CN110268328A - 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
CN110268328A
CN110268328A CN201780086103.6A CN201780086103A CN110268328A CN 110268328 A CN110268328 A CN 110268328A CN 201780086103 A CN201780086103 A CN 201780086103A CN 110268328 A CN110268328 A CN 110268328A
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blue
chemical formula
bis
sensitive resin
epoxy resin
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CN201780086103.6A
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CN110268328B (en
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申奎澈
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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    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—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

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mathematical Physics (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention relates to a kind of 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, photoinitiator, photopolymerizable compound, thermal curing agents and solvent as adhesive resin, wherein, the thermal curing agents include one of multifunctional cycloaliphatic epoxy resin, silane-modified epoxy resin and phenol aldehyde type epoxy resin 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.However, a part of light is colored device and absorbs and light efficiency during the light irradiated from light source penetrates colour filter Decline, and the problem of colorrendering quality declines due to occur the characteristic of the pigment contained in the colour filter.
In particular, not required nothing more than excellent as colour filter uses in the various fields headed by various image display devices Different pattern properties, and while require high color reproduction rate, it is desirable that the property as excellent high brightness and high contrast Energy.In order to solve this problem, it proposes and is manufactured using the colour filter of the self-luminous photosensitive polymer combination comprising quantum dot Method.
KR published patent the 2013-0000506th be related to a kind of display device, discloses and include color converting The related content of display device, which includes: multiple wavelength convert particles, the wavelength for conversion light；And it is more A colour filter particle, for absorbing the light of predetermined band in above-mentioned light.
But the photosensitive polymer combination developed so far in order to manufacture colour filter is unable to fully meet with excellent The effect at excellent visual angle is provided while different pattern properties, heat resistance and resistance to stability.
Summary of the invention
Technical problem
The object of the present invention is to provide a kind of can also to prevent blue pixel in the case where not including blue quantum dot The blue-sensitive resin combination of efficiency decline and reduction manufacturing cost is shown using the colour filter and image of the composition manufacture Showing device.
Technical solution
The present invention provides a kind of blue-sensitive resin combination, comprising scattering particles, blue colorant, as adhesive Cardo class adhesive resin, photoinitiator, photopolymerizable compound, thermal curing agents and the solvent of resin, which is characterized in that on State thermal curing agents include one of multifunctional cycloaliphatic epoxy resin, silane-modified epoxy resin and phenol aldehyde type epoxy resin with On.
In addition, the present invention provides a kind of colour filter, including the blue being made of above-mentioned blue-sensitive resin combination Pattern layer.
In addition, the present invention provides a kind of image display device, the light source including above-mentioned colour filter and transmitting blue light.
Beneficial effect
Excellent heat resistance and Huang will not occur at high temperature for the present invention due to comprising blue-sensitive resin combination Become the variation that luminous intensity may be not present.Further it is provided that one kind can be by making degassing occurrence quantity minimize and work in panel When the image retention that is likely to occur in removal freely and the electrode because being formed in caused by the back taper during developing process between pixel Broken string and improve the undesirable colour filter of display.Furthermore it is possible to provide a kind of high quality image quality with excellent visual angle from Shine colour filter.
Specific embodiment
The present invention relates to a kind of blue-sensitive resin combinations.Blue-sensitive resin combination of the invention is not although Comprising blue quantum dot, also due to comprising scattering particles, blue colorant, as the Cardo class adhesive tree of adhesive resin Rouge and thermal curing agents, therefore can prevent the efficiency of blue pixel from declining and reduce manufacturing cost.
Specifically, blue-sensitive resin combination of the invention may include scattering particles, blue colorant, as viscous Cardo class adhesive resin, photoinitiator, photopolymerizable compound, thermal curing agents and the solvent of mixture resin.In particular, by Include multifunctional cycloaliphatic epoxy resin, silane-modified epoxy resin and phenol as above-mentioned thermal curing agents in composition of the invention More than one of aldehyde type epoxy resin, therefore scheme including the use of the blue that blue-sensitive resin combination of the invention manufactures The colour filter of pattern layer is capable of providing a kind of following colour filter, the excellent heat resistance of the colour filter and Huang will not occur at high temperature Become and the variation of luminous intensity may be not present, and is minimized by the occurrence quantity that makes to deaerate and be likely to occur in panel work It removes freely and improves due to being formed in the broken string of electrode between pixel caused by the back taper during developing process aobvious in image retention Show bad.Furthermore it is possible to provide a kind of colour filter of high quality image quality with excellent visual angle, one kind is more specifically provided Self-luminous colour filter and image display device including the self-luminous colour filter.
In the following, composition of the invention is described in detail.
Scattering particles
Scattering particles of the invention form excellent fine pattern in the case where average grain diameter is 30 to 500nm, from this From the point of view of any preferably.At this point, can expect the sufficient scattering effect of incident light in the case where average grain diameter belongs to above range The problem that scattering particles are deposited in composition will not occur for fruit, can obtain the light emitting layer surface of 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、 ITO、IZO、ATO、ZnO-Al、Nb2O3, SnO, MgO and their combination composition one of group more than.As needed, may be used With the material for using the compound with unsaturated bond by acrylate etc. to be surface-treated.
For above-mentioned scattering particles, the content in average grain diameter and overall composition is limited, so as to sufficiently mention The luminous intensity of high colour filter.
