CN106980230A - Photosensitive polymer combination, colour filter and display device using the photosensitive polymer combination - Google Patents

Photosensitive polymer combination, colour filter and display device using the photosensitive polymer combination Download PDF

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Publication number
CN106980230A
CN106980230A CN201610890509.7A CN201610890509A CN106980230A CN 106980230 A CN106980230 A CN 106980230A CN 201610890509 A CN201610890509 A CN 201610890509A CN 106980230 A CN106980230 A CN 106980230A
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photosensitive polymer
polymer combination
methyl
photoepolymerizationinitiater initiater
composition
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CN106980230B (en
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山口尚人
塩田大
田所惠典
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Tokyo Ohka Kogyo Co Ltd
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Tokyo Ohka Kogyo Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—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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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Architecture (AREA)
  • Engineering & Computer Science (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

Even the present invention provides a kind of with good sensitivity and when photosensitive polymer combination contains opacifier or light exposure deficiency, it can also suppress the photosensitive polymer combination and the colour filter and display device using the photosensitive polymer combination of the pattern generation undercut after development.The present invention uses a kind of photosensitive polymer combination, it contains (A) photopolymerizable compound and the oximes Photoepolymerizationinitiater initiater represented by (B) following formulas (1), and further contains (C) Photoepolymerizationinitiater initiater different from above-mentioned (B) composition.

Description

Photosensitive polymer combination, the colour filter using the photosensitive polymer combination and aobvious Showing device
The application is the applying date：2 months 2012 17 days, application number：201210036333.0, denomination of invention：Photonasty tree The divisional application of oil/fat composition, the colour filter using the photosensitive polymer combination and display device.
Technical field
The present invention relates to a kind of photosensitive polymer combination, the colour filter using the photosensitive polymer combination and display dress Put.
Background technology
The structure of the display devices such as liquid crystal display is that liquid crystal layer is clipped in two panels and is formed with mutually relative and paired electrode Substrate between.Also, it is formed with the inside of a plate base by the assorted pixel region such as red (R), green (G) and blue (B) The colour filter of composition.Black-face picture tube is conventionally formed with the colour filter, to divide each pixel regions such as red, green and blueness Domain.
Colour filter is typically manufactured by photoetching (lithography) method.That is, first by the photosensitive resin composition of black Thing is coated on substrate, makes it carry out exposed and developed forming black-face picture tube after drying.Then, to red, green and indigo plant The colors photosensitive polymer combination such as color, is repeated coating, drying, exposure and develops, to form colors in ad-hoc location Pixel region, thus manufactures colour filter.
Black-face picture tube is the pattern being made up of the photosensitive polymer combination containing opacifier, and by suppressing each colour Plain region light leak improves the contrast of display device and obtains good colour rendering.Also, as described above, make colour filter The black-face picture tube that initial period is formed has the effect that：It is used to insertion after formation colour assorted pixel region Photosensitive polymer combination recess, to form assorted pixel region in ad-hoc location.
In recent years, when manufacturing liquid crystal display, people have attempted to improve the light-proofness of black-face picture tube and enter one Step improves the picture contrast of display on a liquid crystal display.Therefore, it is necessary to the photonasty for forming black-face picture tube Substantial amounts of opacifier is added in resin combination.But, if substantial amounts of opacifier be added in photosensitive polymer combination, Then when the film to being coated on the photosensitive polymer combination formed on substrate is exposed, for making photosensitive polymer combination The light of solidification is difficult to reach the bottom of film, so as to can drastically decline with the sensitivity of hardening resin composition and cause solidification It is bad.
Generated by being exposed to the Photoepolymerizationinitiater initiater contained as photosensitive polymer combination fractions Free radical, the free radical polymerize the polymerizable compound contained by photosensitive polymer combination, so that photonasty tree Oil/fat composition solidifies.Therefore, it is known that the species of the Photoepolymerizationinitiater initiater contained by photosensitive polymer combination is to photoresist The sensitivity of composition has an impact.Also, in recent years with liquid crystal display production number of units increase, the production quantity of colour filter Also in increase, from the viewpoint of further raising productivity ratio, demand is a kind of can to form the Gao Ling of pattern under low light exposure Sensitivity photosensitive polymer combination.In the case, as the photopolymerization for the sensitivity that can improve photosensitive polymer combination Initiator, patent document 1 and 2 proposes the oxime ester compound with cycloalkyl.In embodiment described in patent document 1 and 2 Specifically disclose following chemical formula (a) and (b) (patent document 1) and following chemical formula (c) and (d) (patent document 2) institute table The compound shown.
[changing 1]
Patent document 1：People's Republic of China's publication publication the 101565472nd
Patent document 2：People's Republic of China's publication publication the 101508744th
The content of the invention
Can be by using the compound represented by above-mentioned chemical formula (a)~(d) as Photoepolymerizationinitiater initiater, to make Gao Ling Sensitivity photosensitive polymer combination.But, the present inventor etc. has found, if come using these compounds as Photoepolymerizationinitiater initiater Black-face picture tube is formed, though being then provided with good sensitivity, the pattern form of the black-face picture tube formed has following ask Topic.
Generally, in the situation for the pattern that the colour filter for liquid crystal display is formed using photosensitive polymer combination Under, such as shown in Fig. 1 (a), the section of the pattern in the direction of the width is that section 1 is generally trapezoidal, above-mentioned trapezoidal in from base 1a Wider, narrower from the nearlyer width of the top margin 1b shape of nearlyer width.Now, the section 1 of pattern and filter substrate (not shown) Between formed angle θ be acute angle.
