CN110121679A - Blue-sensitive resin combination, the colour filter and image display device manufactured using the composition - Google Patents

Blue-sensitive resin combination, the colour filter and image display device manufactured using the composition Download PDF

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Publication number
CN110121679A
CN110121679A CN201780081423.2A CN201780081423A CN110121679A CN 110121679 A CN110121679 A CN 110121679A CN 201780081423 A CN201780081423 A CN 201780081423A CN 110121679 A CN110121679 A CN 110121679A
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China
Prior art keywords
carbon atom
blue
atom number
chemical formula
alkyl
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CN201780081423.2A
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Chinese (zh)
Inventor
李喻珍
金亨柱
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Dongwoo Fine Chem Co Ltd
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Dongwoo Fine Chem Co Ltd
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Publication of CN110121679A publication Critical patent/CN110121679A/en
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

Abstract

The present invention relates to blue-sensitive resin combinations, the colour filter and image display device that are manufactured using the composition, above-mentioned blue-sensitive resin combination includes scattering particles, blue colorant, Cardo class adhesive resin, Photoepolymerizationinitiater initiater, photopolymerizable compound, UV absorbent and solvent as adhesive resin, and above-mentioned UV absorbent includes one of benzotriazole, triazines and benzophenone or more.

Description

Blue-sensitive resin combination, the colour filter and image manufactured using the composition Display device
Technical field
It is shown the present invention relates to a kind of blue-sensitive resin combination, using the colour filter and image of the composition manufacture Device.
Background technique
Colour filter is can to realize small pixel and extracting red, these three colors of green and blue from white light The film-type optical component of unit, the size of a pixel are tens of to hundreds of microns or so.This colour filter is using successively layer Structure made of folded black matrix layer and pixel portion, wherein the black matrix layer is formed on the transparent substrate with defined pattern with right Boundary part between each pixel carries out shading, which is in order to form each pixel that multiple color is (usually red Color (R), green (G) and blue (B)) three primary colors arranged with defined sequence.
In recent years, as one of the method for realizing colour filter, using the pigment that pigment-dispersing type photoresist is utilized Dispersion method, but the light irradiated from light source penetrate colour filter during, a part of light be colored device absorb and under light efficiency Drop, and the problem of colorrendering quality declines due to occur the characteristic of the pigment contained in the colour filter.
In order to solve this problem, the colour filter using the self-luminous photosensitive polymer combination comprising quantum dot is proposed Manufacturing method.
Specifically, proposing in KR published patent 2007-0094679 by having by quantum dot (Quantum Dot) formed color-filter layer and improve colorrendering quality, proposing in KR published patent 2009-0036373 can lead to It crosses to replace with existing colour filter and luminous efficiency is improved by luminescent layer that quantum dot phosphor forms and improves display quality.
In addition, the photosensitive polymer combination developed so far in order to make colour filter be unable to fully meet it is excellent The necessary conditions such as pattern properties, heat resistance.
Summary of the invention
Technical problem
The object of the present invention is to provide developing powder, excellent and craftsmanship is excellent, when forming cured film excellent heat resistance and Xanthochromia will not occur at high temperature may be not present the variation of luminous intensity, and is capable of forming the fine pattern of specified value and has Excellent pattern properties can be realized the colour filter especially self-luminous colour filter for the bad problem of realization for improving fine pixel Blue-sensitive resin combination, the colour filter and image display device manufactured using the composition.
Technical solution
The present invention provides a kind of blue-sensitive resin combination, and above-mentioned blue-sensitive resin combination includes scattering Grain, blue colorant, the Cardo class adhesive resin as adhesive resin, photopolymerizable compound, Photoepolymerizationinitiater initiater, UV absorbent and solvent, above-mentioned UV absorbent include one of benzotriazole, triazines and benzophenone or more.
In addition, the present invention provide it is a kind of include the blue color patterns layer being made of above-mentioned blue-sensitive resin combination filter Color device.
In addition, the present invention provides a kind of image display device including above-mentioned colour filter and the light source for emitting blue light.
Beneficial effect
For the present invention by including UV absorbent in above-mentioned blue-sensitive resin combination, which includes benzo It more than one of triazole type, triazines and benzophenone, should so as to realize colour filter especially self-luminous colour filter The excellent heat resistance of colour filter and xanthochromia will not occur at high temperature the variation of luminous intensity may be not present, be capable of forming specified value Fine pattern, and improve the bad problem of realization of fine pixel with excellent pattern properties.Furthermore it is possible to provide one Kind has the self-luminous colour filter of the high quality image quality at excellent visual angle.
Specific embodiment
Blue-sensitive resin combination of the invention may include scattering particles, blue colorant, as adhesive resin Cardo class adhesive resin, Photoepolymerizationinitiater initiater, photopolymerizable compound, thermal curing agents and solvent.On especially since Stating UV absorbent includes one of benzotriazole, triazines and benzophenone or more, therefore including the use of of the invention Blue-sensitive resin combination is come the excellent heat resistance of the colour filter of the blue color patterns layer manufactured and will not occur at high temperature The variation of luminous intensity may be not present in xanthochromia, it is possible to provide a kind of fine pattern for being capable of forming specified value and improves fine pixel Realize the colour filter especially self-luminous colour filter of bad problem.Furthermore, it is possible to provide a kind of high quality with excellent visual angle The colour filter of image quality especially self-luminous colour filter and the image display device including the colour filter.
In the following, composition of the invention is described in detail.
Scattering particles
The metal oxide that it is 10 to 1000nm with average grain diameter that scattering particles of the invention, which can be, it is more preferably average Partial size be 30 to 300nm range the case where.At this point, can not expect incident light in the case where average grain diameter is less than above range Sufficient dispersion effect, average grain diameter be greater than above range in the case where, scattering particles precipitate in composition or nothing The light emitting layer surface of method acquisition homogeneous quality.
Above-mentioned metal oxide can be comprising selected from by Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni、Cu、Zn、Ga、Ge、Rb、Sr、Y、Mo、Cs、Ba、La、Hf、W、Tl、Pb、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、 The oxide of one of the group of Er, Tm, Yb, Ti, Sb, Sn, Zr, Nb, Ce, Ta, In and their combination composition metal.More For body, above-mentioned metal oxide be can be selected from by Al2O3、SiO2、ZnO、ZrO2、BaTiO3、TiO2、Ta2O5、Ti3O5、 ZnO、Nb2O3, SnO, MgO and their combination composition one of group more than.As needed, it also can be used by acrylic acid The material that the compound with unsaturated bond of ester etc. is surface-treated.
For above-mentioned scattering particles, containing in average grain diameter and overall composition can be suitably adjusted as needed Amount, so as to sufficiently improve the luminous intensity of colour filter.
In addition, the total weight relative to the solid component in blue-sensitive resin, may include the upper of 0.1 to 50 weight % Scattering particles are stated, can preferably be used by 5 to 30 weight %.In situation of the content in above-mentioned preferred scope of scattering particles Under, the reinforcing effect of luminous intensity can be obtained, and can ensure the stability of composition.
Blue colorant
In blue colorant of the invention, as the specific enumerable color index of blue pigment (dyeing association, family (The Society of Dyers and Colourists) publish) in be classified as the compound of pigment, more specifically can enumerate as Under color index (C.I.) number pigment, but might not be limited by the pigment.Concrete example explanation, as blue pigment C.I. pigment blue 15 can be enumerated: 3,15:4,15:6,16,21,28 and 76 etc. are preferably comprised selected from by C.I. pigment blue 15: 3, face It is more than one of group that material basket 15:6 and pigment blue 16 form.
Blue colorant of the invention can further include blue dyes, can enumerate color index (dye as blue dyes Se Jia association (The society of Dyers and Colourists) publishes) in be classified as compound or the dyeing of dyestuff The well known dyestuff recorded in handbook (dyers).
The above-mentioned dyestuff further used is specifically enumerated,
As C.I. solvent dye,
C.I. solvent blue 5,35,36,37,44,45,59,67 and 70 etc. can be enumerated, more preferably comprising C.I. solvent blue 35, 36, one of 44,45 and 70 or more.
In addition, as C.I. acid dyes,
Can enumerate C.I. Blue VRS, 7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83, 86、87、90、92、96、103、112、113、120、129、138、147、150、158、171、182、192、210、242、243、 256,259,267,278,280,285,290,296,315,324:1,335 and 340 etc., wherein more preferably including C.I. acid blue One of 80 and 90 or more.
In addition, as C.I. direct dyes,
Can enumerate C.I. directly indigo plant 38,44,57,70,77,80,81,84,85,86,90,93,94,95,97,98,99, 100、101、106、107、108、109、113、114、115、117、119、137、149、150、153、155、156、158、159、 160、161、162、163、164、166、167、170、171、172、173、188、189、190、192、193、194、196、198、 199、200、207、209、210、212、213、214、222、228、229、237、238、242、243、244、245、247、248、 250,251,252,256,257,259,260,268,274,275 and 293 etc..
Can enumerate C.I. medium indigo plant 1,2,3,7,8,9,12,13,15,16,19,20,21,22,23,24,26,30,31, 32,39,40,41,43,44,48,49,53,61,74,77,83 and 84 etc..
Above-mentioned blue dyes independently can be used or be combined two or more and use.
Blue colorant of the invention can further include the violet colorant as additional colorant.Violet colorant can More than one of violet pigment and cudbear, the specific enumerable C.I. pigment violet 1 of above-mentioned violet pigment, 14,19, 23,29,32,33,36,37 and 38 etc., wherein more preferably including C.I. pigment Violet 23.
The specific enumerable C.I. solvent violet of cudbear, C.I. acid violet, C.I. acid violet, C.I. medium purple etc., but simultaneously It is not limited to this.
Specifically, above-mentioned C.I. solvent violet can enumerate C.I. solvent purple 8,9,13,14,36,37,47 and 49 etc., it is more excellent Choosing includes C.I. solvent violet 13.C.I. acid violet 6B, 7,9,17,19 and 66 etc. can be enumerated as C.I. acid violet, are more preferably wrapped Acid violet containing C.I. 66.As the direct purple of C.I. can enumerate C.I. directly purple 47,52,54,59,60,65,66,79,80,81, 82,84,89,90,93,95,96,103 and 104 etc..
In addition, can enumerate C.I. medium purple 1,2,4,5,7,14,22,24,30,31,32,37,40,41,44,45,47, 48,53 and 58 etc..
Relative to the total weight of the solid component in blue-sensitive resin, the above-mentioned indigo plant of 0.1 to 50 weight % can be used The above-mentioned blue colorant of 0.5 to 30 weight % preferably can be used in chromatic colorant agent.Meet above-mentioned model in the content of blue colorant In the case where enclosing, it is able to suppress reflected ambient light, and efficiently shows colour light emitting intensity, it can be ensured that viscosity stabilization Property.