It in the present invention, may include 0.5 to 35 weight % relative to the total weight % of blue-sensitive resin combination Scattering particles preferably may include the scattering particles of 1 to 30 weight %.If the content of scattering particles is less than above range, nothing The luminous intensity that method ensures, in contrast to this in the case where the content of scattering particles is more than above range, not only Do not have stronger luminous intensity and increase effect, and the stability that composition occurs declines problem, therefore within the above range Suitably use scattering particles.
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..
It in the present invention, may include 0.5 to 40 weight % relative to the total weight % of blue-sensitive resin combination Blue colorant preferably may include the blue colorant of 0.5 to 30 weight %.It is met the above range in the content of blue colorant In the case where, it is able to suppress reflected ambient light, and efficiently show colour light emitting intensity, it can be ensured that viscosity stability.
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 the compound indicated with chemical formula 1-1 and chemical formula 1-2.
[chemical formula 1-1]
[chemical formula 1-2]
In above-mentioned chemical formula 1-1 or chemical formula 1-2, R1、R2、R3And R4Separately it isWherein, the alkyl or hydroxyl that X is hydrogen atom, carbon atom number is 1 to 5, R5For hydrogen atom Or the alkyl that carbon atom number is 1 to 5.
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 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 and/or acrylic compounds alkali soluble Property resin.If molecular weight is within the above range, the hardness with film is improved and residual film ratio height, non-exposed portion are in developer solution In 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.
It in the present invention, may include 1.0 to 50 weight % relative to the total weight % of blue-sensitive resin combination Adhesive resin preferably may include the adhesive resin of 5.0 to 30 weight %.If the content of above-mentioned adhesive resin is above-mentioned In range, then deposit in developer solution dissolubility sufficiently, non-pixel portion be not likely to produce on substrate development residue and develop when The film for being not susceptible to the pixel portion of exposure portion is reduced 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.
It may include the optical polymerism of 0.5 to 20 weight % relative to the total weight % of blue-sensitive resin combination Object is closed, preferably may include the photopolymerizable compound of 1.0 to 10 weight %.Including the photopolymerizable compound in above range In the case where, sensitivity will not decline, and the adherence of photo-sensitive resin is too strong and film-strength is insufficient, will not send out in development Raw pattern loss problem.
Photoinitiator
Photoinitiator used in the present invention plays the sensitivity of enhancing photosensitive polymer combination and mentions large-duty Effect, preferably comprises acetophenone compounds.As acetophenone compounds, such as diethoxy acetophenone, 2- hydroxyl can be enumerated Base-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- methylphenyl-sulfanyl)-2- morpholino propane-1- ketone, 2- Benzyl -2- dimethylamino -1- (4- morphlinophenyl) butane -1- ketone, 2- hydroxy-2-methyl [4- (1- methyl ethylene) benzene Base] propane -1- ketone oligomer etc., can preferably enumerate 2- benzyl -2- dimethylamino -1- (4- morphlinophenyl) butane -1- Ketone etc..Furthermore, it is possible to which the Photoepolymerizationinitiater initiater other than above-mentioned acetophenones is applied in combination.Photopolymerization other than above-mentioned acetophenones Initiator, which can be enumerated, generates the living radical producing agent of living radical, sensitizer, acid agent etc. by irradiation light.As Living radical producing agent, such as benzoin class compound, benzophenone compound, thioxanthene ketone class compound, three can be enumerated Piperazine class compound etc..As 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 thioxanthene ketone class compound, such as 2-isopropylthioxanthone, 4- can be enumerated Isopropyl thioxanthone, 2,4- diethyl thioxanthone, bis- clopenthixal ketone of 2,4-, the chloro- 4- propoxythioxanthone of 1- etc..As triazines Compound, such as bis- (trichloromethyl) -6- (4- the methoxyphenyl) -1,3,5-triazines of 2,4-, bis- (three chloromethanes of 2,4- can be enumerated Base) -6- (4- methoxyl group naphthalene) -1,3,5- triazine, bis- (trichloromethyl) -6- (4- the methoxyl-styrene) -1,3,5- of 2,4- Bis- (the trichloromethyl) -6- of triazine, 2,4- [2- (5- methylfuran -2- base) vinyl] -1,3,5- triazine, bis- (three chloromethanes of 2,4- Base) -6- [2- (furans -2- base) vinyl] -1,3,5- triazine, bis- (the trichloromethyl) -6- of 2,4- [2- (4- diethylamino -2- Aminomethyl phenyl) vinyl] -1,3,5- triazine, bis- (the trichloromethyl) -6- of 2,4- [2- (3,4- Dimethoxyphenyl) vinyl] - 1,3,5- triazine etc..As above-mentioned living radical producing agent, 2,4,6- trimethyl benzoyl diphenyl bases can be used for example Phosphine oxide, 2,2,-bis- (Chloro-O-Phenyls) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxaline, 10- butyl -2- chloro-acridine ketone, 2- second Base anthraquinone, 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- acetyl can be enumerated Phenyl dimethyl sulfonium tosilate, 4- acetoxyl group phenyl methyl benzyl sulfonium hexafluoro antimonate, triphenylsulfonium are to first Benzene sulfonate, triphenylsulfonium hexafluoro antimonate, diphenyl iodine tosilate, diphenyl iodine hexafluoro antimonate etc. Salt, nitrobenzyl tosylate class, benzoin toluenesulfonic acid salt etc..In addition, as living radical producing agent, it is above-mentioned There is also the compounds for generating living radical and acid simultaneously in compound, for example, triazine system Photoepolymerizationinitiater initiater can also be used Make acid agent.
