general formula (b-I-II) is carried out Narration in detail.
[chemical formula 26]
In formula (b-I-II), R13Each independently represent hydrogen atom or methyl, R14Indicate have cyclic hydrocarbon group as side chain Divalent alkyl, R15And R16Each independently represent the optionally divalent aliphatic group with substituent group, m and n table each independently Show that 0~2 integer, * indicate bonding position.
(R14)
In above-mentioned general formula (b-I-II), R14Indicate that there is divalent alkyl of the cyclic hydrocarbon group as side chain.
As cyclic hydrocarbon group, aliphatic cyclic group or aromatic group can be enumerated.
The quantity of ring with aliphatic cyclic group is not particularly limited, usually 1 or more, preferably 2 or more, and Usually 10 or less, preferably 5 or less, more preferably 3 or less.By being set as above-mentioned lower limiting value or more, there are easy Strong film is obtained, shaggy tendency is not likely to produce, in addition, being easy to inhibit hereinafter, existing by being set as above-mentioned upper limit value The film when deterioration of sensitivity, development is reduced, to the tendency for making image resolution ratio improve.
In addition, the carbon atom number of aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and it is excellent It is selected as 40 or less, more preferably 30 or less, further preferably 20 or less, particularly preferably 15 or less.Under being set as above-mentioned More than limit value, exist and be easy to get strong film, be not likely to produce shaggy tendency, in addition, by being set as above-mentioned upper limit value Hereinafter, film when there is the deterioration for being easy to inhibit sensitivity, development is reduced, to the tendency for making image resolution ratio improve.
As the concrete example of the cycloaliphatic ring in aliphatic cyclic group, can enumerate cyclohexane ring, cycloheptane ring, cyclodecane ring, Cyclododecane ring, norbornane ring, isoborneol alkane ring, adamantane ring, cyclododecane ring etc..In these, from photosensitive color From the viewpoint of the residual film ratio and image resolution ratio of composition, preferred adamantane ring.
On the other hand, the quantity of ring possessed by aromatic group is not particularly limited, usually 1 or more, preferably 2 More than a, it is more preferably 3 or more, and usually 10 or less, preferably 5 or less, more preferably 4 or less.Pass through It is set as above-mentioned lower limiting value or more, exists and is easy to get strong film, is not likely to produce shaggy tendency, in addition, by being set as Above-mentioned upper limit value is hereinafter, film when there is the deterioration for being easy to inhibit sensitivity, development is reduced, to make image resolution ratio improve Tendency.
As aromatic group, the carbon atom number of aromatic cyclic hydrocarbon group, aromatic heterocycle, aromatic group can be enumerated Usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, particularly preferably 12 or more, and And preferably 40 or less, more preferably 30 or less, further preferably 20 or less, particularly preferably 15 or less.On being set as Lower limiting value or more is stated, exists and is easy to get strong film, is not likely to produce shaggy tendency, in addition, on by being set as above-mentioned Limit value is hereinafter, there are patterned properties to become good tendency.
As the concrete example of the aromatic rings in aromatic group, phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, ring, simultaneously can be enumerated Four phenyl ring, pyrene ring, BaP ring,Ring, benzo phenanthrene ring, acenaphthene ring, fluoranthene ring, fluorenes ring etc..In these, from patterned property Viewpoint consideration, preferably fluorenes ring.
In addition, with cyclic hydrocarbon group as in the divalent alkyl of side chain, divalent alkyl is not particularly limited, it can be cited for example that The aromatic rings of the divalent of the aliphatic group of divalent, the aromatic group of divalent, 1 or more divalent aliphatic group and 1 or more The group that group links.
As the aliphatic group of divalent, straight-chain, branched, cricoid divalent aliphatic group can be enumerated.These are worked as In, from the viewpoint of development dissolubility, the preferred divalent aliphatic group of straight-chain, on the other hand, from developer solution is reduced to exposing From the viewpoint of being impregnated with of light portion, preferably cricoid divalent aliphatic group.Its carbon atom number is usually 1 or more, preferably 3 with Above, more preferably 6 or more, additionally, it is preferred that for 25 or less, more preferably 20 or less, further preferably 15 or less.By being set as More than above-mentioned lower limiting value, exist and be easy to get strong film, be not susceptible to rough surface, to become good to the adaptation of substrate Good tendency, in addition, by being set as above-mentioned upper limit value hereinafter, film when there is the deterioration for being easy to inhibit sensitivity, development is reduced, To the tendency for making image resolution ratio improve.
The concrete example of straight-chain aliphatic group as divalent can enumerate methylene, ethylidene, n-propylene, positive Asia Butyl, positive pentylidene, positive hexylidene, positive heptamethylene etc..In these, from the viewpoint of the outspoken nature of skeleton, preferred methylene Base.
As the branched aliphatic group of divalent, in the straight-chain aliphatic group that the divalent described in front can be enumerated Structure with methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl etc. as side chain.
The quantity of the ring of cyclic aliphatic group with divalent is not particularly limited, usually 1 or more, preferably 2 More than, and usually 10 or less, preferably 5 or less, more preferably 3 or less.By being set as above-mentioned lower limiting value or more, In the presence of form strong film, substrate adaptation becomes good tendency, in addition, by be set as above-mentioned upper limit value hereinafter, exist hold Film when deterioration, the development of sensitivity is easily inhibited to reduce, to the tendency for making image resolution ratio improve.Cyclic annular fat as divalent The concrete example of fat race group, can enumerate from cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, Group obtained from 2 hydrogen atoms is eliminated on the rings such as isoborneol alkane ring, adamantane ring, cyclododecane ring.In these, from bone From the viewpoint of the outspoken nature of frame, group obtained from 2 hydrogen atoms is preferably eliminated from adamantane ring.
The substituent group that aliphatic group as divalent optionally has, can enumerate hydroxyl, methyl, ethyl, n-propyl, The alkyl of the carbon atom numbers such as isopropyl, normal-butyl, sec-butyl, tertiary butyl, amyl, isopentyl 1~5；The carbon such as methoxyl group, ethyoxyl The alkoxy of atomicity 1~5；Hydroxyl；Nitro；Cyano；Carboxyl etc..In these, from the viewpoint of synthesis easiness, preferably It is unsubstituted.
In addition, the aromatic group as divalent, can enumerate aromatic cyclic hydrocarbon group group and the heteroaromatic of divalent of divalent Group.Its carbon atom number is usually 4 or more, is preferably 5 or more, is more preferably 6 or more, and preferably 30 or less, more preferably It is 20 or less, further preferably 15 or less.By being set as above-mentioned lower limiting value or more, exists and be easy to get strong film, be not easy Rough surface occurs, to become good tendency to the adaptation of substrate, in addition, by being set as above-mentioned upper limit value hereinafter, depositing It is being easy that film when deterioration, the development of sensitivity is inhibited to reduce, to the tendency for making image resolution ratio improve.
As the aromatic series hydrocarbon ring in the aromatic cyclic hydrocarbon group group of divalent, it can be monocycle can also be condensed ring, can enumerate Such as phenyl ring with 1 free valency, naphthalene nucleus, anthracene nucleus, phenanthrene ring, ring, aphthacene ring, pyrene ring, BaP ring,Ring, benzo The groups such as phenanthrene ring, acenaphthene ring, fluoranthene ring, fluorenes ring.Can be monocycle in addition, as the heteroaromatic in aromatic heterocyclic group Can also be condensed ring, it can be cited for example that with the furan nucleus of 1 free valency, benzofuran ring, thiphene ring, benzothiophene ring, Pyrrole ring, pyrazole ring, imidazole ring,Diazole ring, indole ring, carbazole ring, pyrrolo- imidazole ring, pyrrolo-pyrazole ring, pyrrolo- Pyrrole ring, Thienopyrroles ring, thienothiophene ring, furans and pyrrole ring, furans and furan nucleus, thienofuran ring, benzo It is differentIt is azoles ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, different Quinoline ring, cinnolines (cinnoline) ring, quinoxaline ring, phenanthridines ring, benzimidazole ring,Phenazine ring, quinazoline ring, quinazolinone Ring,The groups such as ring.In these, from the viewpoint of patterned property, preferably phenyl ring or naphthalene nucleus, more preferable fluorenes ring.
The substituent group that aromatic group as divalent optionally has, can enumerate hydroxyl, methyl, methoxyl group, ethyl, Ethyoxyl, propyl, propoxyl group etc..It is preferably unsubstituted from the viewpoint of development dissolubility in these.
In addition, the base that the aromatic group of the divalent as 1 or more divalent aliphatic group and 1 or more links Group can enumerate the aromatic group of the aliphatic group and 1 or more foregoing divalent of 1 or more foregoing divalent The group to link.
The quantity of the aliphatic group of divalent is not particularly limited, usually 1 or more, preferably 2 or more, and leads to Often it is 10 or less, preferably 5 or less, more preferably 3 or less.By being set as above-mentioned lower limiting value or more, there are easy To strong film, it is not likely to produce rough surface, to become good tendency to the adaptation of substrate, in addition, on by being set as Upper limit value is stated hereinafter, in the presence of being easy that film when deterioration, the development of sensitivity is inhibited to reduce, to make inclining for image resolution ratio raising To.
The quantity of the aromatic group of divalent is not particularly limited, usually 1 or more, preferably 2 or more, and leads to Often it is 10 or less, preferably 5 or less, more preferably 3 or less.By being set as above-mentioned lower limiting value or more, there are easy To strong film, it is not likely to produce rough surface, to become good tendency to the adaptation of substrate, in addition, on by being set as Upper limit value is stated hereinafter, in the presence of being easy that film when deterioration, the development of sensitivity is inhibited to reduce, to make inclining for image resolution ratio raising To.
The group that the aromatic group of divalent as 1 or more divalent aliphatic group and 1 or more links Concrete example can enumerate group etc. shown in above-mentioned formula (b-I-I-A)~(b-I-I-F).In these, from the outspoken nature of skeleton From the viewpoint of the hydrophobization of film, group shown in preferably above-mentioned formula (b-I-I-C).
The bond styles of cyclic hydrocarbon group and above-mentioned divalent alkyl as side chain are not particularly limited, it can be cited for example that：Fat Fat race group, aromatic group 1 hydrogen atom replaced by the side chain made of state, 1 carbon original comprising aliphatic group State that is sub and constituting the cyclic hydrocarbon group as side chain.
(R15、R16)
In above-mentioned general formula (b-I-II), R15And R16Each independently represent the optionally divalent fatty group with substituent group Group.
The aliphatic group of divalent can enumerate straight-chain, branched, cricoid divalent aliphatic group.In these, from From the viewpoint of dissolubility of developing, the preferred divalent aliphatic group of straight-chain, on the other hand, from developer solution is reduced to exposure portion Be impregnated with from the viewpoint of, preferably cricoid divalent aliphatic group.Its carbon atom number is usually 1 or more, is preferably 3 or more, more Preferably 6 or more, additionally, it is preferred that for 20 or less, more preferably 15 or less, further preferably 10 or less.By being set as above-mentioned More than lower limiting value, exist and be easy to get strong film, be not susceptible to rough surface, to become good to the adaptation of substrate Tendency, in addition, by being set as above-mentioned upper limit value hereinafter, being reduced in the presence of film when being easy the deterioration of inhibition sensitivity, developing, thus The tendency for making image resolution ratio improve.
The concrete example of straight-chain aliphatic group as divalent can enumerate methylene, ethylidene, n-propylene, positive Asia Butyl, positive pentylidene, positive hexylidene, positive heptamethylene etc..In these, from the viewpoint of the outspoken nature of skeleton, preferred methylene Base.
As the branched aliphatic group of divalent, in the straight-chain aliphatic group that the divalent described in front can be enumerated Structure with methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl etc. as side chain.
The quantity of the ring of cyclic aliphatic group with divalent is not particularly limited, usually 1 or more, preferably 2 More than, and usually 12 or less, preferably 10 or less.By being set as above-mentioned lower limiting value or more, exist to be formed it is strong Film, substrate adaptation become good tendency, in addition, being easy to inhibit sensitivity hereinafter, existing by being set as above-mentioned upper limit value Film when deteriorating, developing is reduced, to the tendency for making image resolution ratio improve.Cyclic aliphatic group as divalent it is specific Example, can enumerate from cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isoborneol alkane ring, Buddha's warrior attendant Group obtained from 2 hydrogen atoms is eliminated on the rings such as alkane ring, cyclododecane ring, bicyclopentadiene.In these, from skeleton From the viewpoint of outspoken nature, group obtained from 2 hydrogen atoms is preferably eliminated from bicyclopentadiene ring, adamantane ring.
The substituent group that aliphatic group as divalent optionally has, can enumerate hydroxyl, methyl, ethyl, n-propyl, The alkyl of the carbon atom numbers such as isopropyl, normal-butyl, sec-butyl, tertiary butyl, amyl, isopentyl 1~5；The carbon such as methoxyl group, ethyoxyl The alkoxy of atomicity 1~5；Hydroxyl；Nitro；Cyano；Carboxyl etc..In these, from the viewpoint of synthesis easiness, preferably It is unsubstituted.
(m、n)
In above-mentioned general formula (b-I-II), the integer of m and n expressions 0~2.By being set as above-mentioned lower limiting value or more, there are figures Case adaptability becomes good, is not likely to produce shaggy tendency, in addition, by being set as above-mentioned upper limit value hereinafter, existing aobvious Shadow becomes good tendency.From the viewpoint of developability, preferably m and n are 0, on the other hand, from pattern adaptability, surface From the viewpoint of coarse, preferably m and n are 1 or more.
In addition, from the viewpoint of the adaptation to substrate, part-structure is shown in preferably above-mentioned general formula (b-I-II) Part-structure shown in the following general formula (b-I-II-1).
[chemical formula 27]
In formula (b-I-II-1), R13、R15、R16, m and n it is identical as the meaning in above-mentioned formula (b-I-II), RαIndicate optional The cyclic hydrocarbon group of 1 valence with substituent group, the integer that p is 1 or more.Phenyl ring in formula (b-I-II-1) can be further arbitrary Substituent group substitution, * indicate bonding position.
(Rα)
In above-mentioned general formula (b-I-II-1), RαIndicate the cyclic hydrocarbon group of optionally 1 valence with substituent group.
As cyclic hydrocarbon group, aliphatic cyclic group or aromatic group can be enumerated.
The quantity of ring possessed by aliphatic cyclic group is not particularly limited, usually 1 or more, preferably 2 or more, and And usually 6 or less, preferably 4 or less, more preferably 3 or less.By being set as above-mentioned lower limiting value or more, exist to be formed Strong film is not likely to produce shaggy tendency, in addition, by being set as above-mentioned upper limit value hereinafter, there are patterned property changes Obtain good tendency.
In addition, the carbon atom number of aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and it is excellent It is selected as 40 or less, more preferably 30 or less, further preferably 20 or less, particularly preferably 15 or less.Under being set as above-mentioned More than limit value, exist and to form strong film, be not likely to produce shaggy tendency, in addition, by being set as above-mentioned upper limit value hereinafter, There are patterned properties to become good tendency.
As the concrete example of the cycloaliphatic ring in aliphatic cyclic group, can enumerate cyclohexane ring, cycloheptane ring, cyclodecane ring, Cyclododecane ring, norbornane ring, isoborneol alkane ring, adamantane ring, cyclododecane ring etc..It is special from strong film in these From the viewpoint of property, preferred adamantane ring.
On the other hand, the quantity of ring possessed by aromatic group is not particularly limited, usually 1 or more, preferably 2 More than a, it is more preferably 3 or more, and usually 10 or less, preferably 5 or less.By be set as above-mentioned lower limiting value with On, exist and to form strong film, be not likely to produce shaggy tendency, in addition, being schemed hereinafter, existing by being set as above-mentioned upper limit value Case characteristic becomes good tendency.
As aromatic group, aromatic cyclic hydrocarbon group group, aromatic heterocyclic group can be enumerated.In addition, aromatic group Carbon atom number be usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 with Under, further preferably 15 or less.By being set as above-mentioned lower limiting value or more, exist to form that strong film, to be not likely to produce surface thick Rough tendency, in addition, by being set as above-mentioned upper limit value hereinafter, there are patterned properties to become good tendency.
As the concrete example of the aromatic rings in aromatic group, phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, fluorenes ring etc. can be enumerated. In these, from the viewpoint of development dissolubility, preferred fluorenes ring.
As the substituent group that cyclic hydrocarbon group optionally has, can enumerate hydroxyl, methyl, ethyl, n-propyl, isopropyl, The alkyl of the carbon atom numbers such as normal-butyl, sec-butyl, tertiary butyl, amyl, isopentyl 1~5；The carbon atom numbers such as methoxyl group, ethyoxyl 1 ~5 alkoxy；Hydroxyl；Nitro；Cyano；Carboxyl etc..In these, from the viewpoint of synthesis easiness, do not take preferably Generation.
The integer of 1 or more p expressions, preferably 2 or more, and preferably 3 or less.By being set as above-mentioned lower limiting value or more, There are film curing degrees and residual film ratio to become good tendency, in addition, by being set as above-mentioned upper limit value hereinafter, there are developability to become Good tendency.
In these, from the viewpoint of strong film curing degree, preferably RαFor the aliphatic cyclic group of 1 valence, more preferably Adamantyl.
As described above, the phenyl ring in formula (b-I-II-1) can further be replaced by arbitrary substituent group.As the substitution Base, it can be cited for example that hydroxyl, methyl, methoxyl group, ethyl, ethyoxyl, propyl, propoxyl group etc..The quantity of substituent group is without spy It does not limit, can be 1, or 2 or more.
It is preferably unsubstituted from the viewpoint of patterned property in these.
It is exemplified below the concrete example of part-structure shown in above-mentioned formula (b-I-II-1).
[chemical formula 28]
[chemical formula 29]
[chemical formula 30]
[chemical formula 31]
[chemical formula 32]
In addition, from the viewpoint of the outspoken nature of skeleton and film hydrophobization, shown in preferably above-mentioned general formula (b-I-II) Separation structure is part-structure shown in the following general formula (b-I-II-2).
