CN109952535A - Photosensitive composition, dispersible pigment dispersion, spaced walls, organic electroluminescent device, image display device and illumination - Google Patents

Photosensitive composition, dispersible pigment dispersion, spaced walls, organic electroluminescent device, image display device and illumination Download PDF

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Publication number
CN109952535A
CN109952535A CN201780070424.7A CN201780070424A CN109952535A CN 109952535 A CN109952535 A CN 109952535A CN 201780070424 A CN201780070424 A CN 201780070424A CN 109952535 A CN109952535 A CN 109952535A
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methyl
mass
ring
mentioned
photosensitive composition
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小野由香子
泽井良尚
伊藤敦哉
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Mitsubishi Chemical Corp
Mitsubishi Kasei Corp
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Mitsubishi Kasei Corp
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Priority to CN202410172111.4A priority Critical patent/CN118151488A/en
Publication of CN109952535A publication Critical patent/CN109952535A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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    • 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
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    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1063—Esters of polycondensation macromers of alcohol terminated polyethers
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    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • C09B67/0063—Preparation of organic pigments of organic pigments with only macromolecular substances
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/008—Preparations of disperse dyes or solvent dyes
    • C09B67/0082—Preparations of disperse dyes or solvent dyes in liquid form
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

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Abstract

First project of the invention is, provides that the amount of gas evolved after forming solidfied material is few, excellent in reliability, and the good photosensitive composition of adaptation of the fine pattern in the developing procedure when making solidfied material.The photosensitive composition of the invention of first method contains (A) colorant, (B) dispersing agent, (C) adhesive resin, (D) photopolymerization monomer and (E) Photoepolymerizationinitiater initiater, wherein, (A) colorant includes (A1) organic black pigments, (A1) organic black pigments contain selected from the following general formula (I) compound represented, the geometric isomer of the compound, the salt of the compound, and at least one of salt of geometric isomer of the compound, (B) dispersing agent includes acrylic dispersants, (C) adhesive resin includes (C1) epoxy (methyl) acrylate of 75 mass % or more.

Description

Photosensitive composition, dispersible pigment dispersion, spaced walls, organic field luminescence Element, image display device and illumination
Technical field
The present invention relates to photosensitive compositions, in addition, further relating to make in the photosensitive composition Dispersible pigment dispersion, the spaced walls being made of the photosensitive composition, the organic field for having the spaced walls cause hair Optical element, image display device and illumination.
Background technique
The arrangement of liquid crystal molecule under the action of the ON/OFF of the voltage applied to liquid crystal is utilized in liquid crystal display (LCD) The property that mode changes.On the other hand, each component for constituting the unit of LCD is by using photoetching process as the benefit of representative mostly It is formed with the method for photosensitive composite.For the photosensitive composite, due to its fine structure easy to form, also It is easy to carry out the such reason of the processing for big picture substrate, from now on, the scope of application of photosensitive composite has into one Walk widened trend.
In addition, having studied utilization along with panel construction and the easy of manufacturing process and being lithographically formed between so-called column The method of parting, the column spacer are used in order to which the interval holding of 2 plate bases in liquid crystal display panel is constant, closely Nian Lai, also developed by light spacer it is integrated with black matrix" made of colour spacer.But between such coloring Parting it is also desirable to have more than a certain amount of volume resistivity, certain phase below other than common shape, compression property To dielectric constant, so that even if being directly loaded up the short circuit that will not cause circuit on TFT element.
As such coloring spacer, propose use a variety of organic coloring pigments as pigment coloring spacer, And the coloring spacer of organic black pigments is used.A kind of pass through is described in patent document 1 will specific organic black Pigment and dispersant package and with excellent dispersibility, light-proofness and with the photonasty of low relative dielectric constant Color composition.
On the other hand, the image comprising organic electroluminescent device (also referred to as organic electroluminescent device, organic EL) is aobvious The visualitys such as contrast, the field angle of showing device, responsiveness are excellent, and can be realized low consumption electrification, thin light and Therefore the flexibilityization of display unit main body attracts attention as follow-on flat-panel monitor (FPD).
Organic electroluminescent device has a structure that and clamps between wherein at least one a pair of electrodes with translucency There is the organic layer comprising luminescent layer or various functions layers.Image display device is by driving each pixel to be configured with organic field The panel of electroluminescent element performs image display.
In the past, such organic electroluminescent device was formed after spaced walls (box dam) on substrate, by spaced walls The area inner layer of encirclement folds luminescent layer or various functions layers to manufacture.
In order to form luminescent layer etc. in the region surrounded by spaced walls, as long as using material sublimation is made under vacuum conditions And the vapour deposition method to form a film is attached on substrate.In addition, in recent years, using wet as casting, spin-coating method, ink jet printing method The method that method technique forms a film attracts attention.Especially ink jet printing method can also reduce in the case where large area is made Film thickness is uneven, and the reduction of the High precision, materials'use amount of the display of differentiation coating when can be realized based on coating, The raising of yield rate, therefore, the film build method as organic layer in larger panel are suitable.
In addition, as the method for being readily formed above-mentioned spaced walls, it is known to by using photosensitive polymer combination Photoetching process come the method that forms spaced walls.
Existing technical literature
Patent document
Patent document 1: International Publication No. 2015/046178
Summary of the invention
Problems to be solved by the invention
In recent years, it is desirable that after forming the solidfied material for constituting image display device etc., what reduction was generated by the solidfied material Degassing.Especially in organic electroluminescent device, it is strongly required to reduce the degassing generated by spaced walls when element shines.This It is due to if more by the amount of gas evolved that the solidfied material of spaced walls etc. generates, existing and causing element in organic electroluminescent device Service life reduction a possibility that.
On the other hand, in image display device, for high-resolution models, the solidfied material for needing to constitute it is fine Change, it is desirable that even fine pattern is also fully closely sealed with substrate etc. in developing procedure.
The inventors of the present invention have found that the degassing of photosensitive coloring composition documented by patent document 1 is more, in reality after study With there are problems.
In addition, in patent document 1, also without recording and implying that the spaced walls for organic electroluminescent device are answered With, the inventors of the present invention form discovery when purposes is studied for the spaced walls in organic electroluminescent device, although for The adaptation of the pattern of size required by the model of usual resolution ratio is enough, but for required by high-resolution models that The adaptation of the fine pattern of sample is simultaneously insufficient.
First project of the invention is to provide a kind of photosensitive composition, the degassing after formation solidfied material It measures less, is excellent in reliability, and the adaptation of the fine pattern in the developing procedure when making solidfied material is good.
In addition, the present invention is provided the spaced walls formed using the photosensitive composition, has the spaced walls Organic electroluminescent device, the image display device comprising the organic electroluminescent device and illumination.
In addition, the second project of the invention provide a kind of spaced walls for being used to form organic electroluminescent device color sensation Photosensitive resin composition, the amount of gas evolved after forming solidfied material are few, excellent in reliability.
In addition, the present invention is provided the spaced walls formed using the photosensitive composition, has the spaced walls Organic electroluminescent device, the image display device comprising the organic electroluminescent device and illumination.
In addition, third project of the invention is to provide the photosensitive polymer combination for constituting the first project of solution Dispersible pigment dispersion.
Solution to the problem
The inventors of the present invention by further investigation as a result, it has been found that, by containing specific organic black pigments, today contain The photosensitive composition etc. of a certain amount of above special adhesive resin, can solve the above subject, to complete The present invention.
That is, purport of the invention is as described below.
[1] a kind of photosensitive composition, contains: (A) colorant, (B) dispersing agent, (C) adhesive resin, (D) photopolymerization monomer and (E) Photoepolymerizationinitiater initiater, wherein
(A) colorant includes (A1) organic black pigments, and (A1) organic black pigments contain selected from following logical Formula (I) compound represented, the geometric isomer of the compound, the geometry of the salt of the compound and the compound are different At least one of the salt of structure body,
(B) dispersing agent includes acrylic dispersants,
(C) adhesive resin includes (C1) epoxy (methyl) acrylate of 75 mass % or more,
[chemical formula 1]
(in formula (I), Ra1And Ra6Each independently represent hydrogen atom, CH3、CF3, fluorine atom or chlorine atom；
Ra2、Ra3、Ra4、Ra5、Ra7、Ra8、Ra9And Ra10Each independently represent hydrogen atom, halogen atom, Ra11、COOH、 COORa11、COO-、CONH2、CONHRa11、CONRa11Ra12、CN、OH、ORa11、COCRa11、OOCNH2、OOCNHRa11、 OOCNRa11Ra12、NO2、NH2、NHRa11、NRa11Ra12、NHCORa12、NRa11CORa12, N=CH2, N=CHRa11, N=CRa11Ra12、 SH、SRa11、SORa11、SO2Ra11、SO3Ra11、SO3H、SO3 -、SO2NH2、SO2NHRa11Or SO2NRa11Ra12；
Also, it is selected from Ra2With Ra3、Ra3With Ra4、Ra4With Ra5、Ra7With Ra8、Ra8With Ra9And Ra9With Ra10At least one of It combines optionally mutually Direct Bonding or passes through oxygen atom, sulphur atom, NH or NRa11Bridging and be mutually bonded；
Ra11And Ra12It is former to each independently represent the alkyl of carbon atom number 1~12, the naphthenic base of carbon atom number 3~12, carbon The alkynyl of the alkenyl of subnumber 2~12, the cycloalkenyl of carbon atom number 3~12 or carbon atom number 2~12.)
[2] photosensitive composition described in above-mentioned [1], wherein described in (C) adhesive resin (C1) content ratio of epoxy (methyl) acrylate is 85 mass % or more.
[3] photosensitive composition described in above-mentioned [1] or [2], wherein (C1) epoxy (methyl) propylene Acid ester resin includes to have epoxy (methyl) acrylate of repeat unit structure shown in the following general formula (II) and have One or both of epoxy (methyl) acrylate of part-structure shown in the following general formula (III),
[chemical formula 2]
(in formula (II), R11Indicate hydrogen atom or methyl；
R12Indicate divalent alkyl optionally with substituent group；
Phenyl ring in formula (II) is optionally further replaced by arbitrary substituent group；
* bonding position is indicated.)
[chemical formula 3]
(in formula (III), R13Each independently represent hydrogen atom or methyl；
R14Indicate that there is divalent alkyl of the cyclic hydrocarbon group as side chain；
R15And R16Each independently represent divalent aliphatic group optionally with substituent group；
M and n each independently represents 0~2 integer；
* bonding position is indicated.)
[4] photosensitive composition described in any one of above-mentioned [1]~[3], wherein the acrylic compounds point Powder is the acrylic dispersants containing nitrogen-atoms.
[5] photosensitive composition described in any one of above-mentioned [1]~[4], wherein relative to the coloring The all solids ingredient of photosensitive polymer combination, the content ratio of (A) colorant are 60 mass % or less.
[6] photosensitive composition described in any one of above-mentioned [1]~[5], wherein (A) colorant Further include one or both of (A2) organic coloring pigments and (A3) carbon black.
[7] photosensitive composition described in any one of above-mentioned [1]~[6], wherein (A) colorant In (A1) organic black pigments content ratio be 10 mass % or more.
[8] photosensitive composition described in any one of above-mentioned [1]~[7] is used to form organic field cause The spaced walls of light-emitting component.
[9] a kind of photosensitive composition, be used to form organic electroluminescent device spaced walls Color sensation photosensitive resin composition, the photosensitive composition contain: (A) colorant, (B) dispersing agent, (C) adhesive tree Rouge, (D) photopolymerization monomer and (E) Photoepolymerizationinitiater initiater, wherein
(A) colorant includes (A1) organic black pigments, and (A1) organic black pigments contain selected from following logical Formula (I) compound represented, the geometric isomer of the compound, the geometry of the salt of the compound and the compound are different At least one of the salt of structure body,
(C) adhesive resin includes (C1) epoxy (methyl) acrylate of 75 mass % or more,
[chemical formula 4]
(in formula (I), Ra1And Ra6Each independently represent hydrogen atom, CH3、CF3, fluorine atom or chlorine atom；
Ra2、Ra3、Ra4、Ra5、Ra7、Ra8、Ra9And Ra10Each independently represent hydrogen atom, halogen atom, Ra11、COOH、 COORa11、COO-、CONH2、CONHRa11、CONRa11Ra12、CN、OH、ORa11、COCRa11、OOCNH2、OOCNHRa11、 OOCNRa11Ra12、NO2、NH2、NHRa11、NRa11Ra12、NHCORa12、NRa11CORa12, N=CH2, N=CHRa11, N=CRa11Ra12、 SH、SRa11、SORa11、SO2Ra11、SO3Ra11、SO3H、SO3 -、SO2NH2、SO2NHRa11Or SO2NRa11Ra12；
Also, it is selected from Ra2With Ra3、Ra3With Ra4、Ra4With Ra5、Ra7With Ra8、Ra8With Ra9And Ra9With Ra10At least one of It combines optionally mutually Direct Bonding or passes through oxygen atom, sulphur atom, NH or NRa11Bridging and be mutually bonded；
Ra11And Ra12It is former to each independently represent the alkyl of carbon atom number 1~12, the naphthenic base of carbon atom number 3~12, carbon The alkynyl of the alkenyl of subnumber 2~12, the cycloalkenyl of carbon atom number 3~12 or carbon atom number 2~12.)
[10] photosensitive composition described in above-mentioned [9], wherein described in (C) adhesive resin (C1) content ratio of epoxy (methyl) acrylate is 85 mass % or more.
[11] photosensitive composition described in above-mentioned [9] or [10], wherein (C1) epoxy (methyl) third Alkene acid ester resin includes epoxy (methyl) acrylate and tool with repeat unit structure shown in the following general formula (II) There is one or both of epoxy (methyl) acrylate of part-structure shown in the following general formula (III),
[chemical formula 5]
(in formula (II), R11Indicate hydrogen atom or methyl；
R12Indicate divalent alkyl optionally with substituent group；
Phenyl ring in formula (II) is optionally further replaced by arbitrary substituent group；
* bonding position is indicated.)
[chemical formula 6]
(in formula (III), R13Each independently represent hydrogen atom or methyl；
R14Indicate that there is divalent alkyl of the cyclic hydrocarbon group as side chain；
R15And R16Each independently represent divalent aliphatic group optionally with substituent group；
M and n each independently represents 0~2 integer；
* bonding position is indicated.)
[12] photosensitive composition described in any one of above-mentioned [9]~[11], wherein relative to described The all solids ingredient of color sensation photosensitive resin composition, the content ratio of (A) colorant are 60 mass % or less.
[13] photosensitive composition described in any one of above-mentioned [9]~[12], wherein (A) coloring Agent further includes one or both of (A2) organic coloring pigments and (A3) carbon black.
[14] photosensitive composition described in any one of above-mentioned [9]~[13], wherein (A) coloring The content ratio of (A1) organic black pigments in agent is 10 mass % or more.
[15] a kind of spaced walls, the photosensitive composition structure as described in any one of above-mentioned [1]~[14] At.
[16] a kind of organic electroluminescent device has spaced walls described in above-mentioned [15].
[17] a kind of image display device, it includes organic electroluminescent devices described in above-mentioned [16].
[18] a kind of illumination, it includes organic electroluminescent devices described in above-mentioned [16].
[19] a kind of dispersible pigment dispersion, contains: (A) colorant, (B) dispersing agent and (C) adhesive resin, wherein
(A) colorant includes (A1) organic black pigments, and (A1) organic black pigments contain selected from following logical Formula (I) compound represented, the geometric isomer of the compound, the geometry of the salt of the compound and the compound are different At least one of the salt of structure body,
(B) dispersing agent includes acrylic dispersants,
(C) adhesive resin includes (C1) epoxy (methyl) acrylate,
[chemical formula 7]
(in formula (I), Ra1And Ra6Each independently represent hydrogen atom, CH3、CF3, fluorine atom or chlorine atom；
Ra2、Ra3、Ra4、Ra5、Ra7、Ra8、Ra9And Ra10Each independently represent hydrogen atom, halogen atom, R11、COOH、 COORa11、COO-、CONH2、CONHRa11、CONRa11Ra12、CN、OH、ORa11、COCRa11、OOCNH2、OOCNHRa11、 OOCNRa11Ra12、NO2、NH2、NHRa11、NRa11Ra12、NHCORa12、NRa11CORa12, N=CH2, N=CHRa11, N=CRa11Ra12、 SH、SRa11、SORa11、SO2Ra11、SO3Ra11、SO3H、SO3 -、SO2NH2、SO2NHRa11Or SO2NRa11Ra12；
Also, it is selected from Ra2With Ra3、Ra3With Ra4、Ra4With Ra5、Ra7With Ra8、Ra8With Ra9And Ra9With Ra10At least one of It combines optionally mutually Direct Bonding or passes through oxygen atom, sulphur atom, NH or NRa11Bridging and be mutually bonded；
Ra11And Ra12It is former to each independently represent the alkyl of carbon atom number 1~12, the naphthenic base of carbon atom number 3~12, carbon The alkynyl of the alkenyl of subnumber 2~12, the cycloalkenyl of carbon atom number 3~12 or carbon atom number 2~12.)
[20] dispersible pigment dispersion described in above-mentioned [19], wherein relative to 100 mass parts of (A) colorant, (B) point The content ratio of powder is 10 mass parts or more.
[21] dispersible pigment dispersion described in dispersible pigment dispersion described in above-mentioned [19] or [20], wherein (C1) epoxy (methyl) acrylate includes epoxy (methyl) acrylate with repeat unit structure shown in the following general formula (II) Resin and one or both of epoxy (methyl) acrylate with part-structure shown in the following general formula (III),
[chemical formula 8]
(in formula (II), R11Indicate hydrogen atom or methyl；
R12Indicate divalent alkyl optionally with substituent group；
Phenyl ring in formula (II) is optionally further replaced by arbitrary substituent group；
* bonding position is indicated.)
[chemical formula 9]
(in formula (III), R13Each independently represent hydrogen atom or methyl；
R14Indicate that there is divalent alkyl of the cyclic hydrocarbon group as side chain；
R15And R16Each independently represent divalent aliphatic group optionally with substituent group；
M and n each independently represents 0~2 integer；
* bonding position is indicated.)
[22] dispersible pigment dispersion described in any one of above-mentioned [19]~[21], wherein the acrylic dispersants are Acrylic dispersants containing nitrogen-atoms.
[23] dispersible pigment dispersion described in any one of above-mentioned [19]~[22], is used to manufacture coloring phototonus resin group Close object.
The effect of invention
Some way according to the present invention, it is few, excellent in reliability to provide the amount of gas evolved after forming solidfied material, and The good photosensitive composition of adaptation of the fine pattern in developing procedure when making solidfied material.In addition, by The amount of gas evolved of the solidfied material that photosensitive composition of the invention is formed when in use is few, as its service life of light-emitting component Reduction less, it is excellent in reliability.
In addition, another way according to the present invention, a kind of amount of gas evolved after can providing formation solidfied material is few, reliability is excellent The photosensitive composition of different, to be used to form organic electroluminescent device spaced walls.In addition, by of the invention The solidfied material amount of gas evolved when in use that color sensation photosensitive resin composition is formed is few, the reduction as its service life of light-emitting component less, It is excellent in reliability.
In addition, dispersible pigment dispersion according to the present invention, is capable of providing above-mentioned photosensitive composition.
Specific embodiment
Hereinafter, the present invention is described in detail.It should be noted that following record is the one of embodiments of the present invention A example, the present invention are not limited to these examples in the range of without departing from its main points.
It should be noted that in the present invention, " (methyl) acrylic acid " expression " acrylic acid and/or methacrylic acid ", separately Outside, " all solids ingredient " refers to, the whole components in photosensitive composition or dispersible pigment dispersion in addition to solvent. In addition, in the present invention, the numberical range indicated using "~" indicates the numerical value for being included in the record of "~" front and back as lower limit value And the range of upper limit value.
In addition, in the present invention, the meaning of " (co) polymer " includes single polymers (homopolymer) and copolymer (copolymerization Both polymer), in addition, the meaning of " (acid) acid anhydride ", " ... sour (acid anhydride) " includes both sour and its acid anhydrides.
In the present invention, interval wall material refer to box dam material, wall material, walling material, similarly, spaced walls refer to box dam, Wall, wall.Spaced walls be for example for dividing the component of the functional layer (organic layer) in active drive type organic electroluminescent device, It is to be coated with the material for constituting functional layer simultaneously based on vapor deposition or ink-jet etc. on the region (pixel region) after division It is dried, to form pixel being made of functional layer and spaced walls etc. and use.
In the present invention, weight average molecular weight refers to dividing equally again for the conversion of the polystyrene based on GPC (gel permeation chromatography) Son amount (Mw).
In the present invention, reliability refers to reliability when organic electroluminescent device driving, in particular, showing about image Device refers to expression reliability, about illumination, refers to luminous reliability.
The photosensitive composition of the 1st aspect of the present invention is for solving above-mentioned first project, wherein above-mentioned (A) colorant includes (A1) organic black pigments, and (A1) organic black pigments contain selected from logical formula (I) institute described later The salt of the geometric isomer of the geometric isomer of the compound, above compound that show, the salt of above compound and above compound At least one of, above-mentioned (B) dispersing agent include acrylic dispersants, above-mentioned (C) adhesive resin include 75 mass % with On (C1) epoxy (methyl) acrylate.
The photosensitive composition of the 2nd aspect of the present invention is for shape for solving above-mentioned second project At the photosensitive composition of the spaced walls of organic electroluminescent device, wherein above-mentioned (A) colorant includes that (A1) has Machine black pigment, (A1) organic black pigments contain selected from logical formula (I) compound represented described later, above-mentioned chemical combination At least one of the geometric isomer of object, the salt of above compound and salt of geometric isomer of above compound, it is above-mentioned (C) adhesive resin includes (C1) epoxy (methyl) acrylate of 75 mass % or more.
The dispersible pigment dispersion of the 3rd aspect of the present invention is for solving above-mentioned third project, wherein above-mentioned (A) colorant packet Containing (A1) organic black pigments, (A1) organic black pigments contain selected from logical formula (I) compound represented described later, At least one in the salt of the geometric isomer of the geometric isomer of above compound, the salt of above compound and above compound Kind, above-mentioned (B) dispersing agent includes acrylic dispersants, and above-mentioned (C) adhesive resin includes (C1) epoxy (methyl) acrylic acid Ester resin.
Hereinafter, unless otherwise specified, " photosensitive composition of the invention " refers to above-mentioned first method Photosensitive composition and both photosensitive compositions of second method.
[1] ingredient and composition of photosensitive composition
The ingredient and its composition that constitute photosensitive composition of the invention are illustrated.
Photosensitive composition (hereinafter, sometimes referred to simply as " photosensitive polymer combination ") of the invention contains (A) colorant, (B) dispersing agent, (C) adhesive resin, (D) photopolymerization monomer and (E) Photoepolymerizationinitiater initiater, in addition, usually Also contain solvent.
[1-1] (A) colorant
(A) colorant in photosensitive composition and dispersible pigment dispersion of the invention includes (A1) organic black Pigment (hereinafter, sometimes referred to as " (A1) organic black pigments "), is somebody's turn to do (A1) organic black pigments and contains selected from the following general formula (I) institute The compound (hereinafter, sometimes referred to as " compound (I) ") that shows, the geometric isomer of above compound, above compound salt and At least one of salt of geometric isomer of above compound.
In this wise, by the inclusion of (A1) organic black pigments, it is believed that high resistance, low-k and high shading may be implemented Rate.Further, since it is possible to obtain the solidfied material of the tone closer to black, when can be used to form and be shown in image The colorant of the spaced walls of the big organic electroluminescent device of shared area ratio in the image display area of device.In addition, By using (A1) organic black pigments, dispersibility, keeping quality are also good, in the colored photosensitive for containing (A1) organic black pigments In property resin combination, pattern adaptability when development is also good.
[chemical formula 10]
In formula (I), Ra1And Ra6Each independently represent hydrogen atom, CH3、CF3, fluorine atom or chlorine atom；
Ra2、Ra3、Ra4、Ra5、Ra7、Ra8、Ra9And Ra10Each independently represent hydrogen atom, halogen atom, Ra11、COOH、 COORa11、COO-、CONH2、CONHRa11、CONRa11Ra12、CN、OH、ORa11、COCRa11、OOCNH2、OOCNHRa11、 OOCNRa11Ra12、NO2、NH2、NHRa11、NRa11Ra12、NHCORa12、NRa11CORa12, N=CH2, N=CHRa11, N=CRa11Ra12、 SH、SRa11、SORa11、SO2Ra11、SO3Ra11、SO3H、SO3 -、SO2NH2、SO2NHRa11Or SO2NRa11Ra12；
Also, it is selected from Ra2With Ra3、Ra3With Ra4、Ra4With Ra5、Ra7With Ra8、Ra8With Ra9And Ra9With Ra10At least one of It combines optionally mutually Direct Bonding or passes through oxygen atom, sulphur atom, NH or NR11Bridging and be mutually bonded；
Ra11And Ra12It is former to each independently represent the alkyl of carbon atom number 1~12, the naphthenic base of carbon atom number 3~12, carbon The alkynyl of the alkenyl of subnumber 2~12, the cycloalkenyl of carbon atom number 3~12 or carbon atom number 2~12.
There is the geometric isomer of logical formula (I) compound represented nuclear structure below (wherein, to be omitted in structural formula Substituent group), trans- trans isomer may be most stable of.
[chemical formula 11]
In the case that logical formula (I) compound represented is anionic property, preferably using any known suitable sun from Son, such as metal, organic and inorganic or metal organic cation, be specially alkali metal, alkaline-earth metal, transition metal, primary amine, secondary Obtained from the quaternary ammoniums such as the tertiary amines such as amine, trialkylamine, tetra-allkylammonium or Organometallic complexes compensate its charge Salt.In addition, in the case that the geometric isomer of logical formula (I) compound represented is anionic property, preferably same salt.
About the substituent group of logical formula (I), from the tendency aspect increased with screening rate, substituent group preferably below. This is because, it is believed that substituent group below does not absorb, and will not affect to the form and aspect of pigment.
Ra2、Ra4、Ra5、Ra7、Ra9And Ra10Each independently be preferably hydrogen atom, fluorine atom or chlorine atom, more preferably Hydrogen atom.
Ra3And Ra8It is each independently preferably hydrogen atom, NO2、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。
R1And R6It is each independently preferably hydrogen atom, CH3Or CF3, more preferably hydrogen atom.
It is preferably selected from R1With R6、R2With R7、R3With R8、R4With R9And R5With R10At least one of combination it is identical, more preferably R1With R6Identical, R2With R7Identical, R3With R8Identical, R4With R9Identical and R5With R10It is identical.
The alkyl of carbon atom number 1~12 is, for example, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl Base, tert-butyl, 2- methyl butyl, n-pentyl, 2- amyl, 3- amyl, 2,2- dimethyl propyl, n-hexyl, heptyl, n-octyl, 1,1,3,3- tetramethyl butyl, 2- ethylhexyl, 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, ramie base (thujyl), norbornene, bornyl, norcarane alkyl, caryl,Alkyl, Norpinane base, pinane base, 1- adamantyl or 2- adamantyl.
The alkenyl of carbon atom number 2~12 is, for example, vinyl, allyl, 2- propylene-2- base, 2- butene-1-base, 3- fourth Alkene -1- base, 1,3- butadiene -2- base, 2- amylene -1- base, 3- 2-pentenyl, 2-Base -1- butylene -3- base, 2- methyl -3- Butene-2-base, 3- methyl-2-butene-1- base, 1,4- pentadiene-3- base, hexenyl, octenyl, nonenyl, decene base or ten Dialkylene.
The cycloalkenyl of carbon atom number 3~12 be, for example, 2- cyclobutane -1- base, 2- cyclopentene -1- base, 2- cyclohexene -1- base, 3- cyclohexene -1- base, 2,4- cyclohexadiene -1- base, 1- pairsAlkene -8- base, 4 (10)-limonene -10- bases, 2- norbornene -1- Base, 2,5- norbornadiene -1- base, 7,7- dimethyl -2,4- norcarane diene -3- base or camphyl.
The alkynyl of carbon atom number 2~12 is, for example, 1- propine -3- base, 1- butine -4- base, 1- pentyne -5- base, 2- methyl - 3- crotonylene-base, 1,4- pentadiine -3- base, 1,3- pentadiine -5- base, 1- hexin -6- base, cis- 3- methyl -2- amylene -4- Alkynes -1- base, trans- 3- methyl -2- amylene -4- alkynes -1- base, 1,3- hexadiine -5- base, 1- octyne -8- base, 1- n-heptylacetylene -9- base, 1- Decine -10- base or 1- dodecyne -12- base.