In the present invention, the total weight relative to blue-sensitive resin combination may include the light of 0.1 to 15 weight % Initiator preferably may include the photoinitiator of 0.4 to 10 weight %.If the content of photoinitiator is within the above range, have There are intensity, the pixel portion table of the pixel portion for making blue-sensitive resin combination high-sensitivity and the composition being used to be formed The excellent tendency of the flatness in face, therefore preferably.
In addition, the present invention also may include photopolymerization initiator.Photopolymerization initiator sometimes with Photoepolymerizationinitiater initiater group It closes and uses, be the change that uses in order to promote the polymerization for the photopolymerizable compound for causing polymerization by Photoepolymerizationinitiater initiater Close object.As photopolymerization initiator, aminated compounds, alkoxy anthracene compound, thioxanthene ketone class compound etc. can be enumerated.
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- can be enumerated Dimethoxy anthracene, 2- ethyl -9,10- dimethoxy anthracene, 9,10- diethoxy anthracene, 2- ethyl -9,10- diethoxy anthracene etc..Make For thioxanthones based compound, such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- diethyl thioxanthone, 2 can be enumerated, Chloro- 4- propoxythioxanthone of bis- clopenthixal ketone of 4-, 1- etc..The Photoepolymerizationinitiater initiater (D) can use individually or by multiple combinations. In addition, commercially available product also can be used as photopolymerization initiator, as commercially available photopolymerization initiator, such as can enumerate Trade name " EAB-F " (manufacturer: Baotugu Chemical 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.
Thermal curing agents
The thermal curing agents for including in the present invention play the deeply-curing of enhancing film and the effect of mechanical strength.Of the invention Thermal curing agents may include one of multifunctional cycloaliphatic epoxy resin, silane-modified epoxy resin and phenol aldehyde type epoxy resin with On.
Above-mentioned multifunctional cycloaliphatic epoxy resin is prepared and making diolefin compound that polymerization reaction occur, and is implemented according to one Example can be the cycloaliphatic epoxy resin of the compound comprising being indicated with chemical formula 3 or 4.
[chemical formula 3]
In above-mentioned chemical formula 3, n, m and l be 1~20 integer.
[chemical formula 4]
<3,4- epoxycyclohexyl -3,4- epoxycyclohexyl formic acid esters>
In addition, above-mentioned phenol aldehyde type epoxy resin is also possible to cresol novolac, following chemical formula 5 can be according to an embodiment Epoxy resin.
[chemical formula 5]
In above-mentioned chemical formula 5, o be 1~20 integer.
In addition, paracresol phenol aldehyde type epoxy resin (Sumiepoxy can be enumerated as commercially available phenol aldehyde type epoxy resin ESCN195XL- Sumitomo Chemical (strain) manufacture) and alicyclic epoxide compound " CEL-2021 ", alicyclic solid epoxidic tree It is rouge " EHPE-3150 ", epoxidized polybutadiene " PB3600 ", flexible aliphatic epoxide " CEL-2081 ", lactone-modified (being manufactured by Daisel chemical industry Co., Ltd) such as epoxy resin " PCL-G ".In addition to this, " Celloxide can be enumerated 2000 ", " EPOLED GT-3000 ", " GT-4000 " (being manufactured by Daisel chemical industry Co., Ltd).Conduct in them The curability of the ESCN-195XL of phenol aldehyde type epoxy resin is most excellent, in cycloaliphatic epoxy resin, " CEL-2021P " and " The curability of EHPE-3150 " is most excellent.These compounds also may be used singly or in combination of two or more, can also be with The other kinds of compound combination indicated later.
Above-mentioned silane-modified epoxy resin is the reactant of hydroxyl-containing epoxy resin and alkoxy silane.Contain hydroxyl as above-mentioned Base epoxy, such as bisphenol-type epoxy resin, phenol aldehyde type epoxy resin, glycidyl ester type epoxy resin, shrink can be enumerated Glyceramine type epoxy resin, linear aliphatic epoxy resins and aliphatic epoxy resin and biphenyl type epoxy resin etc..Wherein It is preferable to use bisphenol-type epoxy resin and phenol aldehyde type epoxy resins.Bisphenols and chloromethyloxirane or Alpha-Methyl can be passed through The reaction of the halogenated epoxide of chloromethyloxirane etc. obtains above-mentioned bisphenol-type epoxy resin.As above-mentioned bis-phenol The aldehyde of class, such as phenol or 2 can be enumerated, 6- dihalo phenol and formaldehyde, acetaldehyde, acetone, acetophenone, cyclohexanone, benzophenone etc. The reaction product of class or ketone and because dihydroxy benzenes sulphur peracid caused by aoxidize etherificate between product, hydroquinone Reaction product etc..It is especially most widely used using as the bisphenol-A of bisphenols, bis-phenol in these bisphenol-type epoxy resins S, Bisphenol F or their hydrogen additive be obtained bisphenol-type epoxy resin, and preferably.In addition, bisphenol-type epoxy resin has There is the hydroxyl that can be reacted with aftermentioned alkoxy silane.The hydroxyl need not have constitutes all points of bisphenol-type epoxy resin Son totally has hydroxyl as bisphenol-type epoxy resin.Although for example, indicating bisphenol type epoxy tree with following chemical formula 1 Rouge, but also may include the substance that m is 1 or more or the substance that m is O.
[chemical formula 6]
In above-mentioned chemical formula 6, q be 1 to 34 integer.