[chemical formula 33]
In formula (b-I-II-2), R13、R15、R16, m and n it is identical as the meaning in above-mentioned formula (b-I-II), RβIndicate optional The cyclic hydrocarbon group of divalent with substituent group.Phenyl ring in formula (b-I-II-2) can further be replaced by arbitrary substituent group, * Indicate bonding position.
(Rβ)
In above-mentioned formula (b-I-II-2), RβIndicate the cyclic hydrocarbon group of the optionally divalent with substituent group.
As cyclic hydrocarbon group, aliphatic cyclic group or aromatic group can be enumerated.
The quantity of ring possessed by aliphatic cyclic group is not particularly limited, usually 1 or more, preferably 2 or more, and And usually 10 or less, preferably 5 or less.By being set as above-mentioned lower limiting value or more, exists and to form strong film, be not easy to produce Raw shaggy tendency, in addition, by being set as above-mentioned upper limit value hereinafter, when there is the deterioration for being easy to inhibit sensitivity, development Film reduce, to make image resolution ratio improve tendency.
In addition, the carbon atom number of aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and it is excellent It is selected as 40 or less, more preferably 35 or less, further preferably 30 or less.By being set as above-mentioned lower limiting value or more, there is inhibition The coarse tendency of film when development, in addition, by being set as above-mentioned upper limit value hereinafter, there is the deterioration for being easy to inhibit sensitivity, aobvious Film when shadow is reduced, to the tendency for making image resolution ratio improve.
As the concrete example of the cycloaliphatic ring in aliphatic cyclic group, can enumerate cyclohexane ring, cycloheptane ring, cyclodecane ring, Cyclododecane ring, norbornane ring, isoborneol alkane ring, adamantane ring, cyclododecane ring etc..In these, from storage stability From the viewpoint of, preferred adamantane ring.
On the other hand, the quantity of ring possessed by aromatic group is not particularly limited, usually 1 or more, preferably 2 More than a, it is more preferably 3 or more, and usually 10 or less, preferably 5 or less.By be set as above-mentioned lower limiting value with On, exist and to form strong film, be not likely to produce shaggy tendency, in addition, being held hereinafter, existing by being set as above-mentioned upper limit value Film when deterioration, the development of sensitivity is easily inhibited to reduce, to the tendency for making image resolution ratio improve.
As aromatic group, aromatic cyclic hydrocarbon group group, aromatic heterocyclic group can be enumerated.In addition, aromatic group Carbon atom number be usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and preferably 40 or less, 30 or less, further preferably 20 or less, particularly preferably 15 or less are more preferably.By being set as above-mentioned lower limiting value More than, exist and to form strong film, be not likely to produce shaggy tendency, in addition, by be set as above-mentioned upper limit value hereinafter, in the presence of It is easy that film when deterioration, the development of sensitivity is inhibited to reduce, to the tendency for making image resolution ratio improve.
As the concrete example of the aromatic rings in aromatic group, phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, fluorenes ring etc. can be enumerated. In these, from the viewpoint of developability, preferred fluorenes ring.
As the substituent group that cyclic hydrocarbon group optionally has, can enumerate hydroxyl, methyl, ethyl, n-propyl, isopropyl, The alkyl of the carbon atom numbers such as normal-butyl, sec-butyl, tertiary butyl, amyl, isopentyl 1~5；The carbon atom numbers such as methoxyl group, ethyoxyl 1 ~5 alkoxy；Hydroxyl；Nitro；Cyano；Carboxyl etc..In these, from the viewpoint of convieniently synthesized property, do not take preferably Generation.
In these, from the viewpoint of storage stability and electrical characteristics, preferably RβFor the aliphatic cyclic group, more excellent of divalent It is selected as the adamantane ring group of divalent.
On the other hand, from the viewpoint of the agent of low hygroscopicity of film and patterned property, preferably RβFor the fragrant ring group of divalent The fluorenes ring group of group, more preferably divalent.
As described above, the phenyl ring in formula (b-I-II-2) can further be replaced by arbitrary substituent group.As the substitution Base, it can be cited for example that hydroxyl, methyl, methoxyl group, ethyl, ethyoxyl, propyl, propoxyl group etc..The quantity of substituent group is without spy It does not limit, can be 1, or 2 or more.
Alternatively, it is also possible to which 2 phenyl ring are linked up via substituent group.As substituent group in this case, can enumerate- O-、-S-、-NH-、-CH2Wait the group of divalents.
It is preferably unsubstituted from the viewpoint of patterned property in these.In addition, from film reduction etc. is not likely to produce From the viewpoint of, preferably methyl replaces.
It is exemplified below the concrete example of part-structure shown in above-mentioned formula (b-I-II-2), it should be noted that the * tables in example Show bonding position.
[chemical formula 34]
[chemical formula 35]
[chemical formula 36]
[chemical formula 37]
On the other hand, from the viewpoint of film residual film ratio and patterned property, shown in preferably above-mentioned formula (b-I-II) Part-structure is part-structure shown in following formula (b-I-II-3).
[chemical formula 38]
In formula (b-I-II-3), R13、R14、R15、R16, m and n it is identical as the meaning in above-mentioned formula (b-I-II), RZIndicate hydrogen Atom or polyacid residue.
So-called polyacid residue refers to, from eliminating 1 valence group obtained from 1 OH base in polyacid or its acid anhydrides.It needs It is noted that can also further remove another OH base and with the R in other molecules shown in formula (b-I-II-3)ZAltogether With, that is, it can also be via RZMultiple formulas (b-I-II-3) are linked up.
As polyacid, can enumerate selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, Hexahydrophthalic acid, Pyromellitic Acid, trimellitic acid, benzophenone tetrabasic carboxylic acid, methylhexahydrophthaacid acid, endo-methylene group One kind or two kinds of tetrahydrophthalic acid, hexahydro carbic acid, methyl tetrahydrophthalic acid, bibenzene tetracarboxylic with On.
In these, from the viewpoint of patterned property, preferably maleic acid, succinic acid, itaconic acid, phthalic acid, Tetrahydrophthalic acid, hexahydrophthalic acid, Pyromellitic Acid, trimellitic acid, bibenzene tetracarboxylic, more preferably tetrahydrochysene neighbour benzene Dioctyl phthalate, bibenzene tetracarboxylic, tetrahydrophthalic acid, bibenzene tetracarboxylic.
(b-I-II) part shown in above-mentioned formula (b-I-II-3) contained in 1 molecule of epoxy (methyl) acrylate Structure can be a kind of or two or more, can also for example be mixed RZFor the structure and R of hydrogen atomZFor polyacid The structure of residue.
In addition, shown in above-mentioned formula (b-I-II) contained in 1 molecule of (b-I-II) epoxy (methyl) acrylate The quantity of part-structure is not particularly limited, preferably 1 or more, more preferably 3 or more, and preferably 20 or less, More preferably 15 or less, further preferably 10 or less.By being set as above-mentioned lower limiting value or more, exist be easy to get it is strong Film, be not likely to produce rough surface, electrical characteristics become good tendency, in addition, by be set as above-mentioned upper limit value hereinafter, exist hold Film when deterioration, the development of sensitivity is easily inhibited to reduce, to the tendency for making image resolution ratio improve.
Pass through the polystyrene of (b-I-II) epoxy (methyl) acrylate that gel permeation chromatography (GPC) measures The weight average molecular weight (Mw) of conversion is not particularly limited, and preferably 1000 or more, more preferably 2000 or more, and preferably 30000 or less, be more preferably 20000 or less, further preferably 10000 or less, still more preferably be 7000 or less, especially Preferably 5000 or less.By being set as above-mentioned lower limiting value or more, there are patterned properties to become good tendency, in addition, passing through Above-mentioned upper limit value is set as hereinafter, in the presence of being easy to get strong film, being not likely to produce shaggy tendency.
(b-I-II) acid value of epoxy (methyl) acrylate is not particularly limited, preferably 10mgKOH/g or more, More preferably 20mgKOH/g or more, further preferably 40mgKOH/g or more, still more preferably be 60mgKOH/g or more, Particularly preferably 80mgKOH/g or more, it is most preferably 100mgKOH/g or more, and preferably 200mgKOH/g or less, more excellent It is selected as 150mgKOH/g or less, further preferably 120gKOH/g or less.By being set as above-mentioned lower limiting value or more, there are easy The tendency of strong film is obtained, in addition, by being set as above-mentioned upper limit value hereinafter, there is the raising of development dissolubility, image resolution ratio Become good tendency.
＜ (b-II) is containing repetitive unit α of the side chain with ethylenic unsaturated bond and from the repetition list of unsaturated carboxylic acid (methyl) the acrylic copolymeric resins ＞ of first β
(b-II) (methyl) acrylic copolymeric resins contain repetitive unit α and source of the side chain with ethylenic unsaturated bond In the repetitive unit β of unsaturated carboxylic acid.Think by with repetitive unit α, it can be ensured that reliability, by with repetitive unit β can make surface smoothness good.
As long as repetitive unit α side chains have the repetitive unit of ethylenic unsaturated bond, it is not particularly limited, Ke Yiju Go out the repetitive unit of such as chemical constitution shown in the following general formula (I).
[chemical formula 39]
In above-mentioned formula (I), R1And R2Each independently represent hydrogen atom or methyl, R3Indicate the connection group of divalent.
As the connection group of divalent, the alkylidene optionally with substituent group or the optional divalent with substituent group can be enumerated Aromatic group.
As alkylidene, straight-chain, branched or cricoid alkylidene can be enumerated, carbon atom number is preferably 1 or more, More preferably 2 or more, it is more preferably 3 or more, and preferably 20 or less, is more preferably 15 or less, further preferably 10 or less, still more preferably it is 8 or less, particularly preferably 5 or less.By being set as above-mentioned lower limiting value or more, there are reactivity The tendency of raising, in addition, by being set as above-mentioned upper limit value hereinafter, there are the tendencies of thermal fluidity reduction.
As the concrete example of alkylidene, it is sub- that methylene, ethylidene, propylidene, butylidene, isobutylene, ring can be enumerated Hexyl etc..In these, from the viewpoint of reactivity, preferably methylene, ethylidene or propylidene, more preferable propylidene.
As the aromatic group of divalent, aromatic cyclic hydrocarbon group group and the aromatic heterocyclic group of divalent of divalent can be enumerated, Its carbon atom number is preferably 4 or more, is more preferably 5 or more, is more preferably 6 or more, and preferably 30 or less, more preferably It is 20 or less, further preferably 15 or less, particularly preferably 10 or less.By being set as above-mentioned lower limiting value or more, there is reaction Property improve tendency, in addition, by being set as above-mentioned upper limit value hereinafter, there are the tendencies of thermal fluidity reduction.
It can also be condensed ring that aromatic series hydrocarbon ring in being rolled into a ball as aromatic cyclic hydrocarbon group, which can be monocycle, it can be cited for example that Phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, ring, aphthacene ring, pyrene ring, BaP ring,Ring, benzo phenanthrene ring, acenaphthene ring, fluoranthene ring, fluorenes The groups such as ring.
Can be monocycle can also be condensed ring, Ke Yiju in addition, as the aromatic heterocycle in aromatic heterocyclic group Go out for example furan nucleus, benzofuran ring, thiphene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring,Diazole ring, indoles Ring, carbazole ring, pyrrolo- imidazole ring, pyrrolo-pyrazole ring, pyrrolopyrrole ring, Thienopyrroles ring, thienothiophene ring, furan It mutters and pyrrole ring, furans and furan nucleus, thienofuran ring, benzisoxaAzoles ring, benzisothiazole ring, benzimidazole ring, pyrrole Phenazine ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinolin ring, cinnolines (cinnoline) ring, quinoxaline ring, Phenanthridines ring, benzimidazole ring,Phenazine ring, quinazoline ring, quinazolinone ring,The groups such as ring.
In addition, the substituent group that the aromatic group as alkylidene and divalent optionally has, can enumerate halogen atom, benzene Base, hydroxyl, carboxyl etc., in these, from the viewpoint of reactivity, preferred hydroxyl.
In addition, as chemical constitution shown in above-mentioned logical formula (I), from the viewpoint of reactivity, preferably the following general formula (I- 1) or chemical constitution shown in (I-2), chemical constitution shown in more preferable the following general formula (I-1).
[chemical formula 40]
In above-mentioned formula (I-1) and formula (I-2), R1Indicate hydrogen atom or methyl.
Chemical constitution shown in above-mentioned general formula (I-1), (I-2) can by make the unsaturated compound containing epoxy group with It is formed from the repetitive unit addition of (methyl) acrylic acid.
On the other hand, as the repetitive unit β from unsaturated carboxylic acid, it can be cited for example that from the weight of acrylic acid Multiple unit, the repetitive unit from methacrylic acid, the repetitive unit from crotonic acid, the repetition list from itaconic acid Member, the repetitive unit from maleic acid, the repetitive unit from fumaric acid etc., in these, from the viewpoint of thermal fluidity Consider, repetitive unit, the repetitive unit from methacrylic acid for being preferably derived from acrylic acid, more preferable the following general formula (II) Shown in chemical constitution repetitive unit.
[chemical formula 41]
In above-mentioned formula (II), R3Each independently represent hydrogen atom or methyl.
In addition, (b-II) (methyl) acrylic copolymeric resins are other than above-mentioned repetitive unit α and β, it can also be into one Step includes repetitive unit γ.As repetitive unit γ, can enumerate from olefinics unsaturation chemical combination such as (methyl) acrylate The repetitive unit of object, for example, from reliability, developing time adjustment from the viewpoint of, preferably have following formula (IIIa) shown in Part-structure repetitive unit.
[chemical formula 42]
In formula (IIIa), R1d~R4dEach independently represent hydrogen atom or the alkyl of carbon atom number 1~10, R5dAnd R6dRespectively From hydrogen atom or the alkyl of carbon atom number 1~10 is independently indicated, in addition, R5dAnd R6dOptionally link and forms ring.R5dAnd R6dEven Knot and the ring that is formed is preferably cycloaliphatic ring, can be the arbitrary ring in saturated rings or unsaturation ring, preferably carbon atom number 5~ 6。
R1d~R4dIn the carbon atom number of alkyl be usually 1 or more, and usually 10 or less, preferably 8 or less, it is more excellent It is selected as 5 or less.By being set as above-mentioned upper limit value hereinafter, in the presence of the deliquescent tendency of suitable development is obtained.
In these, from the viewpoint of dissolubility, preferably R1d~R4dFor hydrogen atom.
R5dAnd R6dIn the carbon atom number of alkyl be usually 1 or more, and usually 10 or less, preferably 8 or less, more Preferably 5 or less.By being set as above-mentioned lower limiting value or more, exists and show suitable deliquescent tendency, in addition, on by being set as Upper limit value is stated hereinafter, in the presence of hydrophilic tendency can be kept.
In these, from the viewpoint of development dissolubility, preferably R5dAnd R6dFor hydrogen atom or R5dAnd R6dConnection and Form the cycloaliphatic ring of carbon atom number 5~6.
In above-mentioned formula (IIIa), preferably there is structure shown in following formula (IIIb), (IIIc) or (IIId).By leading Enter these part-structures, there are possibility to increase heat resistance, the tendency of intensity.
[chemical formula 43]
As the repetitive unit with part-structure shown in above-mentioned formula (IIIa), from the viewpoint of curability, preferably Repetitive unit shown in following formula (III)s.
[chemical formula 44]
In formula (III), R4Indicate hydrogen atom or methyl, R5Indicate part-structure shown in above-mentioned formula (IIIa).
On the other hand, the olefinic unsaturated compound as the sources repetitive unit γ, in addition to above-mentioned formula (IIIa) Shown in part-structure (methyl) acrylate other than, can also enumerate for example：α-, o-, m-, p- alkyl, the nitre of styrene The phenylethylenes such as base, cyano, amide, ester derivant, butadiene, 2,3 dimethyl butadiene, isoprene, chlorobutadiene etc. two Alkenes, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (first Base) acrylic acid peopentyl ester, (methyl) isoamyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) dodecylacrylate, (methyl) acrylic acid ring pentyl ester, (methyl) acrylate Ester, (methyl) acrylic acid 2- methyl cyclohexyls, (methyl) acrylic acid dicyclohexyl maleate, (methyl) isobornyl acrylate, (methyl) Acrylic acid Buddha's warrior attendant alkyl ester, (methyl) allyl acrylate, (methyl) propargylacrylate, (methyl) phenyl acrylate, (methyl) Acrylic acid naphthalene ester, (methyl) acrylic acid anthracene ester, (methyl) acrylic acid anthryl nonyl ester, (methyl) acrylic acid pepper ester, (methyl) third Olefin(e) acid salicyl ester, (methyl) acrylic acid furans ester, (methyl) acrylic acid chaff ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) third Olefin(e) acid pyrans ester, (methyl) benzyl acrylate, (methyl) phenylethyl, (methyl) acrylic acid cresols ester, (methyl) propylene Acid -1,1,1- trifluoro ethyl esters, (methyl) perfluoroethyl ethyl ester, (methyl) perfluoroethyl n-propyl, (methyl) acrylic acid are complete Fluorine isopropyl ester, (methyl) acrylic acid triphenylmethyl, (methyl) acrylic acid isopropyl phenyl ester, (methyl) acrylic acid 3- (N, N- diformazans Base amino) (methyl) acrylate such as propyl ester, (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate Class, (methyl) acrylamide, N, N- dimethyl (methyl) acrylamide, N, N- diethyl (methyl) acrylamide, N, N- dipropyls Base (methyl) acrylamide, N, (methyl) propylene such as N- diisopropyls (methyl) acrylamide, (methyl) acrylic acid anthryl amide Amides, (methyl) acryloyl aniline, (methyl) acrylonitrile, methacrylaldehyde, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene, The vinyl compounds such as n-vinyl pyrrolidone, vinylpyridine, vinyl acetate class, citraconic acid diethylester, maleic acid two Two esters of the unsaturated dicarboxylics such as ethyl ester, diethyl fumarate, diethyl itaconate, N-phenylmaleimide, N- cyclohexyl The list such as maleimide, N- lauryls maleimide, N- (4- hydroxy phenyls) maleimide maleimide, N- (first Base) free-radical polymerised compound as acryloyl phthalimide etc..