In the case where the self-luminous photoresist comprising quantum dot, it can reduce quantum efficiency and its performance decline, Especially price is high in the case where blue quantum dot, therefore there is expense to rise problem, and weaker to high-temperature technology and have There is technique limitation, but the present invention does not include blue quantum dot and includes blue colorant and scattering particles, so as to prevent from filtering The efficiency of the color device especially blue pixel of self-luminous colour filter declines.
Adhesive resin
Adhesive resin of the invention includes Cardo class adhesive resin.Above-mentioned Cardo class adhesive resin has with light Or the reactivity and alkali solubility of the effect generation of heat, and the decentralized medium as coloured material plays a role.Included in this hair Cardo class adhesive resin in bright blue-sensitive resin combination is played as the bonding agent resin to scattering particles to be made With as long as can be dissolved in then unrestricted in the resin for manufacturing alkaline-based developer used in the development step of colour filter System.
Cardo class adhesive resin of the invention may include in the compound indicated with chemical formula 1-1 and chemical formula 1-2 It is one or more of.
[chemical formula 1-1]
[chemical formula 1-2]
In above-mentioned chemical formula 1-1 or chemical formula 1-2,
R1、R2、R3And R4Separately haveWherein,
The alkyl or hydroxyl that X is hydrogen atom, carbon atom number is 1 to 5；
R5The alkyl for being 1 to 5 for hydrogen atom or carbon atom number.
In the present invention, the compound indicated with above-mentioned chemical formula 1-1 is closed by the compound indicated with following chemical formula 2-1 At, and can use the compound that is indicated with chemical formula 2-2 with the compound that chemical formula 1-2 is indicated to synthesize.
In the present invention, the compound indicated with above-mentioned chemical formula 1-1 is closed by the compound indicated with following chemical formula 2-1 At, and can use the compound that is indicated with chemical formula 2-2 with the compound that chemical formula 1-2 is indicated to synthesize.
[chemical formula 2-1]
[chemical formula 2-2]
Specifically, can be with the compound that above-mentioned chemical formula 1-1 is indicated with chemical formula 1-1-1 and chemical formula 1-1-2 It more than one of compound of expression, can be with the compound that above-mentioned chemical formula 1-2 is indicated with chemical formula 1-2-1 and chemistry It is more than one of compound that formula 1-2-2 is indicated.
[chemical formula 1-1-1]
[chemical formula 1-1-2]
[chemical formula 1-2-1]
[chemical formula 1-2-2]
It can be by making selected from by bis- (the 3- cortex cinnamomi acid diesters) fluorenes (9,9-bis (3-cinnamic diester) of 9,9- Fluorene), bis- (3- cinnamon oil, the 4- hydroxy phenyl) fluorenes (9,9-bis (3-cinnamoil, 4-hydroxyphenyl) of 9,9- Fluorene), bis- (glycidyl methacrylate ether) fluorenes (9,9-bis (the glycidyl methacrylate of 9,9- Ether) fluorene), the bis- two cinnamate (9,9-bis (3,4- of (3,4- dihydroxy phenyl) fluorenes of 9,9- Dihydroxyphenyl) fluorene dicinnamic ester), 3,6- 2-glycidyl methyl acrylate ether spiral shell (fluorenes -9,9- xanthene) (3,6-diglycidyl methacrylate ether spiro (fluorene-9,9-xantene)), 9,9- bis- (3- allyl, 4- hydroxy phenyl fluorenes) (9,9-bis (3-allyl, 4-hydroxyphenylfluorene)), 9,9- Bis- (4- allyloxy phenyl) fluorenes (9,9-bis (4-allyloxyphenyl) fluorene) and bis- (the 3,4- metering systems of 9,9- Acid diesters) fluorenes (9,9-bis (3,4-methacrylic diester) fluorene) composition at least one of group be selected from By as the maleic anhydride of anhydride compound, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrobenzene The group or be selected from that acid anhydride, methylene methylene tetrabydrophthalic anhydride, chlorendic anhydride and methyl tetrahydrophthalic anhydride form By as the pyromellitic acid anhydride of acid dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride and Biphenyl Ether tetrabasic carboxylic acid At least one of the group of the aromatic polycarboxylic acid acid anhydride composition of dianhydride etc. is reacted to prepare above-mentioned Cardo class adhesive resin, But not limited to this.
The present invention can further comprise the acrylic compounds alkali soluble resins as adhesive resin.The acrylic compounds alkali soluble Property resin can for example enumerate carboxyl group-containing monomer and can with the monomer be copolymerized other monomers copolymer etc..As list containing carboxyl Body, for example, can enumerate unsaturated monocarboxylic or such as unsaturated dicarboxylic, unsaturated tricarboxylic acids have in the molecule one with The unsaturated carboxylic acid etc. of the unsaturated polybasic carboxylic acid of upper carboxyl etc..Here, as unsaturated monocarboxylic, such as propylene can be enumerated Acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid etc..As unsaturated dicarboxylic, such as maleic acid, richness can be enumerated Horse acid, itaconic acid, citraconic acid, mesaconic acid etc..Unsaturated polybasic carboxylic acid can be acid anhydrides, specifically, can enumerate maleic anhydride, Itaconic anhydride, citraconic anhydride etc..In addition, unsaturated polybasic carboxylic acid is also possible to its single (2- acryloxyalkyl) ester, such as Mono succinate (2- acryloyl-oxyethyl) ester, mono succinate (2- methacryloxyethyl) ester, O-phthalic can be enumerated Sour single (2- acryloyl-oxyethyl) ester, phthalic acid list (2- methacryloxyethyl) ester etc..Unsaturated polynary carboxylic Acid can also be list (methyl) acrylate of its two ends dicarboxyl based polyalcohol, such as can enumerate ω-carboxy-polycaprolactone list Acrylate, ω-carboxy-polycaprolactone monomethacrylates etc..These carboxyl group-containing monomers can respectively individually or by two kinds with On be used in mixed way.As the other monomers that can be copolymerized with above-mentioned carboxyl group-containing monomer, such as styrene, Alpha-Methyl benzene second can be enumerated Alkene, adjacent vinyltoluene, vinyltoluene, to vinyltoluene, p-chlorostyrene, o-methoxystyrene, meta-methoxy Styrene, to methoxy styrene, adjacent vinyl benzyl methyl ether, vinyl benzyl methyl ether, to vinyl benzyl ylmethyl Ether, adjacent vinylbenzyl glycidyl ether, vinylbenzyl glycidyl ether, to vinylbenzyl glycidyl ether, indenes etc. Aromatic ethenyl compound；Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic acid N-propyl, n propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, methacrylic acid The secondary butyl ester of N-butyl, isobutyl acrylate, Isobutyl methacrylate, sec-butyl acrylate, methacrylic acid, the tertiary fourth of acrylic acid Ester, Tert-butyl Methacrylate, acrylic acid 2- hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid 2- hydroxy propyl ester, first Base acrylic acid 2- hydroxy propyl ester, acrylic acid 3- hydroxy propyl ester, methacrylic acid 3- hydroxy propyl ester, acrylic acid 2- hydroxybutyl, first Base acrylic acid 2- hydroxybutyl, acrylic acid 3- hydroxybutyl, methacrylic acid 3- hydroxybutyl, acrylic acid 4- hydroxybutyl, first Base acrylic acid 4- hydroxybutyl, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, third Olefin(e) acid cyclohexyl, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, acrylic acid 2- methoxy acrylate, methyl Acrylic acid 2- methoxy acrylate, acrylic acid 2- phenoxy ethyl, methacrylic acid 2- phenoxy ethyl, methoxyl group diethylene glycol third Olefin(e) acid ester, methoxyl group diethylene glycol methacrylate, methoxy triethylene acrylate, methoxy triethylene methyl-prop Olefin(e) acid ester, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxyl group dipropylene glycol acrylate, Methoxyl group dipropylene glycol methyl acrylate, isobornyl acrylate, isobornyl methacrylate, acrylic acid dicyclopentadiene Ester, methacrylic acid dicyclopentadienyl ester, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (methyl) acrylic acid norbornyl ester, acrylic acid 2- Hydroxyl -3- phenoxy-propyl, methacrylic acid 2- hydroxyl -3- phenoxy-propyl, glycerol mono-acrylate, glycerol monomethacrylate The unsaturated carboxylate types such as acid esters；Acrylic acid 2- amino ethyl ester, methacrylic acid 2- amino ethyl ester, acrylic acid 2- dimethylamino Ethyl ester, methacrylic acid 2- dimethylamino ethyl ester, acrylic acid 2- amino propyl ester, methacrylic acid 2- amino propyl ester, acrylic acid 2- dimethylamino propyl ester, methacrylic acid 2- dimethylamino propyl ester, acrylic acid 3- amino propyl ester, methacrylic acid 3- amino The unsaturated carboxylic acids aminoalkyl esters such as propyl ester, acrylic acid 3- dimethylamino propyl ester, methacrylic acid 3- dimethylamino propyl ester Class；The unsaturated carboxylic acids glycidol esters such as glycidyl acrylate, glycidyl methacrylate；Vinyl acetate, The generating vinyl carboxylates esters such as vinyl propionate, vinyl butyrate, vinyl benzoate；Vinyl methyl ether, vinyl ethyl ether, alkene The unsaturated ethers such as propyl glycidyl ether；The cyanidings second such as acrylonitrile, methacrylonitrile, α-chloro-acrylonitrile, vinylidene cyanide Alkenyl compound；Acrylamide, Methacrylamide, α-chloroacrylamide, N-2- hydroxyethyl acrylamide, N-2- hydroxyl second The unsaturated acyls amine such as butylmethacrylamide；Maleimide, benzyl maleimide, N-phenylmaleimide, N- ring The unsaturated acyls imines such as hexyl maleimide；The aliphatic conjugated dienes such as 1,3- butadiene, isoprene, chlorobutadiene Class；And polystyrene, polymethyl acrylate, polymethyl methacrylate, polyacrylic acid N-butyl, the positive fourth of polymethylacrylic acid Ester, polysiloxanes etc. have single acryloyl group or the polymeric monomer class of monomethacrylate acyl group etc. in the end of polymer molecular chain. These monomers can respectively individually or be use mixing two or more.In particular, as that can be copolymerized with above-mentioned carboxyl group-containing monomer Other monomers, due to the monomer with norborny skeleton, the monomer with adamantane framework and the list with rosin skeleton There is the tendency for reducing relative dielectric constant in the large volumes monomer such as body, therefore preferably.
It is 20 to 200 as Cardo class adhesive resin of the invention and/or acrylic compounds alkali soluble resins preferred acid number The range of (KOH mg/g).If acid value within the above range, improves the dissolubility in developer solution, non-exposed portion is easy dissolution And sensitivity increases, result remains in the development of the pattern of exposure portion and can improve residual film ratio (film remaining Ratio), therefore preferably.Here, acid value be as the amount (mg) of required potassium hydroxide when neutralizing acrylic polymer 1g and The value of measurement can usually be titrated by using potassium hydroxide aqueous solution and be found out.Furthermore it is preferred that passing through gel permeation chromatography (GPC；Using tetrahydrofuran as eluting solvent) measurement polystyrene convert weight average molecular weight (hreinafter referred to as " Weight-average molecular Amount ") it is 2,000~200,000, is preferably 3,000~100,000 Cardo class adhesive resin or acrylic compounds alkali solubility Resin.If molecular weight is within the above range, hardness raising and residual film ratio height, non-exposed portion with film are in developer solution The tendency that dissolubility is excellent and resolution ratio improves, therefore preferably.
