CN110446975A - Blue-sensitive resin combination, the colour filter and image display device manufactured using it - Google Patents
Blue-sensitive resin combination, the colour filter and image display device manufactured using it Download PDFInfo
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- CN110446975A CN110446975A CN201780088708.9A CN201780088708A CN110446975A CN 110446975 A CN110446975 A CN 110446975A CN 201780088708 A CN201780088708 A CN 201780088708A CN 110446975 A CN110446975 A CN 110446975A
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
-
- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- 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)
- Spectroscopy & Molecular Physics (AREA)
- Nonlinear Science (AREA)
- Chemical & Material Sciences (AREA)
- Optics & Photonics (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
Abstract
The colour filter and image display device that the present invention provides a kind of blue-sensitive resin combination, it is utilized to manufacture, the blue-sensitive resin combination includes scattering particles, blue colorant, Cardo class adhesive resin, photoinitiator, photopolymerizable compound and solvent as adhesive resin, wherein, the photopolymerizable compound includes the photopolymerizable compound containing alkylene oxide.
Description
Technical field
The present invention relates to a kind of blue-sensitive resin combinations, the colour filter and image display device that are manufactured using it.
Background technique
Colour filter is can to realize small pixel and extracting red, these three colors of green and blue from white light
The film-type optical component of unit, the size of a pixel are tens of to hundreds of microns or so.This colour filter is using successively layer
Structure made of folded black matrix layer and pixel portion, wherein the black matrix layer is formed on the transparent substrate with defined pattern with right
Boundary part between each pixel carries out shading, which is in order to form each pixel that multiple color is (usually red
Color (R), green (G) and blue (B)) three primary colors arranged with defined sequence.
In recent years, as one of the method for realizing colour filter, using the pigment that pigment-dispersing type photoresist is utilized
Dispersion method, but the light irradiated from light source penetrate colour filter during, a part of light be colored device absorb and under light efficiency
Drop, and the problem of colorrendering quality declines due to occur the characteristic of the pigment contained in the colour filter.
In order to solve this problem, the colour filter using the self-luminous photosensitive polymer combination comprising quantum dot is proposed
Manufacturing method.
Specifically, proposing in KR published patent 2007-0094679 by having by quantum dot (Quantum
Dot) formed color-filter layer and improve colorrendering quality, proposing in KR published patent 2009-0036373 can lead to
It crosses to replace with existing colour filter and luminous efficiency is improved by luminescent layer that quantum dot phosphor forms and improves display quality.
But the photosensitive polymer combination developed so far in order to manufacture colour filter is unable to fully meet in technique
The condition that sufficient developing powder control when use, fine pattern formed, excellent light efficiency and visual angle ensure etc..
Summary of the invention
Technical problem
The object of the present invention is to provide a kind of blue-sensitive trees that can be realized colour filter especially self-luminous colour filter
Oil/fat composition, the colour filter and image display device manufactured using it, the colour filter can control developing powder, remove fine figure
The residue of case, to solve problem due to technologic residue, and it is bad to improve display, it is ensured that excellent light efficiency
And visual angle.
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, the blue-sensitive
Resin combination is characterized in that the photopolymerizable compound includes the photopolymerizable compound containing alkylene oxide.
In addition, the present invention provides a kind of colour filter, the blue including being formed by above-mentioned blue-sensitive resin combination is schemed
Pattern layer.
In addition, the present invention provides a kind of image display device, comprising: above-mentioned colour filter；And the light source of transmitting blue light.
Beneficial effect
The present invention provides a kind of colour filter, includes the light containing alkylene oxide in above-mentioned blue-sensitive resin combination
Polymerizable compound removes the residue of pattern to control developing powder, and then solves to ask because what technologic residue occurred
Topic, and improve the bad problem of display, improve the undeveloped problem of resist.Furthermore it is possible to provide a kind of by adjusting taper
And the self-luminous colour filter of the high quality image quality with excellent visual angle.
Specific embodiment
Blue-sensitive resin combination of the invention may include scattering particles, blue colorant, as adhesive resin
Cardo class adhesive resin, photoinitiator, photopolymerizable compound and solvent, in particular, above-mentioned photopolymerizable compound packet
Containing the photopolymerizable compound containing ethylene oxide or propylene oxide, including the use of blue-sensitive resin combination of the invention
Developing powder can be controlled come the colour filter of the blue color patterns layer manufactured, the residue of pattern is removed and solves because of technologic residue
The problem.A kind of show that bad problem is improved and the non-visualization problems of resist are improved furthermore it is possible to provide
Colour filter especially self-luminous colour filter.Furthermore it is possible to provide a kind of colour filter of high quality image quality with excellent visual angle
Especially self-luminous colour filter and the image display device including the colour filter.
In the following, structure of the invention is described in detail.
Scattering particles
The metal oxide that it is 10 to 1000nm with average grain diameter that scattering particles of the invention, which can be, it is more preferably average
Partial size be 30 to 500nm range the case where.At this point, can not expect incident light in the case where average grain diameter is less than above range
Sufficient dispersion effect, average grain diameter be greater than above range in the case where, scattering particles precipitate in composition or nothing
The light emitting layer surface of method acquisition homogeneous quality.
Above-mentioned metal oxide can be comprising selected from by Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe,
Ni、Cu、Zn、Ga、Ge、Rb、Sr、Y、Mo、Cs、Ba、La、Hf、W、Tl、Pb、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、
The oxide of one of the group of Er, Tm, Yb, Ti, Sb, Sn, Zr, Nb, Ce, Ta, In and their combination composition metal.More
For body, above-mentioned metal oxide be can be selected from by Al2O3、SiO2、ZnO、ZrO2、BaTiO3、TiO2、Ta2O5、Ti3O5、
ZnO、Nb2O3, it is more than one of the group of compositions such as SnO, MgO.As needed, having by acrylate etc. also can be used
The material that the compound of unsaturated bond is surface-treated.
For above-mentioned scattering particles, containing in average grain diameter and overall composition can be suitably adjusted as needed
Amount, so as to sufficiently improve the luminous intensity of colour filter.
In addition, the total weight relative to the solid component in blue-sensitive resin, may include the upper of 0.1 to 50 weight %
Scattering particles are stated, can preferably be used by 5 to 30 weight %.In situation of the content in above-mentioned preferred scope of scattering particles
Under, the reinforcing effect of luminous intensity can be obtained, and can ensure the stability of composition.
Blue colorant
In blue colorant of the invention, as the specific enumerable color index of blue pigment (dyeing association, family (The
Society of Dyers and Colourists) publish) in be classified as the compound of pigment, more specifically can enumerate as
Under color index (C.I.) number pigment, but might not be limited by the pigment.Concrete example explanation, as blue pigment
C.I. pigment blue 15 can be enumerated: 3,15:4,15:6,16,21,28 and 76 etc. are preferably comprised selected from by C.I. pigment blue 15: 3, face
It is more than one of group that material basket 15:6 and pigment blue 16 form.
Blue colorant of the invention can further include blue dyes, can enumerate color index (dye as blue dyes
Se Jia association (The society of Dyers and Colourists) publishes) in be classified as compound or the dyeing of dyestuff
The well known dyestuff recorded in handbook (dyers).
The above-mentioned dyestuff further used is specifically enumerated,
As C.I. solvent dye,
C.I. solvent blue 5,35,36,37,44,45,59,67 and 70 etc. can be enumerated, more preferably comprising C.I. solvent blue 35,
36, one of 44,45 and 70 or more.
In addition, as C.I. acid dyes,
Can enumerate C.I. Blue VRS, 7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,
86、87、90、92、96、103、112、113、120、129、138、147、150、158、171、182、192、210、242、243、
256,259,267,278,280,285,290,296,315,324:1,335 and 340 etc., wherein more preferably including C.I. acid blue
One of 80 and 90 or more.
In addition, as C.I. direct dyes,
Can enumerate C.I. directly indigo plant 38,44,57,70,77,80,81,84,85,86,90,93,94,95,97,98,99,
100、101、106、107、108、109、113、114、115、117、119、137、149、150、153、155、156、158、159、
160、161、162、163、164、166、167、170、171、172、173、188、189、190、192、193、194、196、198、
199、200、207、209、210、212、213、214、222、228、229、237、238、242、243、244、245、247、248、
250,251,252,256,257,259,260,268,274,275 and 293 etc..