In these, in order to assign superior heat resistance and intensity, as olefinic unsaturated compound, using selected from benzene At least one of ethylene, (methyl) benzyl acrylate and single maleimide are effective.
(b-II) manufacturing method of (methyl) acrylic copolymeric resins is not particularly limited, can be by that will correspond to weight (methyl) acrylate compounds copolymerization of each repetitive unit of multiple unit α~γ obtains.Furthermore it is also possible to utilize with lower section Method obtains：(methyl) glycidyl acrylate, α-ethyl glycidyl base (methyl) acrylate, 3,4- epoxies are obtained first Butyl (methyl) acrylate, 3,4- epoxycyclohexyl-methyls (methyl) acrylate, 4- hydroxybutyls (methyl) acrylate The olefinics such as (methyl) acrylate containing epoxy group such as glycidyl ether and (methyl) acrylic acid, (methyl) acrylate are not The copolymer of saturated compounds, then by the epoxy group addition contained by olefinic unsaturated monocarboxylic and the co-polymer.
(b-II) content ratio of the above-mentioned repetitive unit α in (methyl) acrylic copolymeric resins is usually 10 moles of % Above, it is preferably 12 moles of % or more, more preferably 15 moles of % or more, further preferably 18 moles of % or more, more into one Step is preferably 20 moles of % or more, particularly preferably 22 moles of % or more, is most preferably 25 moles of % or more, and preferably 40 Mole % or less, more preferably 35 moles of % or less, further preferably 30 moles of % or less, still more preferably it is 25 to rub You are % or less.By being set as above-mentioned lower limiting value or more, there is the tendency it is easy to ensure that reliability, in addition, on by being set as above-mentioned Limit value hereinafter, in the presence of it is easy to ensure that surface smoothness tendency.
In addition, the content ratio of the above-mentioned repetitive unit β in (b-II) (methyl) acrylic copolymeric resins is preferably 20 Mole % or more, more preferably 30 moles of % or more, further preferably 40 moles of % or more, be most preferably 50 moles of % with On, and preferably 70 moles of % or less, more preferably 60 moles of % or less, further preferably 50 moles of % or less.Pass through Be set as above-mentioned lower limiting value or more, exist it is easy to ensure that deliquescent tendency of developing, in addition, by being set as above-mentioned upper limit value hereinafter, In the presence of it is easy to ensure that reliability tendency.
In addition, the content ratio of the above-mentioned repetitive unit γ in (b-II) (methyl) acrylic copolymeric resins is usually 0 Mole % or more, preferably 10 moles of % or more, more preferably 20 moles of % or more, further preferably 30 moles of % or more, And preferably 60 moles of % or less, more preferably 50 moles of % or less, further preferably 40 moles of % or less.By being set as More than above-mentioned lower limiting value, there are adaptations to become good tendency, in addition, being easy by being set as above-mentioned upper limit value hereinafter, existing Ensure the tendency of reliability.
The polystyrene of (b-II) (methyl) acrylic copolymeric resins measured by gel permeation chromatography (GPC) changes The weight average molecular weight (Mw) of calculation is usually 3000 or more, is preferably 5000 or more, is more preferably 10000 or more, further preferably Be 15000 or more, and usually 50000 or less, preferably 30000 or less, more preferably 20000 or less.By being set as above-mentioned More than lower limiting value, there are reliabilities to become good tendency, in addition, by being set as above-mentioned upper limit value hereinafter, there is development dissolving Property becomes good tendency.
(b-II) acid value of (methyl) acrylic copolymeric resins is not particularly limited, preferably 100mgKOH/g or more, More preferably 130mgKOH/g or more, further preferably 160mgKOH/g or more, particularly preferably 180mgKOH/g More than, and preferably 400mgKOH/g or less, more preferably 300mgKOH/g or less, further preferably 200mg KOH/g or less.By being set as above-mentioned lower limiting value or more, exist it is easy to ensure that deliquescent tendency of developing, in addition, on by being set as State upper limit value hereinafter, in the presence of it is easy to ensure that reliability tendency.
Can include a kind of weight containing side chain with ethylenic unsaturated bond in the photosensitive coloring composition of the present invention (b-II) (methyl) acrylic copolymeric resins of the multiple unit α and repetitive unit β from unsaturated carboxylic acid, in addition, also may be used To include two or more.Including in the case of of more than two kinds, from the viewpoint of being easy to get effect of the present invention, it is at least one kind of with On resin in, preferably the content ratio of its repetitive unit α be above range in.
On the other hand, in the photosensitive coloring composition that another way is related to, there is olefinic containing side chain comprising 2 kinds (b-II) (methyl) acrylic copolymer tree of the repetitive unit α of unsaturated bond and repetitive unit β from unsaturated carboxylic acid It, can on the basis of whole repetitive units of (b-II) (methyl) acrylic copolymeric resins of its all kinds in the case of fat So that the content ratio of repetitive unit α contained therein is in above range.Similarly, the content ratio of repetitive unit β can be with The ratio being set as on the basis of whole repetitive units of (b-II) (methyl) acrylic copolymeric resins of all kinds.It is wrapping Also the same in the case of γ containing repetitive unit, content ratio can be set as (b-II) (methyl) acrylic acid with all kinds Ratio on the basis of whole repetitive units of class copolymer resins.
The other alkali soluble resin ＞ of ＜
(b) alkali soluble resin used in the present invention in addition to above-mentioned (b-I) epoxy (methyl) acrylate and on It states other than (b-II) (methyl) acrylic copolymeric resins, can also include other alkali soluble resins.
Other alkali soluble resins there is no limit, from commonly used resin in photosensitive coloring composition selection be It can.It can be cited for example that Japanese Unexamined Patent Publication 2007-271727 bulletins, Japanese Unexamined Patent Publication 2007-316620 bulletins, Japanese Unexamined Patent Publication Adhesive resin etc. described in 2007-334290 bulletins etc..In addition, from the viewpoint of the compatibility with pigment, dispersant etc. Consider, it is preferable to use acrylic resin, more preferably can use the alkali described in Japanese Unexamined Patent Publication 2014-137466 bulletins can Soluble resin.
＜ (c) Photoepolymerizationinitiater initiaters ＞
(c) Photoepolymerizationinitiater initiater is directly to absorb light and cause decomposition reaction or hydrogen abstraction reaction, to polymerize with generation The ingredient 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.
As Photoepolymerizationinitiater initiater, it can be cited for example that Japanese Unexamined Patent Application 59-152396 bulletins, Japanese Unexamined Patent Application 61- The Metallocenic compound for including cyclopentadiene titanium compound described in No. 151197 bulletins；Remember in Japanese Unexamined Patent Publication 2000-56118 bulletins The Hexaarylbiimidazole derivative of load；Halomethylation described in Japanese Unexamined Patent Publication 10-39503 bulletinsOxadiazole derivative, The N- such as halogen methyl Striazine derivative, N- phenylglycines aryl-alpha-amido acids, N- aryl-a-amino acid salt, N- virtues The free radicals activators such as base-a-amino acid esters, alpha-aminoalkyl benzophenone derivatives；Japanese Unexamined Patent Publication 2000-80068 bulletins, Oxime ester derivative etc. described in Japanese Unexamined Patent Publication 2006-36750 bulletins etc..
Specifically, it for example, as luxuriant titanium derivative class, can enumerate：Titanocene dichloride, bicyclopentadiene Base diphenyl titanium, dicyclopentadienyl two (2,3,4,5,6- phenyl-pentafluoride -1- bases) titanium, (2,3,5,6- tetra- of dicyclopentadienyl two Fluorobenzene -1- bases) titanium, dicyclopentadienyl two (2,4,6- trifluoro-benzene -1- bases) titanium, (2,6- difluorobenzenes-the 1- of dicyclopentadienyl two Base) titanium, dicyclopentadienyl two (2,4 difluorobenzene -1- bases) titanium, two (methyl cyclopentadienyl) two (five fluorine of 2,3,4,5,6- Benzene -1- bases) titanium, two (methyl cyclopentadienyl) two (2,6- difluorobenzene -1- bases) titanium, dicyclopentadienyl [bis- fluoro- 3- of 2,6- (propyl- 1- yls)-benzene -1- bases] titanium etc..
In addition, as diimidazole derivative species, can enumerate：2 aggressiveness of 2- (2 '-chlorphenyl) -4,5- diphenyl-imidazoles, 2- 2 aggressiveness of (2 '-chlorphenyl) -4,5- two (3 '-methoxyphenyl) imidazoles, 2 aggressiveness of 2- (2 '-fluorophenyl) -4,5- diphenyl-imidazoles, 2 aggressiveness of 2- (2 '-methoxyphenyl) -4,5- diphenyl-imidazoles, 2 aggressiveness of (4 '-methoxyphenyl) -4,5- diphenyl-imidazoles etc..
In addition, as halomethylationOxadiazole derivative can be enumerated：2- trichloromethyls -5- (2 '-benzofuranyl) - 1,3,4-Diazole, 2- trichloromethyls -5- [β-(2 '-benzofuranyl) vinyl] -1,3,4-Diazole, 2- trichloromethyls- 5- [β-(2 '-(6 "-benzofuranyl) vinyl)] -1,3,4-Diazole, 2- trichloromethyl -5- furyls -1,3,4-Two Azoles etc..
In addition, as halogen methyl Striazine derivative class, can enumerate：Bis- (three chloromethanes of 2- (4- methoxyphenyls) -4,6- Base) s-triazine, bis- (trichloromethyl) s-triazine of 2- (4- methoxyl groups naphthalene) -4,6-, 2- (4- ethoxynaphthyls) -4,6- bis- (three Chloromethyl) s-triazine, bis- (trichloromethyl) s-triazine of 2- (4- carbethoxyl groups naphthalene) -4,6- etc..
In addition, as alpha-aminoalkyl benzophenone derivatives class, can enumerate：2- methyl-1s-[4- (methyl mercapto) phenyl] -2- Morpholinopropane -1- ketone, 2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls)-butanone -1,2- benzyl -2- dimethylaminos Base -1- (4- morpholino phenyls) butane -1- ketone, 4- dimethyl aminoethyls benzoic ether, 4- dimethylamino isoamyl benzene first Acid esters, 4- diethyl aminos benzoylformaldoxime, 4- dimethylaminos propiophenone, 2- ethylhexyl -1,4- dimethyl aminobenzoates, Bis- (the 4- diethylaminos benzal) cyclohexanone of 2,5-, 7- diethylaminos -3- (4- diethylaminos benzoyl) cumarin, 4- (diethylamino) chalcone etc..
As Photoepolymerizationinitiater initiater, especially from sensitivity, plate-making property this point from the point of view of, oxime ester compound be it is effective, The case where using alkali soluble resin comprising phenolic hydroxyl group etc., is unfavorable in terms of sensitivity, and therefore, such sensitivity is excellent Oxime ester compound is particularly useful.Oxime ester compound due to having the structure for absorbing ultraviolet light, transmission simultaneously in its structure The structure of luminous energy and the structure generated free radicals, it is therefore, high a small amount of sensitivity and thermal response is stablized, even if on a small quantity Also highly sensitive photosensitive coloring composition can be obtained.
As oxime ester compound, it can be cited for example that the following general formula (IV) compound represented.
[chemical formula 45]
In above-mentioned formula (IV), R21aIndicate hydrogen atom, the alkyl optionally with substituent group or the optional virtue with substituent group Fragrant cyclic group.
R21bIndicate the arbitrary substituent group comprising aromatic rings or miscellaneous aromatic rings.
R22aIt indicates optionally with substituent group alkanoyl or the optional aroyl with substituent group.
R21aIn the carbon atom number of alkyl be not particularly limited, examined from the viewpoint of dissolubility, sensitivity in a solvent Consider, usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less.As The concrete example of alkyl can enumerate methyl, ethyl, propyl, cyclopentyl ethyl, propyl etc..
As the substituent group that alkyl optionally has, can enumerate aromatic group, hydroxyl, carboxyl, halogen atom, amino, Amide groups, 4- (2- methoxyl group -1- methyl) ethyoxyl -2- aminomethyl phenyls or N- acetyl group-N- acetoxyl group amino etc., from synthesis It is preferably unsubstituted from the viewpoint of easiness.
As R21aIn aromatic group, can enumerate aromatic cyclic hydrocarbon group group and aromatic heterocyclic group.Fragrant ring group The carbon atom number of group is not particularly limited, from the viewpoint of the dissolubility to photosensitive coloring composition, preferably 5 or more. In addition, from the viewpoint of developability, preferably 30 or less, more preferably 20 or less, further preferably 12 or less.
As the concrete example of aromatic group, phenyl, naphthalene, pyridyl group, furyl etc. can be enumerated, in these, from From the viewpoint of developability, preferred phenyl or naphthyl, more preferable phenyl.
As the substituent group that aromatic group optionally has, hydroxyl, carboxyl, halogen atom, amino, amide can be enumerated Base, alkyl etc., from the viewpoint of developability, preferably hydroxyl, carboxyl, more preferably carboxyl.
In these, from the viewpoint of developability, preferably R21aOptionally to have the alkyl of substituent group, more preferably not Substituted alkyl, further preferably methyl.
In addition, as R21b, preferably optionally substituted carbazyl, optionally substituted thioxanthene ketone group or optionally taken The diphenylsulfide base in generation.In these, from the viewpoint of inhibiting N-Methyl pyrrolidone (NMP) to dissolve out, preferred optional quilt Substituted diphenylsulfide base.
In addition, R22aIn the carbon atom number of alkanoyl be not particularly limited, from dissolubility in a solvent, sensitivity Viewpoint considers, usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably 10 with Under, further preferably 5 or less.As the concrete example of alkanoyl, acetyl group, acetyl (ethyloyl) base, propionyl can be enumerated Base, bytyry etc..
As the substituent group that alkanoyl optionally has, aromatic group, hydroxyl, carboxyl, halogen atom, ammonia can be enumerated Base, amide groups etc., it is preferably unsubstituted from the viewpoint of synthesis easiness.
In addition, R22aIn the carbon atom number of aroyl be not particularly limited, from dissolubility in a solvent, sensitivity Viewpoint considers, usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably 10 with Under.As the concrete example of aroyl, benzoyl, naphthoyl etc. can be enumerated.
As the substituent group that aroyl optionally has, hydroxyl, carboxyl, halogen atom, amino, amide groups, alkane can be enumerated Base etc., it is preferably unsubstituted from the viewpoint of synthesis easiness.
In these, from the viewpoint of sensitivity, preferably R22aOptionally to have the alkanoyl of substituent group, more preferably Unsubstituted alkanoyl, further preferably acetyl group.
In above-mentioned logical formula (IV) compound represented, from the viewpoint of inhibiting NMP dissolutions, preferred the following general formula (V) institute The compound shown.
[chemical formula 46]
In above-mentioned logical formula (V), R23It indicates optionally with substituent group alkyl or the optional aromatic group with substituent group.
R24Indicate the alkyl optionally with substituent group or the optional aromatic group with substituent group.
R25Group shown in expression hydroxyl, carboxyl or the following general formula (V-1), h indicate 0~5 integer.
Phenyl ring shown in formula (V) can further have substituent group.
[chemical formula 47]
R25c-R25b-R25a-* (V-1)
In formula (V-1), R25aExpression-O- ,-S- ,-OCO- or-COO-.
R25bIndicate the optionally alkylidene with substituent group.
R25bAlkylene moiety can also be blocked by-O- ,-S- ,-COO- or-OCO- 1~5 time.R25Alkylene moiety There can be branched building block, or cyclohexylene.
R25cIndicate hydroxyl or carboxyl.
R23In the carbon atom number of alkyl be not particularly limited, examined from the deliquescent viewpoint to photosensitive coloring composition Consider, preferably 1 or more.In addition, from the viewpoint of developability, preferably 20 or less, more preferably 10 or less, further preferably For 8 or less, be still more preferably 5 or less, particularly preferably 3 or less.
As the concrete example of alkyl, methyl, hexyl, cyclopentyl-methyl etc. can be enumerated, in these, from the sight of developability Point consideration, preferably methyl or hexyl, more preferable methyl.
As the substituent group that alkyl optionally has, fragrant ring group, hydroxyl, carboxyl, halogen atom, amino, acyl can be enumerated Amido etc., from the viewpoint of alkali-developable, preferably hydroxyl, carboxyl, more preferable carboxyl.In addition, from the viewpoint of synthesis easiness Consider, it is preferably unsubstituted.
As R23In aromatic group, can enumerate aromatic cyclic hydrocarbon group group and aromatic heterocyclic group.Fragrant ring group The carbon atom number of group is not particularly limited, from the viewpoint of the dissolubility to photosensitive coloring composition, preferably 5 or more. In addition, from the viewpoint of developability, preferably 30 or less, more preferably 20 or less, further preferably 12 or less.
As the concrete example of aromatic group, phenyl, naphthalene, pyridyl group, furyl etc. can be enumerated, in these, from From the viewpoint of developability, preferred phenyl or naphthyl, more preferable phenyl.
As the substituent group that aromatic group optionally has, hydroxyl, carboxyl, halogen atom, amino, amide can be enumerated Base, alkyl etc., from the viewpoint of developability, preferably hydroxyl, carboxyl, more preferable carboxyl.
In these, from the viewpoint of developability, preferably R23For the alkyl optionally with substituent group, do not take more preferably The alkyl in generation, further preferably methyl.
R24In the carbon atom number of alkyl be not particularly limited, from the viewpoint of sensitivity, preferably 1 or more.In addition, From the viewpoint of sensitivity, preferably 20 or less, more preferably 10 or less, further preferably 5 or less, still more preferably It is 3 or less.