This bisphenol-type epoxy resin for example can also be and reacting phosphorus compound as P Modification biphenol type epoxy Resin uses.
For example, can be by obtaining halogenated epoxide reaction in phenol novolacs and cresol novolac resin Above-mentioned phenol aldehyde type epoxy resin.
For example, above-mentioned shrink can be obtained by other alkali acids and chloromethyloxirane reaction for making phthalic acid etc. Glycerol ester type epoxy resin.
For example, can be and the polyamines and chloromethyloxirane for making diaminodiphenylmethane, isocyanuric acid etc. be reacted Obtain above-mentioned glycidyl amine type epoxy resin.
For example, above-mentioned linear aliphatic epoxy tree can be obtained and the peracid using Peracetic acid etc. is to handle olefines Rouge and aliphatic epoxy resin.
For example, above-mentioned biphenyl type epoxy resin can be obtained by reacting bisphenols and chloromethyloxirane.
The preferred value of the epoxide equivalent of hydroxyl-containing epoxy resin is different according to the construction of hydroxyl-containing epoxy resin.It can basis Purposes suitably selects to use hydroxyl-containing epoxy resin.In general, using the very few hydroxyl-containing epoxy resin ingredient of epoxide equivalent In the case of be used as protective film when, due to exist and substrate close property decline the case where, hydroxyl-containing epoxy resin ingredient Epoxide equivalent is preferably 180 or more.
In addition, using the excessive hydroxyl-containing epoxy resin ingredient of epoxide equivalent, have and alkoxy silane When reaction the case where gelation, therefore the epoxide equivalent of hydroxyl-containing epoxy resin ingredient is preferably 5,000 or less.
Preferred epoxide equivalent is 200 to 400.
In addition, the alkoxy silane for sol-gel method generally can be used as above-mentioned alkoxy silane.
For example, the compound or their partial condensate indicated with chemical formula 7 can be enumerated.
[chemical formula 7]
R6pSi(OR7)4-p
In chemical formula 7, p indicates 0 or 1 integer, and R6 expression can have the functional group being directly connected on carbon atom Carbon atom number be 1 to 6 alkyl, carbon atom number be 1 to 6 aryl or carbon atom number be 2 to 6 unsaturated aliphatic it is residual Base, the alkyl that R7 indicates hydrogen atom or carbon atom number is 1 to 6, multiple R7 difference are identical or different.
More specifically, as the above-mentioned functional group about R6, such as vinyl, sulfydryl, epoxy group, epoxy third can be enumerated Oxygroup etc..
In addition, so-called " partial condensate " refers to the ring by being condensed in the alkoxy silane indicated with above-mentioned chemical formula 7 Substance obtained from a part of oxygroup.Can by acid or alkali and in the presence of water hydrolyzable above-mentioned alkoxy silane and Obtain this partial condensate.
It as the concrete example of this alkoxy silane, can enumerate: such as tetramethoxy-silicane, tetraethoxysilane, 4 third oxygen The tetraalkoxysilane class of base silane, tetraisopropoxysilan, four butoxy silanes etc.；Such as methyltrimethoxysilane, methyl Triethoxysilane, methyl tripropoxy silane, three butoxy silane of methyl, ethyl trimethoxy silane, ethyl triethoxy Silane, n-propyl trimethoxy silane, n-propyl triethoxysilane, isopropyltri-methoxysilane, isopropyl triethoxy Silane, vinyltrimethoxysilane, vinyltriethoxysilane, 3- glycidoxypropyltrime,hoxysilane, 3- ring Oxygen propoxypropyl triethoxysilane, 3-mercaptopropyi trimethoxy silane, 3- Mercaptopropyltriethoxysilane, phenyl three Methoxy silane, phenyl triethoxysilane, 3,4- epoxy cyclohexylethyl trimethoxy silane, 3,4- expoxycyclohexyl The trialkoxysilanes of ethyl triethoxysilane etc.；Or their partial condensate etc..
The partial condensates of the tetramethoxy-silicane or alkyl trimethoxysilane that are wherein preferably indicated with following chemical formula 8 Object.
[chemicals 8]
(in chemical formula 8, R3The alkyl for being 1 to 6 for methoxyl group or carbon atom number, the integer that n is 1 to 7).
The average mark of the partial condensate of the tetramethoxy-silicane or alkyl trimethoxysilane that are indicated with above-mentioned chemical formula 8 Son amount preferably 260 to 2,000 or so, more preferably 260 to 890 or so.The tetramethoxy-silicane or alkyl trimethoxy silicon For the partial condensate of alkane when reacting with hydroxyl epoxy components, unreacted alkoxy silane ingredient is together with methanol Evaporation is without to flowing out outside class, therefore from operation preferably.In addition, there is no such as in this partial condensate The toxicity expressed by corresponding monomer, therefore preferably.
In above-mentioned chemical formula 8, the value (n) of average units repeatedly is preferably 11 hereinafter, more preferably 7 or less.At this Value be greater than 11 in the case where, dissolubility be deteriorated and be not easily dissolved in hydroxyl-containing epoxy resin or organic solvent, therefore have with The tendency of the reactivity decline of hydroxyl-containing epoxy resin.
Silane-modified asphalt mixtures modified by epoxy resin is obtained by the dealcoholization condensation reaction of above-mentioned hydroxyl-containing epoxy resin and alkoxy silane Rouge.As long as the usage rate of hydroxyl-containing epoxy resin and alkoxy silane is and alkoxy is in obtained silane-modified asphalt mixtures modified by epoxy resin The identical ratio of practical remaining ratio is then not particularly limited in rouge, but preferably by the silicon reduced mass of alkoxy silane/contain The quality (mass ratio) of hydroxyl epoxy resin is set as 0.01 to 3 range.