Can enumerate C.I. medium indigo plant 1,2,3,7,8,9,12,13,15,16,19,20,21,22,23,24,26,30,31,
32,39,40,41,43,44,48,49,53,61,74,77,83 and 84 etc..
Above-mentioned blue dyes independently can be used or be combined two or more and use.
Blue colorant of the invention can further include the violet colorant as additional colorant.Violet colorant can
More than one of violet pigment and cudbear, the specific enumerable C.I. pigment violet 1 of above-mentioned violet pigment, 14,19,
23,29,32,33,36,37 and 38 etc., wherein more preferably including C.I. pigment Violet 23.
The specific enumerable C.I. solvent violet of cudbear, C.I. acid violet, C.I. acid violet, C.I. medium purple etc., but simultaneously
It is not limited to this.
Specifically, above-mentioned C.I. solvent violet can enumerate C.I. solvent purple 8,9,13,14,36,37,47 and 49 etc., it is more excellent
Choosing includes C.I. solvent violet 13.C.I. acid violet 6B, 7,9,17,19 and 66 etc. can be enumerated as C.I. acid violet, are more preferably wrapped
Acid violet containing C.I. 66.As the direct purple of C.I. can enumerate C.I. directly purple 47,52,54,59,60,65,66,79,80,81,
82,84,89,90,93,95,96,103 and 104 etc..
In addition, can enumerate C.I. medium purple 1,2,4,5,7,14,22,24,30,31,32,37,40,41,44,45,47,
48,53 and 58 etc..
Relative to the total weight of the solid component in blue-sensitive resin, the above-mentioned indigo plant of 0.1 to 50 weight % can be used
The above-mentioned blue colorant of 0.5 to 30 weight % preferably can be used in chromatic colorant agent.Meet above-mentioned model in the content of blue colorant
In the case where enclosing, it is able to suppress reflected ambient light, and efficiently shows colour light emitting intensity, it can be ensured that viscosity stabilization
Property.
The present invention does not include blue quantum dot and includes blue colorant and scattering particles, so as to prevent colour filter special
It is not the efficiency decline of the blue pixel of self-luminous colour filter.
Adhesive resin
Adhesive resin of the invention includes Cardo class adhesive resin.Above-mentioned Cardo class adhesive resin has with light
Or the reactivity and alkali solubility of the effect generation of heat, and the decentralized medium as coloured material plays a role.Included in this hair
Cardo class adhesive resin in bright blue-sensitive resin combination is played as the bonding agent resin to scattering particles to be made
With as long as can be dissolved in then unrestricted in the resin for manufacturing alkaline-based developer used in the development step of colour filter
System.
Cardo class adhesive resin of the invention may include in the compound indicated with chemical formula 1-1 and chemical formula 1-2
It is one or more of.
[chemical formula 1-1]
[chemical formula 1-2]
In above-mentioned chemical formula 1-1 or chemical formula 1-2,
R1、R2、R3And R4Separately 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.
In the present invention, the compound indicated with above-mentioned chemical formula 1-1 is closed by the compound indicated with following chemical formula 2-1
At, and can use the compound that is indicated with chemical formula 2-2 with the compound that chemical formula 1-2 is indicated to synthesize.
In the present invention, the compound indicated with above-mentioned chemical formula 1-1 is closed by the compound indicated with following chemical formula 2-1
At, and can use the compound that is indicated with chemical formula 2-2 with the compound that chemical formula 1-2 is indicated to synthesize.
[chemical formula 2-1]
[chemical formula 2-2]
Specifically, can be with the compound that above-mentioned chemical formula 1-1 is indicated with chemical formula 1-1-1 and chemical formula 1-1-2
It more than one of compound of expression, can be with the compound that above-mentioned chemical formula 1-2 is indicated with chemical formula 1-2-1 and chemistry
It is more than one of compound that formula 1-2-2 is indicated.
[chemical formula 1-1-1]
[chemical formula 1-1-2]
[chemical formula 1-2-1]
[chemical formula 1-2-2]
It can be by making selected from by bis- (the 3- cortex cinnamomi acid diesters) fluorenes (9,9-bis (3-cinnamic diester) of 9,9-
Fluorene), bis- (3- cinnamon oil, the 4- hydroxy phenyl) fluorenes (9,9-bis (3-cinnamoil, 4-hydroxyphenyl) of 9,9-
Fluorene), bis- (glycidyl methacrylate ether) fluorenes (9,9-bis (the glycidyl methacrylate of 9,9-
Ether) fluorene), the bis- two cinnamate (9,9-bis (3,4- of (3,4- dihydroxy phenyl) fluorenes of 9,9-
Dihydroxyphenyl) fluorene dicinnamic ester), 3,6- 2-glycidyl methyl acrylate ether spiral shell
(fluorenes -9,9- xanthene) (3,6-diglycidyl methacrylate ether spiro (fluorene-9,9-xantene)),
9,9- bis- (3- allyl, 4- hydroxy phenyl fluorenes) (9,9-bis (3-allyl, 4-hydroxyphenylfluorene)), 9,9-
Bis- (4- allyloxy phenyl) fluorenes (9,9-bis (4-allyloxyphenyl) fluorene) and bis- (the 3,4- metering systems of 9,9-
Acid diesters) fluorenes (9,9-bis (3,4-methacrylic diester) fluorene) composition at least one of group be selected from
By as the maleic anhydride of anhydride compound, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrobenzene
The group or be selected from that acid anhydride, methylene methylene tetrabydrophthalic anhydride, chlorendic anhydride and methyl tetrahydrophthalic anhydride form
By as the pyromellitic acid anhydride of acid dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride and Biphenyl Ether tetrabasic carboxylic acid
At least one of the group of the aromatic polycarboxylic acid acid anhydride composition of dianhydride etc. is reacted to prepare above-mentioned Cardo class adhesive resin,
But not limited to this.
The present invention can further comprise the acrylic compounds alkali soluble resins as adhesive resin.The acrylic compounds alkali soluble
Property resin can for example enumerate carboxyl group-containing monomer and can with the monomer be copolymerized other monomers copolymer etc..As list containing carboxyl
Body, for example, can enumerate unsaturated monocarboxylic or such as unsaturated dicarboxylic, unsaturated tricarboxylic acids have in the molecule one with
The unsaturated carboxylic acid etc. of the unsaturated polybasic carboxylic acid of upper carboxyl etc..Here, as unsaturated monocarboxylic, such as propylene can be enumerated
Acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid etc..As unsaturated dicarboxylic, such as maleic acid, richness can be enumerated
Horse acid, itaconic acid, citraconic acid, mesaconic acid etc..Unsaturated polybasic carboxylic acid can be acid anhydrides, specifically, can enumerate maleic anhydride,
Itaconic anhydride, citraconic anhydride etc..In addition, unsaturated polybasic carboxylic acid is also possible to its single (2- acryloxyalkyl) ester, such as
Mono succinate (2- acryloyl-oxyethyl) ester, mono succinate (2- methacryloxyethyl) ester, O-phthalic can be enumerated
Sour single (2- acryloyl-oxyethyl) ester, phthalic acid list (2- methacryloxyethyl) ester etc..Unsaturated polynary carboxylic
Acid can also be list (methyl) acrylate of its two ends dicarboxyl based polyalcohol, such as can enumerate ω-carboxy-polycaprolactone list
Acrylate, ω-carboxy-polycaprolactone monomethacrylates etc..These carboxyl group-containing monomers can respectively individually or by two kinds with
On be used in mixed way.As the other monomers that can be copolymerized with above-mentioned carboxyl group-containing monomer, such as styrene, Alpha-Methyl benzene second can be enumerated
Alkene, adjacent vinyltoluene, vinyltoluene, to vinyltoluene, p-chlorostyrene, o-methoxystyrene, meta-methoxy
Styrene, to methoxy styrene, adjacent vinyl benzyl methyl ether, vinyl benzyl methyl ether, to vinyl benzyl ylmethyl
Ether, adjacent vinylbenzyl glycidyl ether, vinylbenzyl glycidyl ether, to vinylbenzyl glycidyl ether, indenes etc.
