CN110268324A - 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 PDF

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Publication number
CN110268324A
CN110268324A CN201780085893.6A CN201780085893A CN110268324A CN 110268324 A CN110268324 A CN 110268324A CN 201780085893 A CN201780085893 A CN 201780085893A CN 110268324 A CN110268324 A CN 110268324A
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chemical formula
blue
sensitive resin
resin combination
colour filter
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CN110268324B (en
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赵成培
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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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)
  • Nonlinear Science (AREA)
  • Spectroscopy & Molecular Physics (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)
  • Liquid Crystal (AREA)

Abstract

Colour filter and image display device the present invention relates to a kind of blue-sensitive resin combination and comprising the blue-sensitive resin combination, above-mentioned blue-sensitive resin combination include mercaptan compound, blue colorant, Cardo system adhesive resin, photopolymerizable compound, photoinitiator and solvent as adhesive resin represented by scattering particles, chemical formula 1.

Description

Blue-sensitive resin combination is shown using the colour filter and image of its manufacture Device
Technical field
The present invention relates to blue-sensitive resin combinations, the colour filter and image display device that are manufactured using it.
Background technique
Colour filter be from white light extraction red, these three colors of green and blue and be capable of forming small pixel unit Film-type optical component, the size of a pixel is tens of to hundreds of microns degree.Such colour filter is used and is stacked gradually Structure made of black matrix layer and pixel portion, the black matrix layer are formed in a predetermined pattern on the transparent substrate to each picture Boundary part between element carries out shading, and the pixel portion is by multiple color (in general, red (R), green (G) and blue (B)) Three primary colors arranged in a predefined order to form each pixel.
In recent years, as one of the method for realizing colour filter, using the pigment of the photoresist using pigment-dispersing type Dispersion method.But following problems occur: for the light irradiated from light source during through colour filter, a part of light is colored device suction It receives and light efficiency declines, in addition, color reproduction reduces due to the characteristic of the pigment contained by the colour filter.
In order to solve the problems, the colour filter using the self-luminous photosensitive polymer combination comprising quantum dot is proposed Device manufacturing method.
Specifically, KR published patent the 2007-0094679th discloses by having by quantum dot (Quantum Dot the color-filter layer that) is formed and can be improved colorrendering quality, KR published patent the 2009-0036373rd discloses and passes through Existing colour filter is replaced with to the luminescent layer formed by quantum dot phosphor, improves display so as to improve luminous efficiency Quality.
But the photosensitive polymer combination developed so far in order to manufacture colour filter when being formed as cured film still It is unable to fully meet the conditions such as excellent solvent resistance, adaptation and patternability (fine pattern formative).
Summary of the invention
Technical task
The object of the present invention is to provide a kind of blue-sensitive resin combination, utilize above-mentioned blue-sensitive resin The colour filter and image display device of composition manufacture, above-mentioned blue-sensitive resin combination can be made when being formed as cured film Solvent resistance, adaptation and the excellent colour filter of patternability (fine pattern formative) are made, more particularly to realize self-luminous Colour filter.
The method of solution technology
The present invention provides a kind of blue-sensitive resin combination, and it includes represented by scattering particles, following chemical formula 1 It is mercaptan compound, blue colorant, the Cardo system adhesive resin as adhesive resin, photopolymerizable compound, light-initiated Agent and solvent.
[chemical formula 1]
(in chemical formula 1, Z1For methylene or the alkylidene or alkyl methylene of the linear chain or branched chain of carbon atom number 2 to 10 Base, Y are singly-bound ,-CO- ,-O-CO- or-NHCO-, and the integer that n is 3 to 10, X is the carbon atom that can have one or more ehter bonds The alkyl or n of the n valence of number 2 to 70 are 3 and X is the group of trivalent represented by following chemical formula 2.)
[chemical formula 2]
(in chemical formula 2, Z2、Z3And Z4It is each independently the alkylidene of methylene or carbon atom number 2 to 6, " * " indicates knot Close key.)
In addition, the present invention provides the colour filter of the blue color patterns layer comprising being formed by above-mentioned blue-sensitive resin combination Device.
In addition, the present invention provides the image display device comprising above-mentioned colour filter and the light source for issuing blue light.
Invention effect