But due to the case where hydroxyl-containing epoxy resin is the high molecular weight resin that epoxide equivalent is 400 or so or more Under, there is the case where leading to the high viscosity or gelation of solution because of the progress of dealcoholization, therefore can be by with as follows Mode overcomes the problems, such as this.
1. in order to make one of the hydroxyl equivalent of hydroxyl-containing epoxy resin or the alkoxy equivalent of alkoxy silane become larger, It is preferred that being adjusted to less than 1 or being greater than 1 for above-mentioned equivalent proportion.In particular it is preferred that being adjusted to above-mentioned equivalent proportion less than 0.8 or 1.2 More than.Wherein preferably it is fabricated to 1.2 or more.
2. stopping the method for dealcoholization etc. by way in the reaction to prevent high viscosity or gelatine.For example, can adopt With the distillation for adjusting methanol in reaction system and reaction system is set as return-flow system at the time of gradually high viscosity Removal amount or the method etc. that reaction was completed and keeping reaction system cooling.
Dealcoholysis condensation is carried out while above-mentioned each ingredient is added for example, passing through, and distills the alcohol for removing heated generation Reaction, to manufacture above-mentioned silane-modified epoxy resin.Reaction temperature is preferably 50 DEG C to 130 DEG C, and more preferably 70 DEG C to 110 DEG C, the general reaction time is preferably 1 to 15 hour.Preferably, the polycondensation reaction of alkoxy silane itself in order to prevent, actually The reaction is executed in anhydrous conditions.In addition, in order to shorten the reaction time, it can also be in the unevaporated model of hydroxyl-containing epoxy resin In enclosing, the reaction is executed under reduced pressure.
In addition, in order to promote to react, can be used in previously known catalyst when carrying out above-mentioned dealcoholization condensation reaction The catalyst of non-open loop oxirane ring.As the catalyst, such as can enumerate: as lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, barium, The metal of strontium, zinc, aluminium, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, cadmium, manganese etc.；The oxide of these metals, acylate, halogenation Object, alkoxide etc..Wherein, particularly preferred organotin or organic acid tin, specifically, dibutyl tin dilaurate, tin octoate etc. are Effectively.
In addition it is also possible to execute above-mentioned reaction in a solvent.As long as solvent is dissolution hydroxyl-containing epoxy resin and alkoxy The silane and organic solvent not reacted with them is then not particularly limited.As this organic solvent, dimethyl formyl can be enumerated The aprotic polar solvent of amine, dimethyl acetamide, tetrahydrofuran, methyl ethyl ketone etc..
As silane-modified epoxy resin it is preferable to use commercially available product can enumerate Arakawa Chemical Industries (strain) manufacture commodity Entitled COMPOSERAN E-101, E-102, E-201, E-202, E-211, E-212 etc..
It include above-mentioned with 0.1~30 weight % of mass percent relative to the solid powder in photosensitive polymer combination Silane-modified epoxy resin.In the case where adding above-mentioned silane-modified epoxy resin in a manner of being less than above range, resistance toization Learning drug reduces, in the case where the above-mentioned silane-modified epoxy resin of excessive addition, in terms of heat resistance and developing powder There are problems.
The thermal curing agents contained in blue-sensitive resin combination of the invention are aobvious in the manufacturing process of colour filter (usually at 180~250 DEG C hereinafter, it is preferred that 5~40 minutes more at 200~230 DEG C when the heat treatment of the pixel film of movie queen It is preferred that 10~35 minutes), enhance the crosslinking of adhesive resin and reacting with the carboxyl in adhesive resin, to improve painting The hardness of film and the performance for further improving colour filter.
It in the present invention, may include 0.1~20 weight % relative to the total weight % of blue-sensitive resin combination Thermal curing agents preferably may include the thermal curing agents of 0.1 to 10 weight %.In the feelings comprising the above-mentioned thermal curing agents in above range Under condition, chemical resistance is excellent and does not cause problems in terms of heat resistance and developing powder.
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 in the present invention, may include 10 to 85 weight % relative to the total weight % of blue-sensitive resin combination Solvent preferably comprises the solvent of 15 to 85 quality %.If the content of solvent is within the above range, roll coater, rotation are being utilized When the apparatus for coating such as painting machine, slit spin coater, slit coater (sometimes referred to as die coating machine), flush coater are coated, With the tendency for making coating become excellent, therefore preferably.
Additive
Blue color patterns layer metal oxide photosensitive polymer combination of the invention can further include other as needed 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, polyxyethylated two ethers, polyethylene glycol Two esters, sorbitan fatty ester class, fatty acid modified polyesters, tertiary-amine modified polyurethanes, polyethyleneimine amine Deng other than, 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 total amount relative to above-mentioned metal oxide photosensitive polymer combination, 0.01 to 10 the above-mentioned of weight % can be used to add Add agent, the above-mentioned additive of 0.1 to 10 weight % preferably can be used, more preferably uses the above-mentioned additive of 0.1 to 5 weight %, But not limited to this.