Halogen atom is, for example, fluorine atom, chlorine atom, bromine atom or iodine atom.
Above-mentioned (A1) organic black pigments are preferably selected from the following general formula (I-1) compound represented (hereinafter, sometimes referred to as At least one of " compound (I-1) ") and the geometric isomer of the compound.
[chemical formula 12]
As the concrete example of such organic black pigments, trade name Irgaphor (registered trademark) can be enumerated The organic black pigments of 0100 CF of Black S (BASF AG's system).
The organic black pigments are preferably dispersed in dispersing agent by method described below, use in solvent.In addition, if In dispersion, there are the sulfonic acid of above compound (1) (sulfonic acid substituent) or the sulphurs of the geometric isomer of compound (I) The sulphur of the geometric isomer of the sulfonic acid or above compound (I-1) of acid derivative, particularly above compound (I-1) Acid derivative, then dispersibility, keeping quality improve sometimes.
(A) colorant used in the present invention, can also be containing other other than above-mentioned (A1) organic black pigments Toner.As other colorants, it is preferable to use pigment, pigment can be organic pigment, or inorganic pigment, from high resistant From the perspective of anti-, low-k, organic pigment is more preferably used, in particular, further preferably using organic coloring pigments (hereinafter sometimes referred to " (A2) organic coloring pigments ").
The chemical structure of these pigment is not particularly limited, and can use azo, phthalocyanines, quinoline azone class, benzo miaow Oxazolone class, isoindoline ketone, twoThe organic pigments such as piperazine class, indanthrone kinds, perylene kinds.Hereinafter, hereinafter, with pigment Serial number shows the concrete example for the organic pigment that can be used.Terms such as " the C.I. paratoneres 2 " that is exemplified below refer to that pigment indexes Number (C.I.).
As red pigment, can enumerate: C.I. paratonere 1,2,3,4,5,6,7,8,9,12,14,15,16,17,21,22, 23、31、32、37、38、41、47、48、48:1、48:2、48:3、48:4、49、49:1、49:2、50:1、52:1、52:2、53、 53:1、53:2、53:3、57、57:1、57:2、58:4、60、63、63:1、63:2、64、64:1、68、69、81、81:1、81:2、 81:3、81:4、83、88、90:1、101、101:1、104、108、108:1、109、112、113、114、122、123、144、146、 147、149、151、166、168、169、170、172、173、174、175、176、177、178、179、181、184、185、187、 188、190、193、194、200、202、206、207、208、209、210、214、216、220、221、224、230、231、232、 233、235、236、237、238、239、242、243、245、247、249、250、251、253、254、255、256、257、258、 259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275,276.Wherein it is possible to It is preferred that C.I. pigment red 4 8:1,122,149,168,177,179,194,202,206,207,209,224,242,254 are enumerated, it can More preferably to enumerate C.I. paratonere 177,209,224,254.
It should be noted that from dispersibility, light-proofness invention, it is preferable to use C.I. paratonere 177,254,272, Made in the cured situation of photosensitive composition of the invention using ultraviolet light, as red pigment, it is preferable to use purple The low red pigment of outside line absorptivity more preferably uses C.I. paratonere 254,272 from the above point of view.
As orange (Orange) pigment, can enumerate: C.I. pigment orange 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, from dispersibility, light-proofness aspect, it is preferable to use C.I. pigment orange 13,43,64,72, make the present invention using ultraviolet light The cured situation of photosensitive composition under, as orange pigment, it is preferable to use low orange of absorption of UV Pigment more preferably uses C.I. pigment orange 64,72, particularly preferred C.I. pigment orange 64 from the above point of view.
As blue pigment, can enumerate: C.I. pigment blue 1,1:2,9,14,15,15:1,15:2,15:3,15:4,15:6, 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 more preferably enumerate it is preferred that enumerate C.I. pigment blue 15,15:1,15:2,15:3,15:4,15:6 C.I. pigment blue 15: 6.
It should be noted that from dispersibility, light-proofness aspect, it is preferable to use C.I. pigment blue 15: 6,16,60, Made in the cured situation of photosensitive composition of the invention using ultraviolet light, as blue pigment, it is preferable to use purple The low blue pigment of outside line absorptivity more preferably uses C.I. pigment blue 60 from the above point of view.
As violet pigment, can enumerate: C.I. pigment violet 1,1:1,2,2:2,3,3:1,3:3,5,5:1,14,15,16, 19,23,25,27,29,31,32,37,39,42,44,47,49,50.Wherein, from light-proofness aspect, it is preferable to use C.I. Pigment violet 19,23 more preferably uses C.I. pigment Violet 23.
It should be noted that from dispersibility, light-proofness aspect, it is preferable to use C.I. pigment Violet 23,29, are utilizing purple Outside line makes in the cured situation of photosensitive composition of the invention, as violet pigment, it is preferable to use ultraviolet light is inhaled The low violet pigment of yield more preferably uses C.I. pigment violet 29 from the above point of view.
As the organic coloring face being able to use other than red pigment, orange pigment, blue pigment, violet pigment Material, it can be mentioned, for example viridine green, yellow uitramarines etc..
As viridine green, can enumerate: C.I. naphthol green 1,2,4,7,8,10,13,14,15,17,18,19,26,36, 45,48,50,51,54,55,58.Wherein it is possible to it is preferred that enumerate C.I. pigment Green 7,36.
As yellow uitramarine, can enumerate: C.I. pigment yellow 1,1:1,2,3,4,5,6,9,10,12,13,14,16,17,24, 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 83,117,129,138, 139,150,154,155,180,185, more preferably enumerate C.I. pigment yellow 83,138,139,150,180.
In these pigment, it is preferable to use selected from least one of red pigment and orange pigment with selected from blue pigment and The combination of at least one of violet pigment.In this wise, by using the combination of specific pigment, exist and can be realized high shading The tendency of property.
In above-mentioned, from the viewpoint of light-proofness, tone, preferably contain at least one of following pigment or more.
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
It should be noted that the combination for color is not particularly limited, from the viewpoint of light-proofness, example can be enumerated Such as: the combination of red pigment and blue pigment, the combination of blue pigment and orange pigment, blue pigment and orange pigment and purple The combination etc. of pigment.
In addition, other than above-mentioned organic coloring pigments, other black colorants can be used as other colorants Agent.
In black colorant, from the viewpoint of light-proofness, tone, other than can also using shown in above-mentioned logical formula (I) Other organic black pigments.As other organic black pigments, it is peaceful black etc. that nigrosine, black, match can be enumerated.
In addition, in the present invention, inorganic black pigments can be used.It as inorganic black pigments, can enumerate: carbon black, second Acetylene black, lampblack, bone black, graphite, iron oxide black, titanium are black etc..It, can be preferred from the viewpoint of light-proofness, picture characteristics in these It uses carbon black (hereinafter, sometimes referred to as " (A3) carbon black ").As the example of carbon black, carbon black as described below can be enumerated.
Mitsubishi chemical Co., Ltd's system: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600、MCF88、#5、#10、#20、#25、#30、#32、#33、#40、#44、#45、#47、#50、#52、#55、#650、# 750、#850、#900、#950、#960、#970、#980、#990、#1000、#2200、#2300、#2350、#2400、#2600、# 2650、#3030、#3050、#3150、#3250、#3400、#3600、#3750、#3950、#4000、#4010、OIL7B、OIL9B、 OIL11B、OIL30B、OIL31B
Degussa corporation: 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、SpecialBlack550、SpecialBlack350、SpecialBlack250、SpecialBlack100、 SpecialBlack6、SpecialBlack5、SpecialBlack4、Color Black FW1、Color Black FW2、 Color Black FW2V、Color Black FW18、Color Black FW200、Color Black S160、Color Black S170
Cabot corporation: 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, same as below) XC72R, ELFTEX (registered trademark) -8
Birror corporation: 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
The carbon black obtained from resin coats also can be used in carbon black.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. recorded in such as Japanese Unexamined Patent Publication 09-71733 bulletin.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 ash content with percentage several levels, 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 furnace material for being granulated water and reacting furnace.Wherein, Na and Ca are usual Contain several hundred 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.
Contain the method for the content of the ash content of Na, Ca as these are reduced, it can be using the content pole of stringent selection Na, Ca Few substance is reduced as feedstock oil, fuel oil (or gas) and the reaction terminating water when manufacturing carbon black and strongly for adjusting knot The method of the additive amount of the alkaloid substance of structure.As other methods, it can enumerate and the carbon black produced from furnace is carried out with water, hydrochloric acid etc. It washs and dissolves the method for removing Na, Ca.
Specifically, it is scattered in carbon black mixing 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 being 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 The case where carbon black manufacturing process for having selected raw material or the mode for being individually dissolved in water or acid dissolution can be realized as, but it is logical Cross the total amount 100ppm or less that two ways is applied in combination and is easier to make Na and Ca.
In addition, resin coats the preferred pH6 of carbon black so-called acidic black below.Due to dispersion diameter (agglomerate in water Size, agglomerate size) become smaller, or even the cladding being able to carry out under fine unit, therefore it is preferred that.More preferable average grain diameter 40nm or less, dibatyl phithalate (DBP) uptake 140ml/100g carbon black below.By to exist in above range 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 to shoot several visuals field using electron microscope observation with tens of thousands of times of multiplying power, is passed through Image processing apparatus measures 2000~3000 or so carbon black particles in obtained photo.
The method of the carbon black of spare resin cladding processed is not particularly limited, such as is being suitable for by the use level of carbon black and resin After adjustment, following method can be used:
1. resin and cyclohexanone, toluene, dimethylbenzene equal solvent are mixed and heated dissolution 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 being separated from water carbon black, removes Water simultaneously carries out heating mixing, obtains composition, is sheet by obtained composition molding, makes it dry after being crushed；
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 a solvent, adding carbon black and being mixed, removed after making it dry Solvent has obtained the carbon black that addition attachment (adding) has 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 (being grafted carbon black), 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 in the structure further with the resin of benzene nucleus, this is because it is as amphoteric surfactant It is with better function.
As specific synthetic resin, phenolic resin, melamine resin, xylene resin, phthalic acid can be used The thermosetting resins such as diallyl phthalate resin, glyptal resin, epoxy resin, alkylbenzene resin and polystyrene, polycarbonate, 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-coated amount is 1~30 mass % preferably with respect to carbon black and resin-coated total amount.By setting cladding The amount of rouge is above-mentioned lower limit value or more, there is the tendency for being capable of forming the carbon black sufficiently coated.On the other hand, by setting cladding The amount of rouge is above-mentioned upper limit value hereinafter, making the tendency of favorable dispersibility in the presence of that can prevent resin bonding to each other.
Using resin carry out cladding processing in this wise and the carbon black that is formed can be made according to usual way spaced walls, The light screening material of color spacer uses, and can be made by usual way using the spaced walls, coloring spacer as constituent element Organic illuminating element, colour filter.If using such carbon black, exist can be realized high shading rate and low cost incline To.In addition, can be made between high resistance, the spaced walls of low-k, coloring by being coated with resin to carbon blacksurface The light screening materials such as parting.
In addition, other than above-mentioned organic coloring pigments, black colorant, dye can also be used as other colorants Material.It as the dyestuff that can be used as colorant, can enumerate: azo dyes, anthraquinone dyes, phthalocyanines dye, quinone imides Dyestuff, quinolines dyestuff, nitro class dyestuff, carbonyl class dyestuff, methchlorenes dyes etc..
As azo dyes, it can be mentioned, for example: C.I. acid yellow 11, C.I. acid orange 7, C.I. acid red 37, C.I. Acid red 18 0, C.I. acid blue 29, C.I. directly red 28, C.I. directly red 83, C.I. directly Huang 12, C.I. direct orange 26, C.I. direct green 28, C.I. direct green 59, C.I. active yellow 2, C.I. active red 17, C.I. active red 120, C.I. reactive black 5, C.I. disperse orange 5, C.I. disperse red 58, C.I. disperse blue 165, C.I. alkali blue 41, C.I. Basic Red 18, C.I. medium red 7, C.I. medium Huang 5, C.I. Mordant Black 7 etc..
As anthraquinone dyes, it can be mentioned, for example: C.I. Vat blue 4, C.I. Acid Blue 40, C.I. ACID GREEN 25, C.I. Active blue 19, C.I. reactive blue 49, C.I. disperse red 60, C.I. Disperse Blue-56, C.I. disperse blue 60 etc..
In addition, as phthalocyanines dye, it can be mentioned, for example C.I. vat blues 5 etc. as quinone imides dyestuff can enumerate example Such as C.I. alkali blue 3, C.I. alkali blue 9, as quinolines dyestuff, it can be mentioned, for example C.I. solvent yellow 33s, C.I. Indian yellow 3, C.I. dispersion yellow 64 etc., as nitro class dyestuff, it can be mentioned, for example C.I. Indian yellow 1, C.I. acid orange 3, C.I. disperse yellows 42 etc..
The pigment such as these (A1) organic black pigments, (A2) organic coloring pigments, black colorant are preferably dispersed into average Partial size is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm or less and uses.Wherein, the base of average grain diameter Standard is the number of pigment particles.
It should be noted that the average grain diameter of the pigment is the pigment particle size by being measured by dynamic optical (DLS) at random The value found out.Particle size determination is that the photosensitive composition after sufficiently diluting (is usually diluted and is prepared into 0.005~0.2 mass % of pigment content ratio or so, but according to the different concentration if there is recommendation of determining instrument, then according to The concentration) Lai Jinhang, and be measured at 25 DEG C.
[1-2] (B) dispersing agent
In photosensitive composition and dispersible pigment dispersion of the invention, due to dispersing (A) colorant imperceptibly, And stabilize its dispersity for ensuring that the stability of quality is important, therefore include (B) dispersing agent.
The photosensitive composition of the 1st aspect of the present invention and the dispersible pigment dispersion of the 3rd aspect of the present invention In, (B) dispersing agent includes acrylic dispersants.Acrylic dispersants are due to the soft master with straight-chain molecule structure Skeleton, it can thus be assumed that, being adsorbed in colorant by most adsorption groups makes colorant be homogeneously dispersed in coloring phototonus In resin combination and dispersible pigment dispersion.By being configured at colorant equably in coated film, which becomes fine and close Film, and then, it can be said that be equably configured in coated film by making the colorant as the ingredient insoluble in alkaline developer, development Developer solution is suppressed to being impregnated with inside coated film when processing, and pattern adaptation becomes well, even especially fine pattern, Adaptation also becomes good.
In addition, as acrylic dispersants, preferably with the macromolecule dispersing agent of functional group.In addition, from stably dispersing Property aspect set out, preferably comprise carboxyl；Phosphate；Sulfonic group；Or their salt groups；And the acrylic compounds containing nitrogen-atoms Dispersing agent, wherein preferably comprise the acrylic dispersants of nitrogen-atoms.In addition, from can be with when dispersing the colorants such as pigment From the perspective of a small amount of dispersing agent is dispersed, particularly preferably there is primary amino group, secondary amino group or tertiary amino；Quaternary ammonium salt base；Come Derived from the macromolecule dispersing agent of the basic functionalities such as the nitrogenous heterocyclic group such as pyridine, pyrimidine, pyrazine.These functional groups are as suction The adsorption group for investing colorant works.
As commercially available acrylic dispersants, it can be mentioned, for example DISPERBYK-2000, DISPERBYK-2001, BYK- LPN21116, BYK-LPN6919 etc. (being above BYK-Chemie corporation).
As the acrylic dispersants containing nitrogen-atoms, it is preferable to use having functional group, (functional group mentioned here is As the functional group in front, functional group contained in macromolecule dispersing agent) and monomer containing unsaturated group with do not have There are random copolymer, the graft copolymer, block copolymer of functional group but the monomer formation containing unsaturated group.These copolymerization Object can be manufactured with well known method.
As with functional group and containing the monomer of unsaturated group, (methyl) acrylic acid, 2- (methyl) propylene can be enumerated Acyloxyethyl succinic acid, 2- (methyl) acrylyl oxy-ethyl phthalic acid, 2- (methyl) acrylyl oxy-ethyl hexahydro phthalic acid, Acrylic acid dimer etc. has the unsaturated monomer of carboxyl；Dimethyl aminoethyl (methyl) acrylate, diethylamino second Base (methyl) acrylate and their quaternaries etc. have tertiary amino, quaternary ammonium salt base unsaturated monomer as concrete example.It Can be used alone, or combine two or more use.
As without functional group but containing the monomer of unsaturated group, (methyl) methyl acrylate, (methyl) can be enumerated Ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) propylene Sour isobutyl ester, (methyl) tert-butyl acrylate, (methyl) benzyl acrylate, (methyl) phenyl acrylate, (methyl) acrylic acid ring Own ester, (methyl) phenoxyethyl acrylate, (methyl) acrylic acid phenoxy group methyl esters, (methyl) 2-EHA, (first Base) isobornyl acrylate, (methyl) tricyclodecyl acrylate, (methyl) tetrahydrofurfuryl acrylate, n-vinyl pyrrolidone, Styrene and its derivatives, α-methylstyrene, N- N-cyclohexylmaleimide, N-phenylmaleimide, N- benzyl Malaysia The N- substituted maleimide such as acid imide amine, acrylonitrile, vinyl acetate and poly- (methyl) methyl acrylate polymeric monomer, polystyrene Polymeric monomer, poly- (methyl) acrylic acid 2- hydroxy methacrylate polymeric monomer, polyethylene glycol polymeric monomer, polypropylene glycol polymeric monomer, polycaprolactone Polymeric monomers such as polymeric monomer etc..They can be used alone, or combine two or more use.The side chain conduct of these monomers The affine portion of solvent to mix with solvent plays a role.
From the viewpoint of dispersibility, acrylic dispersants are preferably by the A block with functional group and not have official A-B the or B-A-B block copolymer that the B block that can be rolled into a ball is constituted.In this case, above-mentioned comprising function in addition to deriving from A block Other than group and the part-structure of the monomer containing unsaturated group, can also containing from it is above-mentioned do not include functional group but contain The part-structure of the monomer of unsaturated group, these structures can be with any of random copolymerization or block copolymerization in the A block Form contain.In addition, content of the part-structure without functional group in A block is usually 80 mass % hereinafter, preferably It 50 mass % or less, more preferably 30 mass % or less, further preferably 10 mass % or less, is most preferably 0 mass %.
From the viewpoint of dispersibility, B block preferably only origin derived from above-mentioned without functional group but containing unsaturated group The part-structure of the monomer of group is constituted, can be containing the part-structure from two or more monomer in 1 B block, these knots Structure can be contained in the B block with any form of random copolymerization or block copolymerization.
Living polymerization as shown below can be used for example to prepare in A-B the or B-A-B block copolymer.
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 13]
In said synthesis route, Ar1For 1 valence organic group, Ar2For 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 14]
In said synthesis route, Ar1For 1 valence organic group, Ar2For 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 dispersants, Japanese Unexamined Patent Publication 9-62002 bulletin, P.Lutz can be used, 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 male, 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, The well known method recorded in 20,1473 (1987) etc..
As previously described, the acrylic dispersants that can be used in the present invention can be A-B block copolymer, can also Think B-A-B block copolymer, the A block/B block ratio for constituting its copolymer is not particularly limited, and preferably 1/99~80/20 (mass ratio), more preferably 5/95~60/40 (mass ratio), by make its this within the scope of, exist can ensure dispersibility and Balanced tendency of storage stability.
In addition, in A-B block copolymer that 1g can be used in the present invention, B-A-B block copolymer, quaternary ammonium salt base The amount of group is preferably generally 0.1~10mmol, by make its this within the scope of, existing can ensure good dispersed to incline To.
On the other hand, in such acrylic dispersants, amino can be contained.The amine value of acrylic dispersants is logical Often it is 1~130mgKOH/g or so, preferably 10mgKOH/g or more, more preferably 30mgKOH/g or more, is more preferably 50mgKOH/g or more, particularly preferably 60mgKOH/g or more, additionally, it is preferred that for 120mgKOH/g or less, being more preferably 100mgKOH/g or less, further preferably 90mgKOH/g or less, particularly preferably 80mgKOH/g or less.By being set as above-mentioned More than lower limit value, there are dispersibilities to become good tendency, in addition, by being set as above-mentioned upper limit value hereinafter, depositing after distribution Keeping quality becomes good tendency.As the combination of the upper limit and lower limit, preferably enumerates 10~120mgKOH/g, more preferably enumerates 30~100mgKOH/g, it further preferably enumerates 50~90mgKOH/g, particularly preferably enumerate 60~80mgKOH/g.
Here, the amine value of the acrylic dispersants solid component 1g being equivalent in dispersing agent sample in addition to solvents Alkali number comparable KOH mass indicate, measured by following method.
Accurate weighing dispersing agent 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 electrode, 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 as titration end-point according to the following formula.
Amine value [mgKOH/g]=(561 × V)/(W × S)
It [wherein, W: indicates the dispersing agent sample amount of weighing [g], V: indicating titer [mL], the S in titration end-point: indicating to divide The solid component concentration [quality %] of powder sample.]
The weight average molecular weight (Mw) of acrylic dispersants is not particularly limited, preferably 1000 or more, more preferably It 3000 or more, is more preferably 4000 or more, particularly preferably 5000 or more, additionally, it is preferred that being 50000 or less, more preferable It is 20000 or less, further preferably 15000 or less.By being set as above-mentioned lower limit value or more, there are dispersibilities to become good Tendency, in addition, by being set as above-mentioned upper limit value hereinafter, in the presence of the tendency for being not easy to cause viscosity change.As the upper limit and lower limit Combination preferably enumerates 1000~50000, more preferably enumerates 3000~20000, further preferably enumerate 4000~15000, is special Preferably do not enumerate 5000~15000.
Acrylic dispersants have quaternary ammonium salt group as functional group in the case where, the repetition list comprising quaternary ammonium salt group The chemical structure of member is not particularly limited, but from the viewpoint of dispersibility, and preferably acrylic dispersants have following formula (V)s The repetitive unit of expression (hereinafter, sometimes referred to as " repetitive unit (V) ").
[chemical formula 15]
In above-mentioned formula (V), R31~R33Be each independently hydrogen atom, optionally alkyl with substituent group, optionally with taking The aryl of Dai Ji or the aralkyl optionally 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 (V)31~R33In the optionally carbon atom number of alkyl with substituent group be not particularly limited, usually 1 or more, and preferably 10 or less, more preferably 6 or less, further preferably 4 or less, particularly preferably 2 or less.As alkane The specific example of base can enumerate methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl etc., in these, preferably Methyl, ethyl, propyl, butyl, amyl or hexyl, more preferably methyl, ethyl, propyl or butyl, further preferably methyl Or ethyl.Furthermore it is possible to for the arbitrary form in straight-chain, branched.Furthermore it is also possible to contain cyclohexyl, cyclohexyl methyl Etc. cyclic structures.
The R of above-mentioned formula (V)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, can enumerate phenyl, aminomethyl phenyl, Ethylphenyl, 3,5-dimethylphenyl, diethyl phenyl, naphthalene, anthryl etc., in these, preferably phenyl, aminomethyl phenyl, ethyl Phenyl, 3,5-dimethylphenyl or diethyl phenyl, more preferably phenyl, aminomethyl phenyl or ethylphenyl.
The R of above-mentioned formula (V)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 where, it is excellent from the viewpoint of dispersibility Select the repetitive unit that there are following formula (VI)s to indicate (hereinafter, sometimes referred to as " repetitive unit (VI) ").
[chemical formula 16]
In above-mentioned formula (VI), R35And R36It is each independently hydrogen atom, the alkyl optionally with substituent group, optionally has The aryl of substituent group or the aralkyl optionally with substituent group, R35And R36It can be mutually bonded and form cyclic structure；
R37For hydrogen atom or methyl；
Z is the connection group of divalent.
R as above-mentioned formula (VI)35And R36In optionally with substituent group alkyl, can preferably be employed as above-mentioned formula (V) R31~R33And the group that example goes out.
Similarly, the R as above-mentioned formula (VI)35And R36In optionally with substituent group aryl, can preferably be employed as The R of above-mentioned formula (V)31~R33And the group that example goes out.In addition, the R as above-mentioned formula (VI)35And R36In optionally have substituent group Aralkyl, can preferably be employed as the R of above-mentioned formula (V)31~R33And the group that example goes out.
In these, from the viewpoint of dispersibility, preferably R35And R36It is each independently alkane optionally with substituent group Base, more preferably methyl or ethyl.
R as above-mentioned formula (V)31~R33And the R of above-mentioned formula (VI)35And R36In alkyl, aralkyl or aryl institute optionally The substituent group having can enumerate halogen atom, alkoxy, benzoyl, hydroxyl etc..
In above-mentioned formula (V) and (VI), as connection the group X and Z of divalent, it can be mentioned, for example: carbon atom number 1~10 Alkylidene, the arlydene of carbon atom number 6~12 ,-CONH-R43Base ,-COOR44Base [wherein, R43And R44For singly-bound, carbon atom The alkylidene of number 1~10 or the ether (alkyl oxyalkyl) of carbon atom number 2~10] etc., preferably-COO-R44Base, more preferably For-COO-C2H4Base.
In addition, the Y in above-mentioned formula (V), 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 (V) indicates is not particularly limited, from the viewpoint of dispersibility, relatively In above-mentioned formula (V) indicate repetitive unit content ratio and above-mentioned formula (VI) 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, additionally, it is preferred that being 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.As the combination of the upper limit and lower limit, 5~60 moles of %, are more preferably enumerated It is preferred that enumerating 10~50 moles of %, further preferably enumerating 20~40 moles of %, particularly preferably enumerate 30~35 moles of %.
In addition, the repetitive unit that indicates of above-mentioned formula (V) content ratio shared in whole repetitive units of dispersing agent does not have It is particularly limited to, from the viewpoint of dispersibility, preferably 1 mole of % or more, is more preferably 5 moles of % or more, is further excellent 8 moles of % or more, particularly preferably 10 moles of % or more are selected as, additionally, it is preferred that being 50 moles of % or less, more preferably 30 rubbing You are % or less, further preferably 20 moles of % or less, particularly preferably 15 moles of % or less.Group as the upper limit and lower limit It closes, preferably enumerates 1~50 mole of %, more preferably enumerate 5~30 moles of %, further preferably enumerate 8~20 moles of %, is special It is preferred that enumerating 10~15 moles of %.
The content ratio for the repetitive unit that above-mentioned formula (VI) indicates is not particularly limited, from the viewpoint of dispersibility, phase For above-mentioned formula (V) indicate repetitive unit content ratio and above-mentioned formula (VI) indicate repetitive unit content ratio it is total Preferably 100 moles of % or less, more preferably 90 moles of % or less, meter is more preferably 80 moles of % or less, particularly preferred For 70 moles of % hereinafter, additionally, it is preferred that being 10 moles of % or more, more preferably 30 moles of % or more, further preferably 50 rubbing You are % or more, particularly preferably 60 moles of % or more.As the combination of the upper limit and lower limit, preferably enumerate 10~100 moles of %, More preferably 30~90 moles of % are enumerated, 50~80 moles of % is further preferably enumerated, particularly preferably enumerates 60~70 moles of %.
In addition, the repetitive unit that indicates of above-mentioned formula (VI) content ratio shared in whole repetitive units of dispersing agent does not have It is particularly limited to, from the viewpoint of dispersibility, preferably 5 moles of % or more, is more preferably 10 moles of % or more, is further excellent 15 moles of % or more, particularly preferably 20 moles of % or more are selected as, additionally, it is preferred that being 60 moles of % or less, more preferably 40 rubbing You are % or less, further preferably 30 moles of % or less, particularly preferably 25 moles of % or less.Group as the upper limit and lower limit Close, preferably enumerate 5~600 moles of %, more preferably enumerate 10~40 moles of %, further preferably enumerate 15~30 moles of %, Particularly preferably enumerate 20~25 moles of %.
In addition, from the viewpoint of improve with the compatibility of the adhesive ingredients such as solvent, improve dispersion stabilization, propylene The repetitive unit that preferably there are acids dispersing agent following formula (VII)s to indicate (hereinafter, sometimes referred to as " repetitive unit (VII) ").
[chemical formula 17]
In above-mentioned formula (VII), R40For ethylidene or propylidene；
R41For optionally with the alkyl of substituent group；
R42For hydrogen atom or methyl；
The integer that n is 1~20.