Cardo class adhesive resin and/or acrylic compounds alkali soluble resins molecular weight distribution [weight average molecular weight (Mw)/ Number-average molecular weight (Mn)] it is preferably 1.0 to 6.0, more preferably 1.5 to 6.0.If molecular weight distribution [weight average molecular weight (Mw)/ Number-average molecular weight (Mn)] it is 1.5 to 6.0, then developability is excellent, therefore preferably.
Relative to the total weight of the solid component in blue-sensitive resin, it can be used that 5 to 85 weight %'s is of the invention The adhesive resin of the invention of 5 to 60 weight % preferably can be used in adhesive resin.If the content of adhesive resin is upper State in range, then deposit in developer solution dissolubility sufficiently, non-pixel portion development residue and development are not likely to produce on substrate When be not susceptible to exposed portion the film of pixel portion reduce and the excellent tendency of the omitted property of non-pixel portion, therefore preferably.
Photopolymerizable compound
Photopolymerizable compound contained in blue-sensitive resin combination of the invention is can be in light and aftermentioned Photoepolymerizationinitiater initiater under the action of the compound that polymerize, monofunctional monomer, two functional monomers, other polyfunctional monomers can be enumerated Deng.As the concrete example of monofunctional monomer, nonyl phenyl carbitol acrylate, 2- hydroxyl -3- phenoxy propyl third can be enumerated Olefin(e) acid ester, 2- ethylhexyl carbitol acrylate, 2- hydroxyethylmethacry,ate, n-vinyl pyrrolidone etc..As two The concrete example of functional monomer can enumerate 1,6- hexylene glycol two (methyl) acrylate, ethylene glycol two (methyl) acrylate, new penta Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, bisphenol-A bis- (acryloyl-oxyethyl) ethers, 3- Methyl pentanediol two (methyl) acrylate etc..As the concrete example of other polyfunctional monomers, trimethylolpropane tris can be enumerated (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, pentaerythrite five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc..Wherein, it is preferable to use more than two functions multifunctional list Body.The total weight of solid component relative to blue-sensitive resin combination may include the above-mentioned photopolymerization of 5 to 5 weight % Property compound, preferably may include the above-mentioned photopolymerizable compound of 5 to 45 quality %.Including the optical polymerism in above range In the case where compound, there are it is following tendency and it is preferred that: that is, be not present sensitivity reduction, film-strength is abundant, there is no development When pattern loss, so that pattern building is also excellent in fine pattern portion, and the flatness of resist is excellent.
Photoepolymerizationinitiater initiater
Above-mentioned Photoepolymerizationinitiater initiater used in the present invention may include being selected to be indicated with following chemical formula 3 to chemical formula 5 More than one of compound, due to the compound comprising being indicated with chemical formula 3 to chemical formula 5, has and cause photonasty The free responding of resin combination causes the effect for solidifying and improving sensitivity.
[chemical formula 3]
In chemical formula 3, R8Can be hydrogen atom, halogen atom, hydroxyl, by carbon atom number be 1 to 12 alkyl replace Or unsubstituted phenyl, be 1 to 12 by carbon atom number alkyl-substituted or unsubstituted benzyl, by carbon atom number be 1 to 12 alkyl-substituted or unsubstituted naphthalene or-SRa, RaIt can be hydrogen, the alkyl or benzyl that carbon atom number is 1 to 12 Base.
R9To R12Separately be hydrogen atom, halogen atom, hydroxyl, by carbon atom number be 1 to 12 it is alkyl-substituted Or unsubstituted phenyl, by carbon atom number be 1 to 12 alkyl-substituted or unsubstituted benzyl or by carbon atom number For 1 to 12 alkyl-substituted or unsubstituted naphthalene, the R11And R12Ring can be formed together.
As the example of the compound indicated with chemical formula 3, there is 2- methyl-2-amino (4- morphlinophenyl) ethane -1- Ketone, 2- ethyl -2- amino (4- morphlinophenyl) ethane -1- ketone, 2- propyl -2- amino (4- morphlinophenyl) ethane -1- ketone, 2- butyl -2- amino (4- morphlinophenyl) ethane -1- ketone, 2- methyl-2-amino (4- morphlinophenyl) propane -1- ketone, 2- Methyl-2-amino (4- morphlinophenyl) butane -1- ketone, 2- ethyl -2- amino (4- morphlinophenyl) propane -1- ketone, 2- second Base -2- amino (4- morphlinophenyl) butane -1- ketone, 2- methyl -2- methylamino (4- morphlinophenyl) propane -1- ketone, 2- first Base -2- dimethylamino (4- morphlinophenyl) propane -1- ketone, 2- methyl -2- lignocaine (4- morphlinophenyl) propane -1- ketone Deng.
[chemical formula 4]
In above-mentioned chemical formula 4,
R14Structure be, for example, hydrogen, carbon atom number be 1 to 20 alkyl, carbon atom number be 3 to 8 naphthenic base or not by Replace or substituted phenyl orWherein, the integer that n is 1~4, the integer that m is 1~6；
R15For alkyl, phenyl, substituted-phenyl, benzyl or substituted benzyl with 1~8 carbon atom；
R13For diphenyl sulfide ether, substituted diphenyl sulfide ether, carbazyl, substituted carbazyl, fluorenyl or it is substituted Fluorenyl.
[chemical formula 5]
In above-mentioned chemical formula 5, R16、R17And R18Separately indicate R, OR, COR, SR, CONRR', ROR' or CN；
R and R' indicates that the aryl that the alkyl that carbon atom number is 1 to 20, carbon atom number are 6 to 30, carbon atom number are 7 to 30 Aralkyl or carbon atom number be 2 to 20 heterocycle, the heterocycle that they can be 2 to 20 by halogen atom and/or carbon atom number Base replaces, and the alkylene moiety of alkyl and aralkyl in them can be interrupted by unsaturated bond, ehter bond, thioether bond or ester bond, and And R and R' can be formed together ring；
Y1Indicate that oxygen atom, sulphur atom or selenium atom, m indicate that 0~4 integer, p indicate 0~5 integer；
Q indicates 0 or 1；
R19、R20、R21And R22Separately indicate that hydrogen atom, halogen atom or carbon atom number are 1 to 8 alkyl；
X1And X2Indicate that aryl, carbon atom number that alkyl, carbon atom number that carbon atom number is 1 to 20 are 6 to 30 are 7 to 30 Aralkyl or carbon atom number be 2 to 20 heterocycle, the heterocycle that they can be 2 to 20 by halogen atom and/or carbon atom number Base replaces, and the alkylene moiety of alkyl and aralkyl in them can be interrupted by unsaturated bond, ehter bond, thioether bond or ester bond；
X2Ring can be formed together with adjacent nuclear carbon atom, more specifically can be formed carbon atom number be 6 to 30 aromatic ring；
Y2And Y3Separately indicate oxygen atom, sulphur atom or selenium atom.
Preferably as the alkyl indicated with above-mentioned R and R', such as methyl, ethyl, propyl, isopropyl, butyl, different can be enumerated Butyl, sec-butyl, tert-butyl, amyl, isopentyl, tertiary pentyl, hexyl, heptyl, octyl, iso-octyl, 2- second hexyl, t-octyl, Nonyl, isononyl, decyl, isodecyl, vinyl, aryl, cyclobutenyl, acetenyl, propinyl, methoxy ethyl, ethyoxyl second Base, Among, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyl group ethoxyethyl group, methoxy-propyl, Single methyl fluoride, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoro-ethyl, 2- (benzoxazoles -2'- base) vinyl etc., wherein It is preferred that the alkyl that carbon atom number is 1 to 8.
In addition, for example can preferably enumerate phenyl, trityl, xylyl, ethylo benzene as the aryl indicated with R and R' Base, chlorphenyl, naphthalene, anthryl (anthryl), phenanthryl (phenanthrenyl) etc., wherein further preferably carbon atom number is 6~12 Aryl.In addition, as the aralkyl indicated with R and R', such as can preferably enumerate benzyl, chlorobenzyl, α-methylbenzyl, α, α- The aralkyl that the carbon atom numbers such as dimethyl benzyl, phenylethyl, phenyl vinyl are 7~13.As the heterocycle indicated with R and R' Base, such as can preferably enumerate the heterocycle that the carbon atom numbers such as pyridyl group, pyrimidine radicals, furyl (furyl), thiophenyl are 5~7. In addition, as the ring that R and R' can be formed together, such as can preferably enumerate the carbon atom numbers such as piperidine ring, morpholine ring is 5~7 Ring.In addition, R and R' can be replaced by halogens such as fluorine, chlorine, bromine, iodine, or can be by pyridyl group, pyrimidine radicals, furyl, benzo Oxazole -2- base, THP trtrahydropyranyl, pyrrolidinyl (pyrrolidyl), imidazoles piperidinyl, pyrazolidinyl (pyrazolidyl), tetrahydro Thiazolyl (thiazolidyl), different tetrahydro-thiazoles base (isothiazolidyl), oxazolidinyl (oxazolidyl), isoxazole The carbon atom numbers such as alkyl (isooxazolidyl), piperidyl (piperidyl), piperazinyl (piperadyl), morpholinyl be 5~ 7 heterocycle replaces.
Preferably as with above-mentioned X1And X2The alkyl of expression can enumerate methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, Sec-butyl, tert-butyl, amyl, isopentyl, tertiary pentyl, hexyl, heptyl, octyl, iso-octyl, 2- second hexyl, t-octyl, nonyl, Isononyl, decyl, isodecyl, vinyl, aryl, cyclobutenyl, acetenyl, propinyl, methoxy ethyl, ethoxyethyl group, third Oxygroup ethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyl group ethoxyethyl group, methoxy-propyl, single fluorine first Base, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoro-ethyl, 2- (benzoxazoles -2'- base) vinyl etc., wherein it is preferred that carbon The alkyl that atomicity is 1 to 8.
In addition, as with above-mentioned X1And X2The aryl of expression for example can preferably enumerate phenyl, trityl, xylyl, second Base phenyl, chlorphenyl, naphthalene, anthryl (anthryl), phenanthryl (phenanthrenyl) etc., wherein further preferably carbon atom number is 6 ~12 aryl.In addition, as with X1And X2The aralkyl of expression, for example, can preferably enumerate benzyl, chlorobenzyl, α-methylbenzyl, The aralkyl that the carbon atom numbers such as bis (alpha, alpha-dimethylbenzyl) base, phenylethyl, phenyl vinyl are 7~13.As with X1And X2It indicates Heterocycle, such as can preferably enumerate pyridyl group, pyrimidine radicals, furyl, benzoxazoles -2- base, THP trtrahydropyranyl, pyrrolidinyl (pyrrolidyl), imidazoles piperidinyl, pyrazolidinyl (pyrazolidyl), tetrahydro-thiazoles base (thiazolidyl), different tetrahydro thiophene Oxazolyl (isothiazolidyl), oxazolidinyl (oxazolidyl), isoxazolidinyl (isooxazolidyl), piperidyl (piperidyl), the heterocycle that the carbon atom numbers such as piperazinyl (piperadyl), morpholinyl, thiophenyl are 5 to 7.