But, if using the sense for containing the compound represented by above-mentioned chemical formula (a)~(d) as Photoepolymerizationinitiater initiater Photosensitive resin composition forms black-face picture tube, then as shown in Fig. 1 (b), sometimes with the section bottom of pattern during imaging Dissolve, and the section in the pattern in the direction of the width is the base 2a in section 2 two ends generation undercut 21.Now, scheme The angle θ formed between the section 2 of case and filter substrate (not shown) is obtuse angle.So, if angle θ is obtuse angle, in shape During pixel region assorted into red, green, blueness abutted with black-face picture tube etc., undercut 21 is local to produce bubble.That is, in shape In the case of the film for abutting and being used for the photosensitive polymer combination for forming pixel region with black-face picture tube, undercut 21 is deposited Space in be not mixed into photosensitive polymer combination, the space is remained as bubble.If existed in colour filter this The picture quality of bubble, then serious infringement liquid crystal display device, therefore as a problem.This problem significantly occurs excessive Develop (オ ー バ ー Now pictures) in the case of, i.e. some excess of developing when forming the pattern of black-face picture tube.
The present invention be in view of the foregoing formed by, even if its object is to provide it is a kind of with good sensitivity and It is that when photosensitive polymer combination contains opacifier or light exposure deficiency, can also suppress the pattern generation after development The photosensitive polymer combination of undercut, colour filter and display device using the photosensitive polymer combination.
Further investigation has been repeated in order to solve above-mentioned problem in the present inventor etc., as a result finds, by by following formulas (1) oxime ester compound represented by is applied in combination with other Photoepolymerizationinitiater initiaters, can keep being obtained using oxime ester compound Good sensitivity, and the undercut of pattern can be suppressed, so as to complete the present invention.
The present invention first embodiment be a kind of photosensitive polymer combination, its contain (A) photopolymerizable compound and (B) oximes Photoepolymerizationinitiater initiater represented by following formulas (1), and further gather containing (C) light different from above-mentioned (B) composition Close initiator.
[changing 2]
(in above-mentioned formula (1), l be 1~5 integer, m be that 0~(l+3) integer, n are 1~8 integer, R1It is to have The alkyl of the carbon number 1~11 of substituted base or aromatic radical, the R can with substituent2It is following formulas (2)~(4) institute table Any substituent, the R shown3It is the alkyl or aromatic radical of carbon number 1~11.)
[changing 3]
(in above-mentioned formula (2) and (3), R4It is aromatic radical, the R can with substituent5It is hydrogen atom or there can be substituent Carbon number 1~10 alkyl or aromatic radical.In above-mentioned formula (4), R6It is the aromatic radical can with substituent.)
Also, second embodiment of the present invention is a kind of using colour filter formed by above-mentioned photosensitive polymer combination Device.
Also, third embodiment of the present invention is a kind of display device for having used above-mentioned colour filter.
A kind of with good sensitivity and contain opacifier in photosensitive polymer combination in accordance with the invention it is possible to provide Or in the case that light exposure is not enough, can also suppress the photosensitive polymer combination of the pattern generation undercut after development, use this The colour filter and display device of photosensitive polymer combination.
Brief description of the drawings
Fig. 1 is the ideograph for representing the cross sectional shape of the pattern that is formed by photosensitive polymer combination in the direction of the width, (a) be the cross sectional shape for representing common pattern schematic diagram, (b) is the cross sectional shape for representing to generate the pattern of undercut 21 Schematic diagram.
Embodiment
《Photosensitive polymer combination》
The photosensitive polymer combination of the present invention at least contains (A) photopolymerizable compound, (B) oximes Photoepolymerizationinitiater initiater And (C) Photoepolymerizationinitiater initiater different from above-mentioned (B) composition.Hereinafter, to each contained by the photosensitive composite of the present invention Composition is described in detail.
＜ (A) photopolymerizable compounds ＞
As (A) photopolymerizable compound contained by the photosensitive polymer combination of the present invention (hereinafter also referred to " (A) Composition "), it is not particularly limited, known photopolymerizable compound can be used.Wherein, it is preferably unsaturated with ethene The resin or monomer of group, more preferably they are applied in combination.By by resin and tool with ethene unsaturated group The combination of monomers for having ethene unsaturated group is used, it is possible to increase the curability of photosensitive polymer combination and easily formation figure Case.
[resin with ethene unsaturated group]
As the resin with ethene unsaturated group, it can enumerate：(methyl) acrylic acid, fumaric acid, maleic acid, rich horse Sour mono-methyl, monomethyl ester, (methyl) acrylic acid 2- hydroxyl ethyl esters, glycol monoethyl ether (methyl) acrylate, ethylene glycol Single ether (methyl) acrylate, (methyl) glycerol acrylate, (methyl) acrylamide, acrylonitrile, methacrylonitrile, (first Base) methyl acrylate, (methyl) ethyl acrylate, (methyl) isobutyl acrylate, (methyl) 2-EHA, (first Base) benzyl acrylate, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, (the first of triethylene glycol two Base) acrylate, tetraethylene glycol two (methyl) acrylate, butanediol two (methyl) acrylate, propane diols two (methyl) third Olefin(e) acid ester, trimethylolpropane tris (methyl) acrylate, tetra methylol propane four (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol Six (methyl) acrylate, 1,6- ethylene glycol two (methyl) acrylate, cardo- epoxy diacrylates (cardo epoxy ) etc. diacrylate the oligomeric species being polymerized；Make polyester pre-polymerization obtained by polyalcohols and monoacid or polyacid condensation Thing and (methyl) propylene acid reaction, resulting polyester (methyl) acrylate；Make polyalcohol with 2 NCOs Compound reaction after, then with (methyl) propylene acid reaction, resulting polyurethane (methyl) acrylate；Bisphenol type epoxy tree Fat, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol or cresol novolac epoxy resin, solvable meltability phenolic aldehyde Epoxy resin, triphenol methylmethane type epoxy resin, polycarboxylic acids poly glycidyl ester, polyalcohol poly glycidyl ester, aliphatic or The epoxy resin such as cycloaliphatic epoxy resin, amine epoxy resin, dihydroxy benzene-type epoxy resin and (methyl) propylene acid reaction and obtain Epoxy (methyl) acrylate etc..Moreover, in epoxy (methyl) acrylate, it is suitably polynary using having carried out The resin of anhydride reaction.It should illustrate, in this manual, " meaning of " (methyl) acrylic acid " is " acrylic or methacrylic Acid ".