As the concrete example of alkyl, methyl, ethyl, propyl etc. can be enumerated, in these, is examined from the viewpoint of sensitivity Consider, preferably methyl or ethyl, more preferable methyl.
As the substituent group that alkyl optionally has, halogen atom, hydroxyl, carboxyl, amino, amide groups etc. can be enumerated, from From the viewpoint of alkali-developable, preferably hydroxyl, carboxyl, more preferable carboxyl, on the other hand, from the viewpoint of synthesis easiness, It is preferably unsubstituted.
As R24In aromatic group, can enumerate aromatic cyclic hydrocarbon group group and aromatic heterocyclic group.Its carbon atom Number preferably 30 or less, more preferably 12 hereinafter, and usually 4 or more, preferably 6 or more.By being set as above-mentioned upper limit value Exist as the tendency of low sublimability by being set as above-mentioned lower limiting value or more as highly sensitive tendency hereinafter, existing.
Aromatic cyclic hydrocarbon group group refers to the aromatic cyclic hydrocarbon group group with 1 free valency.The fragrance of aromatic cyclic hydrocarbon group group Race's hydrocarbon ring can be that monocycle can also be condensed ring, can enumerate 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 heterocyclic group refers to the heteroaromatic with 1 free valency.The fragrance of aromatic heterocyclic group Race's heterocycle can be that monocycle can also be condensed ring, it can be cited for example that：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 And it is differentAzoles ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, Isoquinolin ring, cinnolines (cinnoline) ring, quinoxaline ring, phenanthridines ring, benzimidazole ring,Phenazine ring, quinazoline ring, quinazoline Ketone ring,Ring etc..
As the substituent group that aromatic group optionally has, alkyl, halogen atom, hydroxyl, carboxyl etc. can be enumerated.
In these, from the viewpoint of sensitivity, preferably R24For the alkyl optionally with substituent group, do not take more preferably The alkyl in generation, further preferably methyl.
On the other hand, from the viewpoint of plate-making property, preferably R24Optionally to have the aromatic group of substituent group, more preferably For the aromatic hydrocarbyl optionally with substituent group, further preferably unsubstituted aromatic hydrocarbyl, particularly preferably phenyl.
R25For group shown in hydroxyl, carboxyl or above-mentioned general formula (V-1), in these, from sensitivity and the sight of developability It puts and considers, group shown in preferably above-mentioned general formula (V-1).
In above-mentioned general formula (V-1), if front describes, R25aExpression-O- ,-S- ,-OCO- or-COO-, in these, from From the viewpoint of sensitivity and developability, preferably-O- or-OCO-, more preferable-O-.
If front describes, R25bIndicate the optionally alkylidene with substituent group.
R25bIn the carbon atom number of alkylidene be not particularly limited, from the deliquescent sight to photosensitive coloring composition Point consider, preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 10 or less, further preferably 5 or less, 3 or less are particularly preferably.
Alkylidene can be straight chain or branch, can also include cycloaliphatic ring.In these, to photonasty From the viewpoint of the dissolubility of color composition, preferably straight-chain alkyl-sub.
As the concrete example of alkylidene, methylene, ethylidene, propylidene etc. can be enumerated, in these, to photonasty From the viewpoint of the dissolubility of coloured composition, more preferable methylene.
If front describes, R25cFor hydroxyl or carboxyl.From the viewpoint of reliability (liquid crystal pollution), preferably R25cFor Hydroxyl.
In above-mentioned logical formula (V), h indicates 0~5 integer.In particular, from the viewpoint of developability, preferably h is 1 or more, And preferably 4 or less, it is more preferably 3 or less, further preferably 2 or less, most preferably 1.
On the other hand, from the viewpoint of synthesis easiness, preferably h is 0.
As the concrete example of above-mentioned logical formula (IV), (V) oxime ester compound indicated, oxime esters below can be enumerated Close object.
[chemical formula 48]
The manufacturing method of oxime ester compound shown in above-mentioned logical formula (V) is not particularly limited, it can be for example, by Method described in Japanese Unexamined Patent Publication 2000-080068 bulletins manufactures.
In addition, as oxime ester compound, the compound other than above-mentioned logical formula (IV), (V) can also be used, for example, also Japanese Unexamined Patent Publication 2000-80068 bulletins, Japanese Unexamined Patent Publication 2006-36750 bulletins, International Publication No. 2008/ can be used No. 075564, International Publication No. 2009/131189, the oxime ester described in Japanese Unexamined Patent Application Publication 2014-500852 bulletins etc. derive Object etc..
Photoepolymerizationinitiater initiater can be used alone, and can also combine two or more use.
In order to improve induction sensitivity, it can coordinate in Photoepolymerizationinitiater initiater as needed and correspond to image exposure light source Wavelength sensitizing dyestuff, polymerization accelerant.As sensitizing dyestuff, can enumerate：Japanese Unexamined Patent Publication 4-221958 bulletins, day Described in this Unexamined Patent 4-219756 bulletinsTon pigment, Japanese Unexamined Patent Publication 3-239703 bulletins, Japanese Unexamined Patent Publication 5- The cumarin pigment with heterocycle, Japanese Unexamined Patent Publication 3-239703 bulletins described in No. 289335 bulletins, Japanese Unexamined Patent Publication The methylene described in 3- oxos coumarin compound, Japanese Unexamined Patent Publication 6-19240 bulletins described in 5-289335 bulletins Lanaurin and Japanese Unexamined Patent Application 47-2528 bulletins, Japanese Unexamined Patent Application 54-155292 bulletins, Japanese Patent Publication 45- No. 37377 bulletins, Japanese Unexamined Patent Application 48-84183 bulletins, Japanese Unexamined Patent Application 52-112681 bulletins, Japanese Unexamined Patent Application 58- No. 15503 bulletins, Japanese Unexamined Patent Application 60-88005 bulletins, Japanese Unexamined Patent Application 59-56403 bulletins, Japanese Unexamined Patent Publication 2-69 Number bulletin, Japanese Unexamined Patent Application 57-168088 bulletins, Japanese Unexamined Patent Publication 5-107761 bulletins, Japanese Unexamined Patent Publication 5-210240 The pigment etc. with dialkyl amido benzene skeleton described in number bulletin, Japanese Unexamined Patent Publication 4-288818 bulletins.
In these sensitizing dyestufves, preferably amino-containing sensitizing dyestuff more preferably has ammonia in same intramolecular The compound of base and phenyl.Particularly preferred such as 4,4 '-dimethylamino benzophenones, 4,4 '-diethylamino benzophenone, 2- aminobenzophenones, 4- aminobenzophenones, 4,4 '-diaminobenzophenones, 3,3 '-diaminobenzophenones, 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] benzoBis- (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, bis- (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 the compound etc. to dialkylaminophenyl.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, 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) olefinic unsaturated compounds ＞
The photosensitive coloring composition of the present invention includes (d) olefinic unsaturated compound.By including (d) olefinic unsaturation Compound, sensitivity improve.
The olefinic unsaturated compound used in the present invention is the chemical combination that intramolecular has at least one ethylenically unsaturated group Object.Specifically, it can be cited for example that (methyl) acrylic acid, (methyl) alkyl acrylate, acrylonitrile, styrene and have 1 The monoesters etc. that the carboxylic acid of ethylenic unsaturated bond is formed with polyalcohol or monohydric alcohol.
In the present invention, particularly preferably using the multifunctional olefinic with 2 or more ethylenically unsaturated groups in 1 molecule Monomer.The number of ethylenically unsaturated group possessed by multifunctional olefinic type monomers is not particularly limited, usually 2 or more, excellent It is selected as 4 or more, more preferably 5 or more, and preferably 8 or less, more preferably 7 or less.Under being set as above-mentioned More than limit value, exist with highly sensitive tendency, by being set as above-mentioned upper limit value hereinafter, being carried in the presence of dissolubility in a solvent High tendency.
As the example of multifunctional olefinic type monomers, it can be cited for example that：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 The polyols such as polyol and ester obtained from the esterification of unsaturated carboxylic acid and polybasic carboxylic acid etc..
As the ester that above-mentioned aliphatic polyhydroxy compound and unsaturated carboxylic acid are formed, ethylene glycol diacrylate can be enumerated Ester, triethylene glycol diacrylate, trimethylolpropane trimethacrylate, methylolethane triacrylate, pentaerythrite Diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, two seasons penta The acrylic acid of the aliphatic polyhydroxy compounds such as five acrylate of tetrol, dipentaerythritol hexaacrylate, glyceryl acrylate The acrylate of these example compounds is replaced with methacrylate obtained from methacrylate, similarly replaced by ester It is changed to itaconate obtained from itaconate, replace with butenoate obtained from butenoate or replaces with maleate Obtained from maleate etc..
As the ester that aromatic polyhydroxy compounds and unsaturated carboxylic acid are formed, hydroquinone diacrylate can be enumerated Ester, hydroquinone 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 can enumerate the condensation of acrylic acid, phthalic acid and ethylene glycol if enumerating its representative specific example Object；The condensation product of acrylic acid, maleic acid and diethylene glycol；The condensation product of methacrylic acid, terephthalic acid (TPA) and pentaerythrite；Third The condensation product etc. of olefin(e) acid, adipic acid, butanediol and glycerine.
In addition, the example of 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 allyls esters such as allyl ester；The compound etc. containing vinyl such as phthalic acid divinyl base ester.
As above-mentioned carbamate (methyl) esters of acrylic acid, it can be cited for example that：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 the villages Xin Zhong), UA-306H, UA-510H, UF-8001G (the Chemical Co., Ltd. manufacture of Xie Rong societies), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (Japan's synthesis Chemical Co., Ltd. manufactures) etc..
In these, from the viewpoint of curability, as (d) olefinic unsaturated compound, it is preferable to use (methyl) third Olefin(e) acid Arrcostab more preferably uses dipentaerythritol hexaacrylate.
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 it is coated with and becomes easy.
The photosensitive coloring composition of the present invention is usually to draw (a) colorant, (b) alkali soluble resin, (c) photopolymerization Hair agent, (d) olefinic unsaturated compound, (f) dispersant and various other materials used as needed are dissolved or dispersed in molten State in agent uses.In solvent, from the viewpoint of dispersibility, coating, preferable organic solvent.
In organic solvent, from the viewpoint of coating, the solvent that boiling point is 100~300 DEG C of ranges is preferably selected, More preferably select boiling point for the solvent of 120~280 DEG C of ranges.It should be noted that boiling point mentioned here refers in pressure Boiling point under 1013.25hPa.
As such organic solvent, for example, solvent below.
Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, the third two Alcohol list ether, propylene glycol mono-n-butyl ether, glycol tertiary butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list N-butyl ether, methoxy amylalcohol, dipropylene glycol monoethyl ether, 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, propylene glycol 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 diacetates classes such as ethylene acetate, 1,3 butylene glycol diacetate esters, 1,6-HD diacetate esters；
The alkyl acetates 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, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl Ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl Ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, ethylpentyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxy Ketone as pentanone；
Ethyl alcohol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, 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 as gamma-butyrolacton or cyclic annular esters；
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 above-mentioned commercially available organic solvent is equivalent to, 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) " be registered trademark, it is 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 may be used alone or in combination of two or more kinds.
In the case of forming coloring spacer with photoetching process, as organic solvent, it is 100~200 DEG C to preferably select boiling point The organic solvent of (under the conditions of pressure 1013.25hPa, hereinafter, about boiling point all same) range.More preferably there are 120~170 DEG C Boiling point organic solvent.
In above-mentioned organic solvent, constituent good from the harmony of coating, surface tension etc., in composition it is molten From the aspect of Xie Du 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, from the dissolving of the constituent in composition Property consider, particularly preferred propylene glycol monomethyl ether.It should be noted that the polarity of glycol monoalkyl ethers is high, if its additive amount Excessively, then there is pigment to be easy cohesion and the viscosity of the colored resin composition obtained thereafter is made the storage stabilities decline such as to rise Tendency, therefore, the ratio of the glycol monoalkyl ethers in solvent is preferably the 5 mass % of mass %~30, more preferably 5 matter Measure the mass of %~20 %.
It is also preferable to organic solvent (hereinafter, sometimes referred to as " high boiling solvent ") group with 150 DEG C or more boiling points It closes and uses.By being applied in combination with such high boiling solvent, although photosensitive coloring composition becomes difficult to drying, have The effect for preventing the uniform dispersity of the pigment in the case where drastically drying in composition to be destroyed.That is, with for example Prevent from generating the effect of foreign matter defect because of the precipitation of color material etc., solidification in slit spray nozzle front end.In terms of such effect is high Consider, in above-mentioned various solvents, particularly preferred diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetic acid esters and diethyl 2-ethoxyethanol acetic acid esters.
The content ratio of high boiling solvent is preferably the 3 mass % of mass %~50, more preferably 5 mass % in organic solvent ~40 mass %, particularly preferably 5 mass of mass %~30 %.More than for above-mentioned lower limiting value, existing can inhibit for example The tendency of foreign matter defect is generated because of the precipitation of color material etc., solidification in slit spray nozzle front end, in addition, by for above-mentioned upper limit value with Under, it can be slack-off with the drying temperature of composite inhibiting, to which presence can inhibit the productive temp for being dried under reduced pressure technique bad, pre- Bake the tendency of the pin hole this problem of (pre-bake).
It should be noted that the high boiling solvent of 150 DEG C of boiling point or more can be glycol alkyl ether acetate esters, in addition Can be glycol alkyl ether class, in this case, high boiling solvent that can not also be in addition containing 150 DEG C of boiling point or more.
As preferred high boiling solvent, it can be cited for example that 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) colorant imperceptibly disperse and making its dispersity It stabilizes for ensuring that quality stability is important, therefore contains (f) dispersant.
As (f) dispersant, preferably there is the macromolecule dispersing agent of functional group, in addition, from the aspect of dispersion stabilization, It is preferred that having carboxyl；Phosphate；Sulfonic group；Or their alkali；Primary amino group, 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, especially from when disperseing pigment From the viewpoint of capable of being disperseed with a small amount of dispersant, particularly preferably there is primary amino group, secondary amino group or tertiary amino；Quaternary ammonium salt Base；From the macromolecule dispersing agent of the basic functionalities such as the nitrogenous heterocyclic group such as pyridine, pyrimidine, pyrazine.
In addition, as macromolecule dispersing agent, it can be cited for example that：Carbamates dispersant, acrylic dispersants, Dispersant, the polyoxy that polyethyleneimine amine dispersant, polyallyl amine dispersant, the monomer with amino are formed with polymeric monomer Vinyl alkyl ethers dispersant, two esters dispersant of polyoxyethylene, 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 (registered trademark, BASF AG's system can be enumerated Make), DISPERBYK (registered trademark, BYK-Chemie companies manufacture), Disparlon (registered trademark, nanmu this chemical conversion strain formula meeting Society manufactures), SOLSPERSE (registered trademark, Lubrizol companies manufacture), KP (Shin-Etsu Chemial Co., Ltd's manufacture), Polyflow (Kyoeisha Chemical Co., Ltd.'s manufacture), Ajisper (registered trademark, 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 700 or more, preferably 1000 or more, and is usually 100,000 hereinafter, preferably 50, and 000 or less.
In 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 dispersibility, 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, it can be cited for example that DISPERBYK 160~ 166,182 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 Object 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..By being handled above-mentioned dispersion resin with 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：Paraphenylene diisocyanate, Toluene-2,4-diisocyanate, 4- bis- are different Cyanate, Toluene-2,4-diisocyanate, 6- diisocyanate, 4,4 '-methyl diphenylene diisocyanates, 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 Ester, 4,4 '-di-2-ethylhexylphosphine oxides (cyclohexyl isocyanate), ω, alicyclic two isocyanide such as ω '-diisocyanate dimethyl cyclohexanes Acid esters, xylylene diisocyanate, α, α, α ', α '-tetramethyl xylylene diisocyanates 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 polyisocyanates, the preferably tripolymer of organic diisocyanate, most preferably toluene The tripolymer of diisocyanate and the tripolymer of isophorone diisocyanate.They can be used alone, and can also combine Two or more is used.
The manufacturing method of tripolymer as isocyanates can enumerate following method：Use trimerization catalyst appropriate Agent carries out isocyanide such as tertiary amines, phosphine, alkoxide species, metal oxide, metal carboxylate to above-mentioned polyisocyanates The trimerizing of the part of perester radical makes trimerizing terminate, is then removed with solvent extraction, thin-film distillation by adding catalyst poison Unreacted polyisocyanates is removed, to obtain the polyisocyanates containing cyamelide ester group of target.
It, 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, polycarbonate glycol, polyolefin dihydric alcohol etc. and the side of these compounds Substance and the mixture of more than two kinds in them obtained from alkyl alkoxide of the terminal hydroxyl by carbon atom number 1~25.
As polyether Glycols, polyetherdiol, polyethers esterdiol and their mixture of more than two kinds can be enumerated. As polyetherdiol, can enumerate will substance obtained from oxidation polyamino alkenyl or copolymerization, such as it is polyethylene glycol, polypropylene glycol, poly- Ethylene glycol propylene glycol, polyoxy butylen glycol, polyoxy hexylidene glycol, polyoxy octamethylene glycol and the of more than two kinds of theirs mix Close object.
As polyethers esterdiol, can enumerate by make the glycol containing ether or with the mixture and dicarboxyl of other glycol Acid or their anhydride reaction or substance obtained from making oxyalkylene be reacted with polyester-diol, such as poly- (polyoxy butylidene) Adipate ester etc..As polyetherdiol, most preferably polyethylene glycol, polypropylene glycol, polyoxy butylen glycol or these chemical combination Compound made of alkyl alkoxide of the side end hydroxyl of object by carbon atom number 1~25.