The R of above-mentioned formula (VII)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, further preferably 4 or less.Tool as alkyl Body example 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.
In addition, from the viewpoint of relative to the compatibility of the adhesive ingredients such as solvent and dispersibility, in above-mentioned formula (VII) N be preferably 1 or more, more preferably 2 or more, also, preferably 10 or less, more preferably 5 or less.As the upper limit and lower limit Combination, preferably enumerates 1~10 integer, more preferably enumerates 2~5 integer.
In addition, the content ratio that the repetitive unit of above-mentioned formula (VII) expression is shared in whole repetitive units of dispersing agent It is not particularly limited, preferably 1 mole of % or more, more preferably 2 moles of % or more, further preferably 4 moles of % or more, separately Outside, preferably 30 moles of % or less, more preferably 20 moles of % or less, further preferably 10 moles of % or less.In above-mentioned model In the case where in enclosing, existing be can be achieved at the same time relative to the compatibility of the adhesive ingredients such as solvent and inclining for dispersion stabilization To.As the combination of the upper limit and lower limit, 1~30 mole of % is preferably enumerated, 2~20 moles of % is more preferably enumerated, is further excellent Elect 4~10 moles of %.
In addition, from improve dispersing agent relative to the adhesive ingredients such as solvent compatibility, make dispersion stabilization improve sight Point sets out, and the repetitive unit that preferably there are acrylic dispersants more than one the following general formula (VIII) to indicate is (hereinafter, sometimes referred to as For " repetitive unit (VIII) ").
[chemical formula 18]
In above-mentioned formula (VIII), R38For the alkyl optionally with substituent group, the aryl optionally with substituent group or optional tool The aralkyl of substituted base；
R39For hydrogen atom or methyl.
The R of above-mentioned formula (VIII)3In the optionally carbon atom number of alkyl with substituent group be not particularly limited, usually 1 It above, is preferably 2 or more, more preferably 4 or more, additionally, it is preferred that for 10 or less, more preferably 8 or less.As the specific of alkyl Example can enumerate methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, 2- ethylhexyl etc., in these, preferably For methyl, ethyl, propyl, butyl, amyl, hexyl or 2- ethylhexyl, more preferably methyl, ethyl, propyl, butyl or 2- second Base hexyl.Furthermore it is possible to be straight-chain, any form in branched.Alternatively, it is also possible to contain cyclohexyl, cyclohexyl methyl Etc. cyclic structures.
The R of above-mentioned formula (VIII)38In the optionally carbon atom number of aryl with substituent group be not particularly limited, usually 6 More than, additionally, it is preferred that for 16 or less, more preferably 12 or less, further preferably 8 or less.It, can 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 (VIII)38In the optionally carbon atom number of aralkyl with substituent group be not particularly limited, usually 7 or more, additionally, it is preferred that for 16 or less, more preferably 12 or less, further preferably 10 or less.Concrete example as aralkyl Son can enumerate phenyl methyl (benzyl), phenylethyl (phenethyl), phenyl propyl, phenyl butyl, propyloxy phenyl base etc., these In the middle, preferably phenyl methyl, phenylethyl, phenyl propyl or phenyl butyl, more preferably phenyl methyl or phenylethyl.
In these, from the viewpoint of solvent intermiscibility and dispersion stabilization, R38Preferably alkyl or aralkyl, it is more excellent It is selected as methyl, ethyl, butyl, 2- ethylhexyl or phenyl methyl.
As R38In the substituent group that optionally has of alkyl, halogen atom, alkoxy etc. can be enumerated.In addition, as aryl Or the substituent group that aralkyl optionally has, alkyl, halogen atom, alkoxy of chain etc. can be enumerated.In addition, R38Shown in chain Alkyl include any one of straight-chain and branched.
In addition, the repetitive unit that above-mentioned formula (VIII) indicates is repeated in the whole of dispersing agent from the viewpoint of dispersibility Shared content ratio (is that it always contains in the case where the repetitive unit indicated comprising above-mentioned formula (VIII) of more than two kinds in unit It is proportional) it is preferably 30 moles of % or more, more preferably 40 moles of % or more, is more preferably 50 moles of % or more, in addition, Preferably 80 moles of % or less, more preferably 70 moles of % or less.As the combination of the upper limit and lower limit, 30~80 are preferably enumerated Mole %, 40~70 moles of % are more preferably enumerated, further preferably enumerate 50~70 moles of %.
Acrylic dispersants also can have repetitive unit (V), repetitive unit (VI), repetitive unit (VII) and repeat Repetitive unit other than unit (VIII).As the example of such repetitive unit, can enumerate from styrene, Alpha-Methyl benzene The styrene monomers such as ethylene；(methyl) acryloyl chloride etc. (methyl) acryloyl chloride class monomer；(methyl) acrylamide, N- hydroxyl first Base acrylamide etc. (methyl) acrylamide monomers；Vinyl acetate；Acrylonitrile；Allyl glycidyl ether, butenoic acid Glycidol ether；The repetitive unit of the monomers such as N- metering system morpholide.
From the viewpoint of further increasing dispersibility, acrylic dispersants are preferably have A block and B block embedding Section copolymer, the A block have repetitive unit (V) and repetitive unit (VI), the B block do not have repetitive unit (V) and Repetitive unit (VI).The block copolymer is preferably A-B block copolymer or B-A-B block copolymer.By being led in A block Enter quaternary ammonium salt group and tertiary amino, unexpectedly there is the tendency for the dispersibility for significantly improving dispersing agent.In addition, B block is preferred With repetitive unit (VII), in addition, more preferably there is repetitive unit (VIII).
In A block, repetitive unit (V) and repetitive unit can be contained with any form of random copolymerization, block copolymerization (VI).Furthermore it is possible to contain two or more repetitive unit (V) and repetitive unit (VI) 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 block.
Furthermore it is also possible to contain the repetitive unit other than repetitive unit (V) and repetitive unit (VI) in A block, as The example of such repetitive unit can enumerate the repetitive unit etc. from above-mentioned (methyl) acrylic ester monomer.It repeats Content of the repetitive unit in A block other than unit (V) and repetitive unit (VI) is preferably 0~50 mole of %, and more preferably 0 ~20 moles of % are free of the repetitive unit most preferably in A block.
The repetitive unit other than repetitive unit (VII) and (VIII) can be contained in B block, repeat list as such The example of member, 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 morpholide Member.Content of the repetitive unit in B block other than repetitive unit (VII) and repetitive unit (VIII) is preferably 0~50 to rub You are %, more preferably 0~20 mole of %, and the repetitive unit is free of most preferably in B block.
These acrylic dispersants can be used alone, or two or more can also be applied in combination.
In addition, in the photosensitive composition of the 1st aspect of the present invention and the face of the 3rd aspect of the present invention Expect in dispersion liquid, other than mentioned-above acrylic dispersants, (B) dispersing agent can also be containing as shown below other Macromolecule dispersing agent.
As other macromolecule dispersing agents, it can be mentioned, for example: carbamates dispersing agent, the dispersion of polyethyleneimine amine Agent, polyallyl amine dispersing agent, the monomer with amino and the dispersing agent of polymeric monomer formation, polyoxyethylene alkyl ether class are dispersed Agent, two esters dispersing agent of polyoxyethylene, polyethers phosphoric acid class dispersing agent, polyester phosphoric acid class dispersing agent, sorbitan esters of fatty race ester Class dispersing agent, aliphatic modified polyesters dispersing agent etc..
As the specific example of such dispersing agent, can enumerate trade name EFKA (registered trademark, BASF AG's manufacture), DISPERBYK (registered trademark, the manufacture of BYK-Chemie company), Disparlon (registered trademark, nanmu this chemical conversion Co. Ltd. system Make), SOLSPERSE (registered trademark, Lubrizol company 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..
The weight average molecular weight (Mw) of other macromolecule dispersing agents is usually 700 or more, preferably 1000 or more, in addition, logical Often it is 100000 or less, is preferably 50000 or less.
In other macromolecule dispersing agents, from the viewpoint of the dispersibility of pigment, carbamates high score is preferably enumerated Sub- dispersing agent.
In addition, from dispersibility, keeping quality aspect, preferably lifting has alkalinity in carbamates macromolecule dispersing agent Functional group and the macromolecule dispersing agent with polyester key and/or polyethers key.
As carbamates macromolecule dispersing agent, it can be mentioned, for example DISPERBYK160~167,182 series.
If specifically preferred chemical structure of the example as carbamates macromolecule dispersing agent, it can be mentioned, for example By make polyisocyanate compound, intramolecular have 1 or 2 hydroxyl number-average molecular weight 300~10000 compound, There is point of weight average molecular weight 1000~200000 obtained from active hydrogen and the reaction of the compound of tertiary amino with same intramolecular Dissipate resin etc..By being handled with the level Four such as benzyl chloride agent above-mentioned dispersion resin, the whole or one of tertiary amino can be made Portions turn is quaternary ammonium salt base.
It as the example of above-mentioned polyisocyanate compound, can enumerate: paraphenylene diisocyanate, Toluene-2,4-diisocyanate, bis- isocyanide of 4- Acid esters, Toluene-2,4-diisocyanate, 6- diisocyanate, 4,4 '-methyl diphenylene diisocyanates, naphthalene -1,5- diisocyanate, tolidine The aromatic diisocyanates such as diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4- tri- The aliphatic diisocyanates such as methyl hexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, 4,4 '-di-2-ethylhexylphosphine oxides (cyclohexyl isocyanate), ω, the alicyclic diisocyanate such as ω '-diisocyanate dimethyl cyclohexane Ester, xylylene diisocyanate, α, α, α ', α '-tetramethyl xylylene diisocyanate etc. have the aliphatic of aromatic rings Diisocyanate, lysine ester triisocyanate, hendecane -1,6,11- triisocyanate, 1,8- diisocyanate -4- are different Cyanate methyloctane, hexa-methylene -1,3,6- triisocyanate, bicycloheptane triisocyanate, three isocyanide of triphenyl methane The triisocyanates such as acid esters, thiophosphoric acid triphenyl triisocyanate and their tripolymer, hydride and they Polyalcohol addition product etc..As polyisocyanates, the preferably tripolymer of organic diisocyanate, most preferably toluene two The tripolymer of isocyanates and the tripolymer of isophorone diisocyanate.They can be used alone, and can also combine 2 Kind is used above.
The manufacturing method of tripolymer as isocyanates can be listed below method: use trimerization catalyst appropriate, Such as tertiary amines, phosphine, alkoxide species, metal oxide, metal carboxylate etc. carry out isocyanic acid to above-mentioned polyisocyanates The trimerizing of the part of ester group terminates trimerizing by adding catalyst poison, is then removed with solvent extraction, thin-film distillation Unreacted polyisocyanates, to obtain the polyisocyanates containing cyamelide ester group of target.
As the compound of the number-average molecular weight 300~10000 in same intramolecular with 1 or 2 hydroxyl, can enumerate The side end of polyether Glycols, polyester diol, polycarbonate glycol, polyolefin dihydric alcohol etc. and these compounds Substance obtained from alkyl alkoxide of the hydroxyl by carbon atom number 1~25 and the mixture of more than two kinds in them.
As polyether Glycols, polyetherdiol, polyethers esterdiol and their mixture of more than two kinds can be enumerated.Make For polyetherdiol, can enumerate substance obtained from oxidation polyamino alkenyl or copolymerization, such as polyethylene glycol, polypropylene glycol, poly- second two Alcohol propylene glycol, polyoxy butylen glycol, polyoxy hexylidene glycol, polyoxy octamethylene glycol and their mixture of more than two kinds. As polyethers esterdiol, can enumerate by make the glycol containing ether or with the mixture of other glycol and dicarboxylic acids or they Anhydride reaction or substance, such as poly- (polyoxy butylidene) adipate ester obtained from reacting oxyalkylene with polyester-diol etc..
As polyetherdiol, most preferably polyethylene glycol, polypropylene glycol, polyoxy butylen glycol or these compounds Compound made of alkyl alkoxide of the side end hydroxyl by carbon atom number 1~25.
As polyester-diol, can enumerate: dicarboxylic acids (succinic acid, glutaric acid, adipic acid, decanedioic acid, fumaric acid, maleic acid, Phthalic acid etc.) or their acid anhydrides and glycol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 3 the third two Alcohol, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, 3- methyl-1,5- pentanediol, neopentyl glycol, 2- Methyl-1,3-propanediol, 2- methyl-2-propyl -1,3- propylene glycol, 2-butyl-2-ethyl-1,3-propanediol, 1,5- pentanediol, 1,6-HD, 2- methyl -2,4-PD, 2,2,4- trimethyl -1,3- pentanediol, 2- ethyl -1,3- hexylene glycol, 2,5- bis- Methyl -2,5-HD, 1,8- ethohexadiol, 2- methyl-1, the aliphatic diols such as 8- ethohexadiol, 1,9- nonanediol, bis- (hydroxyl first Base) aromatic diols, the N methyldiethanol amine such as alicyclic diols, benzene dimethanol, bis- (hydroxyl-oxethyl) benzene such as hexamethylene etc. N- alkyl dialkanol amine etc.) substance obtained from polycondensation, such as polyethylene glycol adipate, poly adipate succinic acid ester, gather oneself Diacid 1,6- hexylene glycol ester, polyadipate ethylene glycol propylene glycol ester etc., or use above-mentioned glycols or carbon atom number 1~25 Monohydric alcohol is as in polylactone diol obtained from initiator or polylactone monohydric alcohol, such as polycaprolactone glycol, poly- methylpent Ester 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-1,5- pentanediol) can be enumerated Ester etc. can enumerate polybutadiene diol, hydrogenation type polybutadiene diol, hydrogenation type polyisoprene two as polyolefin diols Alcohol etc..
They may be used alone, can also be used in combination of two or more kinds.
It is usually 300~10000 that same intramolecular, which has the number-average molecular weight of the compound of 1 or 2 hydroxyl, preferably 500~6000, more preferably 1000~4000.
In same intramolecular there is the compound of active hydrogen and tertiary amino to be illustrated to used in the present invention.
As hydrogen atom of active hydrogen, the i.e. Direct Bonding on oxygen atom, nitrogen-atoms or sulphur atom, hydroxyl, ammonia can be enumerated Hydrogen atom in the functional groups such as base, sulfydryl, wherein the hydrogen atom of preferred amino, particularly primary amino group.
Tertiary amino is not particularly limited, and it can be mentioned, for example the amino of the alkyl with carbon atom number 1~4 or heterocycle knots 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- diformazan Base -1,3- propane diamine, N, N- diethyl -1,3- propane diamine, N, N- dipropyl -1,3- propane diamine, N, N- dibutyl -1,3- the third two Amine, N, N- dimethyl-ethylenediamine, N, N- diethyl ethylenediamine, N, N- dipropyl ethylenediamine, N, N- dibutyl ethylenediamine, N, N- bis- Methyl-1,4- butanediamine, N, N- diethyl -1,4- butanediamine, N, N- dipropyl -1,4- butanediamine, N, N- dibutyl -1,4- fourth Diamines etc..
In addition, the nitrogen-containing heterocycle in the case where being nitrogen-containing heterocycle structure as tertiary amino, can enumerate: pyrazole ring, imidazoles Ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoAzoles ring, benzo thiophene Nitrogenous 5 circle heterocyclic ring such as azoles ring, diazosulfide ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline Nitrogenous 6 circle heterocyclic ring such as quinoline ring.In these nitrogen-containing heterocycles, preferably imidazole ring or triazole ring.
If these compounds with imidazole ring and amino of specific example, can enumerate 1- (3- aminopropyl) imidazoles, Histidine, 2- aminooimidazole, 1- (2- amino-ethyl) imidazoles etc..In addition, if specific example these with triazole ring and amino Compound, then can enumerate 3- amino-1,2,4-triazole, 5- (2- amino -5- chlorphenyl) -3- phenyl -1H-1,2,4- triazoles, 4- amino -4H-1,2,4- triazole -3,5- glycol, 3- amino-5-phenyl -1H-1,3,4- triazole, 5- amino -1,4- diphenyl - 1,2,3- triazole, 3- amino -1- benzyl -1H-2,4- triazole etc..Wherein, preferably N, N- dimethyl -1,3- propane diamine, N, N- bis- Ethyl -1,3- propane diamine, 1- (3- aminopropyl) imidazoles, 3- amino -1,2,4- triazole.
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, the compound for having the number-average molecular weight 300~10000 of 1 or 2 hydroxyl in same intramolecular are 10~200 mass parts, preferably 20~190 mass parts, more preferably 30~180 mass parts have active in same intramolecular Hydrogen and the compound of tertiary amino are 0.2~25 mass parts, preferably 0.3~24 mass parts.
The manufacture of carbamates macromolecule dispersing agent can be carried out according to the known method that polyurethane resin manufactures. Solvent when as manufacture, usually using ketone such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclopentanone, cyclohexanone, isophorones Class；The esters such as ethyl acetate, butyl acetate, cellosolve acetate；The hydro carbons such as benzene,toluene,xylene, hexane；Diacetone alcohol, isopropyl The chloro things such as the parts such as alcohol, sec-butyl alcohol, tert-butyl alcohol alcohols, methylene chloride, chloroform；The ethers such as tetrahydrofuran, ether；Dimethyl methyl Amide, N-Methyl pyrrolidone, dimethyl sulfoxide isopolarity aprotic solvent etc..They can be used alone, or combination 2 Kind is used above.
In above-mentioned manufacture, usually using urethane catalysts.As the catalyst, it can be mentioned, for example two The tin systems such as butyl tin dilaurate, dioctyl tin dilaurate, dibutyl tin dicaprylate, tin octoate, ferric acetyl acetonade, Tertiary amines such as the iron series such as iron chloride, triethylamine, triethylenediamine etc..They can be used alone, or combines two or more and make With.
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 range, more preferably amount of the control in 5~95mgKOH/g range.Amine value is with acid to basic amine group Carry out acid-base titration, the value corresponding with acid value indicated with the mg number of KOH.When amine value is lower than above range, there are dispersion energy The tendency of power decline, 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 where remaining isocyanate group, if Isocyanate group is further 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 1000~200000, and preferably 2000 ~100000, more preferably 3000~50000 range.More than for above-mentioned lower limit value, there is dispersibility and stably dispersing Property the tendency that improves, by the way that for above-mentioned upper limit value, hereinafter, there are dissolubilities to improve, dispersibility improves, the control of reaction also becomes Readily tendency.
In addition, from this point of dispersion stabilization is improved, (B) dispersing agent is preferably combined with pigment derivative described later It uses.
On the other hand, (B) in the photosensitive composition of the 2nd aspect of the present invention is as long as dispersing agent can Disperse (A) colorant just without any restriction.It specifically, can be above-mentioned acrylic dispersants, or above-mentioned Other macromolecule dispersing agents.In these, from the viewpoint of dispersibility, acrylic dispersants or carbamic acid are preferably comprised Esters macromolecule dispersing agent.
[1-3] (C) adhesive resin
Photosensitive composition and dispersible pigment dispersion of the invention includes (C) adhesive resin.By the inclusion of (C) Adhesive resin can obtain uniform film.(C) adhesive resin is not particularly limited as long as it can obtain uniform film, From the viewpoint of the dissolubility to alkaline developer, preferably alkali soluble resin.
In photosensitive composition and dispersible pigment dispersion of the invention, from the viewpoint of reducing degassing, (C) is viscous Mixture resin is characterized in that, includes (C1) epoxy (methyl) acrylate.(C1) epoxy (methyl) acrylate With upright and outspoken skeleton, heat resistance is high, is not easy to thermally decompose, and since skeleton is upright and outspoken, takes in solidification with array structure, can shape At the high film of bridging property, it can thus be assumed that the amount of gas evolved generated after forming solidfied material is reduced.
In addition, (C1) epoxy (methyl) acrylate is preferred from the viewpoint of the dissolubility for alkaline developer Resin comprising carboxyl or hydroxyl.
(C1) epoxy (methyl) acrylate is preferably by acid or ester compounds and epoxy with ethylenic unsaturated bond Resin addition simultaneously further makes resin obtained from polyacid or its anhydride reaction.Such as it can enumerate: by with olefinic insatiable hunger With key acid carboxyl and epoxy resin epoxy group carry out open loop addition, thus make ethylenic unsaturated bond via ester bond (- COO-) with epoxide addition, while making a carboxyl of multi-anhydride and tree obtained from the hydroxyl addition that generates at this time Rouge.In addition, can also enumerate in addition multi-anhydride while add polyalcohol and carrying out resin obtained from addition.
In addition, further making that there is the compound for the functional group that can be reacted and the carboxyl of resin obtained from above-mentioned react Resin obtained from reaction is also included in above-mentioned (C1) epoxy (methyl) acrylate.
Therefore, epoxy (methyl) acrylic resin does not have epoxy group and and unlimited substantially in chemical structure Due to " (methyl) acrylate ", but since epoxide (epoxy resin) is raw material and " (methyl) acrylate " is it Typical example, therefore named in this wise according to usual.
Here, the epoxy resin refers to also include raw material compound before forming resin by heat cure, makees It can be suitable for selecting to use from well known epoxy resin for the epoxy resin.
In addition, compound obtained from reacting phenoloid with epihalohydrins can be used in epoxy resin.As phenol Compound, preferably 2 yuan or 3 yuan or more of the compound with phenolic hydroxyl group, can be monomer and is also possible to polymer.
It is specific enumerable for example: bisphenol A epoxide resin, bisphenol F epoxy resin, bisphenol-s epoxy resin, phenol novolac epoxy Resin, cresol novolak epoxy, biphenyl novolac epoxy resin, triphenol epoxy resin, phenol polymerize epoxy with bicyclopentane Resin, dihydroxy fluorenes type epoxy resin, alkyl sub-dihydroxy oxygroup fluorenes type epoxy resin, 9,9- bis- (4 '-hydroxy phenyl) fluorenes The diglycidyl ether compound etc. of bis- (4 '-hydroxy phenyl) adamantane of diglycidyl ether compound, 1,1-, as it is above-mentioned that It is preferable to use main chains to have aromatic ring person for sample.
Wherein, from the viewpoint of solidification film-strength is high, preferably bisphenol A epoxide resin, phenol novolac epoxy resins, Bis- (4 '-hydroxy phenyl) fluorenes of epoxides, the 9,9- of the polymer of cresol novolac epoxy, phenol and bicyclopentadiene Epoxides, epoxy resin (diglycidyl ether compound), the epoxy resin with adamantyl with adamantyl Deng, the epoxides of the polymer of further preferred phenol and bicyclopentadiene, 9, the epoxidation of bis- (4 '-hydroxy phenyl) fluorenes of 9- Object, the epoxy resin with adamantyl.
In acid with ethylenic unsaturated bond, preferred olefinic unsaturated monocarboxylic.As the acid with ethylenic unsaturated bond, It can be mentioned, for example: (methyl) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid etc., pentaerythrite three (methyl) Acrylate succinic anhydride addition product, pentaerythrite three (methyl) acrylate tetrabydrophthalic anhydride addition product, two seasons penta Tetrol five (methyl) acrylate succinic anhydride addition product, dipentaerythritol five (methyl) acrylate phthalic anhydride addition Object, dipentaerythritol five (methyl) acrylate tetrabydrophthalic anhydride addition product, (methyl) acrylic acid and 6-caprolactone Reaction product etc..Wherein, from the viewpoint of sensitivity, preferably (methyl) acrylic acid.
As polyacid (acid anhydride), it can be mentioned, for example: succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydro O-phthalic Acid, 3- methyl tetrahydrophthalic acid, 4- methyl tetrahydrophthalic acid, 3- ethyl tetrahydrophthalic acid, 4- ethyl tetrahydro Phthalic acid, hexahydrophthalic acid, 3- methylhexahydrophthaacid acid, 4- methylhexahydrophthaacid acid, 3- ethyl six Hydrogen phthalic acid, 4- ethyl hexahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic, biphenyl tetracarboxylic Acid and their acid anhydrides etc..Wherein, from the viewpoint of reducing degassing, preferably succinic anhydride, maleic anhydride, tetrahydro are adjacent Phthalate anhydride or hexahydrophthalic anhydride, more preferably succinic anhydride or tetrabydrophthalic anhydride, further preferably Tetrabydrophthalic anhydride.
By using polyalcohol, existing can be such that the molecular weight of (C1) epoxy (methyl) acrylate increases, to point Branch is imported in son, to obtain the tendency of the balance of molecular weight and viscosity.Additionally, there are be capable of increasing acidic group into molecule Drug delivery rate is easy to obtain the tendency of the balance of sensitivity, adaptation etc..
As polyalcohol, preferably for example selected from trimethylolpropane, bis- (trihydroxy methyl) propane, pentaerythrite, two seasons Penta tetrol, trimethylolethane, the one kind or two or more polyalcohol in 1,2,3- glycerine.
(C1) acid value of epoxy (methyl) acrylate is not particularly limited, preferably 10mgKOH/g or more, more excellent It is selected as 20mgKOH/g or more, further preferably 40mgKOH/g or more, is still more preferably 60mgKOH/g or more, especially Preferably 80mgKOH/g or more, additionally, it is preferred that for 200mgKOH/g or less, being more preferably 180mgKOH/g or less, further excellent It is selected as 150mgKOH/g or less, is still more preferably 130mgKOH/g or less, particularly preferably 120mgKOH/g or less.Pass through Be set as above-mentioned lower limit value or more, there are the tendencies that the developability in unexposed portion improves, in addition, by be set as above-mentioned upper limit value with Under, there is the tendency for being able to suppress film reduction etc..As the combination of the upper limit and lower limit, preferably enumerate 10~200mgKOH/g, More preferably enumerate 20~180mgKOH/g, further preferably enumerate 40~150mgKOH/g, still more preferably enumerate 60~ 130mgKOH/g, 80~120mgKOH/g is particularly preferably enumerated.
(C1) weight average molecular weight (Mw) of epoxy (methyl) acrylate is not particularly limited, usually 1000 with Upper, preferably 2000 or more, more preferably 3000 or more, further preferably 4000 or more, particularly preferably 5000 or more, separately Outside, usually 30000 or less, preferably 20000 or less, more preferably 15000 or less, further preferably 10000 or less, it is special It You Xuanwei 8000 or less.By being set as above-mentioned lower limit value or more, there is the tendency for being able to suppress film reduction etc., in addition, passing through Above-mentioned upper limit value is set as hereinafter, there are the tendencies that the developability in unexposed portion improves.As the combination of the upper limit and lower limit, preferably It enumerates 1000~30000, more preferably enumerate 2000~20000, further preferably enumerate 3000~15000, still more preferably It enumerates 4000~10000, particularly preferably enumerate 5000~8000.
(C1) epoxy (methyl) acrylate can be synthesized according to known method.Specifically, can make Using the following method: being dissolved in above-mentioned epoxy resin in organic solvent, under the coexisting of catalyst and hot polymerization inhibitor, be added above-mentioned Acid or ester compounds with ethylenic unsaturated bond carry out addition reaction, add polyacid or its acid anhydrides continues to react.
Wherein, as used organic solvent is reacted, methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetic acid can be enumerated It is more than one kind or two kinds of organic solvents such as ester, propylene glycol methyl ether acetate.In addition, three can be enumerated as above-mentioned catalyst The tertiary amines such as ethamine, benzyldimethylamine, 2,4, tribenzyl amine, tetramethyl ammonium chloride, methyl triethyl ammonium chloride, tetraethyl chlorination The phosphorus compounds such as the quaternary ammonium salts such as ammonium, tetrabutylammonium chloride, trimethyl benzyl ammonia chloride, triphenylphosphine, triphenylDengClass Deng one kind or two kinds of more than.In addition, one in quinhydrones, Hydroquinone monomethylether, methylnaphthohydroquinone etc. can be enumerated as polymerization inhibitor Kind or two or more.
In addition, 1 chemistry of epoxy group relative to epoxy resin is worked as acid or ester compounds with ethylenic unsaturated bond Amount, typically 0.7~1.3 chemical equivalent, preferably 0.9~1.1 stoichiometric amount.In addition, when as addition reaction Temperature, the temperature that usually can be set as 60~150 DEG C, be preferably set to 80~120 DEG C.In addition, the use as polyacid (acid anhydride) Amount, relative to above-mentioned addition reaction 1 chemical equivalent of hydroxyl generated, is typically set to 0.1~1.2 chemical equivalent, is preferably set to 0.2~1.1 stoichiometric amount.