In addition, as with X1And X2The halogen atom of expression can enumerate fluorine, chlorine, bromine, iodine.
In addition, using X1And X2The alkyl of expression can enumerate the methyl being substituted with halogen atoms, ethyl, propyl, isopropyl, fourth Base, isobutyl group, sec-butyl, tert-butyl, amyl, isopentyl, tertiary pentyl, hexyl, heptyl, octyl, iso-octyl, 2- ethylhexyl, T-octyl.
X2It can be formed together ring with adjacent nuclear carbon atom, can be more specifically 6 to 30 by carbon atom number Aromatic ring or carbon atom number be 5 to 10 ring formed compound.
As with R19、R20、R21And R22The halogen atom of expression can enumerate fluorine, chlorine, bromine, iodine.
Use R19、R20、R21And R22The alkyl of expression can enumerate methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, Zhong Ding Base, tert-butyl, amyl, isopentyl, tertiary pentyl, hexyl, heptyl, octyl, iso-octyl, 2- ethylhexyl, t-octyl.
It can be following compounds with the compound that above-mentioned chemical formula 5 indicates.
In addition, preferably comprising acetophenone compounds as Photoepolymerizationinitiater initiater.As acetophenone compounds, such as can Enumerate diethoxy acetophenone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, benzil dimethyl ketal, 2- hydroxyl -1- [4- (2- hydroxyl-oxethyl) phenyl]-2- methylpropane-1- ketone, 1- hydroxycyclohexylphenylketone, 2- methyl-1-(4- methylbenzene Sulfenyl) -2- morpholino propane -1- ketone, 2- benzyl -2- dimethylamino -1- (4- morphlinophenyl) butane -1- ketone, 2- hydroxyl - The oligomer etc. of 2- methyl [4- (1- methyl ethylene) phenyl] propane -1- ketone, can preferably enumerate 2- benzyl -2- dimethylamino Base -1- (4- morphlinophenyl) butane -1- ketone etc..
In addition, may include being indicated with following chemical formula 5-1 to 5-8 with the Photoepolymerizationinitiater initiater that above-mentioned chemical formula 3 to 5 indicates Structure.
[chemical formula 5-1]
[chemical formula 5-2]
[chemical formula 5-3]
[chemical formula 5-4]
[chemical formula 5-5]
[chemical formula 5-6]
[chemical formula 5-7]
[chemical formula 5-8]
Furthermore, it is possible to which the Photoepolymerizationinitiater initiater other than above-mentioned acetophenones is applied in combination.
Photoepolymerizationinitiater initiater other than above-mentioned acetophenones can enumerate the activity that living radical is generated by irradiation light Free-radical generating agent, sensitizer, acid agent etc..As living radical producing agent, such as benzoin class compound, two can be enumerated Benzophenone class compound, thioxanthene ketone class compound, compound in triazine class etc..
As above-mentioned benzoin class compound, such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin can be enumerated Isopropyl ether, benzoin isobutyl ether etc..As benzophenone compound, such as benzophenone, o-benzoylbenzoic acid can be enumerated Methyl esters, 4- phenyl benzophenone, 4- benzoyl -4 '-methyldiphenyl thioether, 3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyls) two Benzophenone, 2,4,6- tri-methyl benzophenone etc..
As above-mentioned thioxanthene ketone class compound, such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- bis- can be enumerated Ethyl thioxanthones, bis- clopenthixal ketone of 2,4-, the chloro- 4- propoxythioxanthone of 1- etc..
As above-mentioned compound in triazine class, such as bis- (the trichloromethyl) -6- (4- methoxyphenyl) -1,3 of 2,4- can be enumerated, 5- triazine, 2,4- bis- (trichloromethyl) -6- (4- methoxyl group naphthalene) -1,3,5- triazine, bis- (trichloromethyl) -6- (the 4- first of 2,4- Oxygroup styryl) -1,3,5- triazine, bis- (the trichloromethyl) -6- of 2,4- [2- (5- methylfuran -2- base) vinyl] -1,3, Bis- (the trichloromethyl) -6- of 5- triazine, 2,4- [2- (furans -2- base) vinyl] -1,3,5- triazine, 2,4- bis- (trichloromethyls) - 6- [2- (4- diethylamino -2- aminomethyl phenyl) vinyl] -1,3,5- triazine, bis- (trichloromethyl) -6- [2- (3,4- of 2,4- Dimethoxyphenyl) vinyl] -1,3,5- triazine etc..
As above-mentioned living radical producing agent, the oxidation of 2,4,6- trimethyl benzoyl diphenyl bases can be used for example Phosphine, 2,2,-bis- (Chloro-O-Phenyls) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxaline, 10- butyl -2- chloro-acridine ketone, 2- ethyl anthracene Quinone, benzil, 9,10- phenanthrenequione, camphorquinone, phenylglyoxalates methyl esters, titanocenes compound etc..As above-mentioned acid agent, such as 4- hydroxy phenyl dimethyl sulfonium tosilate, 4- hydroxy phenyl dimethyl sulfonium hexafluoro antimonate, 4- acetoxyl group can be enumerated Pheiiyldimetliyl sulfonium tosilate, 4- acetoxyl group phenyl methyl benzyl sulfonium hexafluoro antimonate, triphenylsulfonium are to toluene sulphur The salt of hydrochlorate, triphenylsulfonium hexafluoro antimonate, diphenyl iodine tosilate, diphenyl iodine hexafluoro antimonate etc. Class, nitrobenzyl tosylate class, benzoin toluenesulfonic acid salt etc..
In addition, there is also generate living radical and acid simultaneously in above compound as living radical producing agent Compound, for example, triazine system Photoepolymerizationinitiater initiater is also used as acid agent.
It may include the above-mentioned light of 0.1 to 20 weight % relative to the total weight of the solid component in blue-sensitive resin Polymerization initiator preferably may include the above-mentioned Photoepolymerizationinitiater initiater of 0.3 to 15 weight %.If above-mentioned Photoepolymerizationinitiater initiater contains Amount within the above range, then has the pixel for making blue-sensitive resin combination high-sensitivity and the composition being used to be formed The excellent tendency of the intensity in portion, the flatness on the pixel portion surface, therefore preferably.
In addition, photopolymerization initiator can be used in the present invention.Photopolymerization initiator is combined with Photoepolymerizationinitiater initiater sometimes It uses, is used to promote the polymerization for the photopolymerizable compound for causing polymerization by above-mentioned Photoepolymerizationinitiater initiater Compound.
As photopolymerization initiator, aminated compounds, alkoxy anthracene compound, thioxanthene ketone class compound can be enumerated Deng.
As aminated compounds, such as triethanolamine, methyl diethanolamine, triisopropanolamine, 4- dimethylamino can be enumerated Yl benzoic acid methyl esters, ethyl 4-dimethylaminobenzoate, 4- dimethylaminobenzoic acid isopentyl ester, benzoic acid 2- dimethylamino Base ethyl ester, 4- dimethylaminobenzoic acid 2- ethylhexyl, N, bis- (dimethylaminos) two of N- dimethyl-p-toluidine, 4,4'- Bis- (diethylamino) benzophenone of Benzophenone (being commonly called as Michler's keton), 4,4'-, bis- (ethylmethylamino) benzophenone of 4,4'- Deng wherein bis- (diethylamino) benzophenone of preferably 4,4'-.
As alkoxy anthracene compound, such as 9,10- dimethoxy anthracene, 2- ethyl -9,10- dimethoxy can be enumerated Anthracene, 9,10- diethoxy anthracene, 2- ethyl -9,10- diethoxy anthracene etc..
As thioxanthones based compound, such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- diethyl can be enumerated Thioxanthones, bis- clopenthixal ketone of 2,4-, the chloro- 4- propoxythioxanthone of 1- etc..
Photoepolymerizationinitiater initiater (D) can use individually or by multiple combinations.In addition, as photopolymerization initiator, it can also To use commercially available product, as commercially available photopolymerization initiator, such as trade name " EAB-F " (manufacturer: soil conservation paddyization can be enumerated Learn Industrial Co., Ltd) etc..
Using these photopolymerization initiators, every 1 mole usually relative to Photoepolymerizationinitiater initiater, the polymerization The usage amount for causing auxiliary agent is usually 10 moles hereinafter, preferably 0.01~5 mole.If the usage amount of the polymerization trigger auxiliary agent Within the above range, then the sensitivity with blue-sensitive resin combination further increases and using the composition formation The tendency that the productivity of colour filter improves, therefore preferably.
UV absorbent
In the present invention, it is able to confirm that UV absorbent not only adjusts what the size of pattern but also prevent in high-temperature technology Xanthochromia and the effect for improving quantum efficiency.
It is commonly known to there is UV absorbent to cannot achieve because of the CD bias of photosensitive polymer combination (CD bias) increase It is used when fine pattern.At this point, CD refers to the convex portion of pattern, CD bias refers to that the pattern magnitude to be formed is greater than to be realized The degree of the size of mask pattern.If adding UV absorbent, caused by can reduce with a part of UV of absorption because of diffraction CD bias, so as to realize required pattern.
In addition, quantum dot is difficult to maintain higher luminous intensity in colour filter manufacturing process because of fragile heat resistance. At this point, higher strong light can be maintained after the baking (Post-bake) after repeatedly if addition UV absorbent Degree.
UV absorbent of the invention more than one of benzotriazole, triazines, benzophenone UV absorbent will be made For essential component.
Well known compound can be used as benzotriazole uv absorbers.Specifically, it is preferable that octyl 3- [the tertiary fourth of 3- Base -4- hydroxyl -5- (5- chloro -2H- benzotriazole -2- base) phenyl] propionic ester, 2- ethylhexyl 3- (3- tert-butyl -4- hydroxyl Base -5- (5- chloro -2H- benzotriazole -2- base) phenyl) propionic ester, [3- [3- (2H- benzotriazole -2- base) -5- (1,1- first Base ethyl) -4- hydroxy phenyl] -1- acetonyl]-w- [3- [3- (2H- benzotriazole -2- base) -5- (1,1-Methylethyl)- 4- hydroxy phenyl] -1- oxopropoxy] poly- (oxygen -1,2- ethylidene), (3- (3- (2H- benzotriazole -2- base) -5- (1,1- bis- Methylethyl) -4- hydroxy phenyl) -1- acetonyl)-hydroxyl poly- (oxygen -1,2- ethylidene), 2- (3- tert-butyl -2- hydroxy-5-methyl Base phenyl) -5- chloro -2H- benzotriazole, 2- (2H- benzotriazole -2- base) -4,6- di-tert-pentyl phenol, 3- (2H- benzo three Oxazolyl) -5- (1,1- dimethyl ethyl) -4- hydroxy-benzenepropanoic acid octyl ester, 2- (2H- benzotriazole -2- base) bis- (1- first of -4,6- Base-1- phenethyl) phenol, 2- (2H- benzotriazole-2- base)-6- (1- methyl-1-phenethyl)-4- (1,1,3,3- tetramethyl fourth Base) phenol etc..