Aromatic ethenyl compound；Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic acid
N-propyl, n propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, methacrylic acid
The secondary butyl ester of N-butyl, isobutyl acrylate, Isobutyl methacrylate, sec-butyl acrylate, methacrylic acid, the tertiary fourth of acrylic acid
Ester, Tert-butyl Methacrylate, acrylic acid 2- hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid 2- hydroxy propyl ester, first
Base acrylic acid 2- hydroxy propyl ester, acrylic acid 3- hydroxy propyl ester, methacrylic acid 3- hydroxy propyl ester, acrylic acid 2- hydroxybutyl, first
Base acrylic acid 2- hydroxybutyl, acrylic acid 3- hydroxybutyl, methacrylic acid 3- hydroxybutyl, acrylic acid 4- hydroxybutyl, first
Base acrylic acid 4- hydroxybutyl, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, third
Olefin(e) acid cyclohexyl, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, acrylic acid 2- methoxy acrylate, methyl
Acrylic acid 2- methoxy acrylate, acrylic acid 2- phenoxy ethyl, methacrylic acid 2- phenoxy ethyl, methoxyl group diethylene glycol third
Olefin(e) acid ester, methoxyl group diethylene glycol methacrylate, methoxy triethylene acrylate, methoxy triethylene methyl-prop
Olefin(e) acid ester, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxyl group dipropylene glycol acrylate,
Methoxyl group dipropylene glycol methyl acrylate, isobornyl acrylate, isobornyl methacrylate, acrylic acid dicyclopentadiene
Ester, methacrylic acid dicyclopentadienyl ester, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (methyl) acrylic acid norbornyl ester, acrylic acid 2-
Hydroxyl -3- phenoxy-propyl, methacrylic acid 2- hydroxyl -3- phenoxy-propyl, glycerol mono-acrylate, glycerol monomethacrylate
The unsaturated carboxylate types such as acid esters；Acrylic acid 2- amino ethyl ester, methacrylic acid 2- amino ethyl ester, acrylic acid 2- dimethylamino
Ethyl ester, methacrylic acid 2- dimethylamino ethyl ester, acrylic acid 2- amino propyl ester, methacrylic acid 2- amino propyl ester, acrylic acid
2- dimethylamino propyl ester, methacrylic acid 2- dimethylamino propyl ester, acrylic acid 3- amino propyl ester, methacrylic acid 3- amino
The unsaturated carboxylic acids aminoalkyl esters such as propyl ester, acrylic acid 3- dimethylamino propyl ester, methacrylic acid 3- dimethylamino propyl ester
Class；The unsaturated carboxylic acids glycidol esters such as glycidyl acrylate, glycidyl methacrylate；Vinyl acetate,
The generating vinyl carboxylates esters such as vinyl propionate, vinyl butyrate, vinyl benzoate；Vinyl methyl ether, vinyl ethyl ether, alkene
The unsaturated ethers such as propyl glycidyl ether；The cyanidings second such as acrylonitrile, methacrylonitrile, α-chloro-acrylonitrile, vinylidene cyanide
Alkenyl compound；Acrylamide, Methacrylamide, α-chloroacrylamide, N-2- hydroxyethyl acrylamide, N-2- hydroxyl second
The unsaturated acyls amine such as butylmethacrylamide；Maleimide, benzyl maleimide, N-phenylmaleimide, N- ring
The unsaturated acyls imines such as hexyl maleimide；The aliphatic conjugated dienes such as 1,3- butadiene, isoprene, chlorobutadiene
Class；And polystyrene, polymethyl acrylate, polymethyl methacrylate, polyacrylic acid N-butyl, the positive fourth of polymethylacrylic acid
Ester, polysiloxanes etc. have single acryloyl group or the polymeric monomer class of monomethacrylate acyl group etc. in the end of polymer molecular chain.
These monomers can respectively individually or be use mixing two or more.In particular, as that can be copolymerized with above-mentioned carboxyl group-containing monomer
Other monomers, due to the monomer with norborny skeleton, the monomer with adamantane framework and the list with rosin skeleton
There is the tendency for reducing relative dielectric constant in the large volumes monomer such as body, therefore preferably.
It is 20 to 200 as Cardo class adhesive resin of the invention and/or acrylic compounds alkali soluble resins preferred acid number
The range of (KOH mg/g).If acid value within the above range, improves the dissolubility in developer solution, non-exposed portion is easy dissolution
And sensitivity increases, result remains in the development of the pattern of exposure portion and can improve residual film ratio (film remaining
Ratio), therefore preferably.Here, acid value be as the amount (mg) of required potassium hydroxide when neutralizing acrylic polymer 1g and
The value of measurement can usually be titrated by using potassium hydroxide aqueous solution and be found out.Furthermore it is preferred that passing through gel permeation chromatography
(GPC；Using tetrahydrofuran as eluting solvent) measurement polystyrene convert weight average molecular weight (hreinafter referred to as " Weight-average molecular
Amount ") it is 2,000~200,000, is preferably 3,000~100,000 Cardo class adhesive resin or acrylic compounds alkali solubility
Resin.If molecular weight is within the above range, hardness raising and residual film ratio height, non-exposed portion with film are in developer solution
The tendency that dissolubility is excellent and resolution ratio improves, therefore preferably.
Cardo class adhesive resin and/or acrylic compounds alkali soluble resins molecular weight distribution [weight average molecular weight (Mw)/
Number-average molecular weight (Mn)] it is preferably 1.0 to 6.0, more preferably 1.5 to 6.0.If molecular weight distribution [weight average molecular weight (Mw)/
Number-average molecular weight (Mn)] it is 1.5 to 6.0, then developability is excellent, therefore preferably.
Relative to the total weight of the solid component in blue-sensitive resin, it can be used that 5 to 85 weight %'s is of the invention
The adhesive resin of the invention of 5 to 60 weight % preferably can be used in adhesive resin.If the content of adhesive resin is upper
State in range, then deposit in developer solution dissolubility sufficiently, non-pixel portion development residue and development are not likely to produce on substrate
When be not susceptible to exposed portion the film of pixel portion reduce and the excellent tendency of the omitted property of non-pixel portion, therefore preferably.
Photopolymerizable compound
Comprising the photopolymerizable compound in blue-sensitive resin combination of the invention be can using light and after
The compound that the effect for the Photoepolymerizationinitiater initiater stated is polymerize, specifically, the optical polymerism comprising alkylene oxide can be enumerated
Object is closed, the photopolymerizable compound comprising ethylene oxide and/or propylene oxide can be preferably enumerated.Comprising being attached with above-mentioned epoxy
In the case where the photopolymerizable compound of ethane and/or propylene oxide, developing powder can be controlled, the residue of pattern is removed and solves
Bad so as to improve display certainly it is possible that because of the various problems that technologic residue occurs, removal resist does not develop, and
And excellent visual angle is formed by adjusting taper etc., the element of high quality image quality can be manufactured.
As the photopolymerizable compound comprising above-mentioned alkylene oxide, modified pentaerythrite (methyl) propylene of alkylene oxide can be enumerated
Modified dipentaerythritol (methyl) acrylate compounds of ester compound, alkylene oxide, the modified trimethylolpropane (first of alkylene oxide
Base) more specifically acrylate compounds and alkylene oxide modified glycerol (methyl) acrylate compounds can enumerate epoxy
It is oxide-modified trimethylolpropane trimethacrylate, ethylene-oxide-modified dipentaerythritol hexaacrylate, ethylene-oxide-modified
Pentaerythritol tetraacrylate, ethylene-oxide-modified pentaerythritol tetraacrylate, epoxy pronane modification pentaerythrite tetrapropylene
Acid esters, ethoxylation pentaerythritol tetraacrylate, six acrylate of ethoxylated dipentaerythritol, pentaerythritol propoxylate
Polyacrylate, six acrylate of propoxylated dipentaerythritol, ethoxylated glycerol triacrylate etc..It more preferably include second
Oxygroup pentaerythritol tetraacrylate, six acrylate of ethoxylated dipentaerythritol, pentaerythritol propoxylate polypropylene
Acid esters.
Blue-sensitive resin combination of the invention can further include the common optical polymerism not comprising alkylene oxide
Compound.Specific enumerable use does not include ethylene oxide and the monofunctional monomer of propylene oxide, two functional monomers, other more officials
The photopolymerizable compound of energy monomer.