Also, as with ethene unsaturated group resin, can suitably using the resin obtained using following methods, That is, epoxide and reactant obtained from the carboxylic acid compound reaction containing unsaturated group are made, it is further anti-with multi-anhydride Resin obtained from answering.
Wherein, the compound preferably represented by following formula (a1).Because its own photo-curable is high, so that it is preferred that the formula (a1) compound represented by.
[changing 4]
In above-mentioned formula (a1), X represents the group represented by following formula (a2).
[changing 5]
In following formula (a2), R1aAlkyl or halogen atom that hydrogen atom, carbon number are 1~6 are separately represented, R2aSeparately represent hydrogen atom or methyl, W represents singly-bound or the group represented by following formula (a3).
[changing 6]
In addition, in above-mentioned formula (a1), Y represents to eliminate the residue of anhydride group (- CO-O-CO-) from dicarboxylic anhydride.Make For dicarboxylic anhydride, for example, it can enumerate maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic acid Acid anhydride, hexahydrophthalic anhydride, MNA (methyl Endomethylenetetrahydrophthalic anhydride), chlorendic anhydride, methyl tetrahydrophthalic anhydride, penta 2 Acid anhydrides etc..
In addition, in above-mentioned formula (a1), Z represents to eliminate the residue of 2 anhydride groups from tetracarboxylic dianhydride.It is used as tetracarboxylic acid Acid dianhydride, for example, can enumerate pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, diphenyl ether tetrabasic carboxylic acid two Acid anhydride etc..
In addition, in above-mentioned formula (a1), m represents 0~20 integer.
In terms of resin solid content, the acid value of the resin with ethene unsaturated group is preferably 10~150mgKOH/ G, more preferably 70~110mgKOH/g.By making acid value be more than 10mgKOH/g, it can obtain being substantially soluble in the dissolving of developer solution Property, thus preferably.Also, by making acid value be below 150mgKOH/g, it can obtain sufficient curability and superficiality can be improved, Thus preferably.
In addition, the matter average molecular weight of the resin with ethene unsaturated group is preferably 1000~40000, is more preferably 2000~30000.By making matter average molecular weight be more than 1000, good heat resistance and film-strength can be obtained, thus preferably. Also, by making matter average molecular weight be less than 40000, good developability is can obtain, thus preferably.
[monomer with ethene unsaturated group]
Monomer with ethene unsaturated group includes monofunctional monomer and polyfunctional monomer.
As monofunctional monomer, it can enumerate:(methyl) acrylamide, methylol (methyl) acrylamide, methoxy (methyl) acrylamide, ethoxyl methyl (methyl) acrylamide, propoxy methyl (methyl) acrylamide, butoxymethoxy Methyl (methyl) acrylamide, N- methylols (methyl) acrylamide, N- hydroxymethyls (methyl) acrylamide, (methyl) propylene Acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2- acrylamides- 2- methyl propane sulfonic acids, tert-butyl acrylamide sulfonate (tert-butyl acrylamide sulfonic acid), (methyl) Methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) third Olefin(e) acid cyclohexyl ester, (methyl) acrylic acid 2- hydroxyl ethyl esters, (methyl) acrylic acid 2- hydroxypropyl acrylates, (methyl) acrylic acid 2- hydroxy butyl esters, (first Base) acrylic acid 2- phenoxy group -2- hydroxypropyl acrylates, 2- (methyl) acryloyl-oxy -2- hydroxypropylphthalates (2- (meth) Acryloyloxy-2-hydroxypropylphthalate), glycerine list (methyl) acrylate (glycerin mono (meth) acrylate), (methyl) tetrahydrofurfuryl acrylate, dimethylamino (methyl) acrylate, (methyl) acrylic acid shrink Glyceride, 2,2,2- trifluoroethyls (methyl) acrylate, the fluoropropyls of 2,2,3,3- tetra- (methyl) acrylate, phthalic acid Half (methyl) acrylate of derivative etc..Can be used alone these monofunctional monomers, can also two or more be applied in combination.
On the other hand, as polyfunctional monomer, it can enumerate：Ethylene glycol two (methyl) acrylate, (first of diethylene glycol two Base) acrylate, tetraethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, polypropylene glycol two (methyl) Acrylate, butanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-HD two (methyl) third Olefin(e) acid ester, trimethylolpropane tris (methyl) acrylate, glycerine two (methyl) acrylate, pentaerythritol triacrylate, Tetramethylol methane tetraacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate, pentaerythrite two (methyl) Acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) Double (4- (methyl) the acryloxy diethoxy phenyl) third of acrylate, dipentaerythritol six (methyl) acrylate, 2,2- Alkane, 2,2- double (4- (methyl) acryloxypolyethoxyphenyl) propane, 2- hydroxyls -3- (methyl) acryloxypropyls (methyl) acrylate, ethylene glycol diglycidylether two (methyl) acrylate, (first of diethylene glycol diglycidyl glycerin ether two Base) acrylate, o-phthalic acid diglycidyl ester two (methyl) acrylate, glycerol tri-acrylate, glycerine bunching water Poly- (methyl) acrylate of glycerin ether, carbamate (methyl) acrylate (urethane (meth) acrylate) are (that is, sub- Benzyl group diisocyanates), trimethyl hexamethylene diisocyanate and hexamethylene diisocyanate and (methyl) acrylic acid 2- Reactant, di-2-ethylhexylphosphine oxide (methyl) acrylamide, (methyl) acrylamide methylene ether, polyalcohol and the N- hydroxyls of hydroxyl ethyl ester three The polyfunctional monomers such as the condensation product of methyl (methyl) acrylamide, and triacryl formal (triacryl formal) Deng.Can be used alone these polyfunctional monomers, can also two or more be applied in combination.
Relative to the mass parts of solid constituent total amount 100 of photosensitive polymer combination, (A) composition is photopolymerizable compound Content be preferably 10~99.9 mass parts.It is by making the content of (A) composition relative to the mass parts of total amount 100 of solid constituent More than 10 mass parts, the pattern to be formed can be made to obtain sufficient heat resistance and chemical resistance.