As polyester-diol, can enumerate：Dicarboxylic acids (succinic 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, propylene glycol, dipropylene glycol, three Propylene glycol, 1,2- butanediols, 1,3 butylene glycol, 1,4- butanediols, 2,3- butanediols, 3- methyl-1s, 5- pentanediols, new penta 2 Alcohol, 2- methyl-1,3-propanediols, 2- methyl-2-propyl -1,3- propylene glycol, 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, 2,5- dimethyl -2,5-HD, 1,8- ethohexadiols, 2- methyl-1s, it is the aliphatic diols such as 8- ethohexadiols, 1,9- nonanediols, double Aromatic diols, the N- methyl diethanols such as the alicyclic diols such as (methylol) hexamethylene, benzene dimethanol, bis- (hydroxyl-oxethyl) benzene N- alkyl dialkanol amines such as amine etc.) substance 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 atom 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 atom number 1~25 alcohol is the polycaprolactone that initiator obtains.
As polycarbonate glycol, poly- carbonic acid (1,6- hexylene glycol) ester, poly- carbonic acid (3- methyl-1s, 5- penta 2 can be enumerated Alcohol) ester etc. can enumerate the poly- isoamyl of polybutadiene diol, hydrogenation type polybutadiene diol, hydrogenation type two as polyolefin diols 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 It is 500~6,000, more preferably 1,000~4,000.
In same intramolecular there is the compound of active hydrogen and tertiary amino to illustrate to being used in the present invention.
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 the hydrogen atom of preferred amino, particularly primary amino group.
Tertiary amino is not particularly limited, it can be cited for example that the amino or heterocycle of the alkyl with carbon atom number 1~4 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-1,3- 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 enumerate：Pyrazole ring, miaow Azoles ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoAzoles ring, benzo Nitrogenous 5 circle heterocyclic ring such as thiazole ring, diazosulfide ring, it is pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, different Nitrogenous 6 circle heterocyclic ring such as quinoline ring.In these nitrogen heterocyclic rings, preferably imidazole ring or triazole ring.
If these compounds with imidazole ring and amino of specific example can enumerate 1- (3- aminopropyls) miaow Azoles, histidine, 2- aminooimidazoles, 1- (2- amino-ethyls) imidazoles etc..In addition, if specific example these with triazole ring and ammonia The compound of base, then can enumerate 3- amino-1,2,4-triazoles, 5- (2- amino -5- chlorphenyls) -3- phenyl -1H-1, and 2,4- tri- Azoles, 4- amino -4H-1,2,4- triazole -3,5- glycol, 3- amino-5-phenyl -1H-1,3,4- triazoles, 5- amino -1,4- hexichol Base -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) imidazoles, 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 100 mass parts of compound in same intramolecular there is the compound of number-average molecular weight 300~10,000 of 1 or 2 hydroxyl to be 10~200 mass parts, preferably 20~190 mass parts, more preferably 30~180 mass parts have active in same intramolecular The compound of hydrogen and tertiary amino is 0.2~25 mass parts, preferably 0.3~24 mass parts.
Known method that the manufacture of carbamates macromolecule dispersing agent is manufactured according to polyurethane resin carries out.As Solvent when manufacture, usually using ketones such as acetone, methyl ethyl ketone, 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 diacetone alcohol, isopropanol, secondary The chloro things such as the parts such as butanol, tert-butyl alcohol alcohols, dichloromethane, chloroform；The ethers such as tetrahydrofuran, ether；Dimethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide isopolarity 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, it can be cited for example that 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 the amine value after reaction that same intramolecular, which has the import volume of the compound of active hydrogen and tertiary amino, In the amount of 1~100mgKOH/g ranges, more preferably amount of the control in 5~95mgKOH/g ranges.Amine value is with acid to basic amine group Carry out acid-base titration, the value corresponding with acid value indicated with the mg numbers of KOH.When amine value is less than above range, there are dispersion energy The tendency that power declines, in addition, if it exceeds above range, then developability is easily reduced.
It should be noted that in above reaction in macromolecule dispersing agent in the case of remaining isocyanate group, if Isocyanate group further is destroyed with alcohol, amino-compound, then the ageing stability of product is got higher, 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 range.When the molecular weight is less than 1,000, dispersibility and stably dispersing Property is poor, if it exceeds 200,000, then decreased solubility, the control of bad dispersibility, simultaneous reactions becomes difficult.
As acrylic polymer dispersant, it is preferable to use (functional group mentioned here is as height with functional group The functional group that functional group contained in dispersal agent molecule describes in front) and monomer containing unsaturated group with 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 It is manufactured with well known method.
As the monomer with functional group and containing unsaturated group, (methyl) acrylic acid, 2- (methyl) third can be enumerated Alkene acyloxyethyl succinic 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, quaternary ammonium salt base unsaturated monomer 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) phenoxyethyl 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, polyethylene glycol polymeric monomer, polypropylene glycol polymeric monomer, gathers in oneself poly- (methyl) acrylic acid 2- hydroxy methacrylates polymeric monomer Polymeric monomers such as ester polymeric monomer etc..They can be used alone, or combine two or more use.
Acrylic polymer dispersant particularly preferably by with functional group A blocks with without functional group B block A-B the or B-A-B block copolymers of composition, at this point, above-mentioned comprising functional group and containing unsaturated group in addition to deriving from A blocks Other than 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 80 mass % hereinafter, preferably 50 mass % are hereinafter, more excellent It is selected as 30 mass % or less.
B block includes the part-structure without functional group but the monomer containing unsaturated group from above-mentioned, 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.
Living polymerization as shown below for example can be used to prepare in A-B the or B-A-B block copolymers.
Living polymerization includes living anion polymerization method, anion living polymerization method, radical living polymerization method, In, the polymerization activity kind of living anion polymerization method is anion, such as is indicated by following synthetic routes.
[chemical formula 49]
In said synthesis route, Ar1For 1 valence organic group, Ar2To be different from Ar11 valence organic group, M is that metal is former Son, s and t are respectively 1 or more integer.
The polymerization activity kind of radical living polymerization method is free radical, such as is indicated by following synthetic routes.
[chemical formula 50]
In said synthesis route, Ar1For 1 valence organic group, Ar2To be different from Ar11 valence organic group, j and k are respectively 1 or more integer, RaFor hydrogen atom or 1 valence organic group, RbWith RaDifference is hydrogen atom or 1 valence organic group.
When synthesizing the acrylic polymer dispersant, may be used Japanese Unexamined Patent Publication 9-62002 bulletins, 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, Well 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, constitute the A blocks of its copolymer/B block than preferably 1/99~80/20, particularly preferably 5/95~ 60/40 (mass ratio), by making it that can ensure that dispersibility and the balanced of storage stability are inclined within the scope of this, to exist 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 making it within the scope of this, inclining for good dispersibility can be ensured by existing To.
It should be noted that in such block copolymer, the ammonia generated in the fabrication process would generally be contained sometimes Base, amine value is 1~100mgKOH/g or so, from the viewpoint of dispersibility, preferably 10mgKOH/g or more, is more preferably 30mgKOH/g or more, further preferably 50mgKOH/g or more, and preferably 90mgKOH/g or less, more preferably 80mgKOH/g or less, further preferably 75mgKOH/g or less.
Here, the amine value of the dispersant of these block copolymers etc. is with being equivalent in dispersant sample in addition to solvents The comparable KOH mass of alkali number of solid constituent 1g indicates, is measured by following method.
Accurate weighing dispersant 0.5~1.5g of sample in the beaker of 100mL, with the acetic acid of 50mL, using having The automatic titration device of pH electrodes, with the HClO of 0.1mol/L4Acetic acid solution carries out acid-base titration to the solution, and titration pH is bent The inflection point of line finds out amine value according to the following formula as titration end-point.
Amine value [mgKOH/g]=(561 × V)/(W × S)
[wherein, W：Indicate the dispersant sample amount of weighing [g], V：Indicate titer [mL], the S in titration end-point：It indicates 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 value basis and its type, Generally preferable acid value junior, usually 10mgKOH/g is hereinafter, its weight average molecular weight (Mw) is preferably 1000~100,000 Range.By making it be there is the tendency that can ensure good dispersibility in above range.
Concrete structure with quaternary ammonium salt group as the macromolecule dispersing agent of functional group is not particularly limited, but from From the viewpoint of dispersibility, the repetitive unit preferably with following formula (i) expression (hereinafter, sometimes referred to as " repetitive unit (i) ").
[chemical formula 51]
In above-mentioned formula (i), R31~R33It is each independently hydrogen atom, optionally alkyl with substituent group, optional with taking The aryl of Dai Ji or the optionally aralkyl with substituent group, R31~R33In 2 or more can be mutually bonded and form cyclic annular knot Structure.R34For hydrogen atom or methyl, X is the connection group of divalent, Y-For counter anion.
The R of above-mentioned formula (i)31~R33In the optionally carbon atom number of alkyl with substituent group be not particularly limited, usually 1 or more, and preferably 10 hereinafter, more preferably 6 or less.As the specific example of alkyl, methyl, ethyl, third can be enumerated Base, butyl, amyl, hexyl, heptyl, octyl etc., in these, preferably methyl, ethyl, propyl, butyl, amyl or hexyl, More preferably methyl, ethyl, propyl or butyl.Furthermore it is possible to for the arbitrary form in straight-chain, branched.Furthermore it is also possible to Contain the cyclic structures such as cyclohexyl, cyclohexyl methyl.
The R of above-mentioned formula (i)31~R33In the optionally carbon atom number of aryl with substituent group be not particularly limited, usually 6 or more, and preferably 16 hereinafter, more preferably 12 or less.As the specific example of aryl, phenyl, methylbenzene can be enumerated Base, ethylphenyl, 3,5-dimethylphenyl, diethyl phenyl, naphthalene, anthryl etc., in these, preferably phenyl, aminomethyl phenyl, second Base phenyl, 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 atom number of aralkyl with substituent group be not particularly limited, usually It is 7 or more, and preferably 16 hereinafter, more preferably 12 or less.As the specific example of aralkyl, phenyl methylidene can be enumerated Base, phenyl-ethylene, phenylpropylene, phenyl butylidene, phenyl isopropylidene etc., in these, preferably phenylmethylene, benzene Base ethylidene, phenylpropylene or phenyl butylidene, more preferable phenylmethylene or phenyl-ethylene.
In these, from the viewpoint of dispersibility, preferably R31~R33It is each independently alkyl or aralkyl, specifically Ground, preferably R31And R33It is each independently methyl or ethyl and R32For phenylmethylene or phenyl-ethylene, more preferable R31And R33For methyl and R32For phenylmethylene.
In addition, above-mentioned macromolecule dispersing agent have tertiary amine as functional group in the case of, it is excellent from the viewpoint of dispersibility Select the repetitive unit that there is following formula (ii) to indicate (hereinafter, sometimes referred to as " repetitive unit (ii) ").
[chemical formula 52]
In above-mentioned formula (ii), R35And R36It is each independently hydrogen atom, the alkyl optionally with substituent group, optionally has The aryl of substituent group or the optionally aralkyl with substituent group, R35And R36It can be mutually bonded and form cyclic structure, R37For hydrogen Atom or methyl, Z are the connection group of divalent.
In addition, the R as above-mentioned formula (ii)35And R36In optionally with substituent group alkyl, can preferably be employed as State the R of formula (i)31~R33And exemplary group.
Similarly, the R as above-mentioned formula (ii)35And R36In optionally with substituent group aryl, can preferably be employed as The R of above-mentioned formula (i)31~R33And exemplary group.In addition, the R as above-mentioned formula (ii)35And R36In optionally with substituent group Aralkyl can preferably be employed as the R of above-mentioned formula (i)31~R33And exemplary group.
In these, R35And R36It is preferred that being each independently the optionally alkyl with substituent group, 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 group having can enumerate halogen atom, alkoxy, benzoyl, hydroxyl etc..
In above-mentioned formula (i) and (ii), as connection the group X and Z of divalent, it can be cited for example that：Carbon atom number 1~10 Alkylidene, carbon atom number 6~12 arlydene ,-CONH-R43Base ,-COOR44Base [wherein, R43And R44It is former for singly-bound, carbon The alkylidene of subnumber 1~10 or the ether (alkyl oxyalkyl) of carbon atom number 2~10] etc., preferably-COO-R44Base.
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 repetitive unit that above-mentioned formula (i) indicates is not particularly limited, from the viewpoint of dispersibility, relatively In above-mentioned formula (i) indicate repetitive unit content ratio and above-mentioned formula (ii) indicate repetitive unit content ratio it is total Preferably 60 moles of % or less, more preferably 50 moles of % or less, meter is more preferably 40 moles of % or less, particularly preferred For 35 moles of % hereinafter, and preferably 5 moles of % or more, more preferably 10 moles of % or more, further preferably 20 rubbing You are % or more, particularly preferably 30 moles of % or more.
Contain in addition, the repetitive unit of above-mentioned formula (i) expression is shared in whole repetitive units of macromolecule dispersing agent Ratio is not particularly limited, from the viewpoint of dispersibility, preferably 1 mole of % or more, more preferably 5 moles of % or more, into One step is preferably 10 moles of % or more, and preferably 50 moles of % or less, preferably 30 moles of % or less, more preferably 20 is rubbed You are % or less, particularly preferably 15 moles of % or less.
Contain in addition, the repetitive unit of above-mentioned formula (ii) expression is shared in whole repetitive units of macromolecule dispersing agent Ratio is not particularly limited, from the viewpoint of dispersibility, preferably 5 moles of % or more, more preferably 10 moles of % or more, into One step be preferably 15 moles of % or more, particularly preferably 20 moles of % or more, and preferably 60 moles of % or less, more preferably 40 moles of % or less, further preferably 30 moles of % or less, particularly preferably 25 moles of % or less.
In addition, from improve with the compatibility of the adhesive ingredients such as solvent, so that dispersion stabilization is improved from the viewpoint of, high score The repetitive unit that sub- dispersant is preferably indicated with following formula (iii) (hereinafter, sometimes referred to as " repetitive unit (iii) ").
[chemical formula 53]
In above-mentioned formula (iii), R40For ethylidene or propylidene, R41For the alkyl optionally with substituent group, R42For hydrogen atom Or methyl, the integer that n is 1~20.
The R of above-mentioned formula (iii)41In the optionally carbon atom number of alkyl with substituent group be not particularly limited, usually 1 with Above, preferably 2 or more, and preferably 10 or less, more preferably 6 or less.As the specific example of alkyl, first can be enumerated Base, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl etc., in these, preferably methyl, ethyl, propyl, butyl, penta Base or hexyl, more preferably methyl, ethyl, propyl or butyl.Furthermore it is possible to be any form in straight-chain, branched.Separately Outside, the cyclic structures such as cyclohexyl, cyclohexyl methyl can also be contained.
In addition, from the viewpoint of the compatibility and dispersibility relative to adhesive ingredients such as solvents, in above-mentioned formula (iii) N be preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less.
Contain in addition, the repetitive unit of above-mentioned formula (iii) expression is shared in whole repetitive units of macromolecule dispersing agent It is proportional to be not particularly limited, preferably 1 mole of % or more, more preferably 2 moles of % or more, further preferably 4 moles of % More than, and preferably 30 moles of % or less, more preferably 20 moles of % or less, further preferably 10 moles of % or less. In the case of in above range, there is the compatibility and dispersion stabilization that can be achieved at the same time relative to adhesive ingredients such as solvents Tendency.
In addition, from improve dispersant relative to the adhesive ingredients such as solvent compatibility, make dispersion stabilization improve sight Point considers that repetitive unit of the macromolecule dispersing agent preferably with following formula (iv) expression is (hereinafter, sometimes referred to as " repetitive unit (iv)”)。
[chemical formula 54]
In above-mentioned formula (iv), R38Have for the alkyl optionally with substituent group, the aryl optionally with substituent group or optionally The aralkyl of substituent group.R39For hydrogen atom or methyl.
The R of above-mentioned formula (iv)38In the optionally carbon atom number of alkyl with substituent group be not particularly limited, usually 1 with Above, preferably 2 or more, more preferably 4 or more, and preferably 10 or less, more preferably 8 or less.Concrete example as alkyl Son can enumerate methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl etc., in these, preferably methyl, second Base, propyl, butyl, amyl or hexyl, more preferably methyl, ethyl, propyl or butyl.Furthermore it is possible to be straight-chain, branched In any form.Alternatively, it is also possible to contain the cyclic structures such as cyclohexyl, cyclohexyl methyl.
The R of above-mentioned formula (iv)38In the optionally carbon atom number of aryl with substituent group be not particularly limited, usually 6 with On, and preferably 16 or less, more preferably 12 or less, further preferably 8 or less.It, can be with as the specific example of aryl Phenyl, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl, diethyl phenyl, naphthalene, anthryl etc. are enumerated, in these, preferably Phenyl, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl or diethyl phenyl, more preferably phenyl, aminomethyl phenyl or ethylo benzene Base.
The R of above-mentioned formula (iv)38In the optionally carbon atom number of aralkyl with substituent group be not particularly limited, usually 7 More than, and preferably 16 or less, more preferably 12 or less, further preferably 10 or less.As the specific example of aralkyl, Phenylmethylene, phenyl-ethylene, phenylpropylene, phenyl butylidene, phenyl isopropylidene etc. can be enumerated, in these, Preferably phenylmethylene, phenyl-ethylene, phenylpropylene or phenyl butylidene, more preferably phenylmethylene or phenyl are sub- Ethyl.
In these, from the viewpoint of solvent compatibility and dispersion stabilization, R38Preferably alkyl or aralkyl, it is more excellent It is selected as methyl, ethyl or phenylmethylene.
As R38In the substituent group that optionally has of alkyl, halogen atom, alkoxy etc. can be enumerated.In addition, as virtue The substituent group that base or aralkyl optionally have can enumerate alkyl, halogen atom, alkoxy of chain etc..In addition, R38Shown in The alkyl of chain includes any one of straight-chain and branched.
In addition, from the viewpoint of dispersibility, the whole of repetitive unit that above-mentioned formula (iv) indicates in macromolecule dispersing agent Shared content ratio is preferably 30 moles of % or more, more preferably 40 moles of % or more, is more preferably in repetitive unit 50 moles of % or more, and preferably 80 moles of % or less, more preferably 70 moles of % or less.