As the concrete example of monofunctional monomer, nonyl phenyl carbitol acrylate, 2- hydroxyl -3- phenoxy group third can be enumerated
Base acrylate, 2- ethylhexyl carbitol acrylate, 2- hydroxyethylmethacry,ate, n-vinyl pyrrolidone etc..Make
For the concrete example of two functional monomers, can enumerate 1,6- hexylene glycol two (methyl) acrylate, ethylene glycol two (methyl) acrylate,
Neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, bisphenol-A bis- (acryloyl-oxyethyls)
Ether, 3- methyl pentanediol two (methyl) acrylate etc..As the concrete example of other polyfunctional monomers, trihydroxy methyl third can be enumerated
Alkane three (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, two Ji Wusi
Alcohol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc..Wherein, it is preferable to use more than two functions more officials
It can monomer.Relative to the total weight of the solid component in blue-sensitive resin, the above-mentioned photopolymerization of 5 to 5 weight % can be used
Property compound, preferably can be used the above-mentioned photopolymerizable compound of 5 to 30 quality %.In photopolymerizable compound in above range
In the case where interior, there are it is following tendency and it is preferred that: that is, be not present sensitivity reduction, film-strength is abundant, there is no development when
Pattern loss, so that pattern building is also excellent in fine pattern portion, and the flatness of resist is excellent.
Photoinitiator
Photoepolymerizationinitiater initiater used in the present invention plays the radical reaction for starting photosensitive polymer combination and causes
The effect for hardening and improving sensitivity, preferably comprises acetophenone compounds.As acetophenone compounds, such as two can be enumerated
Acetophenone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, benzil dimethyl ketal, 2- hydroxyl -1- [4- (2- hydroxyl
Base 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
The oligomer etc. of [4- (1- methyl ethylene) phenyl] propane -1- ketone, 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.Acetophenone
Photoepolymerizationinitiater initiater other than class can enumerate living radical producing agent, the sensitization that living radical is generated by irradiation light
Agent, acid agent etc..As living radical producing agent, such as benzoin class compound, benzophenone compound, thiophene can be enumerated
Xanthones compound, compound in triazine class etc..As benzoin class compound, such as benzoin, benzoin methylether, benzene can be enumerated
Benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether etc..As benzophenone compound, for example, can enumerate benzophenone,
Methyl o-benzoylbenzoate, 4- phenyl benzophenone, 4- benzoyl -4 '-methyldiphenyl thioether, 3,3 ', 4,4 '-four (tertiary fourths
Base peroxidating carbonyl) benzophenone, 2,4,6- tri-methyl benzophenone etc..As thioxanthene ketone class compound, such as 2- can be enumerated
Isopropyl thioxanthone, 4-isopropylthioxanthone, 2,4- diethyl thioxanthone, bis- clopenthixal ketone of 2,4-, the chloro- 4- propoxyl group thioxanthene of 1-
Ketone etc..As compound in triazine class, for example, can enumerate bis- (trichloromethyl) -6- (4- the methoxyphenyl) -1,3,5-triazines of 2,4-,
2,4- bis- (trichloromethyl) -6- (4- methoxyl group naphthalene) -1,3,5- triazine, bis- (trichloromethyl) -6- (the 4- methoxybenzene second of 2,4-
Alkenyl) -1,3,5- triazine, bis- (the trichloromethyl) -6- of 2,4- [2- (5- methylfuran -2- base) vinyl] -1,3,5- triazine, 2,
Bis- (the trichloromethyl) -6- of 4- [2- (furans -2- base) vinyl] -1,3,5- triazine, bis- (trichloromethyl) -6- [2- (4- bis- of 2,4-
Ethylamino -2- aminomethyl phenyl) vinyl] -1,3,5- triazine, bis- (trichloromethyl) -6- [2- (the 3,4- dimethoxy benzenes of 2,4-
Base) vinyl] -1,3,5- triazine etc..As above-mentioned living radical producing agent, 2,4,6- trimethylbenzene first can be used for example
Acyl group diphenyl phosphine oxide, 2,2,-bis- (Chloro-O-Phenyls) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxaline, 10- butyl -2- chlorine
Acridone, 2- ethyl hydrazine, 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 antimony can be enumerated
Hydrochlorate, 4- acetoxyl group phenyl dimethyl sulfonium tosilate, 4- acetoxyl group phenyl methyl benzyl sulfonium hexafluoro antimonate, three
Phenyl sulfonium tosilate, triphenylsulfonium hexafluoro antimonate, diphenyl iodine tosilate, diphenyl iodine hexafluoro antimony
Salt, nitrobenzyl tosylate class, benzoin toluenesulfonic acid salt of hydrochlorate etc. etc..In addition, as living radical
Producing agent, there is also the compounds for generating living radical and acid simultaneously in above compound, for example, the photopolymerization of triazine system causes
Agent is also used as acid agent.
It may include that 0.1 to 30 the above-mentioned of weight % is drawn relative to the total weight of the solid component in blue-sensitive resin
Agent is sent out, preferably may include the above-mentioned Photoepolymerizationinitiater initiater of 0.3 to 20 weight %.If the content of above-mentioned Photoepolymerizationinitiater initiater is upper
It states in range, then there is the strong of the pixel portion for making blue-sensitive resin combination high-sensitivity and the composition being used to be formed
It spends, the tendency that the flatness on the pixel portion surface is excellent, therefore preferably.
In addition, photopolymerization initiator can be used in the present invention.Photopolymerization initiator is combined with Photoepolymerizationinitiater initiater sometimes
It uses, is used to promote the polymerization for the photopolymerizable compound for causing polymerization by above-mentioned Photoepolymerizationinitiater initiater
Compound.As photopolymerization initiator, aminated compounds, alkoxy anthracene compound, thioxanthene ketone class compound 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..Photoepolymerizationinitiater initiater (D) can use individually or by multiple combinations.This
Outside, as photopolymerization initiator, commercially available product also can be used, as commercially available photopolymerization initiator, such as quotient can be enumerated
Name of an article " 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.
Solvent
Solvent contained in blue-sensitive resin combination of the invention is not particularly limited, and blue sensitive can be used
Various organic solvents used in property resin combination field.As its concrete example, ethylene glycol single methyl ether, ethylene glycol can be enumerated
The ethylene glycol monoalkyl ethers class such as single ethylether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether；Diethylene glycol dimethyl ether, two
The diethylene glycol dialkyl ethers classes such as ethylene glycol Anaesthetie Ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether；The molten fibre of methyl
The ethylene glycol alkyl ethers acetate esters such as agent acetic acid esters, ethyl cellosolve acetate；Propylene glycol monomethyl ether, propylene glycol list
The alkylidenes such as monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, methoxybutyl acetic acid esters and methoxypentyl acetic acid esters
Glycol alkyl ether acetate esters；Benzene,toluene,xylene, mesitylene etc. are aromatic hydrocarbon；Methyl ethyl ketone, acetone, methylpent
The ketones such as base ketone, methyl iso-butyl ketone (MIBK), cyclohexanone；The alcohols such as ethyl alcohol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol；
The esters such as 3- ethoxyl ethyl propionate, 3- methoxy methyl propionate；Ring-type esters such as gamma-butyrolacton etc..In above-mentioned solvent, from
From the aspect of coating and drying property, the organic solvent that above-mentioned solvent mid-boiling point is 100~200 DEG C can be preferably enumerated, more preferably
The esters knots such as aklylene glycol alkylether acetates class, ketone, 3- ethoxyl ethyl propionate or 3- methoxy methyl propionate can be enumerated
Class is closed, propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, cyclohexanone, 3- ethoxy can be further preferably enumerated
Base ethyl propionate, 3- methoxy methyl propionate etc..Above-mentioned solvent can respectively individually or be use mixing two or more.
It is molten in blue-sensitive resin combination of the invention relative to the total weight of blue-sensitive resin combination
Agent content can be 60 to 90 weight %, preferably comprise the solvent of 60 to 85 weight %.If the content of solvent is in above-mentioned model
In enclosing, then roll coater, spin coater, slit spin coater, slit coater (sometimes referred to as die coating machine), flush coater are being utilized
When equal apparatus for coating are coated, having makes coating become excellent tendency, therefore preferably.