Metal oxide photosensitive polymer combination of the invention can for example be prepared by the following method.It will dissipate in advance It penetrates particle to mix with solvent, is dispersed to average grain diameter using ball mill etc. and reaches 30~500nm.At this point, as needed can also be with Dispersing agent is further used, bonding agent resin part or all can also be cooperated.In obtained dispersion liquid (hereinafter, having When also referred to as abrasive (mill base)) in remaining bonding agent resin, optical polymerism added further with defined concentration Object, Photoepolymerizationinitiater initiater, other compositions used as needed and solvent additional as needed are closed, so as to obtain mesh Mark metal oxide photosensitive polymer combination.
<colour filter and image display device>
Another mode of the invention is related to a kind of comprising to form 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 and can reduce manufacturing cost and in the case where not including blue quantum dot It can prevent the efficiency of blue pixel from declining and having the advantages that excellent visual angle.
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 metal oxide photosensitive polymer combination of the invention, can be and passes through Be coated with the above-mentioned metal oxide photosensitive polymer combination for being used to form blue color patterns layer and be exposed with defined pattern, Development and heat cure and the layer that is 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 must be comprising quantum dots and can It additionally include scattering particles.Specifically, colour filter of the invention may include comprising red quantum dot red pattern layer or Person includes the green pattern layer of green quantum dot, and above-mentioned red pattern layer or green pattern layer may include scattering particles.It is above-mentioned red Chromatic graph 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 that scattering particles in metal oxide photosensitive polymer combination of the invention and metal oxide are related Content.
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.
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 solidfied material containing metal oxide photosensitive polymer combination above-mentioned Blue color patterns layer colour filter and issue blue light light source.
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.
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: 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 ', 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 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 1-2-1
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, 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 1-2-1 is obtained.
[chemical formula 1-2-1]
The synthesis (C-1) of preparation example 4: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 (C-2) of preparation example 5: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 3 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.
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 32 and comparative example 1 to 8: the preparation of blue-sensitive resin combination
According to the composition of following table 1 to 6, the blue-sensitive resin combination of embodiment 1 to 32 and comparative example 1 to 8 is prepared (table 1 indicates that scattering particles, table 2 indicate that blue and purple color material, table 3 to table 5 indicate that the composition of embodiment, table 6 indicate ratio to object Composition compared with example constitutes and content).
[table 1]
[table 2]
Type Name of product Manufacturing company
B-1 B15:6 Fastogen Blue EP-7S DIC
B-2 B15:4 Fastogen Blue 5424 DIC
B-3 B15:3 Heliogen Blue L 7072D BASF
B-4 B16 Pigment Blue 16 CPMA
V-1 V23 Fastogen Super Violet 140V DIC
[table 3]
A. scattering particles (referring to table 1)
B. blue color material/purple color material (referring to table 2)
C. alkali soluble resins: Cardo resinoid (chemical formula C-1)/Cardo resinoid (chemical formula C-2)/acrylic compounds alkali Soluble resin
D. photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA；Nippon Kayaku K. K's system It makes)
E. Photoepolymerizationinitiater initiater: Irgaqure-907 (BASF AG's manufacture)
F. solvent: propylene glycol monomethyl ether
G. thermal curing agents: cycloaliphatic epoxy resin (3/ chemical formula 4 of chemical formula)/novolac epoxy resin (chemical formula 5)/silane Modified epoxy (6/ chemical formula 7 of chemical formula)
[table 4]
A. scattering particles (referring to table 1)
B. blue color material/purple color material (referring to table 2)
C. alkali soluble resins: Cardo resinoid (chemical formula C-1)/Cardo resinoid (chemical formula C-2)/acrylic compounds alkali Soluble resin
D. photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA；Nippon Kayaku K. K's system It makes)
E. Photoepolymerizationinitiater initiater: Irgaqure-907 (BASF AG's manufacture)
F. solvent: propylene glycol monomethyl ether
G. thermal curing agents: cycloaliphatic epoxy resin (3/ chemical formula 4 of chemical formula)/novolac epoxy resin (chemical formula 5)/silane Modified epoxy (6/ chemical formula 7 of chemical formula)
[table 5]
A. scattering particles (referring to table 1)
B. blue color material/purple color material (referring to table 2)
C. alkali soluble resins: Cardo resinoid (chemical formula C-1)/Cardo resinoid (chemical formula C-2)/acrylic compounds alkali Soluble resin
D. photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA；Nippon Kayaku K. K's system It makes)
E. Photoepolymerizationinitiater initiater: Irgaqure-907 (BASF AG's manufacture)
F. solvent: propylene glycol monomethyl ether
G. thermal curing agents: cycloaliphatic epoxy resin (3/ chemical formula 4 of chemical formula)/novolac epoxy resin (chemical formula 5)/silane Modified epoxy (6/ chemical formula 7 of chemical formula)
[table 6]
A. scattering particles (referring to table 1)
B. blue color material/purple color material (referring to table 2)
C. alkali soluble resins: Cardo resinoid (chemical formula C-1)/Cardo resinoid (chemical formula C-2)/acrylic compounds alkali Soluble resin
D. photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA；Nippon Kayaku K. K's system It makes)
E. Photoepolymerizationinitiater initiater: Irgaqure-907 (BASF AG's manufacture)
F. solvent: propylene glycol monomethyl ether
G. thermal curing agents: cycloaliphatic epoxy resin (3/ chemical formula 4 of chemical formula)/novolac epoxy resin (chemical formula 5)/silane Modified epoxy (6/ chemical formula 7 of chemical formula)
The manufacture of colour filter
Colour filter is manufactured using by above-described embodiment and the metal oxide photosensitive polymer combination of comparative example manufacture. That is, above-mentioned each photosensitive polymer combination is coated on glass substrate using spin-coating method, it is then placed into heating plate, and 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: the sensitivity of colour filter and pattern stability
Using the colour filter of the photosensitive polymer combination manufacture by Examples and Comparative Examples as object, measurement sensitivity and figure Case stability.Evaluation criteria about each experiment is as follows.Measurement result is recorded in table 7.