Macromolecule dispersing agent can also have repetitive unit (i), repetitive unit (ii), repetitive unit (iii) and repeat single Repetitive unit other than first (iv).As the example of such repetitive 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 repetitive unit of the monomers such as N- metering system morpholides.
From the viewpoint of further increasing dispersibility, macromolecule dispersing agent is preferably the block with A blocks and B block Copolymer, the A blocks have repetitive unit (i) and repetitive unit (ii), and the B block is without repetitive unit (i) and again Multiple unit (ii).The block copolymer is preferably A-B block copolymers or B-A-B block copolymers.By being imported in A blocks Quaternary ammonium salt group and tertiary amino unexpectedly have the tendency for the dispersibility for significantly improving dispersant.In addition, B block preferably has There is repetitive unit (iii), in addition, more preferably having repetitive unit (iv).
In A blocks, repetitive unit (i) and repetitive unit can be contained with any form of random copolymerization, block copolymerization (ii).Furthermore it is possible to contain two or more repetitive unit (i) and repetitive unit (ii) respectively in 1 A block, in this case, Each repetitive unit can be contained with any form of random copolymerization, block copolymerization in the A blocks.
Furthermore it is also possible to contain the repetitive unit other than repetitive unit (i) and repetitive unit (ii) in A blocks, as The example of such repetitive unit can enumerate the repetitive unit etc. from above-mentioned (methyl) acrylic ester monomer.Weight Content of the repetitive unit in A blocks other than multiple unit (i) and repetitive unit (ii) is preferably 0~50 mole of %, more preferably For 0~20 mole of %, the repetitive unit is free of most preferably in A blocks.
The repetitive unit other than repetitive unit (iii) and (iv) can be contained in B block, as such repetitive 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 repetitive unit in B block other than repetitive unit (iii) and repetitive unit (iv) is preferably 0~50 mole of %, More preferably 0~20 mole of % is free of the repetitive unit most preferably in B block.
In addition, from the aspect of improving dispersion stabilization, preferably (f) dispersant is combined with the pigment derivative described below It uses.
Other gradation composition ＞ of ＜ photosensitive coloring compositions
It, can be suitable for cooperation silane coupling agent etc. other than mentioned component in the photosensitive coloring composition of the present invention Closely sealed enhancer, coating enhancer, development modifying agent, ultra-violet absorber, antioxidant, surfactant, pigment derivative, Photoacid generator, crosslinking agent, polymerization accelerant etc..
(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, the preferably compound etc. of silane coupling agent, phosphorous acidic group.
It, can be various silane coupled by epoxies, (methyl) acrylic compounds, amino etc. as the type of silane coupling agent 1 kind of exclusive use in agent, or two or more is used in mixed way.
As preferred silane coupling agent, it can be cited for example that：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 silanes class, the 3- isocyanic acids third such as the epoxy silanes classes such as the third oxygen propyl group triethoxysilane, 3- urea propyl-triethoxysilicanes The isocynate silanes class such as ethyl triethoxy silicane alkane, the particularly preferably silane coupling agent of epoxy silane class.
As the compound of phosphorous acidic group, the phosphoric acid ester of (methyl) acryloyl group, more preferable the following general formula are preferably comprised (g1), the compound that (g2) or (g3) is indicated.
[chemical formula 55]
In above-mentioned general formula (g1), (g2) and (g3), R51The integer that expression hydrogen atom or methyl, l and l ' they are 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, dysgenic from being brought to various characteristics The low this respect of possibility considers, it is preferable to use nonionic surface active agent, wherein from the aspect of coating, fluorine class, silicon class Surfactant is effective.
As such surfactant, it can be cited for example that：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. manufactures), 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 dispersibility, keeping quality, it can also contain in photosensitive coloring composition of the invention and be helped as dispersion 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 preferred phthalocyanines, quinophthalone class.
As the substituent group 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, heterocycle etc. On pigment skeleton, in the substituent group of above-mentioned pigment derivative, preferred sulfonic group.In addition, can replace on a pigment skeleton These multiple substituent groups.
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 generate acid by ultraviolet light, by being produced when being exposed The effect of raw acid, enables cross-linking reaction to carry out in the presence of the crosslinking agents such as such as melamine compound.Such In photoacid generator, dissolubility preferably in a solvent, particularly molten in the solvent for photosensitive coloring composition The high substance of solution property, such as can enumerate：Diphenyl iodineXylyl iodinePhenyl (to methoxybenzyl) iodineIt is double (m-nitro base) iodineBis- (to tert-butyl-phenyl) iodineBis- (rubigan) iodineBis- (dodecyl) iodineIt is right Isobutyl phenenyl (p-methylphenyl) iodineP-isopropyl phenyl (p-methylphenyl) iodineEtc. Diaryl iodoniumsOr triphenylsulfonium etc. Chloride, bromide or the boron fluoride salt of triaryl matte, hexafluorophosphate, hexafluoro arsenite, aromatic sulphonate, four (five Fluorophenyl) sulfoniums Organic Bor Complex class or the 2- such as borate etc., diphenyl phenacyl sulfonium (normal-butyl) triph-enylborate The triaizine compounds such as bis- (trichloromethyl) triazines of methyl -4,6-, bis- (trichloromethyl) triazines of 2- (4- methoxyphenyls) -4,6- Deng but not limited to this.
(5) crosslinking agent
The present invention photosensitive coloring composition in crosslinking agent can further be added, for example, can be used melamine or Guanamines compound.As these crosslinking agents, it can be mentioned, for example melamine or the chemical combination of guanamines shown in the following general formula (6) Object.
[chemical formula 56]
In formula (6), R61Expression-NR66R67The aryl of base or carbon atom 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 atom 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 R68Indicate hydrogen atom or the alkyl of carbon atom number 1~4.
Here, the aryl of typical carbon atom number 6~12 is phenyl, 1- naphthalenes or 2- naphthalenes, is gone back on these phenyl, naphthalene The substituent groups such as alkyl, alkoxy, halogen atom can be bonded.The carbon atom 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.
Melamine class compound corresponding with general formula (6), the i.e. compound of the following general formula (6-1) include：Six hydroxyl first Base melamine, pentamethylol melamine, tetra methylol melamine, hexamethoxymethyl melamine, pentamethoxyl first Base melamine, tetramethoxymethyl melamine, six ethoxyl methyl melamines etc..
[chemical formula 57]
In formula (6-1), R62、R63、R64、R65、R66And R67In one in the case of aryl, R62、R63、R64And R65In An expression-CH2OR68Base, remaining R62、R63、R64、R65、R66And R67Hydrogen atom or-CH are indicated independently of one another2OR68 Base, here, R68Indicate hydrogen atom or alkyl.
In addition, guanamines compound corresponding with general formula (6), the R i.e. in general 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.
Bis- (hydroxymethyl) phenol of bis- (the hydroxymethyl) -4- methylphenols of 2,6-, 4- tertiary butyls -2,6-, 5- ethyls -1,3- Bis- (hydroxymethyl) perhydro -1,3,5- triazine -2- ketone (common name N- ethyl dihydroxymethyls triazinone) or its dimethyl ether body, dihydroxy Methyl trimethylene urea or bis- (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, two urea of tetra methylol glyoxal (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, amount relative to all solids ingredient 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 type of sulfhydryl compound, 2-mercaptobenzothiazole, 2- sulfydryl benzos can be enumeratedAzoles, 2- sulfydryl benzos Imidazoles, ethanthiol, two mercaptan of the last of the ten Heavenly stems, 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, four mercaptopropionic acid ester of pentaerythrite, four sulfydryl second of pentaerythrite Acid esters, tri-thiol propionic acid trihydroxy ethyl ester, ethylene glycol bis- (3- mercaptobutylates), butanediol bis- (3- mercaptobutylates), 1,4- Bis- (3- sulfydryls butyryl acyloxy) butane, trimethylolpropane tris (3- mercaptobutylates), pentaerythrite four (3- mercaptobutylates), Pentaerythrite three (3- mercaptobutylates), ethylene glycol bis- (3- mercaptoisobutanoics acid esters), butanediol bis- (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) sulfhydryl compound or the multifunctional sulfhydryl compound of aliphatic etc. with heterocycle such as-triketone.These sulfhydryl compounds can 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, relative to all solids ingredient in photosensitive coloring composition The content ratio of amount, (a) colorant is usually 10 mass % or more, preferably 20 mass % or more, more preferably 30 mass % Above, be more preferably 35 mass % or more, particularly preferably 40 mass % or more, and usually 60 mass % or less, More preferably 50 mass % or less, further preferably 48 mass % or less, particularly preferably 46 mass % or less.Passing through will (a) content ratio of colorant is set as above-mentioned lower limiting value or more, exists to obtain the tendency of enough optical density (OD), in addition, logical It crosses and is set as above-mentioned upper limit value hereinafter, in the presence of the tendency for being easy to get enough plate-making characteristics.
In addition, in the case that (a) colorant includes organic pigment, content ratio of the organic pigment relative to (a) colorant Preferably 1 mass % or more, more preferably 5 mass % or more, further preferably 10 mass % or more, still more preferably it is 30 mass % or more, particularly preferably 50 mass % or more, most preferably 70 mass % or more, and usually 100 mass % Below, it is preferably 99 mass % or less, more preferably 95 mass % or less, further preferably 90 mass % or less, more into one Step is preferably 85 mass % or less, particularly preferably 80 mass % or less.By being set as above-mentioned lower limiting value or more, exist to obtain foot The tendency of enough optical density (OD), by being set as above-mentioned upper limit value hereinafter, in the presence of the tendency that can ensure plate-making characteristic.
In addition, in the case that (a) colorant includes organic coloring pigments, organic coloring pigments are relative to (a) colorant Content ratio is preferably 1 mass % or more, more preferably 5 mass % or more, further preferably 10 mass % or more, more into one Step is preferably 30 mass % or more, particularly preferably 50 mass % or more, is most preferably 70 mass % or more, and is usually 100 mass % or less, preferably 99 mass % or less, more preferably 95 mass % or less, further preferably 90 mass % with Under, still more preferably be 85 mass % or less, particularly preferably 80 mass % or less.By being set as above-mentioned lower limiting value or more, In the presence of the tendency of enough optical density (OD) is obtained, by being set as above-mentioned upper limit value hereinafter, in the presence of that can ensure characteristic of making a plate Tendency.
In addition, (a) colorant includes in the case of being selected from least one of red pigment and orange pigment pigment, to be selected from At least one of red pigment and orange pigment pigment relative to the content ratio of (a) colorant be preferably 1 mass % or more, More preferably 2 mass % or more, further preferably 3 mass % or more, and preferably 30 mass % or less, more preferably 20 Quality % or less, further preferably 15 mass % or less, still more preferably it is 10 mass % or less, particularly preferably 7 matter It measures % or less, be most preferably 5 mass % or less.By being set as above-mentioned lower limiting value or more, exist to obtain enough optical density (OD) Tendency, by be set as above-mentioned upper limit value hereinafter, in the presence of can ensure make a plate characteristic tendency.
In addition, (a) colorant includes in the case of being selected from least one of blue pigment and violet pigment pigment, to be selected from At least one of blue pigment and violet pigment pigment relative to the content ratio of (a) colorant be preferably 20 mass % with Upper, more preferably 30 mass % or more, further preferably 40 mass % or more, be still more preferably 50 mass % or more, Particularly preferably 60 mass % or more, most preferably 65 mass % or more, and preferably 90 mass % or less, more preferably 80 Quality % or less, further preferably 70 mass % or less.By being set as above-mentioned lower limiting value or more, light-proofness can be ensured by existing Tendency, by be set as above-mentioned upper limit value hereinafter, in the presence of can ensure make a plate characteristic tendency.
(a) in the case that colorant contains black color material, black color material is preferably relative to the content ratio of (a) colorant 5 mass % or more, more preferably 10 mass % or more, further preferably 15 mass % or more, particularly preferably 20 mass % More than, and preferably 50 mass % or less, more preferably 40 mass % or less, further preferably 35 mass % or less, more Further preferably 30 mass % or less.By being set as above-mentioned lower limiting value or more, exist to obtain inclining for enough optical density (OD) To by being set as above-mentioned upper limit value hereinafter, in the presence of the tendency that can ensure plate-making characteristic.
In addition, in the case that (a) colorant contains organic black pigments, black organic pigment is relative to (a) colorant Content ratio is preferably 1 mass % or more, more preferably 5 mass % or more, is more preferably 10 mass % or more, is especially excellent It is selected as 20 mass % or more, and preferably 50 mass % or less, more preferably 40 mass % or less, further preferably 30 matter Measure % or less, particularly preferably 20 mass % or less.By being set as above-mentioned lower limiting value or more, exist to obtain enough optical density (OD) tendency, by being set as above-mentioned upper limit value hereinafter, in the presence of the tendency that can ensure plate-making characteristic.
(a) in the case that colorant contains carbon black, carbon black is preferably 5 mass % relative to the content ratio of (a) colorant Above, 10 mass % or more, further preferably 15 mass % or more, particularly preferably 20 mass % or more are more preferably, and And preferably 50 mass % or less, more preferably 40 mass % or less, further preferably 35 mass % or less, particularly preferably 30 mass % or less.By being set as above-mentioned lower limiting value or more, exist to obtain the tendency of enough optical density (OD), on being set as Upper limit value is stated hereinafter, in the presence of the tendency that can ensure plate-making characteristic.
Relative to the present invention photosensitive coloring composition all solids ingredient, (b) alkali soluble resin containing than Example is usually 5 mass % or more, preferably 10 mass % or more, more preferably 20 mass % or more, further preferably 25 matter Measure % or more, and usually 85 mass % or less, preferably 80 mass % or less, more preferably 70 mass % or less, further Preferably 60 mass % or less, still more preferably it is 50 mass % or less, particularly preferably 40 mass % or less.By making (b) content ratio of alkali soluble resin is above-mentioned lower limiting value or more, and unexposed portion can be inhibited in developer solution by existing Deliquescent reduction, so as to inhibit the tendency of poor visualization.In addition, by being set as above-mentioned upper limit value hereinafter, in the presence of can be with Developer solution is inhibited to improve the impregnability of exposure portion, so as to inhibit what sharp (sharp) property of pixel, adaptation declined to incline To.
The all solids ingredient of photosensitive coloring composition relative to the present invention, (b-I) epoxy (methyl) acrylate The content ratio of resin is usually 3 mass % or more, preferably 6 mass % or more, more preferably 8 mass % or more, and is led to Often it is 40 mass % or less, preferably 30 mass % or less, more preferably 20 mass % or less, further preferably 15 mass % Below.By being set as above-mentioned lower limiting value or more, there is the tendency that can ensure reliability, in addition, by being set as above-mentioned upper limit value Hereinafter, in the presence of the tendency that can ensure surface smoothness.
(b) content ratio of (b-I) epoxy (methyl) acrylate contained in alkali soluble resin is usually 10 Quality % or more, preferably 20 mass % or more, more preferably 25 mass % or more, further preferably 30 mass % or more, Particularly preferably 40 mass % or more, and usually 90 mass % or less, preferably 80 mass % or less, more preferably 70 matter It measures % or less, further preferably 60 mass % or less, be still more preferably 50 mass % or less, particularly preferably 40 matter Measure % or less.By being set as above-mentioned lower limiting value or more, there is the tendency that can ensure reliability, in addition, on by being set as above-mentioned Limit value is hereinafter, in the presence of the tendency that can ensure surface smoothness.
The all solids ingredient of photosensitive coloring composition relative to the present invention, (b-II) (methyl) acrylic copolymer The content ratio of resin is usually 1 mass % or more, preferably 3 mass % or more, is more preferably 6 mass % or more, further Preferably 8 mass % or more, and usually 40 mass % or less, preferably 30 mass % or less, more preferably 20 mass % Below, it is more preferably 15 mass % or less.By being set as above-mentioned lower limiting value or more, surface smoothness can be ensured by existing Tendency, in addition, by being set as above-mentioned upper limit value hereinafter, in the presence of the tendency that can ensure reliability.
(b) content ratio of (b-II) (methyl) acrylic copolymeric resins contained in alkali soluble resin is usually 10 Quality % or more, preferably 20 mass % or more, more preferably 25 mass % or more, further preferably 30 mass % or more, Particularly preferably 40 mass % or more, and usually 80 mass % or less, preferably 70 mass % or less, more preferably 60 matter Measure % or less, further preferably 50 mass % or less, particularly preferably 40 mass % or less.By be set as above-mentioned lower limiting value with On, there is the tendency that can ensure surface smoothness, in addition, by being set as above-mentioned upper limit value hereinafter, reliable in the presence of that can ensure The tendency of property.
Relative to the present invention photosensitive coloring composition all solids ingredient, (c) Photoepolymerizationinitiater initiater containing than Example is usually 0.1 mass % or more, preferably 0.5 mass % or more, more preferably 1 mass % or more, further preferably 2 matter Measure % or more, still more preferably be 3 mass % or more, particularly preferably 4 mass % or more, and usually 15 mass % with Under, preferably 10 mass % or less, more preferably 8 mass % or less, further preferably 7 mass % or less.By making (c) light The content ratio of polymerization initiator is above-mentioned lower limiting value or more, there is the tendency that sensitivity can be inhibited to decline, on being set as Upper limit value is stated hereinafter, in the presence of can inhibit unexposed portion decreased solubility in developer solution, so as to inhibit poor visualization Tendency.
In the case of using (c) Photoepolymerizationinitiater initiater and polymerization accelerant at the same time, the photonasty relative to the present invention The all solids ingredient of color composition, the content ratio of polymerization accelerant are preferably 0.05 mass % or more, and usually 10 matter % or less, preferably 5 mass % are measured hereinafter, polymerization accelerant relative to 100 mass parts of (c) Photoepolymerizationinitiater initiater is usually 0.1 ~50 mass parts are particularly preferably used with the ratio of 0.1~20 mass parts.By making the content ratio of polymerization accelerant be above-mentioned More than lower limiting value, there is the tendency that the sensitivity for exposure light can be inhibited to decline, by being set as above-mentioned upper limit value hereinafter, In the presence of can inhibit unexposed portion decreased solubility in developer solution, so as to inhibit the tendency of poor visualization.