Well known chemicals can be used as triazines UV absorbent.Specifically, can enumerate 2- (4, dimethyl -1 6-, 3,5- triazine -2- base) -5- ((hexyl) oxygroup)-phenol, 2- (4- (three decyl oxygroup propyl of 2- hydroxyl -3-) oxygroup) -2- hydroxyl Phenyl) -4, bis- (2,4- the 3,5-dimethylphenyl) -1,3,5- triazines of 6-, 2- (4- (2- hydroxyl -3- didecyl oxygroup propyl) oxygroup) - 2- hydroxy phenyl) bis- (2,4- the 3,5-dimethylphenyl) -1,3,5- triazines of -4,6-, 2- (2- hydroxyl -4- (3- (2- ethylhexyl -1- oxygen Base) -2- hydroxypropyl oxygroup) phenyl) bis- (2,4- the 3,5-dimethylphenyl) -1,3,5- triazines of -4,6-, 2,2'- [6- (2,4- diethyl Phenyl) -1,3,5- triazine -2,4- diyl] bis- (5- butoxy phenol), 6- methylheptyl 2- { 4- [(the 4- biphenyl of 4,6- bis- Base) -1,3,5- triazine -2- base] -3- hydroxyphenoxy } propionic ester etc..
Well known compound can be used as benzophenone UV absorbent.Specifically, it is pungent to enumerate 2- hydroxyl -4-n- Base oxygroup benzophenone, ESCALOL 567 etc..
Relative to the total amount of the solid component in blue-sensitive resin, the content of above-mentioned UV absorbent be 0.001 to 10 weight % preferably comprise the above-mentioned UV absorbent of 0.025 to 7 weight %.UV absorbent content within above range In the case where can be improved the effect of absorbent, and will not interfere Photoepolymerizationinitiater initiater effect and being capable of formation figure well Case.
Solvent
Solvent contained in blue-sensitive resin combination of the invention is not particularly limited, and blue sensitive can be used Various organic solvents used in property resin combination field.As its concrete example, ethylene glycol single methyl ether, ethylene glycol can be enumerated The ethylene glycol monoalkyl ethers class such as single ethylether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether；Diethylene glycol dimethyl ether, two The diethylene glycol dialkyl ethers classes such as ethylene glycol Anaesthetie Ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether；The molten fibre of methyl The ethylene glycol alkyl ethers acetate esters such as agent acetic acid esters, ethyl cellosolve acetate；Propylene glycol monomethyl ether, propylene glycol list The alkylidenes such as monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, methoxybutyl acetic acid esters and methoxypentyl acetic acid esters Glycol alkyl ether acetate esters；Benzene,toluene,xylene, mesitylene etc. are aromatic hydrocarbon；Methyl ethyl ketone, acetone, methylpent The ketones such as base ketone, methyl iso-butyl ketone (MIBK), cyclohexanone；The alcohols such as ethyl alcohol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol； The esters such as 3- ethoxyl ethyl propionate, 3- methoxy methyl propionate；Ring-type esters such as gamma-butyrolacton etc..In above-mentioned solvent, from From the aspect of coating and drying property, the organic solvent that above-mentioned solvent mid-boiling point is 100~200 DEG C can be preferably enumerated, more preferably The esters knots such as aklylene glycol alkylether acetates class, ketone, 3- ethoxyl ethyl propionate or 3- methoxy methyl propionate can be enumerated Class is closed, propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, cyclohexanone, 3- ethoxy can be further preferably enumerated Base ethyl propionate, 3- methoxy methyl propionate etc..Above-mentioned solvent can respectively individually or be use mixing two or more.
It is molten in blue-sensitive resin combination of the invention relative to the total weight of blue-sensitive resin combination Agent content can be 60 to 90 quality %, preferably comprise the solvent of 60 to 85 quality %.If the content of solvent is in above-mentioned model In enclosing, then roll coater, spin coater, slit spin coater, slit coater (sometimes referred to as die coating machine), flush coater are being utilized When equal apparatus for coating are coated, having makes coating become excellent tendency, therefore preferably.
Additive
Blue color patterns layer blue-sensitive resin combination of the invention can further include as needed filler, other High-molecular compound, pigment dispersing agent, closely sealed promotor, antioxidant, ultraviolet absorbing agent, anticoagulant etc..
As other above-mentioned high-molecular compounds, the curability tree such as specific enumerable epoxy resin, maleimide resin The thermoplastic resins such as rouge, polyvinyl alcohol, polyacrylic acid, polyalkylene glycol monoalkyl ether, poly- fluoroalkyl, polyester, polyurethane Rouge etc..
As above-mentioned pigment dispersing agent, commercially available surfactant can be used, such as silicon class, fluorine class, esters, sun can be enumerated Surfactants such as ionic species, anionic species, nonionic class, both sexes etc..They can be respectively individually or by two or more combinations It uses.
As above-mentioned surfactant, such as except polyoxyethylene alkyl ether class, polyoxyethylene alkyl phenyl ether class, poly- second two Two esters of alcohol, sorbitan fatty ester class, fatty acid modified polyesters, tertiary-amine modified polyurethanes, polyethyleneimine Other than class etc., the KP (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacture) as trade name, POLYFLOW (common prosperity society chemistry (strain) system can be enumerated Make), EFTOP (manufacture of Tokheimproduct company), MEGAFAC (big Japanese ink chemical industry (strain) manufacture), Flourad (Sumitomo 3M (strain) manufacture), Asahi guard, Surflon (the above are Asahi Glass (strain) manufactures), SOLSPERSE (Jie Likang (strain) manufacture), EFKA (manufacture of EFKA chemical company), PB 821 (aginomoto (strain) manufacture) etc..
As above-mentioned closely sealed promotor, such as vinyltrimethoxysilane, vinyltriethoxysilane, second can be enumerated Alkenyl three (2- methoxy ethoxy) silane, N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane, N- (2- ammonia Base ethyl) -3- TSL 8330,3-aminopropyltriethoxysilane, 3- glycidoxypropyl group trimethoxy Base silane, 3- epoxy propoxy propyl methyl dimethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 3- Chloropropylmethyldimethoxysilane, 3- r-chloropropyl trimethoxyl silane, 3- methacryloxypropyl trimethoxy silane, 3-mercaptopropyi trimethoxy silane etc..As above-mentioned antioxidant, specific enumerable 2,2'- thiobis (4- methyl-6-tert-butyl Base phenol), 2,6 di tert butyl 4 methyl phenol etc..
As ultraviolet absorbing agent, can specifically enumerating 2- (3- tert-butyl -2- hydroxy-5-methyl base phenyl), -5- chlorobenzene is simultaneously Triazole, alkoxy benzophenone etc..
As specific enumerable Sodium Polyacrylate of above-mentioned anticoagulant etc..
Those skilled in the art, which can suitably add, in a range that does not hinder the effect of the present invention uses above-mentioned additive. For example, the above-mentioned of 0.5 to 10 parts by weight can be used to add relative to overall 100 parts by weight of above-mentioned blue-sensitive resin combination Add agent, the above-mentioned additive of 0.1 to 10 parts by weight preferably can be used, more preferably uses the above-mentioned additive of 0.1 to 5 parts by weight, But not limited to this.
Blue-sensitive resin combination of the invention can for example be prepared by the following method.In advance by scattering particles It is mixed with solvent, is dispersed to average grain diameter using ball mill etc. and reaches 30~500nm.At this point, as needed can also be further Using dispersing agent, bonding agent resin part or all can also be cooperated.In obtained dispersion liquid (hereinafter, sometimes referred to as For in abrasive (mill base)) with defined concentration further add remaining bonding agent resin, photopolymerizable compound, Photoepolymerizationinitiater initiater, other compositions used as needed and solvent additional as needed, so as to obtain target indigo plant Color sensation photosensitive resin composition.
<colour filter and image display device>
Another mode of the invention is related to a kind of including forming the blue-sensitive of blue color patterns layer containing being previously described for The colour filter of the blue color patterns layer of the solidfied material of resin combination.
Colour filter of the invention is due to form the blue-sensitive resin combination of blue color patterns layer using being previously described for It is prepared instead of blue quantum dot, therefore has the advantages that can reduce manufacturing cost and can ensure excellent visual angle.
Further, since blue-sensitive resin combination of the invention includes to contain benzotriazole, triazines and hexichol UV absorbent more than one of ketone class, therefore the indigo plant prepared including the use of blue-sensitive resin combination of the invention The colour filter of chromatic graph pattern layer is possibly able to realize following colour filter especially self-luminous colour filter: that is, the colour filter is heat-resisting Property is excellent and xanthochromia does not occur at high temperature the variation of luminous intensity may be not present, and is capable of forming the fine pattern of specified value And the bad problem of realization for improving fine pixel.
Above-mentioned colour filter includes the blue color patterns layer of substrate with the top for being formed in aforesaid substrate.
Aforesaid substrate can be the substrate of above-mentioned colour filter itself, or be also possible to display device etc. in locating for colour filter Position, be not particularly limited.Aforesaid substrate can be glass, silicon (Si), Si oxide (SiOx) or polymeric substrate, above-mentioned Polymeric substrate can be polyether sulfone (polyethersulfone, PES) or polycarbonate (polycarbonate, PC) etc..
Above-mentioned blue color patterns layer is the layer comprising blue-sensitive resin combination of the invention, be can be by coating It states the blue-sensitive resin combination for being used to form blue color patterns layer and is exposed with defined pattern, developed and heat cure And the layer formed, above-mentioned pattern layer can be formed by executing the usually well-known method in this field.
In another embodiment of the invention, above-mentioned colour filter can further comprise selected from by red pattern layer and green It is more than one of group of pattern layer composition.
In another embodiment of the invention, above-mentioned red pattern layer or green pattern layer may include quantum dot and/or Scattering particles.Specifically, colour filter of the invention may include comprising red quantum dot red pattern layer or comprising green The green pattern layer of quantum dot, above-mentioned red pattern layer or green pattern layer may include scattering particles.Above-mentioned red pattern layer or Green pattern layer can issue respectively feux rouges or blue light by the aftermentioned light source for issuing blue light.
It include the scattering particles in above-mentioned red pattern layer or green pattern layer in another embodiment of the invention It may include the metal oxide that average path is 30 to 500nm, content energy relevant to above-mentioned scattering particles and metal oxide Enough applications to include scattering particles in blue-sensitive resin combination of the invention and the relevant content of metal oxide.