Additive
Blue color patterns layer blue-sensitive resin combination of the invention can further include as needed filler, other
High-molecular compound, pigment dispersing agent, closely sealed promotor, antioxidant, ultraviolet absorbing agent, anticoagulant etc..
As other above-mentioned high-molecular compounds, the curability tree such as specific enumerable epoxy resin, maleimide resin
The thermoplastic resins such as rouge, polyvinyl alcohol, polyacrylic acid, polyalkylene glycol monoalkyl ether, poly- fluoroalkyl, polyester, polyurethane
Rouge etc..
As above-mentioned pigment dispersing agent, commercially available surfactant can be used, such as silicon class, fluorine class, esters, sun can be enumerated
Surfactants such as ionic species, anionic species, nonionic class, both sexes etc..They can be respectively individually or by two or more combinations
It uses.
As above-mentioned surfactant, such as except polyoxyethylene alkyl ether class, 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 above-mentioned of 0.5 to 10 parts by weight can be used to add relative to overall 100 parts by weight of above-mentioned blue-sensitive resin combination
Add agent, the above-mentioned additive of 0.1 to 10 parts by weight preferably can be used, more preferably uses the above-mentioned additive of 0.1 to 5 parts by weight,
But not limited to this.
Blue-sensitive resin combination of the invention can for example be prepared by the following method.In advance by scattering particles
It is mixed with solvent, is dispersed to average grain diameter using ball mill etc. and reaches 30~500nm.At this point, as needed can also be further
Using dispersing agent, adhesive resin part or all can also be cooperated.In obtained dispersion liquid (hereinafter, sometimes referred to as
For in abrasive (mill base)) with defined concentration further add remaining adhesive resin, photopolymerizable compound,
Photoepolymerizationinitiater initiater, other compositions used as needed and solvent additional as needed, so as to obtain target indigo plant
Color sensation photosensitive resin composition.
<colour filter and image display device>
Another mode of the invention is related to a kind of including forming the blue-sensitive of blue color patterns layer containing being previously described for
The colour filter of the blue color patterns layer of the solidfied material of resin combination.
Colour filter of the invention is due to form the blue-sensitive resin combination of blue color patterns layer using being previously described for
It is prepared instead of blue quantum dot, therefore has the advantages that can reduce manufacturing cost and can ensure excellent visual angle.
Further, since blue-sensitive resin combination of the invention is poly- comprising the light containing ethylene oxide or propylene oxide
Conjunction property compound, therefore the colour filter energy of the blue color patterns layer manufactured including the use of blue-sensitive resin combination of the invention
Enough realize a kind of following colour filter especially self-luminous colour filter: the colour filter controls developing powder, removes the residue of pattern
And solve because of the technologic residue problem, and show that bad problem is improved, the undeveloped problem of resist obtains
To improvement.
Above-mentioned colour filter includes the blue color patterns layer of substrate with the top for being formed in aforesaid substrate.
Aforesaid substrate can be the substrate of above-mentioned colour filter itself, or be also possible to display device etc. in locating for colour filter
Position, be not particularly limited.Aforesaid substrate can be glass, silicon (Si), Si oxide (SiOx) or polymeric substrate, above-mentioned
Polymeric substrate can be polyether sulfone (polyethersulfone, PES) or polycarbonate (polycarbonate, PC) etc..
Above-mentioned blue color patterns layer is the layer comprising blue-sensitive resin combination of the invention, be can be by coating
It states the blue-sensitive resin combination for being used to form blue color patterns layer and is exposed with defined pattern, developed and heat cure
And the layer formed, above-mentioned pattern layer can be formed by executing the usually well-known method in this field.
In another embodiment of the invention, above-mentioned colour filter can further comprise selected from by red pattern layer and green
It is more than one of group of pattern layer composition.
In another embodiment of the invention, above-mentioned red pattern layer or green pattern layer may include quantum dot and/or
Scattering particles.Specifically, colour filter of the invention may include comprising red quantum dot red pattern layer or comprising green
The green pattern layer of quantum dot, above-mentioned red pattern layer or green pattern layer may include scattering particles.Above-mentioned red pattern layer or
Green pattern layer can issue respectively feux rouges or blue light by the aftermentioned light source for issuing blue light.
It include the scattering particles in above-mentioned red pattern layer or green pattern layer in another embodiment of the invention
It may include the metal oxide that average path is 30 to 500nm, content energy relevant to above-mentioned scattering particles and metal oxide
Enough applications to include scattering particles in blue-sensitive resin combination of the invention and the relevant content of metal oxide.
In the present invention, include the form of above-mentioned red pattern layer or the quantum dot in green pattern layer, structure and its
Content is not limited, and can apply quantum dot usually used in this field.
Colour filter including substrate as described above and pattern layer can further comprise the next door being formed between each pattern,
Also it may further include black matrix, but not limited to this.
In the present invention, above-mentioned colour filter can be self-luminous colour filter.
Another mode of the invention is related to a kind of image display dress including colour filter above-mentioned and the light source for issuing blue light
It sets.For example, image display device of the invention includes the blue of the solidfied material containing blue-sensitive resin combination above-mentioned
The colour filter of pattern layer and the light source for issuing blue light.
Colour filter of the invention can be applied not only to common liquid crystal display device, can also be applied to electroluminance display
The various image display devices such as device, plasm display device, field emission display device.
Include the case where colour filter and above-mentioned light source containing blue color patterns layer of the invention in above-mentioned image display device
Under, existing has the advantages that excellent luminous intensity or visual angle.In addition, including the blue color patterns layer in colour filter of the invention
Due to the advantages of not comprising blue quantum dot, presence can produce manufacturing cost low image display device.
Embodiment
In the following, being described in detail taking the embodiment as an example to illustrate this specification.But in this specification
Embodiment can be deformed into various other ways, and the range that should not be construed as this specification is defined in embodiment described below.This
The embodiment of specification is provided in order to which those of ordinary skill in the art are more completely illustrated with this specification.In addition, with
Under, as long as no specifically mentioned, then it represents that " % " and " part " of content is weight basis.
Synthesis example: the synthesis of adhesive resin
Preparation example 1: acrylic compounds alkali soluble resins
Prepare the flask for having blender, thermometer, reflux condensing tube, dropping funel and nitrogen ingress pipe, and conduct
Benzyl maleimide 7.8g (0.20 mole), acrylic acid 43.2g (0.30 mole), vinyl first is added in monomer dropping funel
After benzene 118.0g (0.50 mole), t-butyl peroxy -2 ethyl hexanoic acid ester 4g, propylene glycol monomethyl ether (PGMEA) 40g
Be stirred and prepare, as chain-transferring agent dropwise adding tank, prepare to be stirred after n-dodecane mercaptan 6g, PGMEA24g is added and
At.Later, into flask import PGMEA 395g, and by the atmosphere in flask from air displacement at nitrogen after, stirring
The temperature of flask is warming up to 90 DEG C simultaneously.Then, monomer and chain-transferring agent are added dropwise since dropping funel.When dropwise addition, tieing up
It is carried out respectively 2 hours while holding 90 DEG C, and is warming up to 110 DEG C after 1h and maintains 3 hours, be then introduced into gas and lead
Enter pipe, starts the bubbling of oxygen/nitrogen=5/95 (v/v) mixed gas.Then, by glycidyl methacrylate 28.4g
[(0.10 mole), (carboxyl relative to the acrylic acid used in this reaction is 33 moles of %)], 2,2 '-di-2-ethylhexylphosphine oxide (4-
Methyl-6-tert-butylphenol) 0.4g, triethylamine 0.8g be added flask in, the reaction was continued at 110 DEG C 8 hours, obtain solid at
Dividing acid value is the Resin A of 70mgKOH/g.Weight average molecular weight by the polystyrene conversion of GPC measurement is 16,000, molecular weight
Being distributed (Mw/Mn) is 2.3.