In addition, for mixing ratio shared in photosensitive coloring composition of the sensitizing dyestuff in the present invention, from spirit It is usually 20 mass % or less, preferably 15 from the viewpoint of sensitivity, in the total solid content in photosensitive coloring composition Quality % or less, more preferably 10 mass % or less.
The all solids ingredient of photosensitive coloring composition relative to the present invention, (d) olefinic unsaturated compound contain Proportional is usually 30 mass % or less, preferably 20 mass % or less, more preferably 15 mass % or less.By making (d) alkene The content ratio of ethylenically unsaturated compounds is above-mentioned upper limit value hereinafter, increasing to the impregnability of exposure portion in the presence of can inhibit developer solution Height, to be easy to get the tendency of good image.It should be noted that (d) content ratio of olefinic unsaturated compound Lower limiting value is usually 1 mass % or more, preferably 5 mass % or more.
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 5 mass % or more, preferably 10 mass % or more, is more preferably 15 mass % or more, is further excellent It is selected as 20 mass % or more, and usually 50 mass % or less, preferably 30 mass % or less.
In the solid constituent of photosensitive coloring composition, (f) content ratio of dispersant be usually 1 mass % or more, Preferably 3 mass % or more, more preferably 5 mass % or more, and usually 30 mass % or less, preferably 20 mass % with Under, more preferably 15 mass % or less, further preferably 10 mass % or less.In addition, (f) dispersant is coloured relative to (a) The content ratio of 100 mass parts of agent is usually 5 mass parts or more, is more preferably 10 mass parts or more, further preferably 15 matter Measure part or more, and usually 50 below mass part, particularly preferably 0 below mass part.By make (f) dispersant containing than Example is above-mentioned lower limiting value or more, there is the tendency for being easy to get enough dispersibilities, by be set as above-mentioned upper limit value hereinafter, in the presence of It can be by inhibiting the tendencies of the declines such as sensitivity, plate-making property with respect to the ratio for reducing other ingredients.
Using closely sealed enhancer, content ratio is relative to all solids in photosensitive coloring composition Ingredient is usually 0.1~5 mass %, preferably 0.2~3 mass %, further preferably 0.4~2 mass %.It is closely sealed by making The content ratio of enhancer is above-mentioned lower limiting value or more, there is the tendency for the improvement effect that can fully obtain adaptation, is led to It crosses and is set as above-mentioned upper limit value hereinafter, in the presence of the tendency that sensitivity can be inhibited to decline, remain residue after development and become defect.
In addition, using surfactant, content ratio is relative to complete in photosensitive coloring composition Portion's solid constituent is usually 0.001~10 mass %, preferably 0.005~1 mass %, further preferably 0.01~0.5 matter It measures %, be most preferably 0.03~0.3 mass %.Content by making surfactant is above-mentioned lower limiting value or more, and there are easy The flatness of film, the tendency of uniformity are shown, by being set as above-mentioned upper limit value hereinafter, in the presence of being easy to show the flat of film Slip, uniformity, and the tendency of the deterioration of other characteristics can be inhibited.
The physical property ＞ of ＜ photosensitive coloring compositions
The photosensitive coloring composition of the present invention can be suitable for coloring spacer and form purposes, be spaced from as coloring From the viewpoint of object, black is preferably presented.In addition, being equivalent to 1 μ of film thickness of film obtained from photosensitive coloring composition solidification The optical density (OD) of m is preferably 1.0 or more, more preferably 1.2 or more, further preferably 1.5 or more, particularly preferably 1.8 More than, and usually 4.0 or less, preferably 3.0 or less, more preferably 2.5 or less.
The manufacturing method ＞ of ＜ photosensitive coloring compositions
The photosensitive coloring composition of the present invention can be made (hereinafter, sometimes referred to as " resist ") according to usual way It is standby.
In general, (a) colorant preferably uses paint shaker, sand mill, ball mill, roller mill, burrstone mill, air-flow in advance Mill, homogenizer etc. carry out decentralized processing.By decentralized processing, (a) colorant is by micronized, therefore, the coating characteristics of resist It is improved.
Decentralized processing is generally preferably with by (a) colorant, (e) solvent, (f) dispersant and (b) alkali soluble resin Part or all of system being applied in combination carries out (hereinafter, will supply the mixture of decentralized processing sometimes and in the processing In obtained composition be known as " ink " or " dispersible pigment dispersion ").In particular, if being divided using macromolecule dispersing agent as (f) Powder, then obtained ink and resist through when thickening be inhibited (dispersion stabilization is excellent), therefore preferably.
Therefore, preferably fabricated at least to contain (a) colorant, (e) solvent and (f) disperse in the process of manufacture resist The dispersible pigment dispersion of agent.As (a) colorant, (e) organic solvent and (f) dispersant that can be used in dispersible pigment dispersion, Those of can preferably be employed as capable of using in photosensitive coloring composition respectively.
It should be noted that being carried out at dispersion for the liquid containing the whole components coordinated in colored resin composition In the case of reason, generated heat release when due to decentralized processing, high response ingredient is likely to occur modification.It is therefore preferable that with System containing macromolecule dispersing agent carries out decentralized processing.
, it is preferable to use the bead or oxygen of 0.1~8mm of grain size or so in the case of making (a) colorant disperse with sand mill 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 range, 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 It adjusts.Dispersion rough standard be：The gloss of ink is controlled so that 20 degree of mirror surface luster (JIS of resist Z8741) reach 50~300 range.In the case of the glossiness of resist is lower, decentralized processing is insufficient, remaining coarse Pigment (color material) particle it is more, developability, adaptation, distinguishing etc. may become inadequate.In addition, if carrying out decentralized processing It is more than above range to gloss value, then pigment is crushed and generates a large amount of ultramicrons, therefore it is impaired to there is dispersion stabilization instead Tendency.
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. measuring.
Then, the ink obtained by above-mentioned decentralized processing is mixed with above-mentioned other ingredients included in resist, Uniform solution is made.In the manufacturing process of resist, since to be mixed into the situation in liquid more for fine dust, because This, obtained resist wishes to be filtered processing by filter etc..
[solidfied material]
It can be by making the photosensitive coloring composition solidification of the present invention obtain solidfied material.Photosensitive coloring composition is solid Solidfied material obtained from change can be preferably used as coloring spacer.
[coloring spacer]
Then, spacer 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 being used to form coloring spacer, as long as the intensity with appropriateness, to its material without spy It does not limit.Transparent substrate is mainly used, as its material, it can be cited for example that the polyesters tree such as polyethylene terephthalate The thermoplastic resins film-making such as the polyolefin resins such as fat, polypropylene, polyethylene, makrolon, polymethyl methacrylate, polysulfones The thermosetting resins pieces or various glass etc. such as material, epoxy resin, unsaturated polyester resin, poly- (methyl) acrylic resin.Its In, from the viewpoint of heat resistance, preferably glass, heat-resistant resin.In addition, also having in substrate surface film forming ITO, IZO etc. The case where transparent electrode.Other than transparent substrate, it can also be formed on tft array.
In order to improve the surface physical properties such as cementability, can also Corona discharge Treatment, ozone be carried out to supporter as needed Film formation processing of the various resins such as processing, silane coupling agent, urethane based resin etc..
The thickness of transparent substrate is usually the range of 0.05~10mm, preferably 0.1~7mm.In addition, carrying out various trees In the case of the film formation processing of fat, film thickness is usually 0.01~10 μm, preferably 0.05~5 μm of range.
(2) spacer is coloured
The photosensitive coloring composition of the present invention is used for same as well known colour filter photosensitive coloring composition Purposes.Hereinafter, the case where for being used as coloring spacer (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.
In general, on the substrate of black light spacer to be arranged, by the methods of coating with the supply sense of membranaceous or pattern-like Photosensitiveness coloured composition, and make solvent seasoning.Then, pattern is carried out by the methods of the photoetching process for being exposed-developing to be formed. Then, additional exposure, heat cure processing are carried out as needed, thus form black light spacer on the substrate.
(3) formation of spacer is coloured
[1] to the supply method of substrate
The photosensitive coloring composition of the present invention is usually supplied with the state being dissolved or dispersed in solvent 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, spray coating method etc. carry out.Furthermore it is possible to by ink-jet method, print process etc. for giving to form pattern-like.
When wherein, using die coating method, the usage amount of coating fluid can be substantially cut down, and completely without using spin-coating method when institute The influence of the smog of attachment etc. can inhibit foreign matter generation etc., be preferred 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 range.In addition, it is important that dry film thickness or most End form at spacer height on entire substrate uniformly.In the case of uneven big, it will produce striped in liquid crystal display panel and lack It falls into.Wherein, it is disposably formed between the different black light of height by photoetching process using the photosensitive coloring composition of the present invention In the case of parting, the height of finally formed black light spacer can be different.
It should be noted that as substrate, substrate well known to glass substrate etc. can be used.In addition, substrate surface is preferred For plane.
[2] drying means
To on substrate supply photosensitive coloring composition after film drying preferably by using hot plate, IR baking ovens, The seasoning of convection oven carries out.It is dry alternatively, it is also possible to combine the decompression for not improving temperature and being dried in pressure-reducing chamber Dry method.
Dry condition according to the type of solvent composition, the performance of drying machine to be used etc. come suitable for selection.It is dry Time according to the type of solvent composition, the performance of drying machine to be used etc. usually 40 DEG C~130 DEG C temperature, 15 seconds ~5 minutes ranges are selected, and are preferably selected in 50 DEG C~110 DEG C of temperature, 30 seconds~3 minutes ranges.
[3] exposure method
Exposure is the mask pattern of minus to be overlapped on the film of photosensitive coloring composition, and shine across the mask pattern The light source of ultraviolet light or luminous ray is penetrated to carry out.In the case of being exposed using exposed mask, may be used 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.Alternatively, it is also possible to swash using without using the utilization of mask pattern The scan exposure mode of light.At this point, as needed, the sensitivity of optical polymerism layer declines caused by oxygen in order to prevent, can It is exposed with being exposed under deoxidizing atmosphere or being formed after the oxygen barrier layers such as polyvinyl alcohol layer on optical polymerism layer Light.
As the preferred embodiment of the present invention, the case where different black light spacers of height are 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 penetrates opening portion).In this way, By centre through opening portion and completely through opening portion average transmittance difference, i.e. the difference of light exposure by generate residual film ratio Difference.
It is known that intermediate transmission is for example made by the rectangular light-shielding pattern of the lightproof unit with small polygon The method etc. of opening portion.Additionally, it is known that being 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 the method etc. made.
Light source is not particularly limited used in above-mentioned exposure.As light source, it can be mentioned, for example：Xenon lamp, halogen lamp, 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, excimer laser, N_2 laser, helium cadmium laser, 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.
Can be the type for the light transmittance that exposure wavelength can be for example controlled with film, as this as optical filter In the case of material, it can be cited for example that Cr compounds (oxide, nitride, oxynitride, fluoride of Cr etc.), MoSi, Si, W, Al etc..
As light exposure, usually 1mJ/cm2Above, it is preferably 5mJ/cm2Above, it is 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 at a distance from mask pattern, usually 10 μm with It is upper, preferably 50 μm or more, more preferably 75 μm or more, in addition, usually 500 μm or less, be preferably 400 μm or less, more excellent It is selected as 300 μm or less.
[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, surfactant, organic solvent, buffer, complexing can further be contained 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 monoethanolamine, diethanol amine or triethanolamine, monomethyl Amine, dimethyl amine or Trimethylamine, monoethylamine, diethylamide or triethylamine, single isopropylamine or diisopropylamine, positive fourth Base amine, monoisopropanolamine, diisopropanolamine (DIPA) or triisopropanolamine, aziridine, ethylene diimine, tetramethylammonium hydroxide (TMAH), the organic basic compounds such as choline.These alkali compounds can be mixture of more than two kinds.
As above-mentioned surfactant, it can be mentioned, 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, it can be mentioned, for example：Isopropanol, benzylalcohol, ethyl cellosolve, butyl cellosolve, ethylene glycol monophenyl ether, Propylene glycol, diacetone alcohol etc..Organic solvent can be used alone, and can also be applied in combination with aqueous solution.
The condition of development treatment is not particularly limited, the range, preferably that can be usually 10 DEG C~50 DEG C in development temperature 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 carry out.
[5] additional exposure and heat cure processing
For the substrate after development, additional exposure can be carried out according to method same as above-mentioned exposure method as needed Light, alternatively, it is also possible to carry out heat cure processing.Heat cure treatment conditions at this time are as follows：Model of the temperature at 100 DEG C~280 DEG C It encloses, the range preferably at 150 DEG C~250 DEG C selects, range selection of the time at 5 minutes~60 minutes.
Size, the shape of coloring spacer etc. of the present invention can be according to the specification etc. for the colour filter for using it with Adjustment, photosensitive coloring composition of the invention especially for by photoetching process be formed simultaneously spacer and auxiliary spacer this The black light spacer that the height of sample is different is useful, in this case, the height of spacer is usually 2~7 μm or so, auxiliary Spacer usually has the height less than spacer, is 0.2~1.5 μm or so.
In addition, from the viewpoint of light-proofness, the optical density (OD) for being equivalent to the coloring spacer of 1 μm of the present invention is preferred Be 1.2 or more, more preferably 1.5 or more, further preferably 1.8 or more, in addition, usually 4.0 or less, preferably 3.0 with Under.Optical density (OD) mentioned here is the value measured by the method described below.
[colour filter]
The colour filter of the present invention has the coloring spacer of above-mentioned such present invention, such as can manufacture as follows：In conduct The glass substrate superimposed layer black matrix" of transparent substrate, pixel shader layer, the face coat of red, green, blue form coloring After spacer, alignment films are formed.
Such colour filter with coloring spacer of the invention and liquid crystal drive side group plate are bonded and form liquid crystal Box injects liquid crystal in being formed by liquid crystal cell, it is possible thereby to manufacture the liquid crystal display dress for having the coloring spacer of the present invention Set equal image display devices.
Embodiment
Then, Examples and Comparative Examples are enumerated more specifically the present invention will be described, but as long as without departing from the present invention's Purport, the present invention is not limited to embodiments below.
The constituent of the photosensitive coloring composition used in following Examples and Comparative Examples is as follows.
＜ organic black pigments ＞
BASF AG manufactures, and Irgaphor (registered trademark) Black S 0100CF (have chemistry shown in following formula (2) Structure)
[chemical formula 58]
＜ alkali soluble resin-A ＞
145 mass parts of propylene glycol methyl ether acetate are stirred while carrying out nitrogen displacement, are warming up to 120 ℃.10 mass parts of styrene, 85.2 mass parts of glycidyl methacrylate 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 3 hours 2,2 '-azos of dropwise addition Then double 8.47 mass parts of -2- methylbutyronitriles continue to have stirred 2 hours at 90 DEG C.Then, air will be become in reaction vessel Displacement puts into three (dimethylaminomethyl) phenol, 0.7 mass parts and 0.12 matter of hydroquinone in 43.2 mass parts of acrylic acid Part is measured, the reaction was continued at 100 DEG C 12 hours.Then, tetrabydrophthalic anhydride (THPA) 56.2 mass parts, triethylamine is added 0.7 mass parts are reacted 3.5 hours at 100 DEG C.Pass through dividing equally again for the GPC alkali soluble resin-A obtained above measured Son amount Mw is about 8400, acid value 80mgKOH/g.
＜ alkali soluble resin-B ＞
By the mixed liquors of 53.9 mass parts of 217.6 mass parts of propylene glycol methyl ether acetate and propylene glycol monomethyl ether on one side into The displacement of row nitrogen is stirred on one side, is warming up to 120 DEG C.Be added dropwise thereto within 3 hours benzyl methacrylate 3.52 mass parts, 58.5 mass parts of methacrylic acid, the mono acrylic ester FA-513M (Hitachi Chemical Co., Ltd.'s system) with tricyclodecane skeleton 66.1 mass parts and 2, the mixed liquor of double 3.8 mass parts of -2- methylbutyronitriles of 2 '-azos, then continue stirring at 90 DEG C 2 hours.Then, air, 27.3 mass parts of input glycidyl methacrylate, three (diformazans will be replaced into reaction vessel Base amino methyl) phenol 0.6 mass parts and 0.1 mass parts of hydroquinone, the reaction was continued at 100 DEG C 12 hours.It obtains in this way Alkali soluble resin-B weight average molecular weight Mw be 16500, acid value 176mgKOH/g.
＜ alkali soluble resin-C ＞
By the mixed liquors of 75.9 mass parts of 303.5 mass parts of propylene glycol methyl ether acetate and propylene glycol monomethyl ether on one side into The displacement of row nitrogen is stirred on one side, is warming up to 120 DEG C.10.4 mass parts of styrene, metering system were added dropwise thereto with 3 hours Sour 34.4 mass parts, mono acrylic ester FA-513M (Hitachi Chemical Co., Ltd.'s system) 66.1 mass with tricyclodecane skeleton Part and 2, the mixed liquor of double 8.7 mass parts of -2- methylbutyronitriles of 2 '-azos, then continues to have stirred 2 hours at 90 DEG C.It connects It, air, 9.9 mass parts of input glycidyl methacrylate, three (dimethylamino first will be replaced into reaction vessel Base) phenol 0.2 mass parts and 0.04 mass parts of hydroquinone, the reaction was continued at 100 DEG C 12 hours.The alkali obtained in this way is solvable Property resin-C weight average molecular weight Mw be 7200, acid value 86mgKOH/g.