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: mistake (error) degree of the pattern of pattern mask after exposure when low light exposure (20~100mJ)
Zero: pattern does not have mistake
△: the situation that WRONG PATTERN is 1~2
×: WRONG PATTERN is 3 or more
(zero, △, × be using 3 D surface shape measurement device optical microscopy carry out confirmation result)
Experimental example 2: the solvent resistance and heat resistance of colour filter are measured
Using the colour filter of the photosensitive polymer combination manufacture by above-described embodiment and comparative example as object, pass through heat resistance With the measurement experiment of solvent resistance, carries out the heat used when manufacturing colour filter or when production liquid crystal display device and be in solvent It is no to show stable evaluation.Measurement result is recorded in table 7.
Evaluate solvent resistance: the leaching in solvent NMP (1-Methyl-2-Pyrrolidone) respectively by the above-mentioned colour filter produced Stain 30 minutes, color change before and after Calculation Estimation and be compared evaluation.At this point, about used formula, according to indicate by Following mathematical expressions (1) of the color change for the three-dimensional colorimeter that L*, a*, b* are defined, to measure and evaluate the color change of front and back, and And it is recorded in following table 7.
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 record its result in following table 7.
Mathematical expression (1) △ Eab*=[(△ L*)2+(△a*)2+(△b*)2]1/2
Zero: △ Eab=is less than 1
Eab=1~3 △: △
×: △ Eab=is greater than 3
Experimental example 3: degassing is tested
The degassing of colour filter about the photosensitive polymer combination manufacture by above-described embodiment and comparative example measures, in benefit Above-mentioned blue-sensitive resin combination is coated on glass substrate with spin-coating method, is then placed into heating plate, and It is maintained 3 minutes at a temperature of 100 DEG C and forms film.Then, on the above-mentioned films place coating mask (area of the pattern: 3 × 3cm), and 100 μm will be set as with the interval of test photomask and irradiates ultraviolet light.At this point, being used as ultraviolet light source 1kw high-pressure mercury comprising g, h, i line etc. is with 100mJ/cm2Illuminance be irradiated, special optical filter is not used. The film of above-mentioned irradiation ultraviolet light is impregnated two minutes in the KOH aqueous development solution of pH10.5 and is developed.It uses After distilled water will be covered with the glass plate cleaning of the film, brushes nitrogen and be allowed to drying, heated in 200 DEG C of heated oven 30 minutes.
The pattern form (film) of thus obtained colour filter is with a thickness of 1~5 μm, and more preferably 2~4 μm or so.Pass through Py- GC/FID analyzes the compound trapped to the above-mentioned thermal decomposition for being formed by film substrate progress 30 minutes at 230 DEG C.
It is as described below to analyze benchmark.Measurement result is shown in table 7.
Deaerate measured value: with 100% benchmark, the value of comparative example 1 is indicated by percentage.The lower the value the more excellent.
Experimental example 4: fine pattern forms experiment
About it is in the colour filter for using the photoresist of above-described embodiment and comparative example to manufacture, by being designed as 100 μ The size for the pattern that the lines of m/space pattern mask obtains is measured using OM equipment (ECLIPSE LV100POL Nikon Corporation) Pattern dimension.Measurement result is recorded in table 6.
If the difference of lines/space pattern mask design value and the obtained measured value of fine pattern be 20 μm with On, then it is difficult to realize fine pixel, if having negative value, means to cause the undesirable critical numerical value of technique.
Embodiment 5: visual angle measurement
To use by above-described embodiment and the photosensitive polymer combination of comparative example manufacture and in the colour filter that manufactures by The part that the pattern of 20 × 20mm square is formed uses goniophotometer (GC-5000L, Japan's electricity color) under light transmission condition The intensity (Intensity) of the light generated with visual angle is measured, and calculates diffusivity using following mathematical expressions 2.In following mathematics In formula 2, I indicates the luminous intensity measured by visual angle, I70、I20And I5It is illustrated respectively in 70 degree, the 20 degree and 5 degree lower values measured.Meaning Taste the higher visual angle of diffusivity it is more excellent.Measurement result is recorded in table 7.
[mathematical expression 2]
Diffusivity=(I70+I20)/2×I5×100
Experimental example 6: measuring reflectance
To use by above-described embodiment and the photosensitive polymer combination of comparative example manufacture and in the colour filter that manufactures by The part that the pattern of 20 × 20mm square is formed uses spectral photometric colour measuring meter CM-3600A (Konica Minolta company), measurement Light reflectivity under light transmission condition, it is meant that the reflectivity determined more it is low then improve reflected ambient light inhibitory effect and to height Quality image quality is advantageous.Measurement result is recorded in table 7.
Embodiment 7: luminous intensity measurement
To use by above-described embodiment and the photosensitive polymer combination of comparative example manufacture and in the colour filter that manufactures by The part that the pattern of 20 × 20mm square is formed, using 365nm Tube type 4W UV irradiating machine (VL-4LC, VILBERLOURMAT), the region of measurement light conversion, for Examples and Comparative Examples, using spectrometer (Spectrum meter, Ocean Optics), to measure the luminous intensity in the region 450nm.Measurement result is recorded in table 7.Mean to determine shines The more high then light efficiency of intensity is higher.