Preparation example 2: the synthesis of the compound of chemical formula 1-1-1
3 ', 6 '-dihydroxy spiral shells (fluorenes -9,9 '-xanthene) (3', 6 ' '-is mixed in the three neck round bottom flask of 3000ml
Dihydroxyspiro (fluorene-9,9-xantene) 364.4g and tert-butyl ammonium bromide 0.4159g, and table chlorine is added
It is heated to 90 DEG C after alcohol 2359g and is allowed to react.It is analyzed by liquid chromatogram, if 3 ', 6 '-dihydroxy spiral shells (fluorenes -9,
9 '-xanthenes) it is completely depleted, then 30 DEG C are cooled to, 50%NaOH aqueous solution (3 equivalent) is slowly added.It is carried out by liquid chromatogram
Analysis, if epichlorohydrin is completely depleted, benefit is washed 3 times after being extracted with dichloromethane, and then keeps organic layer dry using magnesium sulfate
It is evaporated under reduced pressure methylene chloride after dry, and using methylene chloride and methanol and is recrystallized with mixing ratio 50:50.
In 1 equivalent of epoxide, 0.004 equivalent of tert-butyl ammonium bromide, the 2,6- diisobutyl benzene that mixing so synthesizes
After 2.2 equivalent of 0.001 equivalent of phenol and acrylic acid, solvent propylene glycol monomethyl ether acetate 24.89g is added and is mixed.In
Air is blown into 25ml/min in the reaction solution and is heated to 90~100 DEG C of temperature and is allowed to dissolve.In reaction solution gonorrhoea
120 DEG C of temperature are heated under state to be allowed to be completely dissolved.If solution becomes transparent and viscosity is got higher, acid value is measured, and
It is stirred until acid value is lower than 1.0mgKOH/g.Acid value needs 11 hours until reaching target (0.8).Terminate in reaction
Later, the temperature of reactor is reduced to room temperature, obtains the compound of colorless and transparent chemical formula 1-1-1.
[chemical formula 1-1-1]
Preparation example 3: the synthesis of the compound of chemical formula 1-1-2
3 ', the 6 '-dihydroxy spiral shells (fluorenes -9,9 '-xanthene) of mixed chemical formula 2-1 in the three neck round bottom flask of 3000ml
(3', 6 ' '-dihydroxyspiro (fluorene-9,9-xantene) 364.4g and tert-butyl ammonium bromide 0.4159g, and
90 DEG C are heated to after epichlorohydrin 2359g is added and are allowed to react.It is analyzed by liquid chromatogram, if 3 ', 6 '-dihydroxy spiral shells
(9,9 '-xanthene of fluorenes -) is completely depleted, then is cooled to 30 DEG C, is slowly added 50%NaOH aqueous solution (3 equivalent).Pass through liquid phase color
Spectrum is analyzed, if epichlorohydrin is completely depleted, benefit is washed 3 times after being extracted with dichloromethane, and then makes to have using magnesium sulfate
It is evaporated under reduced pressure methylene chloride after machine layer is dry, and using methylene chloride and methanol and is recrystallized with mixing ratio 50:50.
In 1 equivalent of epoxide, 0.004 equivalent of tert-butyl ammonium bromide, the 2,6- diisobutyl benzene that mixing so synthesizes
After 2.2 equivalent of 0.001 equivalent of phenol and methacrylic acid, solvent propylene glycol monomethyl ether acetate 24.89g is added and is mixed
It closes.Air is blown into 25ml/min in the reaction solution and is heated to 90~100 DEG C of temperature and is allowed to dissolve.It is white in reaction solution
120 DEG C of temperature are heated in the state of turbid to be allowed to be completely dissolved.If solution becomes transparent and viscosity is got higher, acid value is measured,
And it is stirred until acid value is lower than 1.0mgKOH/g.Acid value needs 11 hours until reaching target (0.8).It is reacting
After end, the temperature of reactor is reduced to room temperature, obtains the compound of colorless and transparent chemical formula 1-1-2.
[chemical formula 1-1-2]
Preparation example 4: the synthesis of the compound of chemical formula 1-2-1
4,4 '-(9H- xanthene -9,9- diyl) xenol (4,4'- (9H- are mixed in the three neck round bottom flask of 3000ml
Xanthene-9,9-diyl) diphenol) 364.4g and tert-butyl ammonium bromide 0.4159g, and after epichlorohydrin 2359g is added
It is heated to 90 DEG C and is allowed to react.It is analyzed by liquid chromatogram, if 4,4 '-(9H- xanthene -9,9- diyl) xenols are complete
Fully- depleted is then cooled to 30 DEG C, is slowly added 50%NaOH aqueous solution (3 equivalent).It is analyzed by liquid chromatogram, if table
Chloropharin is completely depleted, then washes after benefit is extracted with dichloromethane 3 times, decompression is steamed after then keeping organic layer dry using magnesium sulfate
Methylene chloride is evaporated, and using methylene chloride and methanol and is recrystallized with mixing ratio 50:50.In the ring that mixing so synthesizes
1 equivalent of oxygen compound, 2.2 equivalent of 0.004 equivalent of tert-butyl ammonium bromide, 0.001 equivalent of 2,6- diisobutyl phenol and acrylic acid
Later, solvent propylene glycol monomethyl ether acetate 24.89g is added to be mixed.It is blown into the reaction solution with 25ml/min
Air is simultaneously heated to 90~100 DEG C of temperature and is allowed to dissolve.120 DEG C of temperature are heated in the state of reaction solution gonorrhoea to be allowed to
Fully dissolved.If solution becomes transparent and viscosity is got higher, measure acid value, and until acid value lower than until 1.0mgKOH/g into
Row stirring.Acid value needs 11 hours until reaching target (0.8).After the reaction, the temperature of reactor is reduced to room
Temperature obtains the compound of colorless and transparent chemical formula 1-2-1.
[chemical formula 1-2-1]
Preparation example 5: the synthesis of the compound of chemical formula 1-2-2
4,4 '-(9H- xanthene -9,9- diyl) xenol (4,4'- (9H- are mixed in the three neck round bottom flask of 3000ml
Xanthene-9,9-diyl) diphenol) 364.4g and tert-butyl ammonium bromide 0.4159g, and after epichlorohydrin 2359g is added
It is heated to 90 DEG C and is allowed to react.It is analyzed by liquid chromatogram, if 4,4 '-(9H- xanthene -9,9- diyl) xenols are complete
Fully- depleted is then cooled to 30 DEG C, is slowly added 50%NaOH aqueous solution (3 equivalent).It is analyzed by liquid chromatogram, if table
Chloropharin is completely depleted, then washes after benefit is extracted with dichloromethane 3 times, decompression is steamed after then keeping organic layer dry using magnesium sulfate
Methylene chloride is evaporated, and using methylene chloride and methanol and is recrystallized with mixing ratio 50:50.In the ring that mixing so synthesizes
1 equivalent of oxygen compound, 0.004 equivalent of tert-butyl ammonium bromide, 0.001 equivalent of 2,6- diisobutyl phenol and methacrylic acid 2.2
After equivalent, solvent propylene glycol monomethyl ether acetate 24.89g is added and is mixed.With 25ml/min in the reaction solution
It is blown into air and is heated to 90~100 DEG C of temperature and be allowed to dissolve.120 DEG C of temperature are heated in the state of reaction solution gonorrhoea to be made
Be completely dissolved.If solution becomes transparent and viscosity is got higher, acid value is measured, and until acid value is lower than 1.0mgKOH/g
Only it is stirred.Acid value needs 11 hours until reaching target (0.8).After the reaction, the temperature of reactor is reduced
To room temperature, the compound of colorless and transparent chemical formula 1-2-2 is obtained.
[chemical formula 1-2-2]
The synthesis (A-1) of preparation example 6:Cardo class adhesive resin
Propylene glycol monomethyl ether 600g is added simultaneously in the compound 307.0g of the chemical formula 1-1-1 of preparation example 2
It is allowed to after dissolving, mixes biphenyltetracarboxylic dianhydride 78g and tetraethylammonium bromide 1g, be allowed to slowly heat up and 110~115
It is reacted 4 hours at DEG C.After confirmation anhydride group disappears, 1,2,3,6- tetrabydrophthalic anhydride 38.0g are mixed, at 90 DEG C
Reaction 6 hours, aggregates into Cardo system adhesive resin.Anhydrous thing's vanished is confirmed by IR spectrogram.Weight averaged molecular
Amount is 3500.