＜ (B) oximes Photoepolymerizationinitiater initiater ＞
The present invention photosensitive polymer combination contained by (B) oximes Photoepolymerizationinitiater initiater (hereinafter also referred to " and (B) into Point ") it is compound represented by following formulas (1).As described above, especially, even in the sense for forming black-face picture tube In the case of containing opacifier in this based composition of photosensitive resin composition, oximes Photoepolymerizationinitiater initiater can also assign good spirit Sensitivity, still, on the other hand, undercut may be generated in the pattern formed sometimes.Gather as the light of photosensitive polymer combination Close initiator, the present inventor etc. has found, especially, by by the oximes Photoepolymerizationinitiater initiater of following formulas (1) and following (C) into Subassembly is used, and can assign photosensitive polymer combination good sensitivity, and suppresses to generate undercut in the pattern to be formed, so that Complete the present invention.
[changing 7]
In above-mentioned formula (1), l is 1~5 integer, and m is 0~(l+3) integer, and n is 1~8 integer, R1It is to have The alkyl of the carbon number 1~11 of substituted base or the aromatic radical can with substituent, R2It is following formulas (2)~(4) institute table Any substituent shown, R3It is the alkyl or aromatic radical of carbon number 1~11.In R1In the case of for alkyl, as can have Some substituents, preferably enumerate phenyl, naphthyl etc..Also, in R1In the case of for aromatic radical, as the substituent that can have, It is preferred that enumerating the alkyl of carbon number 1~5, alkoxy, halogen atom etc..
In above-mentioned formula (1), R is used as1, preferably enumerate methyl, ethyl, propyl group, isopropyl, butyl, phenyl, benzyl, first Base phenyl, naphthyl etc., wherein, more preferably methyl or phenyl.Also, in above-mentioned formula (1), it is used as R3, preferably enumerate methyl, second Base, propyl group, isopropyl, butyl, phenyl etc., wherein, more preferably methyl.
[changing 8]
In above-mentioned formula (2) and (3), R4For that can have the aromatic radical of substituent, R5For hydrogen atom or there can be substituent Carbon number 1~10 alkyl or aromatic radical.It is used as R4The substituent that i.e. aromatic radical can have, preferably enumerates carbon atom Alkyl, the alkoxy of carbon number 1~5, halogen atom of number 1~5 etc..Also, in R5In the case of for alkyl, as can have Substituent, preferably enumerate alkoxy, phenyl, naphthyl of carbon number 1~5 etc..
In above-mentioned formula (2) and (3), R is used as4It is preferred that enumerating phenyl, 2- aminomethyl phenyls, 3- aminomethyl phenyls, 4- methylbenzenes Base, 2- ethylphenyls, 3- ethylphenyls, 4- ethylphenyls, 2,3- 3,5-dimethylphenyls, 2,4- 3,5-dimethylphenyls, 2,5- dimethyl Phenyl, 2,6- 3,5-dimethylphenyls, naphthyl, 2- methoxy-1-naphthyls, 9- anthryls etc..In above-mentioned formula (2) and (3), R is used as5It is excellent Choosing enumerate hydrogen atom, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, just oneself Base, phenyl, 3- methyl butyls, 3- methoxybutyls etc., wherein, more preferably ethyl.
In above-mentioned formula (4), R6For that can have the aromatic radical of substituent.In R6The substituent that i.e. aromatic radical can have, preferably Enumerate alkyl, the alkoxy of carbon number 1~5, halogen atom of carbon number 1~5 etc..
It is used as this R6, preferably enumerate phenyl, 2- aminomethyl phenyls, 3- aminomethyl phenyls, 4- aminomethyl phenyls, 2- ethylphenyls, 3- ethylphenyls, 4- ethylphenyls, 2,3- 3,5-dimethylphenyls, 2,4- 3,5-dimethylphenyls, 2,5- 3,5-dimethylphenyls, 2,6- dimethyl Phenyl, naphthyl, to tert-butyl-phenyl, p-methoxyphenyl etc., wherein, more preferably enumerate phenyl.
As (B) oximes Photoepolymerizationinitiater initiater, the compound of following formula can be more specifically enumerated.
[changing 9]
[changing 10]
Relative to the mass parts of total amount 100 of the solid constituent of photosensitive polymer combination, (B) composition is that oximes photopolymerization is drawn The content of hair agent is preferably 0.1~50 mass parts, more preferably 1~45 mass parts.By making it within the above range, it can obtain To sufficient heat resistance and chemical resistance, while improving film forming ability, suppress photocuring bad.
(C) Photoepolymerizationinitiater initiater ＞ different from above-mentioned (B) composition ＜
The present invention photosensitive polymer combination contained by (C) Photoepolymerizationinitiater initiater (hereinafter referred to as " (C) composition ") be A kind of Photoepolymerizationinitiater initiater different from being used as the Photoepolymerizationinitiater initiater of above-mentioned (B) composition.(C) as long as composition with it is above-mentioned (B) the different compound of composition, also can be a kind of oximes Photoepolymerizationinitiater initiater as above-mentioned (B) composition.