＜ alkali soluble resin-D ＞
" ZCR-1642H " (MW=6500, the acid value=98mg-KOH/g) of Nippon Kayaku K. K's manufacture
＜ alkali soluble resin-E ＞
[chemical formula 59]
By epoxide (epoxide equivalent 264) 50g, acrylic acid 13.65g, the methoxybutyl acetic acid esters of above structure 60.5g, triphenylphosphine 0.936g and p methoxy phenol 0.032g are added to the burning for being equipped with thermometer, blender, cooling tube In bottle, it is made to be reacted at 90 DEG C while stirring, until acid value reaches 5mgKOH/g or less.Reaction needs 12 hours, obtains Epoxy acrylic ester solution.
By above-mentioned 25 mass parts of epoxy acrylic ester solution, 0.76 mass parts of trimethylolpropane (TMP), bibenzene tetracarboxylic 3.3 mass parts of dianhydride (BPDA), 3.5 mass parts of tetrabydrophthalic anhydride (THPA) be added to be equipped with thermometer, blender, In the flask of cooling tube, it is to slowly warm up to 105 DEG C while stirring, makes its reaction.
It when resin solution becomes transparent, is diluted with methoxybutyl acetic acid esters, is prepared into 50 matter of solid constituent % is measured, having obtained the weight average molecular weight (Mw) that acid value is 113mgKOH/g, the polystyrene measured by GPC converts is 2600, double bond equivalent is the epoxy methacrylates resin (alkali soluble resin-E) containing carboxyl of 520g/mol.
＜ alkali soluble resin-F ＞
By the mixed liquors of 53.6 mass parts of 214.5 mass parts of propylene glycol methyl ether acetate and propylene glycol monomethyl ether on one side into The displacement of row nitrogen is stirred on one side, is warming up to 120 DEG C.Be added dropwise thereto within 3 hours benzyl methacrylate 68.7 mass parts, 43.9 mass parts of methacrylic acid, the mono acrylic ester FA-513M (Hitachi Chemical Co., Ltd.'s system) with tricyclodecane skeleton 22.0 mass parts and 2, the mixed liquor of double 1.4 mass parts of -2- methylbutyronitriles of 2 '-azos, then continue stirring at 90 DEG C 2 hours.Then, air, 21.3 mass parts of input glycidyl methacrylate, three (diformazans will be replaced into reaction vessel Base amino methyl) phenol 0.5 mass parts and 0.1 mass parts of hydroquinone, the reaction was continued at 100 DEG C 12 hours.It obtains in this way Alkali soluble resin-F weight average molecular weight Mw be 44100, acid value 130mgKOH/g.
＜ alkali soluble resin-G ＞
By the mixed liquors of 52.5 mass parts of 210.1 mass parts of propylene glycol methyl ether acetate and propylene glycol monomethyl ether on one side into The displacement of row nitrogen is stirred on one side, is warming up to 120 DEG C.Be added dropwise thereto within 3 hours benzyl methacrylate 3.52 mass parts, 68.8 mass parts of methacrylic acid, the mono acrylic ester FA-513M (Hitachi Chemical Co., Ltd.'s system) with tricyclodecane skeleton 39.7 mass parts and 2, the mixed liquor of double 3.3 mass parts of -2- methylbutyronitriles of 2 '-azos, then continue stirring at 90 DEG C 2 hours.Then, air, 38.4 mass parts of input glycidyl methacrylate, three (diformazans will be replaced into reaction vessel Base amino methyl) phenol 0.8 mass parts and 0.1 mass parts of hydroquinone, the reaction was continued at 100 DEG C 12 hours.It obtains in this way Alkali soluble resin-G weight average molecular weight Mw be 19100, acid value 198mgKOH/g.
＜ 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 constituted without the B block of quaternary ammonium salt base and amino, amine value are 70mgKOH/g, acid value are 1mgKOH/g or less)
Include following formula (1a) and the repetitive unit of (2a) in the A blocks of dispersant-I, includes following formula (3a) in B block Repetitive unit.The repetitive unit of following formula (1a), (2a) and (3a) is shared in whole repetitive units of dispersant-I to be contained Proportional is respectively 11.1 moles of %, 22.2 moles of %, 6.7 moles of %.
[chemical formula 60]
＜ 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 initiaters ＞
The compound of following structures
[chemical formula 61]
＜ photopolymerization monomers ＞
DPHA：The dipentaerythritol hexaacrylate 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
＜ is equivalent to the measurement ＞ of the optical density (unit OD values) of per unit film thickness
The optical density for being equivalent to per unit film thickness is determined according to sequence below.
First, prepared photosensitive coloring composition is coated on the glass substrate using spinner, and made final Film thickness be 2 μm, be dried under reduced pressure within 1 minute, then dried at 80 DEG C 70 seconds with hot plate.By exposed and developed work After sequence, is heated 20 minutes at 230 DEG C of oven temperature, result in the substrate for being coated with resist.Utilize transmission-type concentration The optical density (OD) for counting substrates of the Gretag Macbeth D200-II to obtaining is measured, and utilizes water chestnutization system strain formula meeting Non-planar contact surfaces/layer cross section shape measure system VertScan (R) 2.0 of society's manufacture measures film thickness, by optical density (OD) and film Thickness calculates the optical density for being equivalent to per unit film thickness.It should be noted that OD values are to indicate that the numerical value of light shielding ability, numerical value are got over It is big to indicate that light-proofness is higher.
＜ NMP dissolution tests ＞
N-Methyl pyrrolidone (NMP) dissolution test has been carried out according to sequence below.
First, prepared photosensitive coloring composition is coated on the glass substrate using spinner, and made final Film thickness be 2 μm, be dried under reduced pressure within 1 minute, then dried at 80 DEG C 70 seconds with hot plate.By exposed and developed work After sequence, is heated 20 minutes at 230 DEG C of oven temperature, result in the substrate for being coated with resist.By made coating There is the substrate of resist to cut out 2 measurement substrates (2.5cm × 1.0cm square), is impregnated in and adds N-Methyl pyrrolidone (NMP) in the 10mL phials of 8mL.Then, by this be put into the phial of measurement substrate in 80 DEG C of heating bath, with quiet The state set 40 minutes implements NMP dissolution tests.Standing takes out phial from heating bath after forty minutes, utilizes light splitting light Degree meter " UV-3100PC " of manufacture (Shimadzu Scisakusho Ltd) to NMP dissolution solution 300~800nm wavelength model It encloses and determines absorbance every 1nm.Light source uses halogen lamp and deuterium lamp (Wavelength-converting 360nm), what detector used It is photomultiplier, using slit width 2nm as determination condition.In addition, sample solution (NMP dissolves out solution) is put into 1cm It is determined in the quartz cell of square.Absorbance is to indicate what light has occurred through jobbie Light intensity in optical spectroscopy The characteristic of the decaying of kind degree, is defined with following formula.
A (absorbance)=- log10(I/I0)(I：Transmitted intensity, I0：Incident intensity)
In addition, light is made to inject sample solution and individual NMP liquid respectively by same light source, will can at this time penetrate individual NMP liquid and the luminous intensity that projects regards I as0, the luminous intensity that will transmit through sample solution and project regard I as.Therefore, above formula (I/I0) what is indicated is light transmission, absorbance A refers to indicating to be worth obtained from the inverse of transmissivity with logarithm.Absorbance A It is used label whens calculating the concentration etc. of the substance contained in sample solution.In the case of absorbance A=0, expression is The unabsorbed state (transmissivity 100%) of all light, in the case of absorbance A=∞, expression be all light not The state (transmissivity 0%) of transmission.That is, absorbance is stronger, indicate that dissolution of the resist painting film component into NMP is more, NMP is resistance to Property is poorer.The spectrogram area (nm) for calculating measured absorbance, by area value less than 20 (nm) as zero, by 20 (nm) with Upper conduct ×, NMP patience is evaluated.The spectrogram area of absorbance as this evaluation criteria can be under each wavelength The sum of absorbance indicates, expression be dissolution resist ingredient summation.
NMP patience evaluation criteria：It is the judgement (300~800nm of wavelength) that the spectrogram area value based on absorbance carries out
○：Less than 20 (nm)
×：20 (nm) or more
The evaluation ＞ of ＜ surface smoothnesss
The evaluation of surface smoothness and following surface roughnesses has been carried out according to sequence below.
First, prepared photosensitive coloring composition is coated on the glass substrate using spinner, and made final Film thickness be 3 μm, be dried under reduced pressure within 1 minute, then dried at 80 DEG C 70 seconds with hot plate.By exposed and developed work After sequence, is heated 20 minutes at 230 DEG C of oven temperature, result in the substrate for being coated with resist.For made painting It is furnished with the substrate of resist, whether there is or not generate fold to the surface after heating in the visual field of 70 μm of 70 μ m using light microscope It is observed.It should be noted that evaluation criteria is as follows.
○：Micron-sized fold is not observed on the surface of pattern
×：It is apparent in the fold of the surface micrometre-grade of pattern
The evaluation ＞ of ＜ surface roughnesses
For the substrate for being coated with resist made in the evaluation ＞ of above-mentioned ＜ surface smoothnesss, water chestnutization system strain is utilized The three-dimensional non-planar contact surfaces shape measure system Micromap of formula commercial firm, using 50 times of optical lenses, with Focus patterns 70 Surface roughness Sa (arithmetic average roughness, nm) is determined in the visual field that 70 μm of μ m.
The preparation ＞ of ＜ dispersible pigment dispersions 1,3 and 4
Pigment, dispersant, dispersing aid, alkali soluble resin and the solvent that table 1 is recorded are according to the quality recorded in table 1 Than being mixed.The solution has been carried out in 25~45 DEG C of range with paint shaker to 3 hours decentralized processings.As Pearl uses the zirconium oxide bead of 0.5mm φ, adds 2.5 times of quality of dispersion liquid.After dispersion, filter is utilized Pearl is detached with dispersion liquid, is prepared for dispersible pigment dispersion 1,3 and 4.
[table 1]
＜ dispersible pigment dispersions 2 (cladding carbon black dispersion liquid) ＞
Carbon black is manufactured using common Audit For Process.Wherein, as feedstock oil, the poor ethylene of Na, Ca, S is used Residue oil, and coke oven gas has been used to be used for burning.In addition, as reaction terminating water, uses 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 blender, on one side with big About 1,000rpm is mixed, and is marginally added to respectively on one side dissolved with epoxy resin " Epikote828 " (Mitsubishi Chemical's strain Formula commercial firm manufactures) the toluene 600g of 60g.About 15 minutes, the carbon black being dispersed in water was fully transferred to toluene side, forms about The particle of 1mm.
Then, it has been carried out removing moisture with the metal mesh of 60 mesh, be then placed in vacuum drier, dry 7 at 70 DEG C Hour, toluene and water are removed completely.
Obtained cladding carbon black, dispersant, pigment derivative and solvent are carried out according to the mass ratio recorded in table 1 Mixing.
It is sufficiently stirred, is pre-mixed using blender.Then, the model using paint shaker at 25~45 DEG C It encloses 6 hours decentralized processings of progress and uses the zirconium oxide bead of 0.5mm φ as pearl, and add matter identical with dispersion liquid Amount, after dispersion, is detached pearl with dispersion liquid using filter, to be prepared for dispersible pigment dispersion 2.
[Examples 1 to 6, comparative example 1~3]
Be added each ingredient, and so that solid constituent ratio is the mixing ratio of table 2, add PGMEA and make solid at It is divided into 22 mass %, is stirred and makes it dissolve, be prepared for photosensitive coloring composition.By the solid of prepared composition at Point ratio is shown in table 2.In addition, unit OD values, NMP dissolution tests, surface smoothness that method as described above is measured And surface roughness evaluation result is shown in table 2.It should be noted that the mass parts table of the photosensitive coloring composition in table 2 Show the mass parts of solid constituent.
[table 2]
By the embodiment 1 of table 2 and the comparison of comparative example 1 and 2 it is found that including (b-I) epoxy (methyl) acrylate The photosensitive coloring composition of (b-II) (methyl) acrylic copolymeric resins while ensuring high light-proofness, reliability and Surface smoothness is also excellent, and (b-II) (methyl) acrylic copolymeric resins, which contain 12 moles of % or more, has olefinic insatiable hunger With the repetitive unit α of key and contain the repetitive unit β from unsaturated carboxylic acid.On the other hand, repetitive unit α is less than 12 The reliability of the comparative example 1 of mole % is bad, in addition, the comparative example 2 without (b-II) (methyl) acrylic copolymeric resins Surface smoothness is bad.
In the case that main resin component is (b-I) epoxy (methyl) acrylate as comparative example 2, it is believed that The heat flow caused by its structure and make surface smoothness it is bad.It can thus be assumed that by using epoxy (methyl) propylene Acid ester resin and (methyl) acrylic copolymer tree containing the repetitive unit from unsaturated carboxylic acid for being not easy heat flow Fat, heat flow are reduced, and can improve surface smoothness.But such (methyl) acrylic copolymeric resins and epoxy (methyl) Acrylate is relatively low compared to usual sensitivity, therefore curability reduces, and reliability can be deteriorated sometimes as the comparative example 1. It can thus be assumed that containing by the repetitive unit α with ethylenic unsaturated bond in raising (methyl) acrylic copolymeric resins Ratio, it can be ensured that enough curability can be realized simultaneously reliability and surface smoothness.
In addition, by the comparison of Examples 1 to 3 it is found that in the case that colorant includes organic pigment and carbon black or comprising The case where selected from least one of red pigment and orange pigment and selected from least one of blue pigment and violet pigment Under, regardless of specific pigment kind, while ensuring high light-proofness, reliability and surface smoothness are also excellent.
In contrast, for colorant is the comparative example 3 of the high carbon black of individual ultraviolet-absorbing, surface is flat Slip is insufficient.
On the other hand, by the comparison of embodiment 2 and 4 it is found that no matter the type of (b-I) epoxy (methyl) acrylate How, reliability is excellent.On the other hand, as long as by the comparison of embodiment 1,5,6 it is found that having olefinic in (b-II) resin The content ratio of the repetitive unit α of unsaturated bond is 12 moles of % or more, regardless of the value of its specific content ratio, reliably Property and surface smoothness are also excellent.
Using specific mode, the present invention is described in detail, but those skilled in the art it should be clear that Without prejudice to the intent and scope of the present invention, various modifications may be made, deformation.It should be noted that the application It is completed based on the Japanese patent application (Japanese Patent Application 2015-252149) that on December 24th, 2015 files an application, content is made It has been introduced in the application for reference.
Industrial applicibility
It is excellent can to provide high light-proofness, high reliability and surface smoothness for photosensitive coloring composition according to the present invention Different solidfied material and coloring spacer, it is furthermore possible to also provide having the image display device of such coloring spacer.Therefore, Present invention reality industrial in each field of photosensitive coloring composition, solidfied material, coloring spacer and image display device It is high with property.

Claims (9)

1. a kind of photosensitive coloring composition, contains：(a) colorant, (b) alkali soluble resin, (c) Photoepolymerizationinitiater initiater, (d) olefinic unsaturated compound, (e) solvent and (f) dispersant, wherein
(a) colorant includes organic pigment and carbon black,
(b) alkali soluble resin includes (b-I) epoxy (methyl) acrylate and (b-II) (methyl) acrylic compounds Copolymer resins, (b-II) (methyl) acrylic copolymeric resins contain the repetitive unit α that side chain has ethylenic unsaturated bond And the repetitive unit β from unsaturated carboxylic acid, also,
The content ratio of the repetitive unit α in (b-II) (methyl) acrylic copolymeric resins be 12 moles of % with On.
2. photosensitive coloring composition according to claim 1, wherein the organic pigment includes to be selected from the following general formula (1) in the salt of the geometric isomer of compound represented, the geometric isomer of the compound, the salt of the compound and the compound At least one organic black pigments,
In formula (1), R11And R16Independently of one another hydrogen atom, CH3、CF3, fluorine atom or chlorine atom；
R12、R13、R14、R15、R17、R18、R19And R20It is independently of one another hydrogen atom, halogen atom, R to each other21、COOH、COOR21、 COO-、CONH2、CONHR21、CONR21R22、CN、OH、OR21、COCR21、OCONH2、OCONHR21、OCONR21R22、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 R20At least one of combination appoint Select mutual Direct Bonding or by oxygen atom, sulphur atom, NH or NR21Bridging and be mutually bonded；
R21And R22The independently of one another alkyl of carbon atom number 1~12, the naphthenic base of carbon atom number 3~12, carbon atom number 2~12 Alkenyl, the cycloalkenyl group of carbon atom number 3~12 or the alkynyl of carbon atom number 2~12.
3. a kind of photosensitive coloring composition, contains：(a) colorant, (b) alkali soluble resin, (c) Photoepolymerizationinitiater initiater, (d) olefinic unsaturated compound, (e) solvent and (f) dispersant, wherein
(a) colorant includes selected from least one of red pigment and orange pigment and to be selected from blue pigment and purple At least one of color pigment,
(b) alkali soluble resin includes (b-I) epoxy (methyl) acrylate and (b-II) (methyl) acrylic compounds Copolymer resins, (b-II) (methyl) acrylic copolymeric resins contain the repetitive unit α that side chain has ethylenic unsaturated bond And the repetitive unit β from unsaturated carboxylic acid, also,
The content ratio of the repetitive unit α in (b-II) (methyl) acrylic copolymeric resins be 12 moles of % with On.
4. photosensitive coloring composition described in any one of claim 1 to 3, wherein under the repetitive unit α has Chemical constitution shown in logical formula (I) is stated,
In formula (I), R1And R2Each independently represent hydrogen atom or methyl, R3Indicate the connection group of divalent.
5. photosensitive coloring composition according to any one of claims 1 to 4, wherein relative to photosensitive color group The all solids ingredient in object is closed, the content ratio of (b-II) (methyl) acrylic copolymeric resins is 1 mass % or more.
6. photosensitive coloring composition according to any one of claims 1 to 5, average every 1 μ of the film after solidification The optical density of m film thickness is 1.0 or more.
7. a kind of solidfied material is to cure photosensitive coloring composition according to any one of claims 1 to 6 to obtain 's.
8. a kind of coloring spacer is formed by the solidfied material described in claim 7.
9. a kind of image display device has coloring spacer according to any one of claims 8.
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