The synthesis (A-2) of preparation example 7:Cardo class adhesive resin
Propylene glycol monomethyl ether 600g is added simultaneously in the compound 307.0g of the chemical formula 1-1-2 of preparation example 3
It is allowed to after dissolving, mixes biphenyltetracarboxylic dianhydride 78g and tetraethylammonium bromide 1g, be allowed to slowly heat up and 110~115
It is reacted 4 hours at DEG C.After confirmation anhydride group disappears, 1,2,3,6- tetrabydrophthalic anhydride 38.0g are mixed, at 90 DEG C
Reaction 6 hours, aggregates into Cardo system adhesive resin.Anhydrous thing's vanished is confirmed by IR spectrogram.Weight averaged molecular
Amount is 3800.
The synthesis (A-3) of preparation example 8:Cardo class adhesive resin
Propylene glycol monomethyl ether 600g is added simultaneously in the compound 307.0g of the chemical formula 1-2-1 of preparation example 4
It is allowed to after dissolving, benzene mixed tetracarboxylic dianhydride 78g and tetraethylammonium bromide 1g are allowed to slowly heat up and at 110~115 DEG C
Lower reaction 4 hours.After confirmation anhydride group disappears, 1,2,3,6- tetrabydrophthalic anhydride 38.0g are mixed, it is anti-at 90 DEG C
It answers 6 hours, aggregates into Cardo system adhesive resin.Anhydrous thing's vanished is confirmed by IR spectrogram.Weight average molecular weight
It is 4500.
The synthesis (A-9) of preparation example 9:Cardo class adhesive resin:
Propylene glycol monomethyl ether 600g is added simultaneously in the compound 307.0g of the chemical formula 1-2-2 of preparation example 5
It is allowed to after dissolving, benzene mixed tetracarboxylic dianhydride 78g and tetraethylammonium bromide 1g are allowed to slowly heat up and at 110~115 DEG C
Lower reaction 4 hours.After confirmation anhydride group disappears, 1,2,3,6- tetrabydrophthalic anhydride 38.0g are mixed, it is anti-at 90 DEG C
It answers 6 hours, aggregates into Cardo system adhesive resin.Anhydrous thing's vanished is confirmed by IR spectrogram.Weight average molecular weight
It is 4900.
Device: HLC-8120GPC (TOSOH Co., Ltd's manufacture)
Column: TSK-GELG4000HXL+TSK-GELG2000HXL (series connection)
Column temperature: 40 DEG C
Mobile phase solvent: tetrahydrofuran
Flow velocity: 1.0mL/ minutes
Injection rate: 50 μ L
Detector: RI
Measure sample concentration: 0.6 weight % (solvent=tetrahydrofuran)
Calibration standard substance: TSK STANDARD POLYSTYRENE the F-40, (east F-4, F-1, A-2500, A-500
Cao Co., Ltd. manufacture)
The ratio of weight average molecular weight obtained above and number-average molecular weight is set as molecular weight distribution (Mw/Mn).
Embodiment 1 to 9 and comparative example 1 to 7: the preparation of blue-sensitive resin combination
According to the composition of following table 1 to 3, the blue-sensitive resin combination of embodiment 1 to 9 and comparative example 1 to 3 is prepared
(table 1 indicates that scattering particles, table 2 indicate the composition composition and content of embodiment and comparative example).
[table 1]
| Type | Average grain diameter | Name of product | Manufacturing company | |
| E-1 | TiO2 | 130nm | PT-401L | Shi Yuan company |
| E-2 | TiO2 | 210nm | CR-63 | Shi Yuan company |
| E-3 | Al2O3 | 50nm | 0.05um alumina powder | Affiliated company |
| E-4 | Al2O3 | 300nm | 0.3um alumina powder | Affiliated company |
[table 2]
0)Colorant: C.I. pigment blue 15: 6
1)Adhesive resin: A-1 to A-5
A-1: preparation example A-1, A-2: preparation example A-2, A-3: preparation example A-3,
A-4: preparation example A-4, A-5: single (2- methacryloxyalkyl) ester
2)Photopolymerizable compound (C):
C-1: ethoxylation pentaerythritol tetraacrylate,
C-2: six acrylate of ethoxylated dipentaerythritol,
C-3: pentaerythritol propoxylate polyacrylate,
C-4: dipentaerythritol hexaacrylate (KAYARAD DPHA；Japanese chemical drug (strain) manufacture)
3)Initiator (D): Irgaqure-907 (manufacture of BASF (BASF) company)
4)Solvent (E): propylene glycol monomethyl ether
The manufacture of colour filter
It is made using by above-described embodiment 1 to 9 and the metal oxide photosensitive polymer combination of the manufacture of comparative example 1 to 7
Make colour filter.That is, above-mentioned each photosensitive polymer combination is coated on glass substrate using spin-coating method, it is then placed into and adds
On hot plate, and 100 DEG C at a temperature of maintain 3 minutes and form film.
Then, mode has the square transmission pattern and 1 to 100 of width × a height of 20mm × 20mm on the above-mentioned films
μm line/space pattern test photomask, be divided into 100um to test between photomask and irradiate ultraviolet light.
At this point, ultraviolet light source utilizes the ultrahigh pressure mercury lamp (trade name USH-250D) of oxtail Motor Corporation, in atmosphere
With 200mJ/cm under atmosphere2Light exposure (365nm) carry out light irradiation, special optical filter is not used.
The above-mentioned film through ultraviolet light irradiation is impregnated 80 seconds in the KOH aqueous development solution of pH10.5 and is carried out
Development.After the glass plate cleaning of the film will be covered with using distilled water, brushes nitrogen and be allowed to drying, in 150 DEG C of heating
It is heated 10 minutes in baking oven, manufactures color filter pattern.The film thickness of the above-mentioned multicolour pattern produced is 5.0 μm.
Experimental example 1: developing powder, sensitivity, pattern stability, taper line width and the form experiment of colour filter
It is pair with the colour filter manufactured by the blue-sensitive resin combination of above-described embodiment 1 to 5 and comparative example 1 to 3
As being evaluated as following Table 3.Evaluation criteria about each experiment is as follows.
Developing powder (sec):<spray developer (Spray Developer) HPMJ mode>non-exposed portion is being developed for development
Start the time required when dissolution in liquid.
Sensitivity: (numerical value is lower, spirit for the degree for the film that formation sensitivity mask fine pattern (1~60) is not peeled off
Sensitivity is more excellent)
Pattern stability: error (error) journey of the pattern of pattern mask after exposure when low light exposure (20~100mJ)
Degree
Zero: pattern does not have mistake
×: WRONG PATTERN 3 or more
Zero, × it is the confirmation result carried out using the optical microscopy of 3 D surface shape measurement device.
Taper line width (μm): line width after the exposure of 100 μm of patterns of pattern mask
[table 3]
In the case where developing powder is more than 60 seconds or more, it can not be manufactured, developed within the specified process time
Speed is more than in the case where 30 seconds or more, and pattern surface roughness is uneven, and it is possible to can reduce the uniformity
(Uniformity).About the embodiment of the present invention 1 to 5, confirm developing powder less than 30 seconds and sensitivity is 60 or less and
It is excellent, have the effect of that pattern stability and taper line width are excellent.On the contrary, in the case of comparative example 1, because not including scattering
Particle and pattern stability is unstable, cause the unbalanced of pattern.In the case where comparative example 2, if only utilizing acrylic resin
It is combined, then cannot be firmly supported scattering particles and blue colorant as Cardo class adhesive resin and shell
From confirming in the case where not including the photopolymerizable compound of ethylene oxide and propylene oxide in the case where comparative example 3
Developing powder significantly reduces, and causes because of longer developing powder the unbalanced of pattern stability difference and pattern.
Experimental example 2: fine pattern measurement
It is manufactured using the metal oxide photoresist prepared by above-described embodiment 1 to 5 and comparative example 1 to 3
In colour filter, the size of the pattern obtained for using the line/space pattern mask designed with 100 μm uses OM equipment
The size of (ECLIPSE LV100POL Nikon Corporation) measurement pattern.The measurement result is recorded in table 4.
[table 4]
| It divides | Fine pattern |
| Embodiment 1 | 18 |
| Embodiment 2 | 15 |
| Embodiment 3 | 19 |
| Embodiment 4 | 17 |
| Embodiment 5 | 15 |
| Comparative example 1 | Pattern is bad |
| Comparative example 2 | Removing |
| Comparative example 3 | Pattern is bad |
If the difference of lines/space pattern mask design value and the measured value of gained fine pattern is 20 μm or more,
Then it is difficult to realize fine pixel.