(C) as long as composition produces the compound of free radical by irradiation ultraviolet radiation or electron ray isoreactivity energy line , it is not particularly limited.As this Photoepolymerizationinitiater initiater, it can enumerate：2- benzyl -2- dimethylaminos -1- (4- morpholino benzene Base) butanone -1,2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholino propane -1- ketone, 2- benzyl -2- dimethylamino -1- (4- Dimethylamino phenyl) butanone -1,2- (4- methyl-benzyls) -2- lignocaines -1- (4- morphlinophenyls) butanone -1,2- methyl - 1- phenyl -2- morpholino propane -1- ketone, 2- methyl isophthalic acids-[4- (hexyl) phenyl] -2- morpholino propane -1- ketone, 2- ethyls -2- Dimethylamino -1- (4- morphlinophenyls) butanone -1 grade alpha-amido ketone Photoepolymerizationinitiater initiater；1- phenyl -2- hydroxy-2-methyls Propane -1- ketone, 1- (4- isopropyl phenyls) -2- hydroxy-2-methyl propane -1- ketone, 4- (2- hydroxyl-oxethyls) phenyl-(2- hydroxyls Base -2- propyl group) the Alpha-hydroxy ketone Photoepolymerizationinitiater initiater such as ketone, 1- hydroxycyclohexylphenylketones；Benzoin, benzoin methyl ether, peace The styrax class photopolymerization such as the fragrant ether of breath, styrax propyl ether, dibenzoyl dimethyl acetal (benzil methyl ketal) trigger Agent；Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4- phenyl benzophenones, dihydroxy benaophenonel, acrylic acid Change benzophenone (acrylated benzophenone), 4- benzoyls, 4 '-methyldiphenyl sulphur, 4,4 '-bis- lignocaine hexichol The benzophenone Photoepolymerizationinitiater initiater such as ketone；Thioxanthones, CTX, 2- methyl thioxanthones, isopropyl thioxanthone, 2,4- The thioxanthene ketone class Photoepolymerizationinitiater initiater such as diisopropylthioxanthone；2,4,6 3 chloro- s-triazine, 2- phenyl -4,6 pairs (trichloromethyl) - S-triazine, -4,6 pairs of (trichloromethyl)-s-triazine of 2- (p-methoxyphenyl), 2- (p-methylphenyl) -4,6 couples (trichloromethyl) - Double (the trichloromethyl) -6- styrene of s-triazine, -4,6 pairs of (trichloromethyl)-s-triazine of 2- ピ ペ ニ Le (pipenyl), 2,4- Base-s-triazine, -4,6 pairs of (trichloromethyl)-s-triazine of 2- (naphtho- -1- bases), 2- (4- methoxyl groups-naphtho- -1- bases) -4,6 couples (trichloromethyl)-s-triazine, 2,4- trichloromethyls-(piperonyl) -6- triazines, 2,4- trichloromethyls-(4 '-methoxy styrene Base) the triazines light such as -6- triazines, -4,6 pairs of (trichloromethyl) -1,3,5- triazines of 2- [4- (4- methoxyl-styrenes) phenyl] Polymerization initiator；Carbazoles Photoepolymerizationinitiater initiater；2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (4- carbethoxy phenyls) - 1,2 '-bis- imidazoles, 2,2 '-bis- (2- bromophenyls) -4,4 ', 5,5 '-four (4- carbethoxy phenyls) -1,2 '-bis- imidazoles, 2,2'- Double (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bis- imidazoles, 2,2 '-bis- (2- dichlorophenyls) -4,4 ', 5,5 '-four benzene Base -1,2 '-bis- imidazoles, 2,2 '-bis- (2,4,6 trichlorophenyls) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bis- imidazoles, 2,2 '-bis- (2- Bromophenyl) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bis- imidazoles, 2,2 '-bis- (2,4- dibromo phenyls) -4,4 ', 5,5 '-tetraphenyl - 1,2 '-bis- imidazoles, 2,2 '-bis- (2,4,6 tribromo phenyl) -4,4 ', 5,5 '-tetraphenyl -1,2 ' double imidazoles systems light such as-bis- imidazoles gathers Close initiator；2- (O- benzoyls oxime) -1- [4- (thiophenyl) phenyl] -1,2- octanediones, 1- (4- methylsulfanyls phenyl) Butane -1,2- butane -2- oxime-O- acetates (1- (4-methyl sulfanyl phenyl) butan-1,2-butan-2- Oxime-O-acetate), 1- (4- methylsulfanyls phenyl) butane -1- ketoxime-O- acetates, oximido (4- methylsulfanyl benzene Base) the oximes photopolymerization such as ethyl acetate-O- acetates, oximido (4- methylsulfanyls phenyl) ethyl acetate-O- benzoic ethers draws Send out agent；Benzimidazoline class Photoepolymerizationinitiater initiater as represented by following formula etc..
[changing 11]
In the above-mentioned Photoepolymerizationinitiater initiater enumerated, preferably using alpha-amido ketone Photoepolymerizationinitiater initiater, benzophenone Photoepolymerizationinitiater initiater, triazines Photoepolymerizationinitiater initiater, carbazoles Photoepolymerizationinitiater initiater.Also, can be used alone above-mentioned photopolymerization Initiator, but also two or more is applied in combination.
Relative to the mass parts of total amount 100 of the solid constituent of photosensitive polymer combination, the content of (C) composition is preferably 0.1~50 mass parts, more preferably 1~45 mass parts.Also, the ratio of by quality ratio, above-mentioned (B) composition and (C) composition The preferably scope of (B) composition/(C) composition=10/1~1/10, more preferably (B) composition/(C) composition=10/1~1/10 Scope.It is above range by making the ratio of (B) composition and (C) composition, the good of photosensitive polymer combination can be kept Sensitivity, and can suppress to generate undercut in the pattern that is formed by photosensitive polymer combination.
＜ (D) colouring agents ＞
The photosensitive polymer combination of the present invention can further contain (D) colouring agent (hereinafter also referred to (D) composition).It is photosensitive Property resin combination by being colouring agent containing (D) composition, preferably be used for for example formed liquid crystal display colour filter.And And, photosensitive polymer combination of the invention is used as (D) composition by containing opacifier, is preferably used for for example forming display dress Black-face picture tube in the colour filter put.
(D) composition contained in photosensitive polymer combination as the present invention, is not particularly limited, preferably uses for example Color index (color index) (C.I.；The Society of Dyers and Colourists societies issue) in be classified Into pigment (Pigment) compound, the colouring agent with following color indexs (C.I.) sequence number can be specifically used.