In the present invention, include the form of above-mentioned red pattern layer or the quantum dot in green pattern layer, structure and its Content is not limited, and can apply quantum dot usually used in this field.
Colour filter including substrate as described above and pattern layer can further comprise the next door being formed between each pattern, Also it may further include black matrix, but not limited to this.
In the present invention, above-mentioned colour filter can be self-luminous colour filter.
Another mode of the invention is related to a kind of image display dress including colour filter above-mentioned and the light source for issuing blue light It sets.For example, image display device of the invention includes the blue of the solidfied material containing blue-sensitive resin combination above-mentioned The colour filter of pattern layer and the light source for issuing blue light.
Colour filter of the invention can be applied not only to common liquid crystal display device, can also be applied to electroluminance display The various image display devices such as device, plasm display device, field emission display device.
Include the case where colour filter and above-mentioned light source containing blue color patterns layer of the invention in above-mentioned image display device Under, existing has the advantages that excellent luminous intensity or visual angle.In addition, including the blue color patterns layer in colour filter of the invention Due to the advantages of not comprising blue quantum dot, presence can produce manufacturing cost low image display device.
Embodiment
In the following, being described in detail taking the embodiment as an example to illustrate this specification.But in this specification Embodiment can be deformed into various other ways, and the range that should not be construed as this specification is defined in embodiment described below.This The embodiment of specification is provided in order to which those of ordinary skill in the art are more completely illustrated with this specification.In addition, with Under, as long as no specifically mentioned, then it represents that " % " and " part " of content is weight basis.
Synthesis example: the synthesis of bonding agent resin
Preparation example 1: acrylic compounds alkali soluble resins
Prepare the flask for having blender, thermometer, reflux condensing tube, dropping funel and nitrogen ingress pipe, and conduct Benzyl maleimide 7.8g (0.20 mole), acrylic acid 43.2g (0.30 mole), vinyl first is added in monomer dropping funel After benzene 118.0g (0.50 mole), t-butyl peroxy -2 ethyl hexanoic acid ester 4g, propylene glycol monomethyl ether (PGMEA) 40g Be stirred and prepare, as chain-transferring agent dropwise adding tank, prepare to be stirred after n-dodecane mercaptan 6g, PGMEA24g is added and At.Later, into flask import PGMEA 395g, and by the atmosphere in flask from air displacement at nitrogen after, stirring The temperature of flask is warming up to 90 DEG C simultaneously.Then, monomer and chain-transferring agent are added dropwise since dropping funel.When dropwise addition, tieing up It is carried out respectively 2 hours while holding 90 DEG C, and is warming up to 110 DEG C after 1h and maintains 3 hours, be then introduced into gas and lead Enter pipe, starts the bubbling of oxygen/nitrogen=5/95 (v/v) mixed gas.Then, by glycidyl methacrylate 28.4g [(0.10 mole), (carboxyl relative to the acrylic acid used in this reaction is 33 moles of %)], 2,2 '-di-2-ethylhexylphosphine oxide (4- Methyl-6-tert-butylphenol) 0.4g, triethylamine 0.8g be added flask in, the reaction was continued at 110 DEG C 8 hours, obtain solid at Dividing acid value is the Resin A of 70mgKOH/g.Weight average molecular weight by the polystyrene conversion of GPC measurement is 16,000, molecular weight Being distributed (Mw/Mn) is 2.3.
Preparation example 2: the synthesis of the compound of chemical formula 1-1-1
3 ', 6 '-dihydroxy spiral shells (fluorenes -9,9 '-xanthene) (3', 6 ' '-is mixed in the three neck round bottom flask of 3000ml Dihydroxyspiro (fluorene-9,9-xantene) 364.4g and tert-butyl ammonium bromide 0.4159g, and table chlorine is added It is heated to 90 DEG C after alcohol 2359g and is allowed to react.It is analyzed by liquid chromatogram, if 3 ', 6 '-dihydroxy spiral shells (fluorenes -9, 9 '-xanthenes) it is completely depleted, then 30 DEG C are cooled to, 50%NaOH aqueous solution (3 equivalent) is slowly added.It is carried out by liquid chromatogram Analysis, if epichlorohydrin is completely depleted, benefit is washed 3 times after being extracted with dichloromethane, and then keeps organic layer dry using magnesium sulfate It is evaporated under reduced pressure methylene chloride after dry, and using methylene chloride and methanol and is recrystallized with mixing ratio 50:50.
In 1 equivalent of epoxide, 0.004 equivalent of tert-butyl ammonium bromide, the 2,6- diisobutyl benzene that mixing so synthesizes After 2.2 equivalent of 0.001 equivalent of phenol and acrylic acid, solvent propylene glycol monomethyl ether acetate 24.89g is added and is mixed.? Air is blown into 25ml/min in the reaction solution and is heated to 90~100 DEG C of temperature and is allowed to dissolve.In reaction solution gonorrhoea 120 DEG C of temperature are heated under state to be allowed to be completely dissolved.If solution becomes transparent and viscosity is got higher, acid value is measured, and It is stirred until acid value is lower than 1.0mgKOH/g.Acid value needs 11 hours until reaching target (0.8).Terminate in reaction Later, the temperature of reactor is reduced to room temperature, obtains the compound of colorless and transparent chemical formula 1-1-1.
[chemical formula 1-1-1]
Preparation example 3: the synthesis of the compound of chemical formula 1-1-2
3 ', the 6 '-dihydroxy spiral shells (fluorenes -9,9 '-xanthene) of mixed chemical formula 2-1 in the three neck round bottom flask of 3000ml (3', 6 ' '-dihydroxyspiro (fluorene-9,9-xantene) 364.4g and tert-butyl ammonium bromide 0.4159g, and 90 DEG C are heated to after epichlorohydrin 2359g is added and are allowed to react.It is analyzed by liquid chromatogram, if 3 ', 6 '-dihydroxy spiral shells (9,9 '-xanthene of fluorenes -) is completely depleted, then is cooled to 30 DEG C, is slowly added 50%NaOH aqueous solution (3 equivalent).Pass through liquid phase color Spectrum is analyzed, if epichlorohydrin is completely depleted, benefit is washed 3 times after being extracted with dichloromethane, and then makes to have using magnesium sulfate It is evaporated under reduced pressure methylene chloride after machine layer is dry, and using methylene chloride and methanol and is recrystallized with mixing ratio 50:50.
In 1 equivalent of epoxide, 0.004 equivalent of tert-butyl ammonium bromide, the 2,6- diisobutyl benzene that mixing so synthesizes After 2.2 equivalent of 0.001 equivalent of phenol and methacrylic acid, solvent propylene glycol monomethyl ether acetate 24.89g is added and is mixed It closes.Air is blown into 25ml/min in the reaction solution and is heated to 90~100 DEG C of temperature and is allowed to dissolve.It is white in reaction solution 120 DEG C of temperature are heated in the state of turbid to be allowed to be completely dissolved.If solution becomes transparent and viscosity is got higher, acid value is measured, And it is stirred until acid value is lower than 1.0mgKOH/g.Acid value needs 11 hours until reaching target (0.8).It is reacting After end, the temperature of reactor is reduced to room temperature, obtains the compound of colorless and transparent chemical formula 1-1-2.
[chemical formula 1-1-2]
Preparation example 4: the synthesis of the compound of chemical formula 1-2-1
4,4 '-(9H- xanthene -9,9- diyl) xenol (4,4'- (9H- are mixed in the three neck round bottom flask of 3000ml Xanthene-9,9-diyl) diphenol) 364.4g and tert-butyl ammonium bromide 0.4159g, and after epichlorohydrin 2359g is added It is heated to 90 DEG C and is allowed to react.It is analyzed by liquid chromatogram, if 4,4 '-(9H- xanthene -9,9- diyl) xenols are complete Fully- depleted is then cooled to 30 DEG C, is slowly added 50%NaOH aqueous solution (3 equivalent).It is analyzed by liquid chromatogram, if table Chloropharin is completely depleted, then washes after benefit is extracted with dichloromethane 3 times, decompression is steamed after then keeping organic layer dry using magnesium sulfate Methylene chloride is evaporated, and using methylene chloride and methanol and is recrystallized with mixing ratio 50:50.In the ring that mixing so synthesizes 1 equivalent of oxygen compound, 2.2 equivalent of 0.004 equivalent of tert-butyl ammonium bromide, 0.001 equivalent of 2,6- diisobutyl phenol and acrylic acid Later, solvent propylene glycol monomethyl ether acetate 24.89g is added to be mixed.It is blown into the reaction solution with 25ml/min Air is simultaneously heated to 90~100 DEG C of temperature and is allowed to dissolve.120 DEG C of temperature are heated in the state of reaction solution gonorrhoea to be allowed to Fully dissolved.If solution becomes transparent and viscosity is got higher, measure acid value, and until acid value lower than until 1.0mgKOH/g into Row stirring.Acid value needs 11 hours until reaching target (0.8).After the reaction, the temperature of reactor is reduced to room Temperature obtains the compound of colorless and transparent chemical formula 1-2-1.
[chemical formula 1-2-1]
Preparation example 5: the synthesis of the compound of chemical formula 1-2-2
4,4 '-(9H- xanthene -9,9- diyl) xenol (4,4'- (9H- are mixed in the three neck round bottom flask of 3000ml Xanthene-9,9-diyl) diphenol) 364.4g and tert-butyl ammonium bromide 0.4159g, and after epichlorohydrin 2359g is added It is heated to 90 DEG C and is allowed to react.It is analyzed by liquid chromatogram, if 4,4 '-(9H- xanthene -9,9- diyl) xenols are complete Fully- depleted is then cooled to 30 DEG C, is slowly added 50%NaOH aqueous solution (3 equivalent).It is analyzed by liquid chromatogram, if table Chloropharin is completely depleted, then washes after benefit is extracted with dichloromethane 3 times, decompression is steamed after then keeping organic layer dry using magnesium sulfate Methylene chloride is evaporated, and using methylene chloride and methanol and is recrystallized with mixing ratio 50:50.In the ring that mixing so synthesizes 1 equivalent of oxygen compound, 0.004 equivalent of tert-butyl ammonium bromide, 0.001 equivalent of 2,6- diisobutyl phenol and methacrylic acid 2.2 After equivalent, solvent propylene glycol monomethyl ether acetate 24.89g is added and is mixed.With 25ml/min in the reaction solution It is blown into air and is heated to 90~100 DEG C of temperature and be allowed to dissolve.120 DEG C of temperature are heated in the state of reaction solution gonorrhoea to be made Be completely dissolved.If solution becomes transparent and viscosity is got higher, acid value is measured, and until acid value is lower than 1.0mgKOH/g Only it is stirred.Acid value needs 11 hours until reaching target (0.8).After the reaction, the temperature of reactor is reduced To room temperature, the compound of colorless and transparent chemical formula 1-2-2 is obtained.