(C1) chemical structure of epoxy (methyl) acrylate is not particularly limited, and goes out from the viewpoint for reducing degassing Hair, preferably comprises epoxy (methyl) acrylate and/or tool with repeat unit structure shown in the following general formula (II) There is epoxy (methyl) acrylate of part-structure shown in the following general formula (III).Due to epoxy (methyl) acrylate Resin is high sensitivity, therefore patterning performance is good, in addition, due to hydrophobic framework, solution rate appropriateness, substrate Adaptation is good.Further, since it is different from acrylic resin, there is upright and outspoken skeleton, and take assortment knot in solidification Structure and be closely crosslinked, therefore, it is considered that can inhibit degassing generation.
In particular, epoxy (methyl) acrylate with repeat unit structure shown in the following general formula (II) and/ Or epoxy (methyl) acrylate with part-structure shown in the following general formula (III) has greatly in central portion volume Upright and outspoken skeleton is formed as the form that the hydrophilic sites such as (methyl) acryloyl group are unfolded on the outside, it is believed that developability becomes good.
[chemical formula 19]
In formula (II), R11Indicate hydrogen atom or methyl；
R12Indicate divalent alkyl optionally with substituent group；
Phenyl ring in formula (II) is optionally further replaced by arbitrary substituent group；
* bonding position is indicated.
[chemical formula 20]
In formula (III), R13Hydrogen atom or methyl are indicated each independently；
R14Indicate that there is divalent alkyl of the cyclic hydrocarbon group as side chain；
R15And R16Each independently represent divalent aliphatic group optionally with substituent group；
M and n each independently represents 0~2 integer；
* bonding position is indicated.
[(C1-1) epoxy (methyl) acrylate]
By means of this, for epoxy (methyl) acrylate with repeat unit structure shown in above-mentioned logical formula (II) (hreinafter referred to as " (C1-1) epoxy (methyl) acrylate ") is described in detail.
[chemical formula 21]
In formula (II), R11Indicate hydrogen atom or methyl；
R12Indicate divalent alkyl optionally with substituent group；
Phenyl ring in formula (II) is optionally further replaced by arbitrary substituent group；
* bonding position is indicated.
(R12)
In above-mentioned formula (II), R12Indicate divalent alkyl optionally with substituent group.
As divalent alkyl, can enumerate divalent aliphatic group, divalent aromatic ring yl, 1 or more divalent aliphatic group and 1 with The group that upper divalent aromatic ring yl links.
Divalent aliphatic group can enumerate straight-chain, branched, cricoid group.In these, from deliquescent sight of developing Point sets out, the preferred group of straight-chain, on the other hand, from the viewpoint of reducing developer solution to being impregnated with of exposure portion, preferred ring The group of shape.Its carbon atom number is usually 1 or more, preferably 3 or more, more preferably 6 or more, additionally, it is preferred that for 20 or less, more It preferably 15 or less, is more preferably 10 or less.By being set as above-mentioned lower limit value or more, exist be easy to get strong film, It is not likely to produce rough surface, good tendency is become to the adaptation of substrate, in addition, by being set as above-mentioned upper limit value hereinafter, depositing It is being easy the surface smoothness of inhibition film, the deterioration of sensitivity, the tendency that resolution ratio improves.As the combination of the upper limit and lower limit, Preferably 1~20, more preferably 3~15, further preferably 6~10 can be enumerated.
It as the concrete example of divalent straight-chain aliphatic group, can enumerate: methylene, ethylidene, sub- n-propyl, sub- positive fourth Base, sub- n-hexyl, sub- n-heptyl etc..In these, from the viewpoint of the outspoken nature of skeleton, preferably methylene.
As the concrete example of divalent branched aliphatic group, isopropyl, sec-butyl, tert-butyl, isopentyl etc. can be enumerated.
The quantity of ring possessed by divalent cyclic aliphatic group is not particularly limited, and usually 1 or more, preferably 2 More than, in addition, usually 12 or less, preferably 10 or less.By being set as above-mentioned lower limit value or more, exist to be formed it is strong Film, substrate adaptation become good tendency, in addition, by being set as above-mentioned upper limit value hereinafter, there is the surface for being easy to inhibit film Flatness, sensitivity deterioration, resolution ratio improve tendency.As the concrete example of divalent cyclic aliphatic group, can enumerate: from Cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isoborneol alkane ring, tristane ring, adamantane Group made of 2 hydrogen atoms is removed on the ring of ring, cyclododecane ring, bicyclopentadiene etc..In these groups, from the rigid of skeleton From the perspective of straightforward, group made of 2 hydrogen atoms is removed preferably from tristane ring, adamantane ring.
As the substituent group that divalent aliphatic group optionally has, can enumerate: the carbon atom numbers such as methoxyl group, ethyoxyl 1~ 5 alkoxy；Hydroxyl；Nitro；Cyano；Carboxyl etc..It is preferably unsubstituted from the viewpoint of synthesizing easiness in these.
In addition, divalent aromatic cyclic hydrocarbon group and divalent aromatic heterocycle can be enumerated as divalent aromatic ring yl.Its carbon atom number Usually 4 or more, preferably 5 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 lower limit value or more, exists and be easy to get strong film, be not likely to produce rough surface, it is right The adaptation of substrate becomes good tendency, in addition, being put down by being set as above-mentioned upper limit value hereinafter, there is the surface for being easy to inhibit film Slip, sensitivity deterioration, resolution ratio improve tendency.
As the aromatic series hydrocarbon ring in divalent aromatic cyclic hydrocarbon group, it can be monocycle, be also possible to condensed ring.As divalent fragrance Race's hydrocarbon cyclic base, it can be mentioned, for example: phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, ring, aphthacene ring, pyrene ring, benzene with 2 free valency And pyrene ring,The group of ring, benzo phenanthrene ring, acenaphthene ring, fluoranthene ring, fluorenes ring etc..
In addition, can be monocycle as the heteroaromatic in divalent aromatic heterocycle, it is also possible to condensed ring.As 2 Valence aromatic heterocycle, it can be mentioned, for example: with the furan nucleus of 2 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 ring, quinoxaline ring, phenanthridines ring, benzimidazole ring,Phenazine ring, quinazoline ring, quinazolinone ring, Azulene ring etc. Group.
In these, from the viewpoint of patterned property, it is however preferred to have the phenyl ring or naphthalene nucleus of 2 free valency, it is more excellent It is selected as the phenyl ring with 2 free valency.
As the substituent group that divalent aromatic ring yl optionally has, hydroxyl, methyl, methoxyl group, ethyl, ethyoxyl, third can be enumerated Base, propoxyl group, glycidyl ether etc..In these, from the viewpoint of development dissolubility, resistance to hygroscopicity, preferably without taking Generation.
In addition, can be arranged as the group to be linked by 1 or more divalent aliphatic group and 1 or more divalent aromatic ring yl It lifts and 1 or more of 1 or more of mentioned-above divalent aliphatic group and mentioned-above divalent aromatic ring yl links Group.
The quantity of divalent aliphatic group is not particularly limited, and usually 1 or more, preferably 2 or more, and be usually 10 or less, preferably 5 or less, more preferably 3 or less.By being set as above-mentioned lower limit value or more, exists and be easy to get by force Solid film, be not likely to produce rough surface, good tendency is become to the adaptation of substrate, in addition, by being set as above-mentioned upper limit value Hereinafter, there is the deterioration of the surface smoothness, sensitivity that are easy to inhibit film, the tendency that resolution ratio improves.
The quantity of divalent aromatic ring yl is not particularly limited, and usually 1 or more, preferably 2 or more, and usually 10 It below, is preferably 5 or less, more preferably 3 or less.By being set as above-mentioned lower limit value or more, exist be easy to get it is strong Film is not likely to produce rough surface, becomes good tendency to the adaptation of substrate, in addition, by being set as above-mentioned upper limit value hereinafter, There are the easy surface smoothness for inhibiting film, the deterioration of sensitivity, the tendency that resolution ratio improves.
It, can as the concrete example of the group to be linked by 1 or more divalent aliphatic group and 1 or more divalent aromatic ring yl Enumerate group shown in following formula (II-A)~(II-F) etc..In these groups, from the hydrophobization of the outspoken nature and film of skeleton Viewpoint is set out, preferably group shown in following formula (II-A), and the * in chemical formula indicates bonding position.
[chemical formula 22]
As described above, the phenyl ring in formula (II) can further be replaced by arbitrary substituent group.As the substituent, it can arrange Citing such as hydroxyl, methyl, methoxyl group, ethyl, ethyoxyl, propyl, propoxyl group.The quantity of substituent group is also not particularly limited, It can be 1, or 2 or more.
It is preferably unsubstituted from the viewpoint of patterned property in these.
In addition, repeat unit structure shown in above-mentioned formula (II) is preferably following from the viewpoint of the simplicity of synthesis Repeat unit structure shown in formula (II-1).
[chemical formula 23]
In formula (II-1), R11And R12It is identical as meaning in above-mentioned formula (II)；
RXIndicate hydrogen atom or polyacid residue；
* bonding position is indicated；
Phenyl ring in formula (II-1) can further be replaced by arbitrary substituent group.
The polyacid residue refers to, from 1 valence group obtained from 1 OH base of removal in polyacid or its acid anhydrides.As Polyacid, can enumerate selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, Pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic, methylhexahydrophthaacid acid, interior methine tetrahydrophthalic acid, six It is more than one kind or two kinds of chlorine 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 tetrahydro neighbour benzene two Formic acid, bibenzene tetracarboxylic, further preferably tetrabydrophthalic anhydride.
Repetitive unit knot shown in above-mentioned formula (II-1) contained in 1 molecule (C1-1) epoxy (methyl) acrylate Structure can may be two or more for one kind, for example, R can be mixedXFor hydrogen atoms and RXFor polyacid residue person.
In addition, being repeated shown in above-mentioned formula (II) contained in 1 molecule (C1-1) epoxy (methyl) acrylate single The quantity of meta structure is not particularly limited, preferably 1 or more, more preferably 3 or more, and preferably 20 or less, more preferably 15 or less.By being set as above-mentioned lower limit value or more, exists and be easy to get strong film, be not likely to produce shaggy tendency, separately Outside, by being set as above-mentioned upper limit value hereinafter, there is the surface smoothness for being easy to inhibit film, the deterioration of sensitivity, resolution ratio is improved Tendency.
(C1-1) the polystyrene conversion measured by gel permeation chromatography (GPC) of epoxy (methyl) acrylate Weight average molecular weight (Mw) be not particularly limited, preferably 1000 or more, more preferably 1500 or more, further preferably 2000 Above, 3000 or more, and preferably 30000 or less are particularly preferably, 20000 or less is more preferably, is more preferably 10000 or less, 8000 or less are particularly preferably.By being set as above-mentioned lower limit value or more, there are photosensitive compositions Residual film ratio become good tendency, in addition, by being set as above-mentioned upper limit value hereinafter, there are resolution ratio to become good tendency. As the combination of the upper limit and lower limit, preferably 1000~30000 can be enumerated, 1500~20000 is more preferably, is more preferably 2000~10000,3000~8000 are particularly preferably.
(C1-1) acid value of epoxy (methyl) acrylate is not particularly limited, preferably 10mgKOH/g or more, more It preferably 20mgKOH/g or more, further preferably 40mgKOH/g or more, is still more preferably 50mgKOH/g or more, special Not You Xuanwei 80mgKOH/g or more, and preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, further Preferably 130mgKOH/g or less, particularly preferably 100mgKOH/g or less.By being set as above-mentioned lower limit value or more, there is development Dissolubility improves, resolution ratio becomes good tendency, in addition, by being set as above-mentioned upper limit value hereinafter, there are coloring phototonus trees The residual film ratio of oil/fat composition becomes good tendency.As the combination of the upper limit and lower limit, preferably 10~200mgKOH/ can be enumerated G, be more preferably 20~150mgKOH/g, further preferably 40~130mgKOH/g, still more preferably for 50~ 100mgKOH/g, particularly preferably 80~100mgKOH/g.
It is exemplified below the concrete example of (C1-1) epoxy (methyl) acrylate.
[chemical formula 24]
[chemical formula 25]
[chemical formula 26]
[chemical formula 27]
[(C1-2) epoxy (methyl) acrylate]
Then, for part-structure shown in above-mentioned logical formula (III) epoxy (methyl) acrylate (with Under, referred to as " (C1-2) epoxy (methyl) acrylate ") it is described in detail.
[chemical formula 28]
In formula (III), R13Each independently represent hydrogen atom or methyl；
R14Indicate that there is divalent alkyl of the cyclic hydrocarbon group as side chain；
R15And R16Each independently represent divalent aliphatic group optionally with substituent group；
M and n each independently represents 0~2 integer；
* bonding position is indicated.
(R14)
In above-mentioned logical formula (III), R14Indicate that there is divalent alkyl of the cyclic hydrocarbon group as side chain.
As cyclic hydrocarbon group, aliphatic ring group or aromatic ring yl can be enumerated.
The quantity of ring possessed by aliphatic ring group is not particularly limited, and usually 1 or more, preferably 2 or more, and And usually 10 or less, preferably 5 or less, more preferably 3 or less.By being set as above-mentioned lower limit value or more, there is appearance It is easy to get to strong film, is not likely to produce shaggy tendency, in addition, being easy suppression hereinafter, existing by being set as above-mentioned upper limit value The surface smoothness of film, sensitivity deterioration, the tendency that resolution ratio improves.As the combination of the upper limit and lower limit, can enumerate excellent It is selected as 1~10, more preferably 2~5, further preferably 2~3.
In addition, the carbon atom number of aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and 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, there is the deterioration of the surface smoothness, sensitivity that are easy to inhibit film, the tendency that resolution ratio improves.As the upper limit and lower limit Combination, preferably 4~40 can be enumerated, more preferably 6~30, further preferably 8~20, particularly preferably 8~15.
As the concrete example of the aliphatic ring in aliphatic ring group, can enumerate cyclohexane ring, cycloheptane ring, cyclodecane ring, Cyclododecane ring, norbornane ring, isoborneol ring, adamantane ring, cyclododecane ring etc..In these, from coloring phototonus tree From the perspective of the residual film ratio and resolution ratio of oil/fat composition, preferably adamantane ring.
On the other hand, the quantity of ring possessed by aromatic ring yl is not particularly limited, usually 1 or more, preferably 2 with Above, more preferably 3 or more, and usually 10 or less, preferably 5 or less, more preferably 4 or less.By being set as More than above-mentioned lower 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 Hereinafter, there is the deterioration of the surface smoothness, sensitivity that are easy to inhibit film, the tendency that resolution ratio improves in upper limit value.As the upper limit With the combination of lower limit, preferably 1~10, more preferably 2~5, further preferably 3~4 can be enumerated.
As aromatic ring yl, aromatic cyclic hydrocarbon group, aromatic heterocycle can be enumerated.In addition, the carbon atom number of aromatic ring yl is usual It is 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, particularly preferably 12 or more, and 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, there are patterned properties to become good tendency.As the combination of the upper limit and lower limit, it can enumerate preferably 4~40, is more excellent Be selected as 6~30, further preferably 8~20, be still more preferably 10~15, particularly preferably 12~15.
It as the concrete example of the aromatic ring in aromatic ring yl, 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 these, from the sight of patterned property Point sets out, preferably fluorenes ring.
In addition, there is cyclic hydrocarbon group to be not particularly limited as the divalent alkyl in the divalent alkyl of side chain, it can be mentioned, for example: Divalent aliphatic group, divalent aromatic ring yl, the base to be linked by 1 or more divalent aliphatic group and 1 or more divalent aromatic ring yl Group.
Divalent aliphatic group can enumerate straight-chain, branched, cricoid group.In these, from deliquescent sight of developing Point sets out, the preferred group of straight-chain, on the other hand, from the viewpoint of reducing developer solution to being impregnated with of exposure portion, preferred ring The group of shape.Its carbon atom number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 or less, more It preferably 20 or less, is more preferably 15 or less.By being set as above-mentioned lower limit value or more, exist be easy to get strong film, It is not likely to produce rough surface, good tendency is become to the adaptation of substrate, in addition, by being set as above-mentioned upper limit value hereinafter, depositing It is being easy the surface smoothness of inhibition film, the deterioration of sensitivity, the tendency that resolution ratio improves.
It as the concrete example of divalent straight-chain aliphatic group, can enumerate: methylene, ethylidene, sub- n-propyl, sub- positive fourth Base, sub- n-hexyl, sub- n-heptyl etc..In these, from the viewpoint of the outspoken nature of skeleton, preferably methylene.
It as the concrete example of divalent branched aliphatic group, can enumerate: the straight-chain aliphatic of the divalent in front There is on group as side chain the knot of methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl etc. Structure.
The quantity of ring possessed by divalent cyclic aliphatic group is not particularly limited, and usually 1 or more, preferably 2 More than, in addition, usually 10 hereinafter, preferably 5 or less, more preferably 3 or less.By be set as above-mentioned lower limit value with On, exist and be easy to get strong film, good tendency is become to the adaptation of substrate, in addition, by being set as above-mentioned upper limit value Hereinafter, there is the deterioration of the surface smoothness, sensitivity that are easy to inhibit film, the tendency that resolution ratio improves.As divalent ring-shaped fat The concrete example of race's group can be enumerated from cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, different ice Group made of 2 hydrogen atoms is removed on the ring of piece alkane ring, adamantane ring, cyclododecane ring etc..In these, from the rigid of skeleton From the perspective of straightforward, group made of 2 hydrogen atoms is removed preferably from adamantane ring.
As the substituent group that divalent aliphatic group optionally has, the carbon atom numbers such as methoxyl group, ethyoxyl 1~5 can be enumerated Alkoxy；Hydroxyl；Nitro；Cyano；Carboxyl etc..It is preferably unsubstituted from the viewpoint of synthesizing easiness in these.
In addition, divalent aromatic cyclic hydrocarbon group and divalent aromatic heterocycle can be enumerated as divalent aromatic ring yl.Its carbon atom number Usually 4 or more, preferably 5 or more, more preferably 6 or more, additionally, it is preferred that for 30 or less, more preferably 20 or less, further Preferably 15 or less.By being set as above-mentioned lower limit value or more, exists and be easy to get strong film, be not likely to produce rough surface, it is right The adaptation of substrate becomes good tendency, in addition, being put down by being set as above-mentioned upper limit value hereinafter, there is the surface for being easy to inhibit film Slip, sensitivity deterioration, resolution ratio improve tendency.
As the aromatic series hydrocarbon ring in divalent aromatic cyclic hydrocarbon group, it can be monocycle, be also possible to condensed ring.As divalent fragrance Race's hydrocarbon cyclic base, it can be mentioned, for example: phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, ring, aphthacene ring, pyrene ring, benzene with 2 free valency And pyrene ring,The group of ring, benzo phenanthrene ring, acenaphthene ring, fluoranthene ring, fluorenes ring etc..
In addition, can be monocycle as the heteroaromatic in divalent aromatic heterocycle, it is also possible to condensed ring.As 2 Valence aromatic heterocycle, it can be mentioned, for example: with the furan nucleus of 2 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 ring, quinoxaline ring, phenanthridines ring, benzimidazole ring,Phenazine ring, quinazoline ring, quinazolinone ring, Azulene ring etc. Group.In these, from the viewpoint of patterned property, it is however preferred to have the phenyl ring or naphthalene nucleus of 2 free valency, more preferably Fluorenes ring with 2 free valency.
As the substituent group that divalent aromatic ring yl optionally has, hydroxyl, methyl, methoxyl group, ethyl, ethyoxyl, propyl, third Oxygroup etc..It is preferably unsubstituted from the viewpoint of dissolubility of developing in these.
In addition, can be arranged as the group to be linked by 1 or more divalent aliphatic group and 1 or more divalent aromatic ring yl It lifts and 1 or more of 1 or more of mentioned-above divalent aliphatic group and mentioned-above divalent aromatic ring yl links Group.
The quantity of divalent aliphatic group is not particularly limited, and usually 1 or more, preferably 2 or more, and be usually 10 or less, preferably 5 or less, more preferably 3 or less.By being set as above-mentioned lower limit value or more, exists and be easy to get by force Solid film, be not likely to produce rough surface, good tendency is become to the adaptation of substrate, in addition, by being set as above-mentioned upper limit value Hereinafter, there is the deterioration of the surface smoothness, sensitivity that are easy to inhibit film, the tendency that resolution ratio improves.
The quantity of divalent aromatic ring yl is not particularly limited, and usually 1 or more, preferably 2 or more, and usually 10 It below, is preferably 5 or less, more preferably 3 or less.By being set as above-mentioned lower limit value or more, exist be easy to get it is strong Film is not likely to produce rough surface, becomes good tendency to the adaptation of substrate, in addition, by being set as above-mentioned upper limit value hereinafter, There are the easy surface smoothness for inhibiting film, the deterioration of sensitivity, the tendency that resolution ratio improves.
It, can as the concrete example of the group to be linked by 1 or more divalent aliphatic group and 1 or more divalent aromatic ring yl Enumerate group shown in above-mentioned formula (II-A)~(II-F) etc..In these groups, from the hydrophobization of the outspoken nature and film of skeleton Viewpoint is set out, group shown in group shown in preferably above-mentioned formula (II-C) or above-mentioned formula (II-D).
The bonding pattern of these divalent alkyls, the cyclic hydrocarbon group as side chain is not particularly limited, it can be mentioned, for example: By the side chain replace aliphatic group, aromatic ring yl 1 hydrogen atom in the way of, 1 carbon atom comprising aliphatic group and Constitute the mode of the cyclic hydrocarbon group as side chain.
(R15、R16)
In above-mentioned logical formula (III), R15And R16Each independently represent divalent aliphatic group optionally with substituent group.
Divalent aliphatic group can enumerate straight-chain, branched, cricoid group.In these, from deliquescent sight of developing Point sets out, the preferred group of straight-chain, on the other hand, from the viewpoint of reducing developer solution to being impregnated with of exposure portion, preferred ring The group of shape.Its carbon atom number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more It preferably 15 or less, is more preferably 10 or less.By being set as above-mentioned lower limit value or more, exist be easy to get strong film, It is not likely to produce rough surface, good tendency is become to the adaptation of substrate, in addition, by being set as above-mentioned upper limit value hereinafter, depositing It is being easy the surface smoothness of inhibition film, the deterioration of sensitivity, the tendency that resolution ratio improves.
It as the concrete example of divalent straight-chain aliphatic group, can enumerate: methylene, ethylidene, sub- n-propyl, sub- positive fourth Base, sub- n-hexyl, sub- n-heptyl etc..In these, from the viewpoint of the outspoken nature of skeleton, preferably methylene.
It as the concrete example of divalent branched aliphatic group, can enumerate: the straight-chain aliphatic of the divalent in front There is on group as side chain the knot of methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl etc. Structure.
The quantity of ring possessed by divalent cyclic aliphatic group is not particularly limited, and usually 1 or more, preferably 2 More than, in addition, usually 12 hereinafter, preferably 10 or less.By being set as above-mentioned lower limit value or more, exists and be easy to get by force Solid film, good tendency is become to the adaptation of substrate, in addition, by be set as above-mentioned upper limit value hereinafter, exist be easy inhibit The surface smoothness of film, sensitivity deterioration, the tendency that resolution ratio improves.It, can as the concrete example of divalent cyclic aliphatic group It enumerates from cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isoborneol alkane ring, adamantane ring, ring Group made of 2 hydrogen atoms is removed on the ring of dodecane ring, bicyclopentadiene etc..In these, from the outspoken nature of skeleton Viewpoint is set out, and group made of 2 hydrogen atoms is removed preferably from adamantane ring.
As the substituent group that divalent aliphatic group optionally has, can enumerate: the carbon atom numbers such as methoxyl group, ethyoxyl 1~ 5 alkoxy；Hydroxyl；Nitro；Cyano；Carboxyl etc..It is preferably unsubstituted from the viewpoint of synthesizing easiness in these.
(m、n)
In above-mentioned logical formula (III), m and n each independently represent 0~2 integer.By being set as above-mentioned lower limit value or more, Become good in the presence of patterning adaptability, be not likely to produce shaggy tendency, in addition, by being set as above-mentioned upper limit value hereinafter, There are developability to become good tendency.From the viewpoint of developability, preferably m and n are 0, on the other hand, are adapted to from patterning From the perspective of property, rough surface, preferably m and n are each independently 1 or more.
In addition, part-structure shown in above-mentioned logical formula (III) is preferably following from the viewpoint of the adaptation to substrate Part-structure shown in general formula (III-1).
[chemical formula 29]
In formula (III-1), R13、R15、R16, m and n it is identical as above-mentioned formula (III) meaning；
RαIndicate 1 valence cyclic hydrocarbon group optionally with substituent group；
The integer that p is 1 or more；
Phenyl ring in formula (III-1) is optionally further replaced by arbitrary substituent group；
* bonding position is indicated.
(Rα)
In above-mentioned general formula (III-1), RαIndicate 1 valence cyclic hydrocarbon group.
As cyclic hydrocarbon group, aliphatic ring group or aromatic ring yl can be enumerated.
The quantity of ring possessed by aliphatic ring group is not particularly limited, and 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 limit value or more, there are easy It obtains strong film, be not likely to produce shaggy tendency, in addition, by being set as above-mentioned upper limit value hereinafter, there is patterning spy Property becomes good tendency.As the combination of the upper limit and lower limit, preferably 1~6 can be enumerated, 2~4 is more preferably, is further excellent It is selected as 2~3.
In addition, the carbon atom number of aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and 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, there are patterned properties to become good tendency.As the combination of the upper limit and lower limit, it can enumerate preferably 4~40, is more excellent It is selected as 6~30, further preferably 8~20, particularly preferably 8~15.
As the concrete example of the aliphatic ring in aliphatic ring 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 perspective of property, preferably adamantane ring.
On the other hand, the quantity of ring possessed by aromatic ring yl is not particularly limited, usually 1 or more, preferably 2 with Above, more preferably 3 or more, and usually 10 or less, preferably 5 or less.By being set as above-mentioned lower limit value or more, deposit It is being easy to get strong film, is being not likely to produce shaggy tendency, in addition, being schemed by being set as above-mentioned upper limit value hereinafter, existing Case characteristic becomes good tendency.As the combination of the upper limit and lower limit, can enumerate preferably 1~10, more preferably 2~5, into One step is preferably 3~5.
As aromatic ring yl, aromatic cyclic hydrocarbon group, aromatic heterocycle can be enumerated.In addition, the carbon atom number of aromatic ring yl is usual For 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, further preferably It is 15 or less.By being set as above-mentioned lower limit 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 hereinafter, there are patterned properties to become good tendency.Group as the upper limit and lower limit It closes, preferably 4~30, more preferably 5~20, further preferably 6~15 can be enumerated.
As the concrete example of the aromatic ring in aromatic ring yl, phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, fluorenes ring etc. can be enumerated.These In the middle, from the viewpoint of dissolubility of developing, preferably fluorenes ring.
It as the substituent group that cyclic hydrocarbon group optionally has, can enumerate: hydroxyl, methyl, ethyl, n-propyl, isopropyl, just The alkyl of the carbon atom numbers such as butyl, sec-butyl, tert-butyl, amyl, isopentyl 1~5；The carbon atom numbers such as methoxyl group, ethyoxyl 1~ 5 alkoxy；Hydroxyl；Nitro；Cyano；Carboxyl etc..It is preferably unsubstituted from the viewpoint of synthesizing easiness in these.
The integer of 1 or more p expression, preferably 2 or more, and preferably 3 or less.By being set as above-mentioned lower limit 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.As the combination of the upper limit and lower limit, preferably 1~3, more preferably 2~3 can be enumerated.
In these, from the viewpoint of strong film curing degree, RαPreferably 1 valence aliphatic ring group, it is more preferably golden Rigid alkyl.
As described above, the phenyl ring in formula (III-1) is optionally further replaced by arbitrary substituent group.As the substituent, It can be mentioned, for example: hydroxyl, methyl, methoxyl group, ethyl, ethyoxyl, propyl, propoxyl group etc..The quantity of substituent group is also without special It limits, can be 1, or 2 or more.
It is preferably unsubstituted from the viewpoint of patterned property in these.
It is exemplified below out the concrete example of part-structure shown in above-mentioned formula (III-1).
[chemical formula 30]
[chemical formula 31]
[chemical formula 32]
[chemical formula 33]
[chemical formula 34]
In addition, part-structure shown in above-mentioned logical formula (III) is excellent from the viewpoint of the outspoken nature of skeleton and film hydrophobization It is selected as part-structure shown in the following general formula (III-2).