C.I. pigment yellow 1 (below due to " C.I. pigment yellows " be identical so only recording sequence number), 3,11,12,13, 14、15、16、17、20、24、31、53、55、60、61、65、71、73、74、81、83、86、93、95、97、98、99、100、101、 104、106、108、109、110、113、114、116、117、119、120、125、126、127、128、129、137、138、139、 147、148、150、151、152、153、154、155、156、166、167、168、175、180、185；
C.I. pigment orange 1 (below due to " C.I. pigment oranges " be identical so only recording sequence number), 5,13,14,16, 17、24、34、36、38、40、43、46、49、51、55、59、61、63、64、71、73；
C.I. pigment violet 1 (below due to " C.I. pigment violets " be identical so only recording sequence number), 19,23,29,30, 32、36、37、38、39、40、50；
C.I. paratonere 1 (below due to " C.I. paratoneres " be identical so only recording sequence number), 2,3,4,5,6,7, 8、9、10、11、12、14、15、16、17、18、19、21、22、23、30、31、32、37、38、40、41、42、48：1、48：2、48： 3、48：4、49：1、49：2、50：1、52：1、53：1、57、57：1、57：2、58：2、58：4、60：1、63：1、63：2、64：1、 81：1、83、88、90：1、97、101、102、104、105、106、108、112、113、114、122、123、144、146、149、 150、151、155、166、168、170、171、172、174、175、176、177、178、179、180、185、187、188、190、 192、193、194、202、206、207、208、209、215、216、217、220、223、224、226、227、228、240、242、 243、245、254、255、264、265；
C.I. pigment blue 1 (below due to " C.I. alizarol saphirols " be same so only recording sequence number), 2,15,15：3、15： 4、15：6、16、22、60、64、66；
C.I. pigment Green 7, C.I. pigment green 36s, C.I. naphthol greens 37；
C.I. pigment brown 23, C.I. pigment brown 25s, C.I. pigment browns 26, C.I. pigment browns 28；
C.I. pigment black 1, C.I. pigment blacks 7.
Also, in the case of by (D) composition as opacifier, black pigment is preferably used as opacifier.As black Color pigment, can be enumerated：The metal oxidation of carbon black, titanium black (titan black), copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver etc. Thing, composite oxides, metal sulfide, metal sulfate or metal carbonate etc., organic matter or inorganic matter can various face Material.In these black pigments, the carbon black with high light-proofness is preferably used.By the way that above-mentioned (B) composition and (C) composition is applied in combination As Photoepolymerizationinitiater initiater, even if using the high black pigment of light-proofness, can also suppress to generate in pattern after development and sting Side.
As carbon black, carbon black known to channel black, furnace black, thermal black, lamp black carbon black etc. can be used, but it is excellent Choosing uses the excellent channel black of light-proofness.And, it is possible to use resin coats carbon black.
The carbon black not coated by resin is less electrically conductive than due to resin coating carbon black, therefore, charcoal is being coated using resin It is less to leak electricity in the case of the black black-face picture tube as liquid crystal display cells such as liquid crystal displays, it can manufacture reliable Property the high and low display of power dissipation.
Also, in order to adjust the tone of carbon black, above-mentioned organic pigment can be suitably added as auxiliary pigment.
In order that above-mentioned (D) composition is dispersed in photosensitive polymer combination, dispersant can be further used.As This dispersant, preferably uses polyethyleneimine amine, polyurethane type resin, crylic acid resin macromolecule dispersing agent.Especially, In the case where using carbon black as (D) composition, crylic acid resin dispersant is preferably used as dispersant.
Also, can individually using or two or more inorganic pigment and organic pigment is applied in combination, but be applied in combination In the case of, relative to the mass parts of total amount 100 of inorganic pigment and organic pigment, the organic pigment used is preferably 10~80 matter Measure the scope, the scope of more preferably 20~40 mass parts of part.
According to the purposes of photosensitive polymer combination, suitably decision is the usage amount of colouring agent in photosensitive polymer combination Can, for example, the mass parts of total amount 100 of the solid constituent relative to photosensitive polymer combination, preferably 5~70 mass parts, more Preferably 25~60 mass parts.By being above range, black-face picture tube or each dyed layer can be formed in target pattern, Thus preferably.
Especially, in the case where using photosensitive polymer combination formation black-face picture tube, photonasty tree is preferably adjusted The amount of opacifier in oil/fat composition, so that the OD values of every 1 μm of coating are more than 4 in black-face picture tube.If in black-face picture tube The OD values of every 1 μm of coating are more than 4, then in the case where being used as the black-face picture tube of liquid crystal display, can be filled That divides displays contrast.
Preferably, after making (D) composition scattered under appropriate concentration using dispersant, be re-used as dispersion liquid be added to it is photosensitive In property resin combination.
The other composition ＞ of ＜
Photosensitive polymer combination of the present invention can be added as needed on various additives.Can specifically enumerate solvent, sensitizer, Curing accelerator, photocrosslinking agent, light sensitizer, disperse additive, filler, adhesion promoter, antioxidant, ultraviolet are inhaled Receive agent, anti flocculant, thermal polymerization inhibitor, defoamer, surfactant etc..
Solvent used in the photosensitive polymer combination of the present invention, for example, can enumerate：Glycol monoethyl ether, ethylene glycol list Ether, ethylene glycol positive propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list positive third Ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, Propane diols list positive propyl ether, propane diols mono-n-butyl ether, dipropylene glycol monomethyl ether, DPE, DPG list positive propyl ether, (poly-) the alkylene glycol monoalkyl ethers classes such as DPG mono-n-butyl ether, Tripropylene glycol monomethyl Ether, tripropylene glycol list ether；Second two Alcohol methyl ether acetate, ethylene glycol monoethylether acetate, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, Propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate etc. (poly-) alkylene glycol monoalkyl ethers acetate esters；Diethyl two Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran；Butanone, cyclohexanone, 2- The ketones such as heptanone, 3- heptanone；The lactic acid alkyl ester classes such as 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester；2- hydroxy-2-methyls third Acetoacetic ester, 3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxypropanoates, 3- ethoxyl ethyl propionates, second Ethoxyacetic acid ethyl ester, hydroxyl ethyl acetate, 2- hydroxy-3-methyls methyl butyrate, 3- methyl -3- methoxybutyl acetic acid esters (3- Methyl-3-methoxy butyl acetate), 3- methyl -3- methoxybutyl propionic esters (3-methyl-3-methoxy Butyl propionate), ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, formic acid just Pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, butyric acid N-butyl, pyruvic acid first Other esters such as ester, ethyl pyruvate, pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, 2- ethyl acetoacetates Class；The arenes such as toluene, dimethylbenzene；The acyls such as 1-METHYLPYRROLIDONE, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide Amine etc..Can be used alone these solvents, can also two or more be applied in combination.