Blue-sensitive resin combination of the invention is by including 1 institute of chemical formula in blue-sensitive resin combination The mercaptan compound of expression can be realized solvent resistance, adaptation and patternability (fine figure when to being formed as cured film Case formative) excellent colour filter, especially self-luminous colour filter.
Specific embodiment
Blue-sensitive resin combination of the invention may include mercaptan chemical combination represented by scattering particles, chemical formula 1 Object, blue colorant, the Cardo system adhesive resin as adhesive resin, photopolymerizable compound, photoinitiator and molten Agent, particularly by comprising mercaptan compound represented by chemical formula 1, thus can be manufactured when being formed as cured film solvent resistance, Adaptation and the excellent colour filter of patternability (fine pattern formative), more particularly to realize self-luminous colour filter.
Hereinafter, the composition that the present invention will be described in detail.
Scattering particles
Scattering particles of the invention can be the metal oxide of the average grain diameter with 10 to 1000nm, and average grain diameter be 30 to 300nm range when it is more preferred.In the case where the average grain diameter of scattering particles is met the above range, can expect by measuring The sufficient dispersion effect for the light that son point issues, and above-mentioned scattering particles occurs and settles or is formed in blue-sensitive composition A possibility that the problem of non-uniform light emitting layer surface, reduces.Above-mentioned metal oxide can for 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, Er, Tm, Yb, Ti, Sb, Sn, Zr, Nb, Ce, Ta, In and their combination group At one of group metal oxide.It more specifically, can be for 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 with On.Optionally, the material that by acrylate etc. there is the compound of unsaturated bond to be surface-treated also can be used.
Above-mentioned scattering particles can optionally come suitably adjust the content in average grain diameter and entire combination object with can Sufficiently improve the luminous intensity of colour filter.
Relative to the feline amount in blue-sensitive resin, the content of above-mentioned scattering particles can for 0.1 to 50 weight % preferably can be 5 to 30 weight %.In the case where the content of scattering particles is met the above range, can be realized Desired luminous intensity, and can reduce occur blue-sensitive resin combination stability decline problem a possibility that.
Mercaptan compound represented by chemical formula 1
The performance of mercaptan compound represented by the chemical formula 1 that the present invention is included makes by blue-sensitive resin combination shape At pattern properties become it is good and improve durability and reliability effect.
[chemical formula 1]
(in chemical formula 1, Z1For methylene or the alkylidene or alkyl methylene of the linear chain or branched chain of carbon atom number 2 to 10 Base, Y are singly-bound ,-CO- ,-O-CO- or-NHCO-, and the integer that n is 3 to 10, X is the carbon atom that can have one or more ehter bonds The alkyl or n of the n valence of number 2 to 70 are 3 and X is the group of trivalent represented by following chemical formula 2.)
[chemical formula 2]
(in chemical formula 2, Z2、Z3And Z4It is each independently the alkylidene of methylene or carbon atom number 2 to 6, " * " indicates knot Close key.).
Preferably, n is 4 or more, preferably 4 to 10 integer, more preferably 4,6 or 8.
As n be 3 when X, the group of trivalent represented by following chemical formula 5 can be enumerated,
As n be 4,6 or 8 when X, respectively can preferably enumerate the group of 4,6 or 8 valences represented by following chemical formula 6.
[chemical formula 3]
(in chemical formula 3, " * " indicates associative key),
[chemical formula 4]
(in chemical formula 4, the integer that m is 0 to 2, " * " indicates associative key).
Mercaptan compound represented by above-mentioned chemical formula 1 may include represented by by chemical formula 5 to chemical formula 12 One or more of the group of compound composition, preferably may include represented by compound represented by chemical formula 5, chemical formula 9 Compound.
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
[chemical formula 8]
[chemical formula 9]
[chemical formula 10]
[chemical formula 11]
[chemical formula 12]
Blue-sensitive resin combination of the invention as comprising mercaptan compound represented by chemical formula 1, thus on When stating blue-sensitive resin combination and being formed as cured film, it is (fine to can be realized solvent resistance, adaptation and patternability Patternability) excellent colour filter, especially self-luminous colour filter.
Mercaptan compound represented by above-mentioned chemical formula 1 can be used alone or be used in combination of two or more.
Relative to the feline amount in blue-sensitive resin combination, the content of above-mentioned mercaptan compound can be with It preferably can be 0.08 to 3 weight % for 0.05 to 5 weight %.
In the case where the content of above-mentioned mercaptan compound is met the above range, in the steady of blue-sensitive resin combination It is advantageous in terms of qualitative, smell, clever density, distinguishing, developability, adaptation.
Blue colorant