[chemical formula 35]
In formula (III-2), R13、R15、R16, m and n it is identical as above-mentioned formula (III) meaning；
RβIndicate divalent cyclic hydrocarbon group optionally with substituent group；
Phenyl ring in formula (III-2) is optionally further replaced by arbitrary substituent group；
* bonding position is indicated.
(Rβ)
In above-mentioned formula (III-2), RβIndicate divalent cyclic hydrocarbon group.
As cyclic hydrocarbon group, aliphatic ring group or aromatic ring yl can be enumerated.
The quantity of ring possessed by aliphatic ring group is not particularly limited, and 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 limit value or more, exists and be easy to get strong film, no Be also easy to produce shaggy tendency, in addition, by be set as above-mentioned upper limit value hereinafter, exist be easy inhibit film surface smoothness, The deterioration of sensitivity, the tendency that resolution ratio improves.As the combination of the upper limit and lower limit, preferably 1~10 can be enumerated, be more preferably 2~5.
In addition, the carbon atom number of aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and 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 limit value or more, there is inhibition The coarse tendency of film when development, in addition, by be set as above-mentioned upper limit value hereinafter, exist the surface smoothness for being easy to inhibit film, The deterioration of sensitivity, the tendency that resolution ratio improves.As the combination of the upper limit and lower limit, preferably 4~40 can be enumerated, be more preferably It 6~35, is more preferably 8~30.
As the concrete example of the aliphatic ring in aliphatic ring 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 perspective of, preferably adamantane ring.
On the other hand, the quantity of ring possessed by aromatic ring yl is not particularly limited, usually 1 or more, preferably 2 with Above, more preferably 3 or more, and usually 10 or less, preferably 5 or less.By being set as above-mentioned lower limit value or more, deposit It is being easy to get strong film, is being not likely to produce shaggy tendency, in addition, being held by being set as above-mentioned upper limit value hereinafter, existing Easily inhibit the surface smoothness of film, the deterioration of sensitivity, the tendency that resolution ratio improves.As the combination of the upper limit and lower limit, can arrange Lift preferably 1~10, more preferably 2~5, further preferably 3~5.
As aromatic ring yl, aromatic cyclic hydrocarbon group, aromatic heterocycle can be enumerated.In addition, the carbon atom number of aromatic ring yl is usual For 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and preferably 40 or less, more preferably It is 30 or less, further preferably 20 or less, particularly preferably 15 or less.By being set as above-mentioned lower limit value or more, there are easy It obtains strong film, be not likely to produce shaggy tendency, in addition, being easy to inhibit hereinafter, existing by being set as above-mentioned upper limit value The surface smoothness of film, sensitivity deterioration, the tendency that resolution ratio improves.As the combination of the upper limit and lower limit, can enumerate preferably It is 4~40, more preferably 6~30, further preferably 8~20, particularly preferably 10~15.
As the concrete example of the aromatic ring in aromatic ring yl, phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, fluorenes ring etc. can be enumerated.These In the middle, from the viewpoint of developability, preferably fluorenes ring.
It as the substituent group that cyclic hydrocarbon group optionally has, can enumerate: hydroxyl, methyl, ethyl, n-propyl, isopropyl, just The alkyl of the carbon atom numbers such as butyl, sec-butyl, tert-butyl, amyl, isopentyl 1~5；The carbon atom numbers such as methoxyl group, ethyoxyl 1~ 5 alkoxy；Hydroxyl；Nitro；Cyano；Carboxyl etc..It is preferably unsubstituted from the viewpoint of synthesizing easiness in these.
In these, from the viewpoint of storage stability and electrical characteristics, RβPreferably divalent aliphatic ring group, more preferable 2 The adamantane ring group of valence.
On the other hand, from the viewpoint of the agent of low hygroscopicity of film and patterned property, RβPreferably divalent aromatic ring yl, more The preferably fluorenes ring base of divalent.
As described above, the phenyl ring in formula (III-2) can further be replaced by arbitrary substituent group.As the substituent, It can be mentioned, for example: hydroxyl, methyl, methoxyl group, ethyl, ethyoxyl, propyl, propoxyl group etc..The quantity of substituent group does not limit especially It is fixed, it can be 1, or 2 or more.Alternatively, it is also possible to via these substituent groups by 2 phenyl ring in formula (III-2) It links together.
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 perspective of, preferably methyl replaces.
It is exemplified below the concrete example of part-structure shown in above-mentioned formula (III-2).
[chemical formula 36]
[chemical formula 37]
[chemical formula 38]
[chemical formula 39]
On the other hand, from the viewpoint of film residual film ratio and patterned property, part-structure shown in above-mentioned formula (III) Preferably part-structure shown in following formula (III-3).
[chemical formula 40]
In formula (III-3), R13、R14、R15、R16, m and n it is identical as above-mentioned formula (III) meaning；
RZIndicate hydrogen atom or polyacid residue.
The polyacid residue refers to, from 1 valence group obtained from 1 OH base of removal in polyacid or its acid anhydrides.It needs Illustrate, can also further remove 1 OH base and with the R in other molecules shown in formula (III-3)ZIt shares, that is, can be with Pass through RZMultiple formulas (III-3) are linked.
As polyacid, can enumerate selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, six Hydrogen phthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic, methylhexahydrophthaacid acid, interior methine tetrahydro It is more than one kind or two kinds of phthalic acid, chlorendic 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 tetrahydro neighbour benzene two Formic acid, bibenzene tetracarboxylic.
Part-structure shown in above-mentioned formula (III-3) contained in 1 molecule (C1-2) epoxy (methyl) acrylate It can be one kind, or two or more, for example, R can be mixedZFor hydrogen atoms and RZFor polyacid residue person.
In addition, partially being tied shown in above-mentioned formula (III) contained in 1 molecule (C1-2) epoxy (methyl) acrylate The quantity of structure is not particularly limited, preferably 1 or more, more preferably 3 or more, and preferably 20 or less, it is more preferable It is 15 or less, further preferably 10 or less.By being set as above-mentioned lower limit value or more, exist be easy to get 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 be easy suppression The surface smoothness of film, sensitivity deterioration, the tendency that resolution ratio improves.
(C1-2) the polystyrene conversion measured by gel permeation chromatography (GPC) of epoxy (methyl) acrylate Weight average molecular weight (Mw) be not particularly limited, preferably 1000 or more, more preferably 2000 or more, further preferably 3000 Above, 3500 or more, and preferably 30000 or less are particularly preferably, 20000 or less is more preferably, is more preferably 10000 or less, it is still more preferably 7000 or less, is particularly preferably 5000 or less.By being set as above-mentioned lower limit value or more, deposit Become good tendency in patterned property, in addition, by be set as above-mentioned upper limit value hereinafter, in the presence of be easy to get strong film, It is not likely to produce shaggy tendency.As the combination of the upper limit and lower limit, preferably 1000~30000 can be enumerated, be more preferably 2000~20000, be more preferably 3000~10000, still more preferably for 3500~7000, particularly preferably 3500~ 5000。
(C1-2) acid value of epoxy (methyl) acrylate is not particularly limited, preferably 10mgKOH/g or more, more It preferably 20mgKOH/g or more, further preferably 40mgKOH/g or more, is still more preferably 60mgKOH/g or more, special Not You Xuanwei 80mgKOH/g or more, and preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, further Preferably 120gKOH/g or less.By being set as above-mentioned lower limit value or more, there is the tendency for being easy to get strong film, in addition, logical It crosses and is set as above-mentioned upper limit value hereinafter, there is the raising of development dissolubility, resolution ratio becomes good tendency.As the upper limit and lower limit Combination, can enumerate preferably 10~200mgKOH/g, more preferably 20~150mgKOH/g, further preferably 40~ It 150mgKOH/g, is still more preferably 60~120mgKOH/g, particularly preferably 80~120mgKOH/g.
(C) adhesive resin contained by photosensitive composition and dispersible pigment dispersion of the invention can also contain (C1) adhesive resin other than epoxy (methyl) acrylate (hreinafter referred to as " (C2) other adhesive resins ").
As (C2) other adhesive resins, it can be mentioned, for example: acrylic resin, contains carboxyl at epoxy resin containing carboxyl Carbamate resins, novolaks resinoid, polyvinylphenols resin etc., these resins can be used alone, A variety of uses can be mixed.
In photosensitive composition of the invention, (C) adhesive resin includes (C1) ring of 75 mass % or more Oxygen (methyl) acrylate.By making to contain 75 mass % or more (C1) epoxy (methyl) propylene in (C) adhesive resin Acid ester resin, it is believed that the heat resistance of solidfied material also improves, and can reduce the amount of gas evolved to be formed and be generated after solidfied material is formed.
(C1) epoxy (methyl) acrylate is 75 mass % or more relative to the content ratio of (C) adhesive resin , it is not particularly limited, preferably 80 weight % or more, more preferably 85 weight % or more, further preferably 90 weights % or more, particularly preferably 95 mass % or more are measured, in addition, usually 100 mass % or less.By be set as above-mentioned lower limit value with On, there is the tendency for inhibiting degassing.As the combination of the upper limit and lower limit, preferably 75~100 mass % can be enumerated, be more preferably It 80~100 mass %, further preferably 85~100 mass %, is still more preferably 90~100 mass %, particularly preferably For 95~100 mass %.
[1-4] (D) photopolymerization monomer
Photosensitive composition of the invention includes (D) photopolymerization monomer.By the inclusion of (D) optical polymerism list Body, sensitivity improve.
(D) photopolymerization monomer used in the present invention is the chemical combination that intramolecular has at least one ethylenically unsaturated group Object.It is specific enumerable for example: (methyl) acrylic acid, (methyl) alkyl acrylate, acrylonitrile, styrene and have 1 olefinic The ester etc. that the carboxylic acid and polyalcohol or monohydric alcohol of unsaturated bond are formed.
In the present invention, however, particularly desirable to use with the multifunctional olefinic list of 2 or more ethylenically unsaturated groups in 1 molecule Body.The quantity of ethylenic unsaturated bond possessed by multifunctional olefinic type monomers is not particularly limited, usually 2 or more, preferably 4 More than a, 5 or more are more preferably, additionally, it is preferred that for 8 or less, more preferably 7 or less.By being set as above-mentioned lower limit value More than, exist as highly sensitive tendency, by being set as above-mentioned upper limit value hereinafter, inclining in the presence of what the dissolubility to solvent improved To.As the combination of the upper limit and lower limit, preferably 2~8, more preferably 4~8, further preferably 5~7 can be enumerated.
As the example of multifunctional olefinic type monomers, it can be mentioned, for example: aliphatic polyhydroxy compound and unsaturated carboxylic acid shape At ester；The ester that aromatic polyhydroxy compounds and unsaturated carboxylic acid are formed；It is more by aliphatic polyhydroxy compound, aromatic series Ester obtained from the esterification of the polyols such as hydroxy compounds and 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, can enumerate hydroquinone diacrylate, Hydroquinone dimethylacrylate, resorcinol diacrylate, resorcinol dimethylacrylate, pyrogaelol Acrylate and methacrylate of the aromatic polyhydroxy compounds such as 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 product of acrylic acid, phthalic acid and ethylene glycol if enumerating its representative specific example； The condensation product of acrylic acid, maleic acid and diethylene glycol；The condensation product of methacrylic acid, terephthalic acid (TPA) and pentaerythrite；Propylene Acid, adipic acid, butanediol and condensation product of glycerol etc..
In addition, the example of multifunctional olefinic type monomers used in the present invention, polyisocyanate compound and hydroxyl (methyl) acrylate or polyisocyanate compound and polyalcohol and hydroxyl (methyl) acrylate reactions 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 is useful.
As above-mentioned carbamate (methyl) esters of acrylic acid, it can be mentioned, for example: DPHA-40H, UX-5000, UX- 5002D-P20, UX-5003D, UX-5005 (Nippon Kayaku K. K's manufacture), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufacture of chemical industry Co., Ltd., the village Xin Zhong), UA-306H, UA-510H, UF-8001G (manufacture of Xie Rong society Chemical Co., Ltd.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (Japan's synthesis Chemical Co., Ltd. manufacture) etc..
In these, from the viewpoint of curability, as (D) photopolymerization monomer, it is preferable to use (methyl) acrylic acid Arrcostab more preferably uses dipentaerythritol hexaacrylate.
They may be used alone, can also be used in combination of two or more kinds.
[1-5] (E) Photoepolymerizationinitiater initiater
Photosensitive composition of the invention contains (E) Photoepolymerizationinitiater initiater.(E) Photoepolymerizationinitiater initiater is direct It absorbs light and causes decomposition reaction or hydrogen abstraction reaction, to have the function of generating the ingredient of polymerization activity free radical.It can also be with The use of the additives such as polymerization accelerant (chain-transferring agent), sensitizing dyestuff is added as needed.
As Photoepolymerizationinitiater initiater, it can be mentioned, for example Japanese Unexamined Patent Application 59-152396 bulletins, Japanese Unexamined Patent Application 61- The Metallocenic compound comprising cyclopentadiene titanium compound recorded in No. 151197 each bulletins；In Japanese Unexamined Patent Publication 2000-56118 bulletin The Hexaarylbiimidazole derivative of record；The halomethylation recorded in Japanese Unexamined Patent Publication 10-39503 bulletinDiazole is derivative The N- such as object, halogen methyl Striazine derivative, N- phenylglycine aryl-alpha-amido acids, N- aryl-a-amino acid salt, The free radicals activators such as N- aryl-a-amino acid esters, alpha-aminoalkyl benzophenone derivatives；Japanese Unexamined Patent Publication 2000-80068 public affairs The oxime ester derivative etc. recorded in report, Japanese Unexamined Patent Publication 2006-36750 bulletin etc..
Specifically, for example, can be enumerated as luxuriant titanium derivative class: titanocene dichloride, dicyclopentadienyl Diphenyl titanium, dicyclopentadienyl two (2,3,4,5,6- phenyl-pentafluoride -1- base) titanium, (the 2,3,5,6- tetrafluoro of dicyclopentadienyl two Benzene -1- base) titanium, dicyclopentadienyl two (2,4,6- trifluoro-benzene -1- base) titanium, (2,6- difluorobenzene -1- of dicyclopentadienyl two Base) titanium, dicyclopentadienyl two (2,4 difluorobenzene -1- base) titanium, two (methyl cyclopentadienyl) two (five fluorine of 2,3,4,5,6- Benzene -1- base) titanium, two (methyl cyclopentadienyl) two (2,6- difluorobenzene -1- base) titaniums, dicyclopentadienyl [the fluoro- 3- of 2,6- bis- (propyl- 1- yl)-benzene -1- base] titanium etc..
In addition, can be enumerated as diimidazole derivative species: 2- (2 '-chlorphenyl) -4,5- diphenyl-imidazole, 2 aggressiveness, 2- 2 aggressiveness of (2 '-chlorphenyl) -4,5- two (3 '-methoxyphenyl) imidazoles, 2 aggressiveness of 2- (2 '-fluorophenyl) -4,5- diphenyl-imidazole, 2 aggressiveness of 2- (2 '-methoxyphenyl) -4,5- diphenyl-imidazole, 2 aggressiveness of (4 '-methoxyphenyl) -4,5- diphenyl-imidazole etc..
In addition, as halomethylationOxadiazole derivative can be enumerated: 2- trichloromethyl -5- (2 '-benzofuranyl) -1, 3,4-Diazole, 2- trichloromethyl -5- [β-(2 '-benzofuranyl) vinyl] -1,3,4-Diazole, 2- trichloromethyl -5- [β-(2 '-(6 "-benzofuranyl) vinyl)] -1,3,4-Diazole, 2- trichloromethyl -5- furyl -1,3,4-Diazole Deng.
In addition, can be enumerated as halogen methyl Striazine derivative class: bis- (three chloromethanes of 2- (4- methoxyphenyl) -4,6- Base) s-triazine, bis- (trichloromethyl) s-triazine of 2- (4- methoxyl group naphthalene) -4,6-, 2- (4- ethoxynaphthyl) -4,6- bis- (three Chloromethyl) s-triazine, bis- (trichloromethyl) s-triazine of 2- (4- carbethoxyl group naphthalene) -4,6- etc..
In addition, can be enumerated as alpha-aminoalkyl benzophenone derivatives class: 2- methyl-1-[4- (methyl mercapto) phenyl]-2- Quinoline base propane -1- ketone, 2- benzyl -2- dimethylamino -1- (4- morpholino phenyl)-butanone -1,2- benzyl -2- dimethylamino Base -1- (4- morpholino phenyl) butane -1- ketone, 4- dimethyl aminoethyl benzoic ether, 4- dimethylamino isoamyl benzene first Acid esters, 4- diethyl amino benzoylformaldoxime, 4- dimethylamino propiophenone, 2- ethylhexyl -1,4- dimethyl aminobenzoate, Bis- (the 4- diethylamino benzal) cyclohexanone of 2,5-, 7- diethylamino -3- (4- diethylamino 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 derivative class (oxime esters Close object and ketoxime ester compound) be it is effective, using the case where including the alkali soluble resin of phenolic hydroxyl group etc. in sensitivity side Face is unfavorable, and therefore, the excellent oxime ester derivative class of such sensitivity (oxime ester compound and ketoxime ester compound) is special It is useful.
As oxime ester compound, the compound comprising part-structure shown in the following general formula (IX) can be enumerated, is preferably arranged Lift oxime ester compound shown in the following general formula (IX-A).
[chemical formula 41]
In formula (IX), R22Indicate the alkanoyl of optionally substituted carbon atom number 2~12 respectively, carbon atom number 1~20 Heteroarylalkanoyl, the enoyl- of carbon atom number 3~25, the cycloalkanoyl of carbon atom number 3~8, carbon atom number 3~20 alcoxyl Carbonyl alkanoyl, the carbobenzoxy alkanoyl of carbon atom number 8~20, the heteroaryl oxygen carbonyl alkanoyl of carbon atom number 3~20, carbon are former The aminoalkylcarbonyl of subnumber 2~10, the aroyl of carbon atom number 7~20, the 4-hetaroylpyrazol of carbon atom number 1~20, carbon atom The alkoxy carbonyl group of number 2~10 or the aryloxy carbonyl of carbon atom number 7~20.
[chemical formula 42]
In formula (IX-A), R21aIndicate hydrogen atom or respectively alkyl, the carbon original of optionally substituted carbon atom number 1~20 The alkenyl of subnumber 2~25, the heteroaryl alkyl of carbon atom number 1~20, the alkoxycarbonyl alkyl of carbon atom number 3~20, carbon atom The carbobenzoxy alkyl of number 8~20, the heteroaryl oxygen carbonyl alkyl of carbon atom number 1~20 or heteroaryl sulfanyl, carbon atom number 1~20 Aminoalkyl, the alkanoyl of carbon atom number 2~12, the enoyl- of carbon atom number 3~25, carbon atom number 3~8 cycloalkanes acyl Base, the aroyl of carbon atom number 7~20, the 4-hetaroylpyrazol of carbon atom number 1~20, the alkoxy carbonyl group of carbon atom number 2~10, carbon are former The aryloxy carbonyl of subnumber 7~20 or the cycloalkyl-alkyl of carbon atom number 1~10；
R21bIndicate the arbitrary substituent group comprising aromatic series hydrocarbon ring or heteroaromatic (hetero-aromatic ring).
It should be noted that R21aIt can be with R21bLink and form ring, connection group can be enumerated optionally to have respectively and be taken Alkylidene, polyvinyl (- (CH=CH) of the carbon atom number 1~10 of Dai Jir), polyacetylene base (- (C ≡ C)r) or by they The group (wherein, the integer that r is 0~3) being composed.
In formula (IX-A), R22aIndicate the alkanoyl of optionally substituted carbon atom number 2~12, carbon atom number 1~20 respectively Heteroaryl oxygen alkanoyl, the enoyl- of carbon atom number 3~25, the cycloalkanoyl of carbon atom number 3~8, carbon atom number 3~20 alkane Oxygen carbonyl alkanoyl, the carbobenzoxy alkanoyl of carbon atom number 8~20, carbon atom number 3~20 heteroaryl oxygen carbonyl alkanoyl, carbon The amino carbonyl of atomicity 2~10, the aroyl of carbon atom number 7~20, the 4-hetaroylpyrazol of carbon atom number 1~20, carbon atom number 2 ~10 alkoxy carbonyl group or the aryloxy carbonyl of carbon atom number 7~20.
As the R in above-mentioned logical formula (IX)22And the R in above-mentioned general formula (IX-A)22a, preferably enumerate carbon atom number 2~12 Alkanoyl, the heteroaryl oxygen alkanoyl of carbon atom number 1~20, carbon atom number 3~8 cycloalkanoyl.
As the R in above-mentioned general formula (IX-A)21a, preferably unsubstituted methyl, ethyl, propyl and by N- acetyl group- The propyl that N- acetoxyl group amino replaces.
In addition, as the R in above-mentioned general formula (IX-A)21b, preferably enumerate optionally substituted carbazyl, optionally taken The fluorenyl in generation, optionally substituted thioxanthene ketone group, optionally substituted diphenyl sulfide base.
In addition, can be enumerated as the arbitrary substituent group in above-mentioned logical formula (IX) and (IX-A): alkyl, aromatic series hydrocarbon ring Base (aryl), aliphatic ring group, aromatic heterocycle, halogen group, hydroxyl, carboxyl, amino, amide groups etc..
As oxime ester compound preferred in the present invention, the compound that specific enumerable following example goes out, but and it is unlimited Due to these compounds.
[chemical formula 43]
[chemical formula 44]
As ketoxime ester compound, the compound comprising part-structure shown in the following general formula (X) can be enumerated, preferably Enumerate ketoxime ester compound shown in the following general formula (X-A).
[chemical formula 45]
In above-mentioned logical formula (X), R24With the R in above-mentioned logical formula (IX)22Meaning is identical.
[chemical formula 46]
In above-mentioned general formula (X-A), R23aIndicate that optionally substituted phenyl, the alkyl of carbon atom number 1~20, carbon are former respectively The alkenyl of subnumber 2~25, the heteroaryl alkyl of carbon atom number 1~20, the alkoxycarbonyl alkyl of carbon atom number 3~20, carbon atom The carbobenzoxy alkyl of number 8~20, the alkylthio alkyl of carbon atom number 2~20, carbon atom number 1~20 heteroaryl oxygen carbonyl alkyl Or the alkene of heteroaryl sulfanyl, the aminoalkyl of carbon atom number 1~20, the alkanoyl of carbon atom number 2~12, carbon atom number 3~25 Acyl group, the cycloalkanoyl of carbon atom number 3~8, the aroyl of carbon atom number 7~20, the 4-hetaroylpyrazol of carbon atom number 1~20, carbon The cycloalkyl-alkyl of the alkoxy carbonyl group of atomicity 2~10, the aryloxy carbonyl of carbon atom number 7~20 or carbon atom number 1~10；
R23bIndicate the arbitrary substituent group comprising aromatic series hydrocarbon ring or heteroaromatic (hetero-aromatic ring).
It should be noted that R23aIt can be with R23bLink and form ring, connection group can be enumerated optionally to have respectively and be taken Alkylidene, polyvinyl (- (CH=CH) of the carbon atom number 1~10 of Dai Jir), polyacetylene base (- (C ≡ C)r) or by they The group (wherein, the integer that r is 0~3) being composed.
In general formula (X-A), R24aIndicate respectively the alkanoyl of optionally substituted carbon atom number 2~12, carbon atom number 3~ 25 enoyl-, the cycloalkanoyl of carbon atom number 4~8, the benzoyl of carbon atom number 7~20, carbon atom number 3~20 heteroaryl Acyl group, the alkoxy carbonyl group of carbon atom number 2~10, the aryloxy carbonyl of carbon atom number 7~20, carbon atom number 2~20 heteroaryl or The alkyl amino-carbonyl of carbon atom number 2~20.
As the R in above-mentioned logical formula (X)24And the R in above-mentioned general formula (X-A)24a, preferably enumerate carbon atom number 2~12 Alkanoyl, the heteroaryl oxygen alkanoyl of carbon atom number 1~20, the cycloalkanoyl of carbon atom number 3~8, carbon atom number 7~20 fragrant acyl Base.
As the R in above-mentioned general formula (X-A)23a, preferably enumerate unsubstituted ethyl, propyl, butyl and by methoxy The ethyl or propyl that base carbonyl replaces.
In addition, as the R in above-mentioned general formula (X-A)23b, preferably enumerate optionally substituted carbazyl, be optionally substituted Fluorenyl, optionally substituted diphenyl sulfide base.
In addition, can be enumerated as the arbitrary substituent group in above-mentioned logical formula (X) and (X-A): alkyl, aromatic cyclic hydrocarbon group (aryl), aliphatic ring group, aromatic heterocycle, halogen group, hydroxyl, carboxyl, amino, amide groups etc..
As the compound that ketoxime ester compound preferred in the present invention, specific enumerable following example go out, but not It is defined in these compounds.
[chemical formula 47]
[chemical formula 48]
These oxime ester compounds and ketoxime ester compound itself are well known compounds, are such as Japanese Unexamined Patent Publications A series of one of the compounds recorded in 2000-80068 bulletin, Japanese Unexamined Patent Publication 2006-36750 bulletin.From sensitive From the perspective of degree, in the present invention, (E) Photoepolymerizationinitiater initiater is preferably oxime ester compound and/or ketoxime ester compound.
Above-mentioned Photoepolymerizationinitiater initiater may be used alone, can also be used in combination of two or more kinds.
It as (E) Photoepolymerizationinitiater initiater, in addition to those specified above, can also enumerate: benzoin methylether, benzoin benzene The benzoin alkyls ethers such as ether, benzoin isobutyl ether, benzoin iso-propylether；2-methylanthraquinone, 2- ethyl hydrazine, 2- tert-butyl anthracene The anthraquinone derivatives such as quinone, 1- chloroanthraquinone；Benzophenone, Michler's keton, 2 methyl benzophenone, 3- methyl benzophenone, 4- methyl The benzophenone derivates such as benzophenone, 2- chlorobenzophenone, 4- bromine benzophenone, 2- carboxyl benzophenone；2,2- dimethoxy Base-2- phenyl acetophenone, 2,2- diethoxy acetophenone, 1- hydroxycyclohexyl phenyl ketone, alpha-hydroxy-2-aminomethyl phenyl third Ketone, 1- hydroxyl -1- Methylethyl-(p-isopropyl phenyl) ketone, 1- hydroxyl -1- (to dodecylphenyl) ketone, 2- methyl
- 1- (4 '-methyl mercapto phenyl) -2- morpholinopropane -1- ketone, 1,1,1- trichloromethyl (to butyl phenyl) ketone etc. Acetophenone derivs；Thioxanthones, 2- ethyl thioxanthones, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4- dimethyl thioxanthone, The thioxanthone derivates such as 2,4- diethyl thioxanthone, 2,4- diisopropylthioxanthone；(dimethylamino)-ethyl benzoate, to diethyl The benzoate derivatives such as benzocaine；The acridine derivatives such as 9- phenylacridine, 9- (p-methoxyphenyl) acridine；9, The phenazene derivatives such as 10- dimethylbiphenyl azophenlyene (9,10-dimethylbenzphenazine)；The anthrones such as benzanthrone are derivative Species etc..
In these Photoepolymerizationinitiater initiaters, from sensitivity, to the dissolubility of solvent, development when the viewpoint of pattern adaptation go out Hair, in oxime ester derivative class, further preferably as compound comprising part-structure shown in above-mentioned logical formula (IX) with Under compound,
[chemical formula 49]
[chemical formula 50]
Alternatively, the compound below as the compound comprising part-structure shown in above-mentioned logical formula (X).
[chemical formula 51]
[chemical formula 52]
[chemical formula 53]
(E) Photoepolymerizationinitiater initiater may be used alone, can also be used in combination of two or more kinds.
In order to improve induction sensitivity, it can according to need the cooperation in (E) Photoepolymerizationinitiater initiater and correspond to image exposure Sensitizing dyestuff, the polymerization accelerant of the wavelength of light source.It as sensitizing dyestuff, can enumerate: Japanese Unexamined Patent Publication 4-221958, Japan The xanthene pigment recorded in Japanese Laid-Open Patent Publication 4-219756 bulletin, Japanese Unexamined Patent Publication 3-239703, Japanese Unexamined Patent Publication 5-289335 The cumarin pigment with heterocycle recorded in number bulletin, Japanese Unexamined Patent Publication 3-239703, Japanese Unexamined Patent Publication 5-289335 Methylene lanaurin, the Yi Ji recorded in the 3- oxo coumarin compound of middle record, Japanese Unexamined Patent Publication 6-19240 bulletin This tekiaki 47-2528, Japanese Unexamined Patent Application 54-155292, Japanese Patent Publication 45-37377, Japanese Unexamined Patent Application 48- No. 84183, Japanese Unexamined Patent Application 52-112681, Japanese Unexamined Patent Application 58-15503, Japanese Unexamined Patent Application 60-88005, Japan Tekiaki 59-56403, Japanese Unexamined Patent Publication 2-69, Japanese Unexamined Patent Application 57-168088, Japanese Unexamined Patent Publication 5-107761, The color with dialkyl amido benzene skeleton recorded in Japanese Unexamined Patent Publication 5-210240, Japanese Unexamined Patent Publication 4-288818 bulletin Element etc..