In above-mentioned solvent, due to showing the excellent dissolubility to above-mentioned (A) composition, (B) composition and (C) composition, And it can improve the dispersiveness of above-mentioned (D) composition, thus preferably propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, the third two Alcohol methyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, second Sour 3- methoxybutyls, particularly preferably using propylene glycol methyl ether acetate, acetic acid 3- methoxybutyls.Solvent is according to photonasty The purposes of resin combination is suitably selected, for example, can enumerate：Relative to photosensitive polymer combination solid constituent it is total 100 mass parts are measured, the content of solvent is 50~900 mass parts or so.
As thermal polymerization inhibitor used in the photosensitive polymer combination of the present invention, for example, it can enumerate quinhydrones, quinhydrones Single ether etc..Also, as defoamer, the compounds such as polysiloxane-based, fluorine class can be enumerated respectively, can as surfactant The compounds such as anionic species, cationic, nonionic are enumerated respectively.
《The compound method of photosensitive polymer combination》
The photosensitive polymer combination of the present invention can be obtained by mixing by the way that all above-mentioned each compositions are put into mixer.And And, it is also possible to filter is filtered so that the photosensitive polymer combination prepared is uniform.
《Pattern formation method》
If forming pattern using the photosensitive polymer combination of the present invention, first by coating roller, reverse coating machine, Bar coating machine etc. contacts the noncontact such as transfer printing type apparatus for coating or circulator (rotary apparatus for coating), curtain flowing coating machine Photosensitive polymer combination is coated on substrate by type apparatus for coating.
Then, the photosensitive polymer combination being applied is dried, forms film.Drying means is not limited especially It is fixed, it can for example use following any method：(1) it is made on hot plate at a temperature of 80~120 DEG C, preferably 90~100 DEG C The method for drying 60~120 seconds；(2) method for placing a few hours~a couple of days at room temperature；(3) put it into warm air heater or The method of dozens of minutes~a few hours to remove solvent etc. in infrared heater.
Then, irradiating the film via negative mask ultraviolet or PRK isoreactivity energy line exposes its part Light.The energy line amount of irradiation can be different according to the composition of photosensitive polymer combination, but are preferably, for example, 30~2000mJ/ cm2Left and right.
Then, the film after exposure is developed by using developer solution, to form the pattern of intended shape.Developing method It is not particularly limited, such as usable infusion process, spray-on process.Can for example be enumerated as developer solution MEA, diethanol amine, The organic species such as triethanolamine, or sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salt etc. the aqueous solution.As described above Illustrate, by using the photosensitive polymer combination of the present invention, the undercut in the pattern that is formed after development can be suppressed.Therefore, If, such as, can in the case where making the colour filter for display device using the photosensitive polymer combination of the present invention Suppress bubble to enter near the interface of each pixel, thus preferably.
Then, bakeed after preferably being carried out at 200 DEG C~250 DEG C to the pattern after development.
The pattern so formed can suitably be used as the pixel of the colour filter in the display device such as liquid crystal display Or black-face picture tube.This colour filter and the use of the display device of the colour filter is also one of present invention.
[embodiment]
Hereinafter, the present invention is described in more detail with embodiment, but the scope of the present invention is not by these realities Apply example restriction.
[preparation of photosensitive polymer combination]
[embodiment 1~20 and comparative example 1~15]
Using following formula B1~B12 compound as oximes Photoepolymerizationinitiater initiater, following formula C1~C9 chemical combination is used Thing is as other Photoepolymerizationinitiater initiaters, to prepare the photosensitive polymer combination of embodiment 1~20 and comparative example 1~15.Under In the oximes Photoepolymerizationinitiater initiater for stating formula B1~B12, the oximes photopolymerization that formula B1~B8 compound meets above-mentioned formula (1) is drawn Send out agent.Photoepolymerizationinitiater initiater in the photosensitive polymer combination of each embodiment and comparative example is as shown in table 1~3.It should illustrate, In table 1~3, the ratio shown in the ratio between " oxime/other " item is represented, is triggered in the photopolymerization contained by photosensitive polymer combination In agent, the mass ratio of oximes Photoepolymerizationinitiater initiater and other Photoepolymerizationinitiater initiaters.
Each photosensitive polymer combination is prepared by the following method：By acetic acid 3- methoxybutyls/cyclohexanone/propane diols list Methyl ether acetate (PGMEA)=60/20/20 (weight ratio) is added to Photoepolymerizationinitiater initiater (oximes and other Photoepolymerizationinitiater initiaters Total amount) 100 mass parts, following Resin As (the mass % of solid constituent 55, solvent：Acetic acid 3- methoxybutyls) 310 mass parts, (content of carbon black is for dipentaerythritol acrylate (DPHA, Nippon Kayaku K. K's system) 175 mass parts and carbon black dispersion liquid 20 mass %, " CF Block ラ ッ Network ", Mikoku Pigment Co., Ltd.'s system) 450 mass parts mixture in be stirred until homogeneous so that solid Body constituent concentration is 15 mass %.
Prepare the of the Resin A that is used during above-mentioned photosensitive polymer combination and Japanese Unexamined Patent Publication 2010-32940 publications Resin A -1 described in 0063~0064 section is identical.