As a result, as confirmed from table 4, confirm poly- in the light comprising being attached with ethylene oxide and propylene oxide
In the case where the embodiment 1 to 4 of conjunction property compound, the fine pattern less than 20 μm is formed.On the contrary, the comparative example 1 to 3 the case where
Under, it confirms and is possible to will form bad fine pattern or removing and can not be confirmed whether to form pattern.
Experimental example 3: luminous intensity measurement
It is manufactured using the metal oxide photoresist prepared by above-described embodiment 1 to 5 and comparative example 1 to 3
In colour filter, by 365nm cast 4W UV illuminator (VL-4LC, VILBER LOURMAT) with the pros of 20mm × 20mm
The part that the pattern of shape is formed measures the transformed region of light, and (Spectrum meter, marine optics are public using spectrometer
Department) to the luminous intensity in embodiment 1 to 5 and the measurement of comparative example 1 to 3 region 450nm.The measurement result is recorded in following tables
5。
[table 5]
| It divides | Luminous intensity |
| Embodiment 1 | 3.46 |
| Embodiment 2 | 3.65 |
| Embodiment 3 | 3.23 |
| Embodiment 4 | 3.53 |
| Embodiment 5 | 3.67 |
| Comparative example 1 | 1.53 |
| Comparative example 2 | Removing |
| Comparative example 3 | 1.22 |
Indicate that the more high then light efficiency of luminous intensity determined is higher.In this regard, confirming referring to table 6 comprising additional
In the case where the embodiment 1 to 5 for having the photopolymerizable compound of ethylene oxide and propylene oxide, luminous intensity shows for 3 or more
It writes and improves.On the contrary, confirming in the case where comparative example 1 to 3, light efficiency reduces for 2 or less
Experimental example 4: the measurement at visual angle
It is manufactured using the metal oxide photoresist prepared by above-described embodiment 1 to 5 and comparative example 1 to 3
In colour filter, using goniophotometer (GC-5000L, Japan's electricity color) in the part that the pattern by 20 × 20mm square is formed
The intensity (Intensity) for the light that measurement is generated with the visual angle under light transmission condition, and diffusivity is calculated using following formula 1.
[formula 1]
Diffusivity=(B70+B20)/2×B5×100
(Bθ=Iθ/cosθ)
I refers to the luminous intensity measured under each angle, B70、B20And B5Refer to the value measured under 70 degree, 20 degree and 5 degree.
[table 6]
| Diffusivity | |
| Embodiment 1 | 88.3 |
| Embodiment 2 | 91.3 |
| Embodiment 3 | 85.7 |
| Embodiment 4 | 89.1 |
| Embodiment 5 | 90.6 |
| Comparative example 1 | 20.6 |
| Comparative example 2 | Removing |
| Comparative example 3 | 30.7 |
Indicate that the more high then visual angle of diffusivity determined is better.To this referring to table 7, confirm comprising being attached with epoxy second
The diffusivity of the embodiment 1 to 5 of the photopolymerizable compound of alkane and propylene oxide is 85 or more, and visual angle significantly improves.On the contrary, In
In the case where comparative example 1 and 3, confirm diffusivity significantly reduces compared with embodiment 1 to 5, visual angle reduce or removing and
It is unable to measure diffusivity.
Industrial feasibility
The present invention provides a kind of colour filter, includes the light containing alkylene oxide in above-mentioned blue-sensitive resin combination
Polymerizable compound removes the residue of pattern to control developing powder, and then solves to ask because what technologic residue occurred
Topic, and improve the bad problem of display, improve the undeveloped problem of resist.Furthermore it is possible to provide a kind of by adjusting taper
And the self-luminous colour filter of the high quality image quality with excellent visual angle.
Claims (16)
1. a kind of blue-sensitive resin combination, comprising scattering particles, blue colorant, photoinitiator, as adhesive tree
The Cardo class adhesive resin of rouge and the photopolymerizable compound containing alkylene oxide as photopolymerizable compound, wherein
The photopolymerizable compound includes the photopolymerizable compound containing alkylene oxide.
2. blue-sensitive resin combination according to claim 1, wherein
The scattering particles include the metal oxide that average grain diameter is 10nm to 1000nm.
3. blue-sensitive resin combination according to claim 1, wherein
The scattering particles include selected from by Al2O3、SiO2、ZnO、ZrO2、BaTiO3、TiO2、Ta2O5、Ti3O5、ZnO、Nb2O3、
It is more than one of group of SnO and MgO composition.
4. blue-sensitive resin combination according to claim 1, wherein
The blue-sensitive resin combination also includes violet colorant.
5. blue-sensitive resin combination according to claim 1, wherein
The blue-sensitive resin combination also includes the photopolymerizable compound without containing alkylene oxide.
6. blue-sensitive resin combination according to claim 1, wherein
The blue colorant includes one of blue pigment and blue dyes or more.
7. blue-sensitive resin combination according to claim 1, wherein
The Cardo class adhesive resin include with one of following chemical formula 1-1 and chemical formula 1-2 compound indicated with
It is upper:
[chemical formula 1-1]
[chemical formula 1-2]
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.
8. 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.
9. 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.
10. blue-sensitive resin combination according to claim 1, wherein
Photopolymerizable compound comprising the alkylene oxide be selected from by ethylene-oxide-modified trimethylolpropane trimethacrylate,
It is ethylene-oxide-modified dipentaerythritol hexaacrylate, ethylene-oxide-modified pentaerythritol tetraacrylate, ethylene-oxide-modified
Pentaerythritol tetraacrylate, epoxy pronane modification pentaerythritol tetraacrylate, ethoxylation pentaerythritol tetraacrylate,
Six acrylate of ethoxylated dipentaerythritol, pentaerythritol propoxylate polyacrylate, propoxylated dipentaerythritol six
It is more than one of group of acrylate and ethoxylated glycerol triacrylate composition.
11. blue-sensitive resin combination according to claim 1, wherein
Relative to the total weight of the solid component in the blue-sensitive resin, include: 0.1 weight %'s to 50 weight % dissipates
Penetrate particle；The blue colorant of 0.1 weight % to 50 weight %；The adhesive resin of 5 weight % to 85 weight %；5 weight %
To the photopolymerizable compound of 50 weight %；The photoinitiator of 0.1 weight % to 30 weight %；And 0.001 weight % to 10
The UV absorbent of weight %, the UV absorbent include one of benzotriazole, triazines and benzophenone or more, phase
For the total weight of the blue-sensitive resin combination, include 60 weight % to the solvent of 90 weight %.
12. a kind of colour filter, including as according to claim 1 to the blue-sensitive resin described in any one of claim 11
The blue color patterns layer that composition is formed.
13. colour filter according to claim 12, wherein
The colour filter further includes more than one of group being made of red pattern layer and green pattern layer.
14. colour filter according to claim 13, wherein
The red pattern layer or the green pattern layer include quantum dot.
15. colour filter according to claim 14, wherein
The colour filter is self-luminous colour filter.
16. a kind of image display device, comprising:
Colour filter according to claim 12；And
Emit the light source of blue light.
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| KR1020170041479A KR102300331B1 (en) | 2017-03-31 | 2017-03-31 | Blue photosensitive resin composition, color filter and image display device produced using the same |
| KR10-2017-0041479 | 2017-03-31 | ||
| PCT/KR2017/013933 WO2018182135A1 (en) | 2017-03-31 | 2017-11-30 | Blue photosensitive resin composition, color filter produced by using same, and image display device |
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| KR (1) | KR102300331B1 (en) |
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| WO2023249070A1 (en) * | 2022-06-22 | 2023-12-28 | 三菱ケミカル株式会社 | Photosensitive resin composition, cured product and method for forming same, partition wall, and image display apparatus |
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| JP2020515898A (en) | 2020-05-28 |
| WO2018182135A9 (en) | 2018-11-08 |
| KR102300331B1 (en) | 2021-09-09 |
| WO2018182135A1 (en) | 2018-10-04 |
| TW201837097A (en) | 2018-10-16 |
| TWI732073B (en) | 2021-07-01 |
| KR20180111076A (en) | 2018-10-11 |
| JP7030837B2 (en) | 2022-03-07 |
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