[chemical formula 1-2-2]
The synthesis (A-1) of preparation example 6:Cardo class adhesive resin
Propylene glycol monomethyl ether 600g is added simultaneously in the compound 307.0g of the chemical formula 1-1-1 of preparation example 2 It is allowed to after dissolving, mixes biphenyltetracarboxylic dianhydride 78g and tetraethylammonium bromide 1g, be allowed to slowly heat up and 110~115 It is reacted 4 hours at DEG C.After confirmation anhydride group disappears, 1,2,3,6- tetrabydrophthalic anhydride 38.0g are mixed, at 90 DEG C Reaction 6 hours, aggregates into Cardo system adhesive resin.Anhydrous thing's vanished is confirmed by IR spectrogram.Weight averaged molecular Amount is 3500.
The synthesis (A-2) of preparation example 7:Cardo class adhesive resin
Propylene glycol monomethyl ether 600g is added simultaneously in the compound 307.0g of the chemical formula 1-1-2 of preparation example 3 It is allowed to after dissolving, mixes biphenyltetracarboxylic dianhydride 78g and tetraethylammonium bromide 1g, be allowed to slowly heat up and 110~115 It is reacted 4 hours at DEG C.After confirmation anhydride group disappears, 1,2,3,6- tetrabydrophthalic anhydride 38.0g are mixed, at 90 DEG C Reaction 6 hours, aggregates into Cardo system adhesive resin.Anhydrous thing's vanished is confirmed by IR spectrogram.Weight averaged molecular Amount is 3800.
The synthesis (A-3) of preparation example 8:Cardo class adhesive resin
Propylene glycol monomethyl ether 600g is added simultaneously in the compound 307.0g of the chemical formula 1-2-1 of preparation example 4 It is allowed to after dissolving, benzene mixed tetracarboxylic dianhydride 78g and tetraethylammonium bromide 1g are allowed to slowly heat up and at 110~115 DEG C Lower reaction 4 hours.After confirmation anhydride group disappears, 1,2,3,6- tetrabydrophthalic anhydride 38.0g are mixed, it is anti-at 90 DEG C It answers 6 hours, aggregates into Cardo system adhesive resin.Anhydrous thing's vanished is confirmed by IR spectrogram.Weight average molecular weight It is 4500.
The synthesis (A-9) of preparation example 9:Cardo class adhesive resin:
Propylene glycol monomethyl ether 600g is added simultaneously in the compound 307.0g of the chemical formula 1-2-2 of preparation example 5 It is allowed to after dissolving, benzene mixed tetracarboxylic dianhydride 78g and tetraethylammonium bromide 1g are allowed to slowly heat up and at 110~115 DEG C Lower reaction 4 hours.After confirmation anhydride group disappears, 1,2,3,6- tetrabydrophthalic anhydride 38.0g are mixed, it is anti-at 90 DEG C It answers 6 hours, aggregates into Cardo system adhesive resin.Anhydrous thing's vanished is confirmed by IR spectrogram.Weight average molecular weight It is 4900.
Device: HLC-8120GPC (TOSOH Co., Ltd's manufacture)
Column: TSK-GELG4000HXL+TSK-GELG2000HXL (series connection)
Column temperature: 40 DEG C
Mobile phase solvent: tetrahydrofuran
Flow velocity: 1.0mL/ minutes
Injection rate: 50 μ L
Detector: RI
Measure sample concentration: 0.6 weight % (solvent=tetrahydrofuran)
Calibration standard substance: TSK STANDARD POLYSTYRENE the F-40, (east F-4, F-1, A-2500, A-500 Cao Co., Ltd. manufacture)
The ratio of weight average molecular weight obtained above and number-average molecular weight is set as molecular weight distribution (Mw/Mn)
Embodiment 1 to 9 and comparative example 1 to 4: the preparation of blue-sensitive resin combination
According to the composition of following table 1 to 3, the blue-sensitive resin combination of embodiment 1 to 9 and comparative example 1 to 4 is prepared (table 1 indicates that scattering particles, table 2 indicate that the composition of embodiment, table 3 indicate the composition composition and content of comparative example).
[table 1]
[table 2]
0)Blue colorant: CI pigment blue 15: 6
1)Bonding agent resin:
A-1: preparation example A-1
A-2: preparation example A-2
A-3: preparation example A-3
A-4: preparation example A-4
A-5: single (2- methacryloxyalkyl) ester
2)Photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA；Japanese chemical drug (strain) manufacture)
3) Photoepolymerizationinitiater initiater
D-1:Irgaqure-907 (BASF AG's system)
D-2:OXE-01 (BASF AG's system)
D-3:OXE-02 (BASF AG's system)
D-4:PBG-327 (troni system, chemical formula 5-3)
5)F-1:TINUVIN 109 (BASF AG's system)-benzotriazole
F-2:TINUVIN 328 (BASF AG's system)-benzotriazole
F-3:TINUVIN 1577 (BASF AG's system)-triazines
F-4:TINUVIN 400 (BASF AG's system)-triazines
F-5:Chimassorb 81 (BASF AG's system)-benzophenone
6)Solvent (E): propylene glycol monomethyl ether
[table 3]
0)Blue colorant: C.I pigment blue 15: 6
1)Bonding agent resin
A-1: preparation example A-1
A-2: preparation example A-2
A-3: preparation example A-3
A-4: preparation example A-4
A-5: single (2- methacryloxyalkyl) ester
2)Photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA；Japanese chemical drug (strain) manufacture)
3)Photoepolymerizationinitiater initiater
D-1:Irgaqure-907 (BASF AG's system)
D-2:OXE-01 (BASF AG's system)
D-3:OXE-02 (BASF AG's system)
D-4:PBG-327 (troni system, chemical formula 5-3)
5)F-1:TINUVIN 109 (BASF AG's system)-benzotriazole
F-2:TINUVIN 328 (BASF AG's system)-benzotriazole
F-3:TINUVIN 1577 (BASF AG's system)-triazines
F-4:TINUVIN 400 (BASF AG's system)-triazines
F-5:Chimassorb 81 (BASF AG's system)-benzophenone
6)Solvent (E): propylene glycol monomethyl ether
The manufacture of colour filter
It is made using by above-described embodiment 1 to 9 and the metal oxide photosensitive polymer combination of the manufacture of comparative example 1 to 4 Make colour filter.That is, above-mentioned each photosensitive polymer combination is coated on glass substrate using spin-coating method, it is then placed into and adds On hot plate, and 100 DEG C at a temperature of maintain 3 minutes and form film.
Then, mode has the square transmission pattern and 1 to 100 of width × a height of 20mm × 20mm on the above-mentioned films μm line/space pattern test photomask, be divided into 100um to test between photomask and irradiate ultraviolet light.
At this point, ultraviolet light source utilizes the ultrahigh pressure mercury lamp (trade name USH-250D) of oxtail Motor Corporation, in atmosphere With 200mJ/cm under atmosphere2Light exposure (365nm) carry out light irradiation, special optical filter is not used.
The above-mentioned film through ultraviolet light irradiation is impregnated 80 seconds in the KOH aqueous development solution of pH10.5 and is carried out Development.After the glass plate cleaning of the film will be covered with using distilled water, brushes nitrogen and be allowed to drying, in 150 DEG C of heating It is heated 10 minutes in baking oven, manufactures color filter pattern.The film thickness of the above-mentioned multicolour pattern produced is 5.0 μm.
Experimental example 1: developing powder, sensitivity, pattern stability and the heat-resistant experiment of colour filter
It is pair with the colour filter manufactured by the blue-sensitive resin combination of above-described embodiment 1 to 9 and comparative example 1 to 4 As being evaluated as following table 4.Evaluation criteria about each experiment is as follows.Developing powder (sec): development < spray developing Device (Spray Developer) HPMJ mode > non-exposed portion starts the time required when dissolution in developer solution
Sensitivity: (numerical value is lower, spirit for the degree for the film that formation sensitivity mask fine pattern (1~60) is not peeled off Sensitivity is more excellent)
Pattern stability: error (error) journey of the pattern of pattern mask after exposure when low light exposure (20~100mJ) Degree
Very outstanding: pattern does not have error
Outstanding: pattern errors are 1~2
Common: pattern errors are 3
Bad: pattern errors are 4 or more
Benchmark is judged for the confirmation result that carries out by the optical microscopy of 3 D surface shape instrument
Evaluation of Heat Tolerance and brightness change: the colour filter prepared by the above method is heated two in 230 DEG C of heating furnace It is heated after hour
In order to measure the color change of front and back, calculated by mathematical expression (1), and confirm Evaluation of Heat Tolerance front and back Brightness (Δ Y) variation, to be confirmed whether to reduce brightness because of hot xanthochromia.
Δ Y (brightness change) degree
Zero: -0.04 or more and 0.00 or less
X: less than -0.04
[table 4]
Therefore, table 4 is checked, the developing powder for confirming embodiment 1 to 9 is 15 or less and the excellent effect with process aspect Fruit, sensitivity be 50 or less and it is excellent, and not the pattern errors after the exposure of pattern mask and pattern stability is very excellent Different, heat resistance is also excellent.
On the contrary, not comprising Cardo class adhesive resin and only using acrylic compounds alkali solubility in the case where comparative example 2 Resin and be not easy to solidify and be easily peeled off and can not measured value.In the case where comparative example 3, it is detached from the suitable of photopolymerizable compound Work as range, it is difficult to be solidified, and pattern is removed.In addition, in the case where comparative example 4, confirm that there is no UV absorptions Agent and be difficult to adjust free radical and be difficult to bear heat resistance.
Experimental example 2: fine pattern forms experiment
It is manufactured using the metal oxide photoresist prepared by above-described embodiment 1 to 9 and comparative example 1 to 4 In colour filter, the size of the pattern obtained for using the line/space pattern mask designed with 100 μm uses OM equipment The size of (ECLIPSE LV100POL Nikon Corporation) measurement pattern.
[table 5]
It divides Fine pattern
Embodiment 1 11
Embodiment 2 15
Embodiment 3 10
Embodiment 4 10
Embodiment 5 13
Embodiment 6 12
Embodiment 7 9
Embodiment 8 13
Embodiment 9 12
Comparative example 1 17
Comparative example 2 Film is torn
Comparative example 3 Film is torn
Comparative example 4 50
If the difference of line/space pattern mask design value and the measured value of obtained fine pattern is 20 μm or more, It is difficult to realize fine pixel, and it is possible to problem occur in terms of the rectilinear propagation of pattern and planarization, and it is possible to be difficult to Taper needed for realizing.
Therefore, it checks table 5, confirms the design value of pattern mask and obtained fine figure in the case where embodiment 1 to 9 The difference of the measured value of case can be realized fine pixel for 20 μm or less, and pattern properties are excellent.
On the contrary, only it is not easy to realize that hardening and generate film tears phenomenon comprising acrylic resin in the case where comparative example 2, It in the case where comparative example 3, is difficult to realize harden because being detached from the proper range of photopolymerizable compound, and generates film and tear It opens.In addition, confirming in the case where comparative example 4, fine pattern is difficult to realize because UV absorbent is not present.