[changing 12]
[changing 13]
[changing 14]
[changing 15]
[table 1]
[table 2]
[table 3]
[evaluation to sensitivity]
According to the sensitivity of following steps respectively to embodiment 1~20 and the photosensitive polymer combination of comparative example 1~15 Evaluated.First, by by photosensitive polymer combination rotary coating on glass substrate (10cm × 10cm), at 90 DEG C Heating 120 seconds, so as to form 1.0 μm of coated film on the surface of glass substrate.Afterwards, it is directed at exposer using mirror surface projection (mirror projection aligner) (ProductName：TME-150RTO, Co., Ltd. ト プ Us Application system), it is wired via being formed Width is the negative-appearing image mask of 10 μm of straight-line pattern, with 50 μm of Gap, in 3 kinds of 30mJ/cm2、60mJ/cm2、120mJ/cm2Exposure Under light quantity, coated film is exposed.Film after exposure is placed in 26 DEG C of the 0.04 mass %KOH aqueous solution and developed 50 seconds Afterwards, the calcination processing of 30 minutes is carried out at 230 DEG C, is obtained respectively in 3 kinds of 30mJ/cm using SEM2、 60mJ/cm2、120mJ/cm2The wire spoke of the straight-line pattern formed under light exposure.Result obtained by use, according to each wire spoke and exposure Amount carries out approximate calculation with least square method, so as to calculate the light exposure for obtaining 10 μm of wire spokes.The result as sensitivity such as Shown in table 1~3.It should illustrate, the smaller sensitivity for representing its photosensitive polymer combination of numerical value of sensitivity is higher.Also, In table 1~3, in order to easily compare each embodiment and comparative example, repetition describes a part of embodiment and the content of comparative example.
[evaluation to pattern form]
Each photosensitive polymer combination of embodiment 1~20 and comparative example 1~15 is exposed according to following steps, connect And the pattern after development is evaluated with the presence or absence of undercut, i.e. pattern form.First, by the way that photosensitive polymer combination is revolved Turn to be coated on glass substrate (10cm × 10cm), heated 120 seconds at 90 DEG C, so as to form 1.0 μ on the surface of glass substrate M coated film.Afterwards, it is directed at exposer (ProductName using mirror surface projection：TME-150RTO, Co., Ltd. ト プ Us Application system) warp By being formed with the negative-appearing image mask for the straight-line pattern that wire spoke is 10 μm, in light exposure 100mJ/cm2It is exposed under (Gap50 μm). Film after exposure is placed on after developing 50 seconds in 26 DEG C of the 0.04 mass %KOH aqueous solution, carried out at 230 DEG C 30 minutes Calcination processing, the engagement angles (coning angle, taper angle) between pattern and substrate are determined with SEM.Should Coning angle is corresponding with the angle θ in Fig. 1 (a) and (b).Measured coning angle is as shown in table 1~3.If coning angle is acute angle, Then represent that undercut is not present in pattern, if coning angle is obtuse angle, then it represents that there is undercut in pattern.
There is the photoresist group of the embodiment 1~20 of (B) composition and (C) composition in table 1~3, the present invention Compound has the sensitivity of practicality.
Also, by the photonasty tree of the photosensitive polymer combination of embodiment 10,11,13,15,16 and comparative example 7~11 Oil/fat composition is compared, then understands to be used as Photoepolymerizationinitiater initiater by the way that above-mentioned (B) composition and (C) composition is applied in combination, formed Pattern coning angle be acute angle, can effectively suppress the undercut of pattern.
Symbol description
1 is not present the section of the pattern of undercut in the direction of the width
2 have the section of the pattern of undercut in the direction of the width

Claims (5)

1. a kind of photosensitive polymer combination, it contains (A) photopolymerizable compound and (B) represented by following formulas (a1) Selected from by the compound group represented by following formula (B1)~(B8) into group in oximes Photoepolymerizationinitiater initiater, and further contain Have (C) be selected from by the compound group represented by following formula (C1)~(C9) into group in Photoepolymerizationinitiater initiater；With mass ratio Meter, (B) composition is (B)/(C)=50/50~90/10 with (C) composition；
[changing 1]
In above-mentioned formula (a1), X is the group represented by following formula (a2), and Y is that anhydride group (- CO-O- is eliminated from dicarboxylic anhydride CO- residue), Z is the residue that 2 anhydride groups are eliminated from tetracarboxylic dianhydride, and m is 0~20 integer；
[changing 2]
In above-mentioned formula (a2), R1aSeparately represent alkyl or halogen atom that hydrogen atom, carbon number are 1~6, R2aPoint Do not represent hydrogen atom or methyl independently, W is following formula (a3)；
[changing 3]
[changing 4]
[changing 5]
2. photosensitive polymer combination as claimed in claim 1, it further contains colouring agent (D).
3. a kind of photosensitive polymer combination, it is used to form black-face picture tube, and containing under (A) photopolymerizable compound, (B) The oximes Photoepolymerizationinitiater initiater represented by formula (1), (C) be selected from different from above-mentioned (B) composition is stated by alpha-amido ketone light to be gathered Close initiator, Alpha-hydroxy ketone Photoepolymerizationinitiater initiater, styrax class Photoepolymerizationinitiater initiater, triazines Photoepolymerizationinitiater initiater, carbazole Class Photoepolymerizationinitiater initiater, double imidazoles systems Photoepolymerizationinitiater initiater, oximes Photoepolymerizationinitiater initiater and benzimidazoline class photopolymerization are drawn The Photoepolymerizationinitiater initiater and (D) opacifier of group that hair agent is constituted, the photosensitive polymer combination contain (D) into Point, so that the OD values of every 1 μm of coating are more than 4 in black-face picture tube；
[changing 6]
In above-mentioned formula (1), l is 1~5 integer, and m is 0~(l+3) integer, and n is 1~8 integer, R1It is can have substitution The alkyl of the carbon number 1~11 of base or the aromatic radical can with substituent, R2It is appointing represented by following formulas (2)~(4) A kind of substituent, R3It is the alkyl or aromatic radical of carbon number 1~11；
[changing 7]
In above-mentioned formula (2) and (3), R4It is the aromatic radical can with substituent, R5It is hydrogen atom, there can be the carbon of substituent former The alkyl or aromatic radical of subnumber 1~10；In above-mentioned formula (4), R6It is the aromatic radical can with substituent.
4. colour filter formed by the photosensitive polymer combination described in a kind of usage right requirement 2 or 3.
5. a kind of display device of the colour filter used described in claim 4.
CN201610890509.7A 2011-02-22 2012-02-17 Photosensitive resin composition, color filter using the same, and display device Active CN106980230B (en)

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