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- aminobenzophenone, 4- aminobenzophenone, 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- (to dimethylaminophenyl) 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. be containing to compound of dialkylaminophenyl etc..Wherein, Most preferably 4,4 '-dialkyl amido benzophenone.
Sensitizing dyestuff also can be used alone, or combine two or more use.
As polymerization accelerant, such as ESCAROL 507 ethyl ester, benzoic acid 2- dimethylaminoethyl 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.
Other gradation compositions of [1-6] photosensitive composition
In photosensitive composition of the invention, in addition to the above ingredients, can be suitable for cooperate it is silane coupled The closely sealed enhancer such as agent, coating enhancer, development modifying agent, ultraviolet absorbing agent, antioxidant, surfactant, pigment spread out Biology etc..
[1-6-1] closely sealed enhancer
In order to improve the adaptation with substrate, can be mentioned in photosensitive composition of the invention containing closely sealed High agent.As closely sealed enhancer, preferably silane coupling agent, compound of phosphorous acidic group etc..
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 mentioned, for example: 3- methacryloxypropyl methyl dimethoxysilane, 3- (methyl) acryloxy silane such as methyl allyl acyloxypropyl trimethoxysilane class, 2- (3,4- epoxycyclohexyl) ethyl three Methoxy silane, 3- glycidoxy-propyltrimethoxy silane, 3- glycidoxypropyl diethoxy silane, 3- epoxy third The ureido silanes classes, 3- isocyanatopropyl such as the epoxy silanes such as oxygen propyl group triethoxysilane class, 3- urea propyl-triethoxysilicane The isocynate silanes class such as triethoxysilane, 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 (XI-A), the compound that (XI-B) or (XI-C) is indicated.
[chemical formula 54]
In above-mentioned general formula (XI-A), (XI-B) and (XI-C), R51Indicate hydrogen atom or methyl；
L and l ' indicates 1~10 integer；
M indicates 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.
[1-6-2] pigment derivative
It, can be containing as dispersion in photosensitive composition of the invention in order to improve dispersibility, keeping quality The pigment derivative of auxiliary agent.
As pigment derivative, azo, phthalocyanines, quinoline azone class, benzimidazole ketone, quinophthalone class, different can be enumerated Indoline 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.
[1-6-3] 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 substance of Xie Xinggao, such as can enumerate: diphenyl iodineXylyl iodinePhenyl (to methoxybenzyl) iodineIt is double (m-nitro base) iodineBis- (to tert-butyl-phenyl) iodineBis- (rubigan) iodineBis- (dodecyl) iodine To isobutyl phenenyl (p-methylphenyl) iodineP-isopropyl phenyl (p-methylphenyl) iodineEtc. Diaryl iodoniumsOr triphenyl Chloride, bromide or boron fluoride salt, hexafluorophosphate, hexafluoro arsenite, the aromatic sulphonate, four of the triaryl mattes such as sulfonium The sulfoniums Organic Bor Complex classes such as (pentafluorophenyl group) borate etc., diphenyl phenacyl sulfonium (normal-butyl) triph-enylborate or The triazines chemical combination such as bis- (trichloromethyl) triazines of person's 2- methyl -4,6-, bis- (trichloromethyl) triazines of 2- (4- methoxyphenyl) -4,6- Object etc., but not limited to this.
[1-6-4] crosslinking agent
Crosslinking agent can further be added in photosensitive composition of the invention, for example, melamine can be used Amine or guanamines compound.As these crosslinking agents, it can be mentioned, for example melamine or guanamines shown in the following general formula (XII) Compound.
[chemical formula 55]
In formula (XII), R61Expression-NR66R67The aryl of base or carbon atom number 6~12；
R61For-NR66R67In the case where base, R62、R63、R64、R65、R66And R67In an expression-CH2OR68Base, moreover, R61In the case where aryl for carbon atom number 6~12, R62、R63、R64And R65In an expression-CH2OR68Base；
R62、R63、R64、R65、R66And R67In remaining group each independently represent hydrogen atom or-CH2OR68Base；
R68Indicate the alkyl of hydrogen atom or carbon atom number 1~4.
Wherein, the aryl of carbon atom number 6~12 is typically phenyl, 1- naphthalene or 2- naphthalene, 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, more preferably methyl.
Melamine class compound corresponding with general formula (XII), i.e. the following general formula (XII-A) compound include: six Melamine methylol, pentamethylol melamine, tetra methylol melamine, hexamethoxymethyl melamine, five methoxies Methyl melamine, tetramethoxymethyl melamine, six ethoxyl methyl melamines etc..
[chemical formula 56]
In formula (XII-A), R62、R63、R64、R65、R66And R67In one in the case where aryl, R62、R63、R64And R65 In an expression-CH2OR68Base；
R62、R63、R64、R65、R66And R67In remaining group each independently represent hydrogen atom or-CH2OR68Base；
R68Indicate hydrogen atom or alkyl.
In addition, guanamines compound corresponding with general formula (XII), the R i.e. in general formula (XII)61For the compound of aryl It include: tetra methylol benzoguanamine, tetramethoxymethyl benzoguanamine, trimethoxy methyl benzoguanamine, tetraethoxy methyl Benzoguanamine etc..
Furthermore it is also possible to be exemplified below the example using the crosslinking agent with methylol or hydroxymethyl alkyl ether:
Bis- (hydroxymethyl) phenol of bis- (the hydroxymethyl) -4- methylphenols of 2,6-, 4- tert-butyl -2,6-, 5- ethyl -1,3- Bis- (hydroxymethyl) perhydro -1,3,5- triazine -2- ketone (common name N- ethyl dihydroxymethyl 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 mass %, particularly preferably 0.5~10 mass %.
[1-6-5] sulfhydryl compound
In addition, the sulfhydryl compound as polymerization accelerant can also be added in order to improve the adaptation to substrate.
As the type of sulfhydryl compound, 2-mercaptobenzothiazole, 2- sulfydryl benzo can be enumeratedAzoles, 2- sulfydryl benzo miaow Azoles, ethanthiol, two mercaptan of the last of the ten Heavenly stems, 1,4- dimethyl sulfydryl benzene, dimercapto propionic acid butanediol ester, dimercapto acetic acid butanediol ester, Glycol dimercaptosuccinate, trimethylolpropane tris mercaptoacetate, dimercapto propionic acid butanediol ester, trimethylolpropane tris Mercaptopropionic acid ester, trimethylolpropane tris mercaptoacetate, four mercaptopropionic acid ester of pentaerythrite, four thioacetic acid of pentaerythrite Ester, tri-thiol propionic acid trihydroxy ethyl ester, ethylene glycol bis- (3- mercaptobutylates), butanediol bis- (3- mercaptobutylates), 1,4- are bis- (3- sulfydryl butyryl acyloxy) butane, trimethylolpropane tris (3- mercaptobutylate), pentaerythrite four (3- mercaptobutylate), season Penta tetrol three (3- mercaptobutylate), ethylene glycol bis- (3- mercaptoisobutanoic acid esters), butanediol bis- (3- mercaptoisobutanoic acid esters), three hydroxyls Methylpropane three (3- mercaptoisobutanoic acid esters), 1,3,5- tri- (3- sulfydryl butoxyethyl group) -1,3,5- triazine -2,4,6 (1H, 3H, 5H)-triketone etc. has sulfhydryl compound or the multifunctional sulfhydryl compound of aliphatic of heterocycle etc..These sulfhydryl compounds can be single Solely using one kind, or two or more can also be used in mixed way.
[1-6-6] surfactant
In order to improve coating, surfactant can also be contained in photosensitive composition of the invention.
As surfactant, can be used 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 fluorine class, organic from the aspect of coating The surfactant of silicon class is effective.
As the commercially available product of these surfactants, it can be mentioned, for example: BM Chemie corporation " BM-1000 ", " BM- 1100 ", DIC corporation " Megafac F-142D ", " Megafac F-172 ", " Megafac F-173 ", " Megafac F- 183”、“Megafac F-470”、“Megafac F-475”、“Megafac F-478”、“Megafac F-554”、“Megafac F-559 ", 3M Japan corporation " FC430 ", NEOS corporation " DFX-18 " etc..
In addition, as organosilicone surfactants, it can be mentioned, for example Dong Li Dow Corning Corporation system " DC3PA ", “SH7PA”、“DC11PA”、“SH21PA”、“SH28PA”、“SH29PA”、“8032Additive”、“SH8400”、BYK Chemie corporation " BYK300 ", " BYK323 ", " BYK325 ", " BYK330 ", SHIN-ETSU HANTOTAI's organosilicon Co. Ltd. system " KP340 " etc. Commercially available product.
As surfactant, the surface other than fluorine class surfactant and organosilicone surfactants can also be contained Activating agent can enumerate nonionic surface active agent, anionic surfactant, cation as other surfactants Type surfactant, amphoteric surfactant etc..
It should be noted that one kind can be used in surfactant, can also in any combination with 2 kinds of ratio combine with Upper use.Wherein, preferably organosilicone surfactants/fluorine class surfactant combination.The organosilicone surfactants/ It can be mentioned, for example BYK Chemie corporation " BYK-300 " or " BYK-330 "/DIC corporations for the combination of fluorine class surfactant " F-475 ", " F-478 ", " F-554 " or " F-559 " etc..
[1-6-7] liquid repellent agent
Photosensitive composition of the invention can also contain liquid repellent agent.In particular, using of the invention Color sensation photosensitive resin composition makes spaced walls, and in the case where utilization ink-jet method production organic electroluminescent device, preferably contains There is liquid repellent agent.By containing liquid repellent agent, the surface of spaced walls can be assigned with liquid-repellant, it is understood that gained spaced walls It can prevent the colour mixture of the pixel of organic layer.
As liquid repellent agent, the compound containing organosilicon, fluoride compound can be enumerated, is preferably enumerated with crosslinked group Liquid repellent agent (hereinafter also referred to " the liquid repellent agent containing crosslinked group ").As crosslinked group, epoxy group or olefinic insatiable hunger can be enumerated And group, from the viewpoint of the liquid repellent constituents outflow for inhibiting developer solution, preferably ethylenically unsaturated group.
It is believed that in the case where using the liquid repellent agent containing crosslinked group can accelerate that coated film will be formed by The cross-linking reaction on the surface Shi Qi is exposed, liquid repellent agent is not easy to flow out in development treatment, as a result, gained spaced walls can be made to show High liquid-repellant out.
In the case where using fluoride compound as liquid repellent agent, there are the fluorine compounds to take on the surface of spaced walls To, play prevent ink exudation and colour mixture effect tendency.More particularly, there are following tendencies: having fluorine atom Group can play and repel ink, prevent from crossing because of ink ink is caused to ooze out and colour mixture due to spaced walls enter adjacent area Effect.
It, can as the liquid repellent agent containing crosslinked group, particularly the concrete example of the fluoride compound containing ethylenically unsaturated group Enumerate for example: perfluoro alkyl sulfonic acid, perfluoro carboxylic acid, perfluoroalkyl oxyalkylene addition product, perfluoroalkyl trialkyl ammonium salts, Oligomer comprising perfluoroalkyl and hydrophilic radical, the oligomer comprising perfluoroalkyl and lipophilic group include perfluoroalkyl, parent The oligomer of water base group and fresh oil group, the carbamate comprising perfluoroalkyl and hydrophilic radical, perfluoroalkyl ester, perfluor alkane The fluorinated organic compounds such as base phosphate.
As the commercially available product of these fluorochemicals, can be used DIC corporation " DEFENSAMCF-300 ", “DEFENSAMCF-310”、“DEFENSAMCF-312”、“DEFENSAMCF-323”、“Megafac RS-72-K”、3M Japan Corporation " Fluorad FC-431 ", " Fluorad FC-4430 ", " Fluorad FC-4432 ", Asahi Glass Co., Ltd's system “Asahi Guard AG710”、“Surfron S-382”、“Surfron SC-101”、“Surfron SC-102”、 " Surfron SC-103 ", " Surfron SC-104 ", " Surfron SC-105 ", " Surfron SC-106 ", Daikin Industries Co. Ltd. system " Optool DAC-HP " etc. is with the commercially available fluorinated organic compound of trade name.
Like this, in the case where using fluoride compound as liquid repellent agent, ratio is contained to the fluorine atom in liquid repellent agent Example is not particularly limited, and preferably fluorine atom content ratio is 1 mass % or more, is more preferably 5 mass % or more, additionally, it is preferred that For 50 mass % or less, more preferably 25 mass % or less.By being set as above-mentioned lower limit value or more, exists and show high contact angle Tendency, in addition, by being set as above-mentioned upper limit value hereinafter, in the presence of the tendency that can inhibit the outflow to pixel portion.
The molecular weight of liquid repellent agent is not particularly limited, and can be the compound of low molecular weight, is also possible to high molecular weight body. The liquid repellent agent of high molecular weight body due to can inhibit be burnt into caused by liquid repellent agent flowing, thus in the presence of can inhibit liquid repellent agent outflow Tendency outside to spaced walls, therefore it is preferred that, from such a viewpoint, the number-average molecular weight of liquid repellent agent is preferably 100 or more, more excellent It is selected as 500 or more, and preferably 100,000 or less, more preferably 10,000 or less.
For the content ratio of liquid repellent agent in photosensitive composition of the invention, relative to all solids Ingredient is usually 0.01 mass % or more, preferably 0.05 mass % or more, more preferably 0.1 mass % or more, and usually 1 Quality % or less, preferably 0.5 mass % or less, more preferably 0.3 mass % or less.By being set as above-mentioned lower limit value or more, In the presence of the tendency for showing high liquid-repellant, in addition, by be set as above-mentioned upper limit value hereinafter, in the presence of can inhibit liquid repellent agent to pixel The tendency of the outflow in portion.
[1-6-8] ultraviolet absorbing agent
Photosensitive composition of the invention can also contain ultraviolet absorbing agent.Ultraviolet absorbing agent be for Following purposes and add: the specific wavelength by absorbing the light source for exposure using ultraviolet absorbing agent, to control Photocuring distribution.By adding ultraviolet absorbing agent, existing, which can get the cone angle after improving development and shape or eliminate, is developing Remain on the tendency of residue of non-exposed portion and other effects afterwards.As ultraviolet absorbing agent, from the sight for the light absorption for hindering initiator Point sets out, and the compound for example between wavelength 250nm~400nm with absorption maximum can be used.
As ultraviolet absorbing agent, preferably benzotriazole compound and/or compound in triazine class.By containing benzo three Azole compounds and/or compound in triazine class, it is believed that initiator can be reduced in the absorptivity of film bottom, reduce film surface layer and film The difference of the solidification area of bottom, to obtain the increase effect of cone angle.
It as benzotriazole compound, can enumerate: 2- (5- methyl -2- hydroxy phenyl) benzotriazole, 2- (2- hydroxyl - 5- tert-butyl-phenyl) -2H- benzotriazole, [3- tertiary butyl-4-hydroxy -5- (the chloro- 2H- benzotriazole -2- base of the 5-) benzene of octyl -3 Base] propionic ester and 2- ethylhexyl -3- [3- tertiary butyl-4-hydroxy -5- (the chloro- 2H- benzotriazole -2- base of 5-) phenyl] propionic ester Mixture, 2- [bis- (bis (alpha, alpha-dimethylbenzyl) base) phenyl of 2- hydroxyl -3,5-] -2H- benzotriazole, 2- (3- tert-butyl -5- first Base -2- hydroxy phenyl) -5- chlorobenzotriazole, 2- (bis- tertiary pentyl -2- hydroxy phenyl of 3,5-) benzotriazole, 2- (2 '-hydroxyls - 5 '-t-octyl phenyl) benzotriazole, 2- (2H- benzotriazole-2- base)-4,6- bis- (1- methyl-1-phenylethyl) phenol, 2- (2H- benzotriazole-2- base)-6- (1- methyl-1-phenylethyl)-4- (1,1,3,3- tetramethyl butyl) phenol, benzenpropanoic acid, 3- The compound of (2H- benzotriazole -2- base) -5- (1,1- dimethyl ethyl) -4- hydroxyl, C7-9 side chain and straight chained alkyl ester.
As commercially available benzotriazole compound, it can be mentioned, for example: SUMISORB 200, SUMISORB 250, SUMISORB 300, SUMISORB 340, SUMISORB 350 (Sumitomo Chemical Co's system), JF77, JF78, JF79, JF80, JF83 (Johoku Chemical Co., Ltd.'s system), TINUVIN PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN326, TINUVIN900, TINUVIN928, TINUVIN928, TINUVIN1130 (BASF AG System), EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, (Taiwan is forever photochemical by EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 Learn industrial group's system), Tomisorb 100, Tomisorb 600 (API Corporation system), SEESORB701, SEESORB702、SEESORB703、SEESORB704、SEESORB706、SEESORB707、SEESORB709(SHIPRO KASEI system), RUVA-93 (Otsuka Chemical Co. Ltd. system) etc..
As compound in triazine class, can enumerate: 2- [4,6- bis- (2,4- xylyl) -1,3,5-triazines -2- base] -5- is pungent Oxygroup phenol, 2- [bis- (2,4- the 3,5-dimethylphenyl) -1,3,5- triazine -2- bases of 4,6-] -5- [3- (dodecyloxy) -2- hydroxyl Propoxyl group] phenol, bis- (2,4- the 3,5-dimethylphenyl) -1,3,5- triazines of 2- (2,4- dihydroxy phenyl) -4,6- and glycidic acid Bis- [2- hydroxyl -4- the butoxy phenyl] -6- (2,4- dibutoxy phenyl) -1 of the reaction product of (2- ethylhexyl) ester, 2,4-, 3-5- triazine etc..In these, from the viewpoint of cone angle and exposure sensitivity, preferably hydroxyphenyltriazinuv compound.
As commercially available compound in triazine class, it can be mentioned, for example: TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, TINUVIN479 (BASF system) etc..
[1-6-9] polymerization inhibitor
Photosensitive composition of the invention can also contain polymerization inhibitor.It is believed that by containing polymerization inhibitor, Since it can hinder free radical polymerization, the cone angle of obtained solidfied material can be increased.
It as polymerization inhibitor, can enumerate: quinhydrones, hydroquinone monomethyl ether, methylnaphthohydroquinone, metoxyphenol, 2,6- di-t-butyl -4- Cresols (BHT) etc..In these polymerization inhibitors, from the viewpoint of polymerization inhibiting capacity, preferably 2,6-di-tert-butyl-4-methylphenol, quinhydrones Or metoxyphenol.
Polymerization inhibitor preferably comprise it is a kind of or two or more.In general, in manufacture (C) adhesive resin, sometimes in the resin Comprising polymerization inhibitor, can also other than polymerization inhibitor contained in resin, in photosensitive polymer combination manufacture addition and its Identical or different polymerization inhibitor.
For the content ratio of polymerization inhibitor in photosensitive composition, relative to coloring phototonus resin group The all solids ingredient for closing object is usually 0.0005 mass % or more, preferably 0.001 mass % or more, more preferably 0.01 matter % or more is measured, and usually 0.1 mass % or less, preferably 0.08 mass % or less, more preferably 0.05 mass % or less. By being set as above-mentioned lower limit value or more, there is the tendency that can increase cone angle, in addition, by being set as above-mentioned upper limit value hereinafter, depositing It is being able to maintain highly sensitive tendency.
[1-6-10] inorganic filler
In addition, in order to improve the intensity as solidfied material, improve the interaction based on the appropriateness with (C) adhesive resin Excellent flatness and cone angle of the coated film of (formation of matrix structure) etc., in photosensitive composition of the invention Inorganic filler can also further be contained.As such inorganic filler, it can be mentioned, for example: talcum, silica, oxidation Aluminium, barium sulfate, magnesia or substance made of being surface-treated to them using various silane coupling agents etc..
As the average grain diameter of these inorganic fillers, usually 0.005~20 μm, preferably 0.01~10 μm.Wherein, The average grain diameter in present embodiment refers to, utilizes the laser diffraction and scattering grain of Beckman Coulter company manufacture etc. Spend the value of distribution measurement device measurement.In these inorganic fillers, especially silica solution and silica sol modified object, due to existing point Dissipate excellent in stability, the simultaneously excellent tendency of the improvement effect of cone angle, therefore preferred cooperation.Coloring phototonus resin of the invention In the case that composition includes these inorganic fillers, contain specific force as it, from the viewpoint of sensitivity, relative to whole Solid component is usually 5 mass % or more, is preferably 10 mass % or more, and usually 80 mass % or less, preferably 70 matter Measure % or less.
[1-7] solvent
Photosensitive composition and dispersible pigment dispersion of the invention usually contains solvent.It, can by containing solvent To disperse the colorants such as pigment in solvent, and it is coated with and becomes easy.
Photosensitive composition of the invention usually with (A) colorant, (B) dispersing agent, (C) adhesive resin, (D) photopolymerization monomer, (E) Photoepolymerizationinitiater initiater and other a variety of materials used as needed are dissolved or dispersed in solvent In state use.Similarly, dispersible pigment dispersion of the invention is usually with (A) colorant, (B) dispersing agent, (C) adhesive resin And other a variety of materials used as needed are dissolved or dispersed in the use of the state in solvent.In solvent, from dispersibility, apply From the perspective of cloth, preferable organic solvent.
In organic solvent, from the viewpoint of coating, preferably selecting boiling point is 100~300 DEG C of (pressure 1013.25hPa Under the conditions of, hereinafter, all the same about boiling point) solvent of range, more preferably select boiling point for the solvent of 120~280 DEG C of ranges.
As such organic solvent, it can be mentioned, for example solvents 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- methoxybutanol, 3- methyl -3- first Oxygroup butanol, triethylene 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- methoxybutyl 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, glycerol, 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- ethoxypropanoate, 3- ethoxyl ethyl propionate, 3- methoxy methyl propionate, 3- methoxypropionic acid Ethyl ester, 3- methoxy propyl propyl propionate, 3- methoxy propyl acid butyl ester, chain as gamma-butyrolacton or cyclic annular esters；
Alkoxy carboxylic acids as 3- methoxypropionic acid, 3- ethoxy-propionic acid；
Halogenated hydrocarbon as chlorobutane, chloropentane；
Ether ketone as methoxy pentanone；
Nitrile as acetonitrile, benzonitrile etc..
As above-mentioned commercially available organic solvent is equivalent to, can enumerate: mineral spirits (Mineral spirit), Varsol#2, Apco#18 solvent, Apco thinner, Socal solvent No.1 and No.2, Solvesso#150, Shell TS28 solvent, 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 where forming spaced walls, coloring spacer with photoetching process, as organic solvent, preferably selecting boiling point is 100 The organic solvent of~200 DEG C of ranges.More preferably there is the organic solvent of 120~170 DEG C of boiling point.
In above-mentioned organic solvent, constituent good from the harmony of coating, surface tension etc., in composition it is molten Xie Du higher aspect is set out, 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, especially from the constituent in composition Dissolubility set out, preferred propylene glycol monomethyl ether.It should be noted that the polarity of glycol monoalkyl ethers is high, if it is added Amount is excessive, then has that pigment is easy cohesion and so that the viscosity of the photosensitive composition obtained thereafter the preservations such as is risen steady The tendency of qualitative decline, therefore, the ratio of the glycol monoalkyl ethers in solvent are preferably 5 mass of mass %~30 %, more excellent It is selected as 5 mass of mass %~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 composition becomes difficult to drying, Have the effect of that the uniform dispersity for preventing the pigment in the case where sharply drying in composition is destroyed.That is, having Such as prevent the effect for generating foreign matter defect because of the precipitation of colorant etc., solidification in slit spray nozzle front end.From such effect From the aspect of height, in above-mentioned various solvents, particularly preferred diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetic acid esters, with And diethylene glycol monoethyl ether 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 limit value, exists and be able to suppress for example The tendency of foreign matter defect is generated because of the precipitation of coloured material etc., solidification in slit spray nozzle front end, in addition, by for the above-mentioned upper limit Value hereinafter, can be slack-off with the drying temperature of composite inhibiting, thus in the presence of be able to suppress be dried under reduced pressure technique productive temp not The tendency of pin trace such problems of good, prebake (pre-bake).
It should be noted that 150 DEG C of boiling point or more of high boiling solvent can be glycol alkyl ether acetate esters, in addition It can be glycol alkyl ether class, in this case, can not also be in addition containing 150 DEG C of boiling point or more of high boiling solvent.
As preferred high boiling solvent, it can be mentioned, for example the diethylene glycol mono-n-butyl ether acetic acid in above-mentioned various solvents Ester, diethylene glycol monoethyl ether acetic acid esters, dipropylene glycol methyl ether acetic acid esters, 1,3 butylene glycol diacetate esters, 1,6-HD two Acetic acid esters, glycerol triacetate etc..
Components matching amount > in < photosensitive composition
In photosensitive composition of the invention, for the content ratio of (A) colorant, relative to coloring All solids component amount in photosensitive polymer combination is usually 20 mass % or more, is preferably 25 mass % or more, more excellent It is selected as 30 mass % or more, and preferably 60 mass % or less, more preferably 50 mass % or less, further preferably 45 matter It measures % or less, be still more preferably 40 mass % or less.By being set as above-mentioned lower limit value or more, exists and be easy to get adequately The tendency of optical density (OD), in addition, by being set as above-mentioned upper limit value hereinafter, in the presence of it is easy to ensure that sufficient image formative is inclined To.As the combination of the upper limit and lower limit, preferably 20~60 mass % can be enumerated, 25~50 mass % is more preferably, is further Preferably 30~45 mass %, particularly preferably 30~40 mass %.
In addition, (A1) organic black pigments are opposite in photosensitive composition and dispersible pigment dispersion of the invention In the content ratio of (A) colorant be usually 10 mass % or more, preferably 30 mass % or more, more preferably 50 mass % with Upper, further preferably 70 mass % or more, be still more preferably 80 mass % or more, particularly preferably 90 mass % with On, and usually 100 mass % or less.By the way that the content ratio of (A1) organic black pigments in (A) colorant is set as More than above-mentioned lower limit value, there is the film that desired black tone can be obtained and the tendency of the high film of intensity can be obtained. As the combination of the upper limit and lower limit, preferably 10~100 mass % can be enumerated, 30~100 mass % is more preferably, is further excellent It is selected as 50~100 mass %, is still more preferably 70~100 mass %, particularly preferably 80~100 mass %, most preferably For 90~100 mass %.
In photosensitive composition and dispersible pigment dispersion of the invention, also has and contain simultaneously in (A) colorant (A1) the case where organic black pigments and (A2) organic coloring pigments.In this case, (A1) organic black pigments are relative to (A) The content ratio of toner is usually 10 mass % or more, preferably 20 mass % or more, is more preferably 30 mass % or more, and Usually 90 mass % or less, preferably 80 mass % or less, more preferably 60 mass % or less.In addition, (A2) organic coloring The content ratio of pigment is usually 10 mass % or more, preferably 20 mass % or more, is more preferably 40 mass % or more, and Usually 90 mass % or less, preferably 80 mass % or less, more preferably 70 mass % or less.By being set as above-mentioned lower limit value More than, there are the tendencies that cone angle reduces, in addition, by being set as above-mentioned upper limit value hereinafter, in the presence of the film that black tone can be obtained Tendency.
In addition, relative to 100 mass parts of (A2) organic coloring pigments, the content ratio of (A1) organic black pigments is usually More than 15 mass parts, preferably more than 20 mass parts, and usually 900 below the mass, preferably 800 below the mass, more Preferably 500 below the mass, further preferably 200 below the mass.