Experimental example 3: luminous intensity measurement
It is manufactured using the metal oxide photoresist prepared by above-described embodiment 1 to 9 and comparative example 1 to 4 In colour filter, by 365nm cast 4W UV illuminator (VL-4LC, VILBER LOURMAT) with the pros of 20mm × 20mm The part that the pattern of shape is formed measures the transformed region of light, and (Spectrometer, marine optics are public using spectrometer Department) to the luminous intensity in embodiment 1 to 9 and the measurement of comparative example 1 to 4 region 450nm.
[table 6]
The luminous intensity determined is higher, it is meant that light efficiency is higher.
Confirm in the case where embodiment 1 to 9 because light emission luminosity be 2 or more due to light efficiency it is excellent.On the contrary, being able to confirm that Tear phenomenon to being not easy to realize hardening and generate film because only including acrylic resin in the case where comparative example 2, and than Light efficiency declines due to UV absorbent is not present in the case where compared with example 4.
Experimental example 4: visual angle measurement
It is manufactured using the metal oxide photoresist prepared by above-described embodiment 1 to 9 and comparative example 1 to 4 In colour filter, using goniophotometer (GC-5000L, Japan's electricity color) in the part that the pattern by 20 × 20mm square is formed The intensity (Intensity) for the light that measurement is generated with the visual angle under light transmission condition, and diffusivity is calculated using following formula 1.
[formula 1]
Diffusivity=(B70+B20)/2×B5×100
(B θ=I θ/cos θ)
I refers to the luminous intensity measured under each angle, B70、B20And B5Refer to the value measured under 70 degree, 20 degree and 5 degree.
[table 7]
The diffusivity determined is higher, it is meant that visual angle is better.Therefore, it checks table 7, is able to confirm that in embodiment 1 to 9 In the case where visual angle be improved.In addition, comparative example 4 the case where and in the case where UV absorbent is not present, diffusivity declines.
Industrial feasibility
The present invention is due to including to contain benzotriazole, triazines and hexichol in above-mentioned blue-sensitive resin combination UV absorbent more than one of ketone class, therefore can be realized following colour filter especially self-luminous colour filter: that is, the filter The excellent heat resistance of color device and xanthochromia does not occur at high temperature the variation of luminous intensity may be not present, and is capable of forming specified value Fine pattern and have excellent pattern properties, the bad problem of realization so as to improve fine pixel.Furthermore it is possible to mention For a kind of self-luminous colour filter of high quality image quality with excellent visual angle.

Claims (16)

1. a kind of blue-sensitive resin combination, comprising scattering particles, blue colorant, as the Cardo of adhesive resin Class adhesive resin, photopolymerizable compound, Photoepolymerizationinitiater initiater, UV absorbent and solvent,
Wherein, the UV absorbent includes one of benzotriazole, triazines and benzophenone or more.
2. blue-sensitive resin combination according to claim 1, wherein
The scattering particles include the metal oxide that average grain diameter is 10 to 1000nm.
3. blue-sensitive resin combination according to claim 1, wherein
The scattering particles include selected from by Al2O3、SiO2、ZnO、ZrO2、BaTiO3、TiO2、Ta2O5、Ti3O5、Nb2O3, SnO and It is more than one of group of MgO composition.
4. blue-sensitive resin combination according to claim 1, wherein
The blue-sensitive resin combination also includes violet colorant.
5. blue-sensitive resin combination according to claim 1, wherein
The blue colorant includes one of blue pigment and blue dyes or more.
6. blue-sensitive resin combination according to claim 1, wherein
The Cardo class adhesive resin includes one in the compound indicated with following chemical formula 1-1 and following chemical formula 1-2 It is more than person,
[chemical formula 1-1]
[chemical formula 1-2]
Wherein, in the chemical formula 1-1 or the chemical formula 1-2,
R1、R2、R3And R4Separately it is
The alkyl or hydroxyl that X is hydrogen atom, carbon atom number is 1 to 5；
R5The alkyl for being 1 to 5 for hydrogen atom or carbon atom number.
7. blue-sensitive resin combination according to claim 1, wherein
The Cardo class adhesive resin includes selected from by bis- (the 3- cortex cinnamomi acid diesters) fluorenes (9,9-bis (3-cinnamic of 9,9- Diester) fluorene), 9,9- bis- (3- cinnamon oil, 4- hydroxy phenyl) fluorenes (9,9-bis (3-cinnamoil, 4- Hydroxyphenyl) fluorene), bis- (glycidyl methacrylate ether) fluorenes (9,9-bis (glycidyl of 9,9- Methacrylate ether) fluorene), the bis- two cinnamate (9,9-bis (3,4- of (3,4- dihydroxy phenyl) fluorenes of 9,9- Dihydroxyphenyl) fluorene dicinnamic ester), 3,6- 2-glycidyl methyl acrylate ether spiral shell (fluorenes -9,9- xanthene) (3,6-diglycidyl methacrylate ether spiro (fluorene-9,9-xantene)), 9,9- bis- (3- allyl, 4- hydroxy phenyl fluorenes) (9,9-bis (3-allyl, 4-hydroxyphenylfluorene)), 9,9- Bis- (4- allyloxy phenyl) fluorenes (9,9-bis (4-allyloxyphenyl) fluorene) and bis- (the 3,4- metering systems of 9,9- Acid diesters) fluorenes (9,9-bis (3,4-methacrylic diester) fluorene) composition at least one of group.
8. blue-sensitive resin combination according to claim 1, wherein
The blue-sensitive resin combination further comprises as the acrylic compounds alkali soluble resins of adhesive resin.
9. blue-sensitive resin combination according to claim 1, wherein
The Photoepolymerizationinitiater initiater include selected from one of compound for being indicated with following chemical formula 3 to following chemical formula 5 with On,
[chemical formula 3]
In the chemical formula 3, R8Can be hydrogen atom, halogen atom, hydroxyl, by carbon atom number be 1 to 12 it is alkyl-substituted Or unsubstituted phenyl, be 1 to 12 by carbon atom number alkyl-substituted or unsubstituted benzyl, by carbon atom number be 1 To 12 alkyl-substituted or unsubstituted naphthalene or-SRa, RaIt can be hydrogen, alkyl or benzyl that carbon atom number is 1 to 12 Base；
R9To R12Separately it is hydrogen atom, halogen atom, hydroxyl, is 1 to 12 alkyl-substituted or not by carbon atom number Substituted phenyl, be by carbon atom number 1 to 12 alkyl-substituted or unsubstituted benzyl or be 1 by carbon atom number To 12 alkyl-substituted or unsubstituted naphthalene；
The R11And R12It can be formed together ring,
[chemical formula 4]
In the chemical formula 4, R13For diphenyl sulfide ether, substituted diphenyl sulfide base, carbazyl, substituted carbazole base, fluorenyl or take For fluorenyl；
R14For hydrogen, carbon atom number be 1 to 20 alkyl, carbon atom number be 3 to 8 naphthenic base, unsubstituted or substituted Phenyl orWherein, the integer that n is 1~4, the integer that m is 1~6；
R15For alkyl, phenyl, substituted-phenyl, benzyl or substituted benzyl with 1~8 carbon atom,
[chemical formula 5]
In chemical formula 5, R16、R17And R18Separately indicate R, OR, COR, SR, CONRR', ROR' or CN；R and R' is indicated The aralkyl or carbon atom number that aryl that alkyl that carbon atom number is 1 to 20, carbon atom number are 6 to 30, carbon atom number are 7 to 30 For 2 to 20 heterocycle, aryl that alkyl that carbon atom number is 1 to 20, carbon atom number are 6 to 30, carbon atom number are 7 to 30 The heterocycle that aralkyl or carbon atom number are 2 to 20 can be replaced by the heterocycle that halogen atom or carbon atom number are 2 to 20, carbon The aralkyl or carbon atom number that aryl that alkyl that atomicity is 1 to 20, carbon atom number are 6 to 30, carbon atom number are 7 to 30 be The alkylene moiety of alkyl and aralkyl in 2 to 20 heterocycle can be by unsaturated bond, ehter bond, thioether bond or ester bond It is disconnected, and R and R' can be formed together ring；
Y1Indicate that oxygen atom, sulphur atom or selenium atom, m indicate that 0~4 integer, p indicate 0~5 integer；
Q indicates 0 or 1；
R19、R20、R21And R22Separately indicate that hydrogen atom, halogen atom or carbon atom number are 1 to 8 alkyl；
X1And X2Indicate the virtue that aryl, carbon atom number that alkyl, carbon atom number that carbon atom number is 1 to 20 are 6 to 30 are 7 to 30 The heterocycle that alkyl or carbon atom number are 2 to 20, aryl that alkyl that carbon atom number is 1 to 20, carbon atom number are 6 to 30, carbon The heterocycle that the aralkyl or carbon atom number that atomicity is 7 to 30 are 2 to 20 can be 2 to 20 by halogen atom or carbon atom number Heterocycle replace, the virtue that aryl that alkyl that carbon atom number is 1 to 20, carbon atom number are 6 to 30, carbon atom number are 7 to 30 The alkylene moiety for the alkyl and aralkyl in heterocycle that alkyl or carbon atom number are 2 to 20 can by unsaturated bond, ehter bond, Thioether bond or ester bond interrupt；
X2Ring can be formed together with adjacent nuclear carbon atom；
Y2And Y3Separately indicate oxygen atom, sulphur atom or selenium atom.
10. blue-sensitive resin combination according to claim 1, wherein
The Photoepolymerizationinitiater initiater includes to be selected from one of group being made of following chemical formula or more,
[chemical formula 5-1]
[chemical formula 5-2]
[chemical formula 5-3]
[chemical formula 5-4]
[chemical formula 5-5]
[chemical formula 5-6]
[chemical formula 5-7]
[chemical formula 5-8]
11. blue-sensitive resin combination according to claim 1, wherein
Relative to the total weight of the solid component in the blue-sensitive resin, include: the scattering of 0.1 to 50 weight % Particle；The blue colorant of 0.1 to 50 weight %；The described adhesive resin of 5 to 85 weight %；5 to 50 weight %'s Photopolymerizable compound；The photoinitiator of 0.1 to 20 weight %；And 0.001 to 10 weight % UV absorbent, it is described UV absorbent includes one of the benzotriazole, triazines and benzophenone or more, relative to the blue sensitive The total weight of property resin combination, the solvent comprising 60 to 90 weight %.
12. a kind of colour filter, including as according to claim 1 to the blue-sensitive resin described in any one of claim 11 The blue color patterns layer that composition is constituted.
13. colour filter according to claim 12, wherein
The colour filter further includes more than one of group being made of red pattern layer and green pattern layer.
14. colour filter according to claim 13, wherein
The red pattern layer or the green pattern layer include quantum dot.
15. colour filter according to claim 14, which is characterized in that
The colour filter is self-luminous colour filter.
16. a kind of image display device, comprising:
Colour filter according to claim 12；And
Emit the light source of blue light.
CN201780081423.2A 2017-03-31 2017-11-30 Blue-sensitive resin combination, the colour filter and image display device manufactured using the composition Pending CN110121679A (en)

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