[table 7]
With thermal curing agents be used together Cardo class adhesive resin and thermal curing agents or Cardo class adhesive resin and In the case where the embodiment 1 to 32 of acrylic compounds alkali soluble resins, confirms and can be realized excellent sensitivity, pattern is stablized Property and fine pattern, and because heat resistance and degassing occurrence quantity it is low due to reliability it is more excellent.On the contrary, not including thermal curing agents In the case where comparative example 1 to 8, confirm sensitivity decline, it is difficult to realize pattern stability and fine pattern, solvent resistance and Heat resistance is bad, and reliability reduces due to the occurrence quantity that deaerates is excessive.
In addition, confirming luminous intensity is comprising the embodiment 1 to 32 of composition of the invention 20000 or more and light efficiency it is high.On the contrary, confirming in the case where comparative example 1 to 8 except comparative example 1 is with outer glow intensity 13200 or less and light efficiency reduce.
In addition, it is outer less than 4 to confirm reflectivity comprising the embodiment 1 to 32 of composition of the invention Boundary's light reflection suppression effect is improved and advantageous to high quality image quality.On the contrary, being confirmed anti-in the case where comparative example 1 to 4 Penetrating rate is 10 or more and the significant decrease of reflected ambient light inhibitory effect.
In the case where the embodiment 1 to 32 of the composition comprising the application, confirming diffusivity is 30 or more and visual angle It is excellent.On the contrary, in the case where comparative example 1 to 8, confirm that diffusivity is 20 or less and visual angle is bad.
Industrial feasibility
The present invention is due to that excellent heat resistance and will not occur xanthochromia at high temperature comprising blue-sensitive resin combination The variation of luminous intensity may be not present.Further it is provided that one kind can be by minimizing degassing occurrence quantity and when panel works The free and electricity because being formed between pixel caused by the back taper during developing process is removed in the afterimage being likely to occur The broken string of pole and improve the undesirable colour filter of display.Furthermore it is possible to provide a kind of high quality image quality with excellent visual angle Self-luminous colour filter.

Claims (17)

1. a kind of blue-sensitive resin combination, comprising scattering particles, blue colorant, as the Cardo of adhesive resin Class adhesive resin, photoinitiator, photopolymerizable compound, thermal curing agents and solvent,
It is characterized in that, the thermal curing agents include multifunctional cycloaliphatic epoxy resin, silane-modified epoxy resin and phenol aldehyde type It is more than one of epoxy resin.
2. blue-sensitive resin combination according to claim 1, wherein
The scattering particles include the metal oxide that average grain diameter is 30 to 500nm.
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 colorant includes one of blue pigment and blue dyes or more.
5. blue-sensitive resin combination according to claim 1, wherein
The blue-sensitive resin combination also includes violet colorant.
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 multifunctional cycloaliphatic epoxy resin includes in the compound indicated with following chemical formula 3 and following chemical formula 4 One of more than,
[chemical formula 3]
In the chemical formula 3, the integer that n, m and l are 1~20,
[chemical formula 4]
10. blue-sensitive resin combination according to claim 1, wherein
The phenol aldehyde type epoxy resin includes the compound indicated with following chemical formula 5,
[chemical formula 5]
In the chemical formula 5, o be 1~20 integer.
11. blue-sensitive resin combination according to claim 1, wherein
The silane-modified epoxy resin is prepared by the dealcoholization condensation reaction of hydroxyl-containing epoxy resin and alkoxy silane.
12. blue-sensitive resin combination according to claim 11, wherein
The hydroxyl-containing epoxy resin is indicated with following chemical formula 6, indicates the alkoxy silane with following chemical formula 7,
[chemical formula 6]
In the chemical formula 6, the integer that q is 1 to 34,
[chemical formula 7]
R6pSi(OR7)4-p
In chemical formula 7, p indicates 0 or 1 integer,
R6 expression can have the alkyl, carbon atom number that the carbon atom number for the functional group being directly connected on carbon atom is 1 to 6 to be The unsaturated aliphatic residue that 1 to 6 aryl or carbon atom number is 2 to 6,
The alkyl that R7 indicates hydrogen atom or carbon atom number is 1 to 6,
Multiple R7 difference are identical or different.
13. blue-sensitive resin combination according to claim 1, wherein
Relative to the total weight % of the blue-sensitive resin, include: the scattering particles of 0.5 to 35 weight %；0.5 to 40 weight Measure the blue colorant of %；The adhesive resin of 1.0 to 50 weight %；The photopolymerizable compound of 0.5 to 15 weight %；0.2 To the photoinitiator of 15 weight %；The thermal curing agents of 0.1 to 20 weight %；And 10 to 85 weight % solvent.
14. a kind of colour filter, including as according to claim 1 to the blue-sensitive resin described in any one of claim 13 The blue color patterns layer that composition is constituted.
15. colour filter according to claim 14, wherein
The colour filter further includes more than one of group being made of red pattern layer and green pattern layer.
16. colour filter according to claim 15, wherein
The red pattern layer or the green pattern layer include quantum dot.
17. a kind of image display device, comprising:
Colour filter according to claim 13；And
Emit the light source of blue light.
CN201780086103.6A 2017-03-31 2017-12-05 Blue photosensitive resin composition, color filter and image display device manufactured by using the same Active CN110268328B (en)

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