In photosensitive composition and dispersible pigment dispersion of the invention, also has and contain simultaneously in (A) colorant (A1) the case where organic black pigments and (A3) carbon black.In this case, (A1) organic black pigments containing relative to (A) colorant Proportional usually 50 mass % or more, preferably 60 mass % or more, and usually 95 mass % or less, preferably 90 matter Measure % or less.In addition, the content ratio of (A3) carbon black is usually 5 mass % or more, preferably 10 mass % or more, and usual For 50 mass % or less, preferably 40 mass % or less.By being set as above-mentioned lower limit value or more, there is that sufficient light can be obtained is close The tendency of (OD) is spent, in addition, by being set as above-mentioned upper limit value hereinafter, normal in the presence of high volumetric resistivity value, low opposite dielectric can be obtained The tendency of fold etc. is not likely to produce when counting, and solidifying.In addition, relative to 100 mass parts of (A3) carbon black, (A1) organic black face The content ratio of material is usually 100 mass parts or more, preferably more than 150 mass parts, and usually 2000 below the mass, it is excellent It is selected as 1000 below the mass.
In addition, also have in (A) colorant while containing in photosensitive composition and dispersible pigment dispersion of the invention There is the case where (A1) organic black pigments, (A2) organic coloring pigments and (A3) carbon black.In this case, (A1) organic black pigments Content ratio relative to (A) colorant is usually 10 mass % or more, preferably 20 mass % or more, and usually 80 matter Measure % or less, preferably 70 mass % or less.In addition, the content ratio of (A2) organic coloring pigments be usually 10 mass % with Upper, preferably 20 mass % or more, and usually 60 mass % or less, preferably 50 mass % or less.In addition, (A3) carbon black Content ratio be usually 5 mass % or more, preferably 10 mass % or more, and usually 50 mass % or less, preferably 40 mass % or less.In this case, relative to 100 mass parts of (A2) organic coloring pigments, (A1) organic black pigments contain Ratio is usually 15 mass parts or more, preferably more than 20 mass parts, and usually 800 below the mass, preferably 700 mass Part or less.In addition, relative to 100 mass parts of (A3) carbon black, the content ratio of (A1) organic black pigments is usually 40 mass parts It above, is preferably 50 mass parts or more, and usually 1000 below the mass, preferably 900 below the mass.
In the solid component of photosensitive composition, the content ratio of (B) dispersing agent be usually 1 mass % with Upper, preferably 3 mass % or more, more preferably 5 mass % or more, and usually 30 mass % or less, preferably 20 matter Measure % or less, more preferably 15 mass % or less, further preferably 10 mass % or less.By be set as above-mentioned lower limit value with On, there are dispersibilities to become good tendency, in addition, by being set as above-mentioned upper limit value hereinafter, in the presence of that can reduce remaining point Powder, developability become good tendency.As the combination of the upper limit and lower limit, can enumerate preferably 1~30 mass %, more preferably For 3~20 mass %, further preferably 5~15 mass %, particularly preferably 5~10 mass %.
In addition, relative to 100 mass parts of (A) colorant, the content ratio of (B) dispersing agent is usually 5 mass parts or more, excellent 10 mass parts or more are selected as, and usually 50 below the mass, preferably 30 below the mass.By be set as above-mentioned lower limit value with On, there are dispersibilities to become good tendency, in addition, by being set as above-mentioned upper limit value hereinafter, in the presence of that can reduce remaining point Powder, developability become good tendency.As the combination of the upper limit and lower limit, can enumerate preferably 5~50 mass parts, more preferably For 10~30 mass parts.
In the photosensitive composition of first method of the present invention, the content ratio of acrylic dispersants does not have Be particularly limited to, in the solid component of photosensitive composition be usually 1 mass % or more, preferably 3 mass % with Upper, more preferably 5 mass % or more, and usually 30 mass % or less, preferably 20 mass % or less, more preferably 15 matter Measure % or less, further preferably 10 mass % or less.By being set as above-mentioned lower limit value or more, there are dispersibilities to become good Tendency, in addition, by be set as above-mentioned upper limit value hereinafter, in the presence of can reduce remaining dispersing agent, developability becomes good and inclines To.As the combination of the upper limit and lower limit, preferably 1~30 mass % can be enumerated, 3~20 mass % is more preferably, is further excellent It is selected as 5~15 mass %, particularly preferably 5~10 mass %.
In addition, the dispersible pigment dispersion of the photosensitive composition of first method of the present invention and Third Way of the present invention In, relative to 100 mass parts of (A) colorant, the content ratio of acrylic dispersants is usually 5 mass parts or more, is preferably More than 10 mass parts, and usually 50 below the mass, preferably 30 below the mass.By being set as above-mentioned lower limit value or more, There are dispersibilities to become good tendency, in addition, by being set as above-mentioned upper limit value hereinafter, in the presence of that can reduce remaining dispersion Agent, developability become good tendency.As the combination of the upper limit and lower limit, preferably 5~50 mass parts can be enumerated, be more preferably 10~30 mass parts.
(C) content ratio of adhesive resin is not particularly limited, relative to coloring phototonus resin combination of the invention The all solids ingredient of object be usually 5 mass % or more, preferably 10 mass % or more, more preferably 20 mass % or more, into One step is preferably 30 mass % or more, is particularly preferably 40 mass % or more, and usually 80 mass % or less, preferably 70 matter Measure % or less, more preferably 60 mass % or less, further preferably 50 mass % or less.By be set as above-mentioned lower limit value with On, there is the tendency for being easy to get strong film, in addition, being easy hereinafter, existing by developer solution pair by being set as above-mentioned upper limit value The tendency of the deterioration for being impregnated with the surface smoothness, sensitivity that are suppressed to lower, easy inhibition film of exposure portion.As the upper limit under The combination of limit can enumerate preferably 5~80 mass %, more preferably 10~70 mass %, further preferably 20~60 matter It measures %, be still more preferably 30~50 mass %, particularly preferably 40~50 mass %.
Relative to all solids ingredient of photosensitive composition of the invention, (C1) epoxy (methyl) acrylic acid The content ratio of ester resin be usually 5 mass % or more, preferably 10 mass % or more, more preferably 20 mass % or more, into One step is preferably 30 mass % or more, is still more preferably 35 mass % or more, particularly preferably 40 mass % or more, and logical It is often 80 mass % or less, preferably 70 mass % or less, more preferably 60 mass % or less, further preferably 50 mass % Below.By being set as above-mentioned lower limit value or more, there is the tendency for being easy to get strong film, in addition, by being set as the above-mentioned upper limit Hereinafter, there is the tendency of the deterioration of the surface smoothness, sensitivity that are easy to inhibit film in value.It, can as the combination of the upper limit and lower limit It enumerates preferably 5~80 mass %, more preferably 10~70 mass %, be more preferably 20~60 mass %, further It preferably 30~60 mass %, particularly preferably 35~60 mass %, is most preferably 40~50 mass %.
In the present invention, epoxy (methyl) acrylate with repeat unit structure shown in above-mentioned logical formula (II) And/or epoxy (methyl) acrylate with part-structure shown in above-mentioned logical formula (III) is in (C) adhesive resin Shared content ratio (comprising being its total content ratio in the case where the two) is not particularly limited, preferably 75 mass % Above, be more preferably 80 mass % or more, further preferably 85 mass % or more, still more preferably for 90 mass % with Upper, particularly preferably 95 mass % or more, in addition, usually 100 mass % or less.By being set as above-mentioned lower limit value or more, deposit Become good tendency in degassing adaptability.As the combination of the upper limit and lower limit, preferably 75~100 mass %, more can be enumerated It preferably 80~100 mass %, further preferably 85~100 mass %, is still more preferably 90~100 mass %, spy It You Xuanwei not 95~100 mass %.
Relative to all solids ingredient of photosensitive composition, the content ratio of (D) photopolymerization monomer is logical It is often 1 mass % or more, preferably 5 mass % or more, more preferably 8 mass % or more, and usually 30 mass % or less, excellent It is selected as 20 mass % or less, more preferably 15 mass % or less.By being set as above-mentioned lower limit value or more, existing becomes high sensitivity Tendency, in addition, by being set as above-mentioned upper limit value hereinafter, there are developability to become good tendency.As the upper limit and lower limit Combination can enumerate preferably 1~30 mass %, more preferably 5~20 mass %, further preferably 8~15 mass %.
Relative to all solids ingredient of photosensitive composition of the invention, (E) Photoepolymerizationinitiater initiater contains Proportional usually 0.1 mass % or more, preferably 0.5 mass % or more, it is more preferably 1 mass % or more, is further preferred For 2 mass % or more, particularly preferably 3 mass % or more, and usually 15 mass % or less, preferably 10 mass % or less, More preferably 8 mass % or less, further preferably 5 mass % or less.By being set as above-mentioned lower limit value or more, there are available The tendency of good sensitivity, in addition, by being set as above-mentioned upper limit value hereinafter, adaptable for developing in the presence of that can ensure Adhesive resin, photopolymerization monomer amount tendency.As the combination of the upper limit and lower limit, preferably 0.1~15 can be enumerated Quality %, more preferably 0.5~10 mass %, further preferably 1~8 mass %, still more preferably for 2~5 mass %, Particularly preferably 3~5 mass %.
In the case where using polymerization accelerant while use (E) Photoepolymerizationinitiater initiater, relative to coloring of the invention The all solids ingredient of photosensitive polymer combination, the content ratio of polymerization accelerant are preferably 0.05 mass % or more, and logical It is often 10 mass % or less, preferably 5 mass % or less.In addition, polymerization accelerant is relative to 100 matter of (D) Photoepolymerizationinitiater initiater Amount part is usually 0.1 mass parts or more, preferably more than 0.2 mass parts, and usually 100 below the mass, preferably 50 weights Below amount portion.
By the way that the content ratio of polymerization accelerant is set as above-mentioned lower limit value or more, exists and good sensitivity can be obtained Tendency, in addition, by being set as upper limit value hereinafter, there are dissolubility of the unexposed portion to developer solution to become good tendency.
In addition, for sensitizing dyestuff mixing ratio shared in photosensitive composition of the invention, From the viewpoint of sensitivity, in all solids ingredient in photosensitive composition be usually 0.5 mass % with Upper, preferably 1 mass % is hereinafter, and usually 20 mass % or less, preferably 15 mass % or less, more preferably 10 mass % Below.
In the case where using closely sealed enhancer, relative to all solids ingredient in photosensitive composition, Content ratio is usually 0.1~5 mass %, preferably 0.2~3 mass %, more preferably 0.4~2 mass %.By will be closely sealed The content ratio of enhancer is set as above-mentioned lower limit value or more, exist improve adaptation tendency, in addition, by be set as upper limit value with Under, exist and good sensitivity can be obtained, and is not likely to produce the tendency of residue after developing.
In addition, in the case where using surfactant, relative to all solids in photosensitive composition at Point, content ratio is usually 0.001~10 mass %, preferably 0.005~1 mass %, more preferably 0.01~0.5 matter It measures %, be most preferably 0.03~0.3 mass %.By the way that the content ratio of surfactant is set as above-mentioned lower limit value or more, deposit In the tendency of flatness, uniformity that coated film can be obtained, in addition, by being set as upper limit value hereinafter, in the presence of can inhibit striped etc. Generation tendency.
It should be noted that photosensitive composition of the invention uses mentioned-above organic solvent, and right It is adjusted and its solid component concentration is made to be usually 5~50 mass %, preferably 10~30 mass %.
The physical property > of < photosensitive composition
Photosensitive composition of the invention can also be preferred for other than spaced walls, coloring spacer Black matrix" forms purposes, from this viewpoint, is preferably in black, is preferably equivalent to 1 μm of film thickness of optical density of its film It (OD) is 0.5 or more, more preferably 0.8 or more, further preferably 1.0 or more, particularly preferably 1.3 or more.
In addition, the spaced walls of such as organic electroluminescent device are in this way, be applied to show in the image of image display device In region in the case where the high component of shared area ratio, preferred hue is closer to black, from this viewpoint, preferably solid Coloration x after change be 0.20 or more, more preferably 0.25 or more, further preferably 0.30 or more, and preferably 0.50 with Under, more preferably 0.45 or less, further preferably 0.40 or less.Additionally, it is preferred that chromaticity y is 0.20 or more, is more preferably 0.25 or more, it is more preferably 0.30 or more, and preferably 0.50 or less, is more preferably 0.45 or less, is further preferred It is 0.40 or less.
[2] ingredient and composition of dispersible pigment dispersion
The ingredient and its composition that constitute dispersible pigment dispersion of the invention are illustrated.
Dispersible pigment dispersion (hereinafter, sometimes referred to simply as " dispersible pigment dispersion ") of the invention disperses containing (A) colorant, (B) Agent and (C) adhesive resin.Usually also further contain solvent.In addition, as described later like that, dispersible pigment dispersion of the invention It can be used preferably as one of raw material used when manufacturing photosensitive composition.
As (A) colorant, (B) dispersing agent used in dispersible pigment dispersion, (C) adhesive resin and solvent, Ke Yiyou Choosing is used as (A) colorant, (B) dispersing agent used in photosensitive composition, (C) adhesive resin and molten Agent those listed.
In dispersible pigment dispersion of the invention, (A) colorant includes mentioned-above (A1) organic black pigments.Coating uses Film obtained from the photosensitive composition of dispersible pigment dispersion manufacture comprising (A1) organic black pigments exists can To realize high impedance, low-k and high shading rate, the tendency of the solidfied material closer to the tone of black is formed.
In addition, (B) dispersing agent includes acrylic dispersants.By using the pigment dispersion comprising acrylic dispersants Liquid manufactures photosensitive composition, and there are pattern adaptations when development to become good tendency.
In addition, (C) adhesive resin includes (C1) epoxy (methyl) acrylate.By using including (C1) epoxy The dispersible pigment dispersion of (methyl) acrylate manufactures photosensitive composition, exists and generates after forming solidfied material Amount of gas evolved reduction tendency.
Components matching amount > in < dispersible pigment dispersion
In dispersible pigment dispersion of the invention, relative to all solids ingredient in dispersible pigment dispersion, (A) colorant contains Ratio is usually 10 mass % or more, preferably 20 mass % or more, more preferably 30 mass % or more, further preferably 40 It quality % or more, is still more preferably 50 mass % or more, particularly preferably 55 mass % or more, and usually 100 matter Measure % or less, preferably 80 mass % or less, more preferably 70 mass % or less, further preferably 60 mass % or less.It is logical It crosses and is set as above-mentioned lower limit value or more, photosensitive composition can be manufactured with suitable solid component concentration, in addition, logical It crosses and is set as above-mentioned upper limit value hereinafter, there are dispersibilities to become good tendency.As the combination of the upper limit and lower limit, can enumerate preferably For 10~80 mass %, more preferably 20~80 mass %, further preferably 30~70 mass %, be still more preferably 40 It~70 mass %, particularly preferably 50~60 mass %, is most preferably 55~60 mass.
In dispersible pigment dispersion of the invention, relative to all solids ingredient in dispersible pigment dispersion, (B) dispersing agent contains Ratio is usually 2 mass % or more, preferably 5 mass % or more, more preferably 10 mass % or more, and usually 50 matter Measure % or less, preferably 40 mass % or less, more preferably 30 mass % or less, further preferably 20 mass % or less, spy It You Xuanwei not 15 mass % or less.By being set as above-mentioned lower limit value or more, there are dispersibilities to become good tendency, in addition, logical It crosses and is set as above-mentioned upper limit value hereinafter, in the presence of that can reduce remaining dispersing agent, obtained photosensitive composition is shown Shadow becomes good tendency.As the combination of the upper limit and lower limit, preferably 2~50 mass %, more preferably 5~40 can be enumerated It quality %, further preferably 5~30 mass %, is still more preferably 5~20 mass %, particularly preferably 10~15 matter Measure %.
In dispersible pigment dispersion of the invention, relative to all solids ingredient in dispersible pigment dispersion, acrylic dispersants Content ratio be usually 2 mass % or more, preferably 5 mass % or more, more preferably 10 mass % or more, and be usually 50 mass % or less, preferably 40 mass % or less, more preferably 30 mass % or less, further preferably 20 mass % with Under, particularly preferably 15 mass % or less.By being set as above-mentioned lower limit value or more, there are dispersibilities to become well, while solid Pattern adaptation also becomes good tendency when the development of compound, in addition, by being set as above-mentioned upper limit value hereinafter, in the presence of obtained by The developability of photosensitive composition become good tendency.As the combination of the upper limit and lower limit, can enumerate preferably For 2~50 mass %, more preferably 5~40 mass %, further preferably 5~30 mass %, be still more preferably 5~20 Quality %, particularly preferably 10~15 mass %.
In dispersible pigment dispersion of the invention, relative to all solids ingredient in dispersible pigment dispersion, (C) adhesive resin Content ratio is usually 5 mass % or more, preferably 10 mass % or more, is more preferably 15 mass % or more, is further preferred For 20 mass % or more, particularly preferably 25 mass % or more, and usually 50 mass % or less, preferably 40 mass % with Under, more preferably 35 mass % or less, further preferably 30 mass % or less.By being set as above-mentioned lower limit value or more, exist Dispersibility becomes good tendency, in addition, by being set as above-mentioned upper limit value hereinafter, in the presence of that can make obtained coloring phototonus Amount of colorant in resin combination optimizes, so as to ensure the tendency of sufficient light-proofness.As the upper limit and lower limit Combination can enumerate preferably 5~50 mass %, more preferably 10~40 mass %, further preferably 15~35 mass %, more Further preferably 20~35 mass %, particularly preferably 25~30 mass %.
In dispersible pigment dispersion of the invention, relative to all solids ingredient in dispersible pigment dispersion, (C1) epoxy (methyl) The content ratio of acrylate be usually 5 mass % or more, preferably 10 mass % or more, more preferably 15 mass % with Upper, further preferably 20 mass % or more, particularly preferably 25 mass % or more, and usually 50 mass % or less, excellent It is selected as 40 mass % or less, more preferably 35 mass % or less, further preferably 30 mass % or less.Under being set as above-mentioned More than limit value, there are the degassing adaptability of solidfied material to become good tendency, in addition, by being set as above-mentioned upper limit value hereinafter, depositing The amount of colorant in obtained photosensitive composition can be made to optimize, so as to ensure sufficient shading The tendency of property.As the combination of the upper limit and lower limit, can enumerate preferably 5~50 mass %, more preferably 10~40 mass %, into One step is preferably 15~35 mass %, is still more preferably 20~35 mass %, particularly preferably 25~30 mass %.
It should be noted that dispersible pigment dispersion of the invention uses mentioned-above organic solvent, and it is adjusted And its solid component concentration is made to be usually 5~50 mass %, preferably 10~30 mass %.
[3] manufacturing method of photosensitive composition
Photosensitive composition (hereinafter, sometimes referred to as " resist ") of the invention can come according to usual way Preparation.
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, organic solvent, (B) dispersing agent and (C) adhesive 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 Obtained in composition be known as " ink " or " dispersible pigment dispersion ").In particular, if using macromolecule dispersing agent as (B) point Powder, then can inhibit obtained ink and resist through when viscosify (dispersion stabilization is excellent), therefore preferably.
Therefore, preferably fabricated at least containing (A) colorant, organic solvent and (B) dispersion in the process of manufacture resist The dispersible pigment dispersion of agent.
It should be noted that being carried out for the liquid containing the whole components cooperated in photosensitive composition In the case where decentralized processing, generated heat release when due to decentralized processing, high response ingredient is likely to occur modification.Therefore, It is preferred that carrying out decentralized processing with the system containing macromolecule dispersing agent.
, it is preferable to use the bead or oxygen of 0.1~8mm of partial size or so in the case where dispersing (A) colorant 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 size of the composition of liquid and decentralized processing device etc., the suitable time of jitter time is not identical, therefore appropriate adjusts Section.The rough standard of dispersion are as follows: the gloss of ink is controlled, so that 20 degree of mirror surface luster (JIS of resist Z8741) reach 50~300 range.By the way that the glossiness of resist is set as above-mentioned lower limit value or more, can inhibit at dispersion It manages insufficient and remains thick pigment (colorant) particle, exist and be easy to make developability, adaptation, resolution ratio etc. more fully to incline To.In addition, by make the above-mentioned upper limit value of gloss value hereinafter, in the presence of can to avoid pigment it is broken and generate a large amount of ultramicrons, To be easy to keep the tendency of dispersion stabilization.
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 mixed liquor 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..
[4] solidfied material and forming method thereof
[4-1] solidfied material
By solidifying photosensitive composition of the invention, available solidfied material.By coloring phototonus tree The solidfied material that oil/fat composition is constituted can be preferably used as spaced walls, coloring spacer.
[4-1-1] spaced walls
Photosensitive composition of the invention can be used for being formed spaced walls, particularly cause to divide organic field The spaced walls of the organic layer of light-emitting component.As the organic layer used in organic electroluminescent device, it can be mentioned, for example Japan As being recorded in special open 2016-165396 bulletin, in hole injection layer, hole transmission layer or on positive hole injecting layer Organic layer used in hole transmission layer.
[4-1-2] colours spacer
In addition, photosensitive composition of the invention other than spaced walls, can also be preferably used as between coloring The resist of parting.In the case that spacer is used for TFT type LCD, cause to make because in the light being incident in TFT sometimes It is malfunctioned for the TFT of switch element, coloring spacer is for preventing the situation (for example, referring to Japanese Unexamined Patent Publication 8-234212 Bulletin).
[4-2] forming method
Then, for having used the spaced walls of photosensitive composition of the invention, having coloured spacer, according to it Manufacturing method is illustrated.In addition, black matrix" and its solidfied material in addition can also be formed after the same method.
[4-2-1] supporter
As the supporter for being used to form spaced walls, colouring spacer, as long as there is the intensity of appropriateness, to its material It is not particularly limited.Transparent substrate is mainly used, as its material, it can be mentioned, for example the polyester such as polyethylene terephthalate The thermoplastic resins such as the polyolefin resins such as resinoid, polypropylene, polyethylene, polycarbonate, polymethyl methacrylate, polysulfones Thermosetting resins piece or the various glass such as film-making material, epoxy resin, unsaturated polyester resin, poly- (methyl) acrylic resin Deng.Wherein, from the viewpoint of heat resistance, preferably glass, heat-resistant resin.In addition, also having in substrate surface film forming ITO, IZO Deng transparent electrode the case where.Other than transparent substrate, it can also be formed on tft array.
In order to improve the surface physical properties such as cementability, it also can according to need and Corona discharge Treatment, ozone carried out to supporter 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 where the film formation processing of rouge, film thickness is usually 0.01~10 μm, preferably 0.05~5 μm of range.
The coating of [4-2-2] photosensitive composition
Coating of the photosensitive composition on substrate can pass through spin-coating method, bar (Wire bar) method, stream Coating, die coating method, rolling method or spray coating method etc. carry out.When wherein, using die coating method, coating fluid usage amount can greatly reduce, And the influence of accompanying smog etc. when absolutely not using spin-coating method can inhibit foreign matter generation etc., come from comprehensive viewpoint See it is preferred.
When the thickness of film is blocked up, pattern development is become difficult sometimes, if excessively thin, is difficult to improve pigment concentration, has Shi Buneng shows desired color.The thickness of film be preferably generally with the film thickness gauge after drying 0.2~10 μm range, More preferably 0.5~6 μm of range, further preferably 1~4 μm of range.
The drying of [4-2-3] film
Dried coating film after base plate coating photosensitive composition is preferably by using hot plate, IR baking oven Or the seasoning of convection oven carries out.Dry condition can be according to the type of above-mentioned solvent composition, the drying machine that uses The suitable selection such as performance.Drying time selects according to the type of solvent composition, performance of the drying machine used etc., usually 40~ 200 DEG C of temperature, the selection of 15 seconds~5 minutes ranges, preferably in 50~130 DEG C of temperature, 30 seconds~3 minutes ranges Selection.
Drying temperature is higher, and film improves the cementability of transparent substrate, but if drying temperature is excessively high, then (C) Adhesive resin decomposes, and induces thermal polymerization sometimes and generates poor visualization.It should be noted that the drying process of the film It can be the hypobaric drying method for not improving temperature and being dried in pressure-reducing chamber.
[4-2-4] exposure
Image exposure is the mask pattern that minus is overlapped on the film of photosensitive composition, and is covered across this Mould pattern irradiates the light source of ultraviolet light or luminous ray to carry out.At this point, the spirit of the optical polymerism layer as caused by oxygen in order to prevent Sensitivity decline can according to need and be exposed again after forming the oxygen such as polyvinyl alcohol layer screening interlayer on the film of optical polymerism Light.Light source used in above-mentioned image exposure is not particularly limited.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；Laser light sources such as argon laser, YAG laser, excimer laser, N_2 laser, helium cadmium laser, semiconductor laser etc..Make When being irradiated with the light of specific wavelength, optical filter also can use.
[4-2-5] development
Spaced walls of the invention, coloring spacer can make as follows: using above-mentioned light source to by coloring phototonus tree After the film that oil/fat composition is formed carries out image exposure, by using organic solvent or include surfactant and alkalization It closes the development of the aqueous solution of object and forms image on substrate.Can further contain in the aqueous solution organic solvent, buffer, Complexing agent, dyestuff or pigment.
It as alkali compounds, can enumerate: sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, bicarbonate 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, monoethanolamine, diethanol amine or triethanolamine, monomethyl amine, Dimethyl amine or Trimethylamine, monoethylamine, diethylamide or triethylamine, single isopropylamine or diisopropylamine, normal-butyl Amine, monoisopropanolamine, diisopropanolamine (DIPA) or triisopropanolamine, aziridine, ethylene diimine, tetramethylammonium hydroxide (TMAH), the organic basic compounds such as choline.These alkali compounds may be mixture of more than two kinds.
As surfactant, it can be mentioned, for example: polyoxyethylene alkyl ether class, polyoxyethylene alkylaryl ether class, polyoxy The nonionic surface active agent such as vinyl alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters；Benzene sulfonamide The anionics tables such as Barbiturates, alkyl naphthalene sulfonic acid salt, alkylsurfuric acid salt, alkyl sulfonates, sulfosuccinate ester salt class Face activating agent；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 in addition 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.
[4-2-6] heat cure processing
Heat cure processing or photocuring processing are implemented to the substrate after development, heat cure processing is preferably implemented.As at this time Heat cure treatment conditions, temperature 100~280 DEG C range, the range preferably at 150~250 DEG C select, the time 5~ Range selection in 60 minutes.
[5] organic electroluminescent device, image display device and illumination
[5-1] organic electroluminescent device
Organic electroluminescent device of the invention have it is mentioned-above be made of photosensitive composition consolidate Compound, such as spaced walls.
For example, can be used the substrate for having spaced walls pattern using method described above manufacture various organic to manufacture Electroluminescent cell.The method for forming organic electroluminescent device is not particularly limited, preferably in the utilization above method in substrate Pass through vapour deposition method, casting, spin-coating method, wet processing as ink jet printing method after the upper pattern for forming spaced walls and forms picture The organic layers such as element, to manufacture organic electroluminescent device, the vapour deposition method be make under vacuum conditions functional material distil and The method to form a film is attached in the region surrounded by spaced walls on substrate.
Use organic electroluminescent device as in the case where the pixel of image display device, needs to prevent certain pixels The light of luminescent layer escapes to other pixels, in addition, needing to prevent the reflection along with exterior light in the case that electrode etc. is metal Image quality reduction, it is therefore preferable that constitute organic electroluminescent device spaced walls assign light-proofness.
In addition, in organic electroluminescent device, due to needing the upper surface and the lower surface to spaced walls to assign electrode, because This, from the perspective of insulation, the preferred high impedance of spaced walls, low-k.Therefore, in order to spaced walls imparting shading Property and use colorant in the case where, it is preferable to use high impedance and low-k above-mentioned (A1) organic black pigments.
[5-2] image display device
As image display device of the invention, it is not particularly limited, can arranges as long as the device for showing image, image Lift liquid crystal display device, organic EL display device etc..It can be mentioned, for example the liquid crystal displays comprising mentioned-above coloring spacer Device, organic EL display device comprising mentioned-above organic electroluminescent device etc..
[5-2-1] liquid crystal display device
As long as liquid crystal display device includes mentioned-above coloring spacer, there is no special limit to its pattern and structure System.For example, black matrix" of the invention is arranged on TFT device substrate, red, green, the pixel of blue are formed, and according to need Surface covering is formed, then forms the transparent electrode of ITO, IZO etc. on image further on it, is shown as colour A part of the component of device, liquid crystal display device etc. uses.In addition, in part planar orientating type driving method (IPS mode) etc. With on the way, transparent electrode is not also formed sometimes.
In general, forming alignment films on colour filter, light spacer is formed in the alignment films, is then bonded with counter substrate And liquid crystal cell is formed, liquid crystal is injected to being formed by liquid crystal cell, is completed with opposite electrode wiring.As alignment films, polyamides The resin film of imines etc. is suitable.When the formation of alignment films, gravure printing method and/or aniline printing method are generallyd use, will be taken Several 10nm are set as to the thickness of film.After being burnt into the curing process for carrying out alignment films by heat, irradiates or rub by using ultraviolet light The processing of wiper is surface-treated, and the inclined surface state of adjustable liquid crystal is processed into.
[5-2-2] organic EL display device
As long as organic EL display device includes mentioned-above organic electroluminescent device, to image display device Pattern and structure are not particularly limited, it is, for example, possible to use active-drive organic electroluminescent device conventionally into Row assembling.For example, can use " organic el display " (OHM company, Heisei on August 20th, 16 distribution, former quiet scholars, Anda Thousand wave vectors, village Tian Yingxing write) in record as method form image display device of the invention.For example, can will emit The organic electroluminescent device of white light is combined with colour filter and is performed image display, can also be different by illuminant colours such as RGB Organic electroluminescent device is combined and is performed image display.
[5-3] illumination
Illumination of the invention includes organic electroluminescent device above-mentioned.Its pattern and structure are not particularly limited, it can To use organic electroluminescent device of the invention conventionally to be assembled.It, can be with as organic electroluminescent device It is simple matrix driving method, is also possible to active matrix drive mode.
In order to make illumination of the invention emit white light, the organic electroluminescent device of transmitting white light also can be used. Furthermore it is possible to the structure in such a way that the organic electroluminescent device combination that illuminant colour is different makes assorted colour mixture become white At can also be constituted in a manner of it can adjust color mixture ratio and assign toning function.
Embodiment
Then, Examples and Comparative Examples are enumerated more specifically the present invention will be described, but as long as without departing from of the invention Purport, the present invention is not limited to embodiments below.
The constituent of photosensitive composition used in following Examples and Comparative Examples is as follows.
< adhesive resin-I >
(weight average molecular weight (Mw) 6500, contains carboxyl at acid value 98mgKOH/g to Nippon Kayaku K. K's system " ZCR-1642H " Epoxy (methyl) acrylate).The resin is equivalent to (C1-1), has the repetitive unit knot indicated by chemical formula (II-1) Structure, R11For methyl, R12For group, R shown in above-mentioned formula (II-A)XFor tetrahydrophthalic acid residue.
< adhesive resin-II >
[chemical formula 57]
By 50 mass parts of epoxide (epoxide equivalent 264), 13.65 mass parts of acrylic acid, methoxyl group of above structure 60.5 mass parts of butylacetic acid ester, 0.936 mass parts of triphenylphosphine and 0.032 mass parts of p methoxy phenol are added to installation In the flask for having thermometer, blender, cooling tube, react it at 90 DEG C, until acid value reaches 5mgKOH/g Below.Reaction needs 12 hours, has obtained epoxy acrylic ester solution.
By above-mentioned 25 mass parts of epoxy acrylic ester solution, 0.74 mass parts of trimethylolpropane (TMP), bibenzene tetracarboxylic 3.95 mass parts of dianhydride (BPDA), 2.7 mass parts of tetrabydrophthalic anhydride (THPA), which are added to, is equipped with thermometer, stirring Machine, cooling tube flask in, be to slowly warm up to 105 DEG C while stirring, make its reaction.
It when resin solution becomes transparent, is diluted with methoxybutyl acetic acid esters, is prepared into 50 matter of solid component % is measured, epoxy containing carboxyl (methyl) acrylate of acid value 112mgKOH/g, weight average molecular weight (Mw) 4100 have been obtained, it should Resin is equivalent to (C1-2).
< adhesive resin-III >
[chemical formula 58]
By epoxide shown in structure above (DIC corporation EPICLON HP7200HH, bicyclopentadiene/benzene The poly epihydric alcohol base ether of phenol polymer, weight average molecular weight 1000, epoxide equivalent 270) 155 mass parts, 41 mass parts of acrylic acid, 0.1 mass parts of p methoxy phenol, 2.5 mass parts of triphenylphosphine, 130 mass parts of propylene glycol methyl ether acetate are added to reaction In container, heating stirring is carried out at 100 DEG C, until acid value reaches 3.0mgKOH/g or less.It is small that acid value reaches target value needs 9 When (acid value 2.9mgKOH/g).Then, then 74 mass parts of tetrahydrophthalic acid are added, reacts 4 hours, obtains at 120 DEG C Adhesive resin-III the solution of acid value 98mgKOH/g, weight average molecular weight (Mw) 3500, the resin are equivalent to (C1-1).
< adhesive resin-IV >
[chemical formula 59]
By structure above indicate 98.0 mass parts of epoxide (epoxide equivalent 245), 28.8 mass parts of acrylic acid, 113.0 mass parts of 3- methoxybutyl acetic acid esters, 1.1 mass parts of triphenylphosphine and 0.02 mass parts of p methoxy phenol are added to It is equipped in the flask of thermometer, blender, cooling tube, is reacted at 90 DEG C while stirring, until acid value reaches 5mgKOH/g Below.Reaction needs 15 hours, has obtained epoxy acrylic ester solution.
Biphenyltetracarboxylic dianhydride (BPDA) 11.8 mass is added into above-mentioned 189.1 mass parts of epoxy acrylate solution Part and 30.4 mass parts of tetrabydrophthalic anhydride (THPA), are to slowly warm up to 105 DEG C while stirring and make its reaction.
It when resin solution becomes transparent, is diluted with 3- methoxybutyl acetic acid esters, is prepared into 55 matter of solid component % is measured, has obtained the adhesive resin-IV of acid value 110mgKOH/g, weight average molecular weight (Mw) 2800, which is equivalent to (C1- 2)。
< adhesive resin-V >
It is stirred while carrying out nitrogen displacement to 145 mass parts of propylene glycol methyl ether acetate, and is warming up to 120 DEG C, 10 mass parts of styrene, 85.2 mass parts of glycidyl methacrylate are added dropwise thereto and there is tricyclodecane skeleton 66 mass parts of monomethacrylates (Hitachi Chemical Co., Ltd. FA-513M), and spend 3 hours and be added dropwise 2,2 '-and is even Nitrogen two (2- methylbutyronitrile) 8.47 mass parts further continue stirring 2 hours at 90 DEG C.Then, will become in reaction vessel Air displacement puts into three (dimethylaminomethyl) phenol, 0.7 mass parts and 0.12 matter of quinhydrones into 43.2 mass parts of acrylic acid Part is measured, continues reaction in 12 hours at 100 DEG C.Then, tetrahydrophthalic acid (THPA) 56.2 mass parts, triethylamine are added 0.7 mass parts are reacted 3.5 hours at 100 DEG C.The weight average molecular weight (Mw) of the adhesive resin-V obtained in this way is about 8400, acid value 80mgKOH/g, double bond equivalent are 480g/mol.
< colorant-I >
BASF AG's system, Irgaphor (registered trademark) Black S 0100CF (have chemistry shown in following formula (I-1) Structure)
[chemical formula 60]
< dispersing agent-I >
BYK-Chemie corporation BYK-LPN21116 (is had the A block of quaternary ammonium salt base and tertiary amino by side chain and is not had The acrylic A-B block copolymer for having the B block of quaternary ammonium salt base and tertiary amino to constitute, amine value 70mgKOH/g, acid value are 1mgKOH/g or less)
It include following formula (3a) in repetitive unit, B block in the A block of dispersing agent-I comprising following formula (1a) and (2a) Repetitive unit, the repetitive unit of following formula (1a), (2a) and (3a) is shared in whole repetitive units of dispersing agent-I to be contained Proportional is respectively 11.1 moles of %, 22.2 moles of %, 6.7 moles of %.
[chemical formula 61]
< dispersing agent-II >
BYK-Chemie corporation DISPERBYK-167 (carbamates macromolecule dispersing agent)
< solvent-I >
PGMEA: propylene glycol methyl ether acetate
< solvent-II >
MB:3- methoxyl group-n-butyl alcohol
< solvent-III >
MBA:3- methoxybutyl acetic acid esters
< Photoepolymerizationinitiater initiater-I >
Bis- ketoboidies > of <
Ethyl carbazole (5g, 25.61mmol) and adjacent naphthoyl chlorine (5.13g, 26.89mmol) are dissolved in the dichloromethane of 30mL In alkane, it is cooled to 2 DEG C in ice-water bath and is stirred, is added to AlCl3(3.41g,25.61mmol).Further in room temperature After lower stirring 3 hours, the 15mL dichloromethane solution of crotonyl chloride (2.81g, 26.89mmol), addition are added into reaction solution AlCl3(4.1g, 30.73mmol) has been futher stirred 30 minutes 1 hour.Reaction solution is poured into ice water 200mL, addition two Chloromethanes 200mL has carried out liquid separation to organic layer.After being dried with the organic layer that anhydrous magnesium sulfate obtains recycling, subtracting Pressure concentration, has obtained two ketoboidies (10g) of white solid.
< oxime body >
By two ketoboidies (3.00g, 7.19mmol), NH2OHHCl (1.09g, 15.81mmol) and sodium acetate (1.23g, It 15.08mmol) is mixed in isopropanol 30mL, flow back within 3 hours.
After reaction, reaction solution is concentrated, ethyl acetate 30mL is added to obtained residue, uses saturated sodium bicarbonate Aqueous solution 30mL, saturated salt solution 30mL are cleaned, and are dried with anhydrous magnesium sulfate.After filtering, organic layer is being subtracted Pressure is concentrated, and solid 3.01g has been obtained.It is purified with column chromatography, has obtained the oxime body of faint yellow solid 2.22g。
< oxime ester body >
Oxime body (2.22g, 4.77mmol) and chloroacetic chloride (1.34g, 17.0mmol) are added in methylene chloride 20mL simultaneously Ice cooling is carried out, triethylamine (1.77g, 17.5mmol) is added dropwise and keeps the state response 1 hour.It is true using thin-layered chromatography After raw material of accepting disappears, water, which is added, stops reaction.2 cleanings are carried out to reaction solution with saturated sodium bicarbonate aqueous solution 5mL, are used Saturated salt solution 5mL carries out 2 cleanings, is dried with anhydrous sodium sulfate.After filtering, organic layer is carried out under reduced pressure dense Contracting, purifies to obtained residue with column chromatography (ethyl acetate/hexane=volume ratio 2/1), has obtained the light of 0.79g Photoepolymerizationinitiater initiater-the I (compound of following chemical structure) of yellow solid.The chemical potential of Photoepolymerizationinitiater initiater-I described below It moves.
1H NMR(CDCl3): δ 1.17 (d, 3H), 1.48 (t, 3H), 1.81 (s, 3H), 2.16 (s, 3H), 2.30 (s, 3H), 3.17-3.32(m,2H),4.42(q,2H),4.78-4.94(br,1H),7.45-7.59(m,5H),7.65(dd,1H),7.95 (m,2H),8.04(m,2H),8.14(dd,1H),8.42(d,1H),8.64(d,1H)
[chemical formula 62]
< photopolymerization monomer >
DPHA: Nippon Kayaku K. K's dipentaerythritol hexaacrylate
< surfactant >
DIC corporation Megafac F-559
< additive >
Nippon Kayaku K. K KAYAMER PM-21 (phosphate containing methylacryloyl)
The preparation > of < dispersible pigment dispersion 1~6
It is the addition of mixing ratio documented by table 1 colorant (pigment) according to the ratio in its solid component, dispersing agent, glues Mixture resin, further mixed solvent become mass ratio documented by table 1.Using paint shaker by the solution 25 ~45 DEG C of range has carried out 3 hours decentralized processings.As pearl, the zirconium oxide bead of 0.5mm φ is used, joined dispersion 2.5 times of quality of liquid.After dispersion, pearl is separated with dispersion liquid using filter, is prepared for dispersible pigment dispersion 1~6.
[table 1]
[Examples 1 to 6, reference example 1 and comparative example 1]
Using the dispersible pigment dispersion 1~6 of above-mentioned preparation, each ingredient is added and the ratio in solid component is made to be table 2 PGMEA is further added in mixing ratio, so that the content ratio of all solids ingredient is 22 mass %, being stirred keeps its molten Solution, is prepared for photosensitive composition.Using obtained photosensitive composition, according to what is described below Method pattern-making is simultaneously evaluated.
[table 2]
(numerical value of the mixing ratio (mass parts) in ※ table indicates the mass parts for being scaled solid component)
The production method > of < spaced walls substrate
(film thickness is vapor-deposited in ito substrate using spinnerITO glass substrate) on be coated with each color sensation Photosensitive resin composition.Then, coated film is formd in heat drying 80 seconds on hot plate at 100 DEG C.
For obtained coated film, using with opening width 5~50 μm of (5~20 μm: 1 μm of intervals, 25~50 μm: 5 μm interval) the exposed masks of linear opening portion of various width implement exposure-processed.Exposing clearance (exposed mask and painting Distance between cloth cover) it is 5 μm.As irradiation light, using the intensity at wavelength 365nm is 32mW/cm2Ultraviolet light, Light exposure is set as 60mJ/cm2.In addition, ultraviolet light irradiation carries out in air.
Then, using the developer solution formed by TMAH (tetramethylammonium hydroxide) aqueous solution of 2.38 mass %, at 25 DEG C Under implement the spray development of hydraulic pressure 0.05MPa after, terminated and developed with pure water, spraying cleaned is washed with water.Spray development Time is adjusted between 10~120 seconds, is set as 1.2 times that dissolution removes the time of unexposed film.
By aforesaid operations, the pattern for removing unnecessary portion has been obtained.To be formed with the substrate of the pattern in an oven, It is heated 45 minutes at 230 DEG C and solidifies pattern, obtained the linear pattern (pattern 1) that film thickness is 2.5 μm.In addition, in addition to It is not used other than exposed mask, has also made the entire surface that film thickness is 2.5 μm according to same sequence and coated pattern (pattern 2).
The evaluation > of < substrate adaptation
By in pattern corresponding with 5~50 μm of linear opening portion pattern resolution remain on substrate well The value of the mask open width (μm) of width reckling is shown in Table 2 as minimum closely sealed in opening portion.The value is smaller, substrate Adaptation is more excellent, it is minimum it is closely sealed if it is 20 μm hereinafter, it can be said that the development adaptation for development is filled in practical Point, especially if being 10 μm hereinafter, it can be said that development excellent adhesion for development.
The evaluation method > of < degassing
About 3mg film is cut out by the substrate of pattern 2, has obtained the sample of degassing measurement.
Using TG-DTA6300 (Hitachi High-Tech Science Corporation system), by sample in air (Flow 200ml/min) determines weight reduction at this time with 10 DEG C/minute from room temperature to 500 DEG C under atmosphere.It will be from room Weight reduction amount when temperature is warming up to 400 DEG C relative to whole adhesive resins amount contained by each photosensitive composition (quality %) is shown in table 2.It should be noted that relative to each photosensitive composition when from room temperature to 400 DEG C The weight reduction amount (quality %) of all solids ingredient be, embodiment 1:26.8, embodiment 2:30.2, embodiment 3:29.7, Embodiment 4:27.9, embodiment 5:30.8, embodiment 6:31.9, reference example 1:25.6, comparative example 1:33.7.
< coloration >
Using the substrate of the pattern 2 of embodiment 1, using aluminium-vapour deposition plate as datum plate, spectrophotometer UV-3100 is utilized (Shimadzu Scisakusho Ltd's system) measures 5 degree of the specular reflectivity at 380~780nm of wavelength from film side, calculates Coloration (D65 light source) in XYZ colour system.
Sx=0.323, sy=0.329 of the substrate of embodiment 1.
It confirmed that the degassing of the coated substrates of the photosensitive composition using Examples 1 to 6 and reference example 1 is special Property is excellent.
In contrast, it is thus identified that use the degassing characteristic of the coated substrates of the photosensitive composition of comparative example 1 Difference.
Compared with the photosensitive composition of comparative example 1, the coloring phototonus tree of Examples 1 to 6 and reference example 1 The content ratio of epoxy (methyl) acrylate is high in the adhesive resin of oil/fat composition.Epoxy (methyl) acrylate tree Rouge is due to being not susceptible to thermally decompose with upright and outspoken skeleton, in addition, since skeleton is upright and outspoken, when solidification takes arrangement architecture, The high film of bridging property is formed, it can thus be assumed that, by improving containing for epoxy (methyl) acrylate in adhesive resin Ratio, degassing characteristic become good.
On the other hand, compared with having used the coated substrates of photosensitive composition of reference example 1, it is thus identified that make Coated substrates with the photosensitive composition of Examples 1 to 6 are excellent in terms of the development adaptation of thread pattern.I.e. Make be reference example 1 photosensitive composition, the spaced walls of the organic electroluminescent device as usual resolution ratio It can fully be applicable in, which imply the photosensitive compositions if it is Examples 1 to 6, then can be applicable to The spaced walls of high-resolution organic electroluminescent device.
, it can be said that dispersing agent contained by the photosensitive composition of reference example 1 is not due to being acrylic compounds dispersion Agent, therefore developer solution is easy to be impregnated in film when development, thread pattern is difficult to remain on substrate.
In contrast, the dispersing agent as contained by the photosensitive composition of Examples 1 to 6 is acrylic compounds point The most of of powder, the main framing of the molecular structure softness with straight-chain, therefore adsorption group are adsorbed in colorant, thus may be used Think, colorant is generally uniformly dispersed in photosensitive composition, in obtained coated film, as developer solution The colorant of insoluble component is equably configured, and is formed as fine and close film, and developer solution being impregnated with into film is suppressed when development, i.e., Make to be thread pattern, also can be formed on substrate.
In addition, in the photosensitive composition of Examples 1 to 6, by using comprising as adhesive resin The dispersible pigment dispersion 1~5 of epoxy (methyl) acrylate prepared, obtained coloring phototonus can be improved The content ratio of epoxy contained in resin combination (methyl) acrylate.

Claims (23)

1. a kind of photosensitive composition, contains: (A) colorant, (B) dispersing agent, (C) adhesive resin, (D) light Polymerizable monomer and (E) Photoepolymerizationinitiater initiater, wherein
(A) colorant includes (A1) organic black pigments, and (A1) organic black pigments contain selected from the following general formula (I) Compound represented, the geometric isomer of the compound, the salt of the compound and the compound geometric isomer At least one of salt,
(B) dispersing agent includes acrylic dispersants,
(C) adhesive resin includes (C1) epoxy (methyl) acrylate of 75 mass % or more,
In formula (I), Ra1And Ra6Each independently represent hydrogen atom, CH3、CF3, fluorine atom or chlorine atom；
Ra2、Ra3、Ra4、Ra5、Ra7、Ra8、Ra9And Ra10Each independently represent hydrogen atom, halogen atom, Ra11、COOH、COORa11、 COO-、CONH2、CONHRa11、CONRa11Ra12、CN、OH、ORa11、COCRa11、OOCNH2、OOCNHRa11、OOCNRa11Ra12、NO2、 NH2、NHRa11、NRa11Ra12、NHCORa12、NRa11CORa12, N=CH2, N=CHRa11, N=CRa11Ra12、SH、SRa11、SORa11、 SO2Ra11、SO3Ra11、SO3H、SO3 -、SO2NH2、SO2NHRa11Or SO2NRa11Ra12；
Also, it is selected from Ra2With Ra3、Ra3With Ra4、Ra4With Ra5、Ra7With Ra8、Ra8With Ra9And Ra9With Ra10At least one of combination Optionally mutually Direct Bonding or pass through oxygen atom, sulphur atom, NH or NRa11Bridging and be mutually bonded；
Ra11And Ra12Each independently represent the alkyl of carbon atom number 1~12, the naphthenic base of carbon atom number 3~12, carbon atom number 2 The alkynyl of~12 alkenyl, the cycloalkenyl of carbon atom number 3~12 or carbon atom number 2~12.
2. photosensitive composition according to claim 1, wherein described in (C) adhesive resin (C1) content ratio of epoxy (methyl) acrylate is 85 mass % or more.
3. photosensitive composition according to claim 1 or 2, wherein (C1) epoxy (methyl) propylene Acid ester resin includes to have epoxy (methyl) acrylate of repeat unit structure shown in the following general formula (II) and have One or both of epoxy (methyl) acrylate of part-structure shown in the following general formula (III),
In formula (II), R11Indicate hydrogen atom or methyl；
R12Indicate divalent alkyl optionally with substituent group；
Phenyl ring in formula (II) is optionally further replaced by arbitrary substituent group；
* bonding position is indicated,
In formula (III), R13Each independently represent hydrogen atom or methyl；
R14Indicate that there is divalent alkyl of the cyclic hydrocarbon group as side chain；
R15And R16Each independently represent divalent aliphatic group optionally with substituent group；
M and n each independently represents 0~2 integer；
* bonding position is indicated.
4. photosensitive composition described in any one of claim 1 to 3, wherein the acrylic compounds point Powder is the acrylic dispersants containing nitrogen-atoms.
5. photosensitive composition according to any one of claims 1 to 4, wherein relative to the coloring The all solids ingredient of photosensitive polymer combination, the content ratio of (A) colorant are 60 mass % or less.
6. photosensitive composition according to any one of claims 1 to 5, wherein (A) colorant into One step includes one or both of (A2) organic coloring pigments and (A3) carbon black.
7. photosensitive composition described according to claim 1~any one of 6, wherein in (A) colorant (A1) organic black pigments content ratio be 10 mass % or more.
8. photosensitive composition according to any one of claims 1 to 7 is used to form organic field and causes hair The spaced walls of optical element.
9. a kind of photosensitive composition is the colored photosensitive for being used to form the spaced walls of organic electroluminescent device Property resin combination, the photosensitive composition contain: (A) colorant, (B) dispersing agent, (C) adhesive resin, (D) Photopolymerization monomer and (E) Photoepolymerizationinitiater initiater, wherein
(A) colorant includes (A1) organic black pigments, and (A1) organic black pigments contain selected from the following general formula (I) Compound represented, the geometric isomer of the compound, the salt of the compound and the compound geometric isomer At least one of salt,
(C) adhesive resin includes (C1) epoxy (methyl) acrylate of 75 mass % or more,
In formula (I), Ra1And Ra6Each independently represent hydrogen atom, CH3、CF3, fluorine atom or chlorine atom；
Ra2、Ra3、Ra4、Ra5、Ra7、Ra8、Ra9And Ra10Each independently represent hydrogen atom, halogen atom, Ra11、COOH、COORa11、 COO-、CONH2、CONHRa11、CONRa11Ra12、CN、OH、ORa11、COCRa11、OOCNH2、OOCNHRa11、OOCNRa11Ra12、NO2、 NH2、NHRa11、NRa11Ra12、NHCORa12、NRa11CORa12, N=CH2, N=CHRa11, N=CRa11Ra12、SH、SRa11、SORa11、 SO2Ra11、SO3Ra11、SO3H、SO3 -、SO2NH2、SO2NHRa11Or SO2NRa11Ra12；
Also, it is selected from Ra2With Ra3、Ra3With Ra4、Ra4With Ra5、Ra7With Ra8、Ra8With Ra9And Ra9With Ra10At least one of combination Optionally mutually Direct Bonding or pass through oxygen atom, sulphur atom, NH or NRa11Bridging and be mutually bonded；
Ra11And Ra12Each independently represent the alkyl of carbon atom number 1~12, the naphthenic base of carbon atom number 3~12, carbon atom number 2 The alkynyl of~12 alkenyl, the cycloalkenyl of carbon atom number 3~12 or carbon atom number 2~12.
10. photosensitive composition according to claim 9, wherein described in (C) adhesive resin (C1) content ratio of epoxy (methyl) acrylate is 85 mass % or more.
11. photosensitive composition according to claim 9 or 10, wherein (C1) epoxy (methyl) third Alkene acid ester resin includes epoxy (methyl) acrylate and tool with repeat unit structure shown in the following general formula (II) There is one or both of epoxy (methyl) acrylate of part-structure shown in the following general formula (III),
In formula (II), R11Indicate hydrogen atom or methyl；
R12Indicate divalent alkyl optionally with substituent group；
Phenyl ring in formula (II) is optionally further replaced by arbitrary substituent group；
* bonding position is indicated,
In formula (III), R13Each independently represent hydrogen atom or methyl；
R14Indicate that there is divalent alkyl of the cyclic hydrocarbon group as side chain；
R15And R16Each independently represent divalent aliphatic group optionally with substituent group；
M and n each independently represents 0~2 integer；
* bonding position is indicated.
12. the photosensitive composition according to any one of claim 9~11, wherein relative to described The all solids ingredient of color sensation photosensitive resin composition, the content ratio of (A) colorant are 60 mass % or less.
13. the photosensitive composition according to any one of claim 9~12, wherein (A) colorant Further include one or both of (A2) organic coloring pigments and (A3) carbon black.
14. the photosensitive composition according to any one of claim 9~13, wherein (A) colorant In (A1) organic black pigments content ratio be 10 mass % or more.
15. a kind of spaced walls, the photosensitive composition described in any one of claim 1~14 is constituted.
16. a kind of organic electroluminescent device has spaced walls described in claim 15.
17. a kind of image display device, it includes the organic electroluminescent devices described in claim 16.
18. a kind of illumination, it includes the organic electroluminescent devices described in claim 16.
19. a kind of dispersible pigment dispersion, contains: (A) colorant, (B) dispersing agent and (C) adhesive resin, wherein
(A) colorant includes (A1) organic black pigments, and (A1) organic black pigments contain selected from the following general formula (I) Compound represented, the geometric isomer of the compound, the salt of the compound and the compound geometric isomer At least one of salt,
(B) dispersing agent includes acrylic dispersants,
(C) adhesive resin includes (C1) epoxy (methyl) acrylate,
In formula (I), Ra1And Ra6Each independently represent hydrogen atom, CH3、CF3, fluorine atom or chlorine atom；
Ra2、Ra3、Ra4、Ra5、Ra7、Ra8、Ra9And Ra10Each independently represent hydrogen atom, halogen atom, R11、COOH、COORa11、 COO-、CONH2、CONHRa11、CONRa11Ra12、CN、OH、ORa11、COCRa11、OOCNH2、OOCNHRa11、OOCNRa11Ra12、NO2、 NH2、NHRa11、NRa11Ra12、NHCORa12、NRa11CORa12, N=CH2, N=CHRa11, N=CRa11Ra12、SH、SRa11、SORa11、 SO2Ra11、SO3Ra11、SO3H、SO3 -、SO2NH2、SO2NHRa11Or SO2NRa11Ra12；
Also, it is selected from Ra2With Ra3、Ra3With Ra4、Ra4With Ra5、Ra7With Ra8、Ra8With Ra9And Ra9With Ra10At least one of combination Optionally mutually Direct Bonding or pass through oxygen atom, sulphur atom, NH or NRa11Bridging and be mutually bonded；
Ra11And Ra12Each independently represent the alkyl of carbon atom number 1~12, the naphthenic base of carbon atom number 3~12, carbon atom number 2 The alkynyl of~12 alkenyl, the cycloalkenyl of carbon atom number 3~12 or carbon atom number 2~12.
20. dispersible pigment dispersion according to claim 19, wherein relative to 100 mass parts of (A) colorant, (B) point The content ratio of powder is 10 mass parts or more.
21. dispersible pigment dispersion described in 9 or 20 according to claim 1, wherein (C1) epoxy (methyl) acrylate Comprising epoxy (methyl) acrylate with repeat unit structure shown in the following general formula (II) and there is the following general formula (III) one or both of epoxy (methyl) acrylate of part-structure shown in,
In formula (II), R11Indicate hydrogen atom or methyl；
R12Indicate divalent alkyl optionally with substituent group；
Phenyl ring in formula (II) is optionally further replaced by arbitrary substituent group；
* bonding position is indicated,
In formula (III), R13Each independently represent hydrogen atom or methyl；
R14Indicate that there is divalent alkyl of the cyclic hydrocarbon group as side chain；
R15And R16Each independently represent divalent aliphatic group optionally with substituent group；
M and n each independently represents 0~2 integer；
* bonding position is indicated.
22. dispersible pigment dispersion described in any one of 9~21 according to claim 1, wherein the acrylic dispersants are to contain There are the acrylic dispersants of nitrogen-atoms.
23. dispersible pigment dispersion described in any one of 9~22 according to claim 1 is used to manufacture coloring phototonus resin group Close object.
CN201780070424.7A 2016-12-02 2017-11-29 Photosensitive composition, dispersible pigment dispersion, spaced walls, organic electroluminescent device, image display device and illumination Pending CN109952535A (en)

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