In blue colorant of the invention, as blue pigment, colour index (dyeing association, family (The can be specifically enumerated Society of Dyers and Colourists) publish) in be classified as the compound of pigment, can more specifically enumerate as follows The pigment of colour index (C.I.) number, but not limited thereto.Blue pigment can specifically enumerate C.I. pigment blue 15: 3,15:4, 15:6,16,21,28 and 76 etc. are preferably comprised selected from by C.I. pigment blue 15: 3, pigment blue 15: the 6, group that pigment blue 16 forms One or more of.
Blue colorant of the invention can further include blue dyes, as blue dyes, can enumerate colour index The compound or dye of dyestuff are classified as in (dyeing association, family (The society of Dyers and Colourists) is published) Documented well known dyestuff in color handbook (Se Ran society).
It is above-mentioned to add the dyestuff used specifically for example:
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 includes C.I. solvent blue 35, one or more of 36,44,45 and 70；
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, wherein more preferably include C.I. acid blue One or more of 80 and 90；
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 can be respectively used singly or in combination of two or more.
Blue colorant of the invention can further include violet colorant as additional colorant.Violet colorant can With comprising one or more of violet pigment and cudbear, above-mentioned violet pigment can specifically enumerate C.I. pigment violet 1,14, 19,23,29,32,33,36,37 and 38 etc., wherein more preferably include C.I. pigment Violet 23.
Cudbear can specifically enumerate C.I. solvent violet, C.I. acid violet, C.I. acid violet, C.I. medium purple etc., but 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., more Preferably comprise C.I. solvent violet 13.As C.I. acid violet, C.I. acid violet 6B, 7,9,17,19 and 66 etc. can be enumerated, it is more excellent Choosing includes C.I. acid violet 66.It is directly purple as 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..
Furthermore, it is possible to 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 feline amount in blue-sensitive resin combination, the content of above-mentioned blue colorant can be with For 0.1 to 50 weight %, can preferably be used according to 0.5 to 30 weight %.With 100 weight % of blue-sensitive resin combination On the basis of, content can be 0.1 to 50 weight %, preferably can be 0.5 to 30 weight %, more preferably can be 1 to 20 weight Measure %.
In the case where the content of above-mentioned blue colorant is met the above range, it is conducive to realize external light reflection inhibitory effect, And a possibility that generation luminous intensity decline problem or viscosity stability decline problem of blue-sensitive resin combination, is low, because And it is advantageous.
The present invention by the inclusion of blue colorant and scattering particles and be free of the sub- point of amount of blue, can also prevent colour filter, Especially the efficiency of the blue pixel of self-luminous colour filter reduces.
Adhesive resin
Adhesive resin of the invention includes Cardo system adhesive resin.Above-mentioned Cardo system adhesive resin have by Light or the reactivity and alkali solubility of heat effect, as coloured material decentralized medium and play a role.Blue sensitive of the invention Property resin combination contained by Cardo system adhesive resin as scattering particles bonding agent resin and play a role, only If just there is no limit for the resin in alkaline-based developer used in development phase when can be dissolved in colour filter manufacture.
Cardo system adhesive resin of the invention may include compound represented by chemical formula 13-1 and chemical formula 13-2 One or more of.
[chemical formula 13-1]
[chemical formula 13-2]
In above-mentioned chemical formula 13-1 and 13-2,
R1、R2、R3And R4It is each independently
X is the alkyl or hydroxyl of hydrogen atom, carbon atom number 1 to 5, R5For hydrogen atom or the alkyl of carbon atom number 1 to 5.
In the present invention, compound represented by above-mentioned chemical formula 13-1 can pass through change represented by following chemical formula 14-1 Object is closed to synthesize, compound represented by chemical formula 13-2 can use compound represented by chemical formula 14-2 to synthesize.
[chemical formula 14-1]
[chemical formula 14-2]
Compound represented by chemical formula 13-1 can be one in compound represented by chemical formula 15 or chemical formula 16 Kind or more, compound represented by chemical formula 13-2 can be one of compound represented by chemical formula 17 or chemical formula 18 More than.
[chemical formula 15]
[chemical formula 16]
[chemical formula 17]
[chemical formula 18]
Above-mentioned Cardo system adhesive resin can be by making selected from by bis- (the 3- cortex cinnamomi diester) fluorenes (9,9-bis (3- of 9,9- Cinnamic diester) fluorene), bis- (3- cinnamoyl, the 4- hydroxy phenyl) fluorenes (9,9-bis (3- of 9,9- Cinnamoil, 4-hydroxyphenyl) fluorene), bis- (methyl propenoic acid glycidyl ether) fluorenes (9,9-bis of 9,9- (glycidyl methacrylate ether) fluorene), bis- two cinnamates of (3,4- dihydroxy phenyl) fluorenes of 9,9- (9, 9-bis (3,4-dihydroxyphenyl) fluorene dicinnamic ester), methacrylic acid 3,6- 2-glycidyl 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- Hydroxyphenlylfluorene), bis- (the 4- allyloxy phenyl) fluorenes (9,9-bis (4-allyloxyphenyl) of 9,9- ) and bis- (the 3,4- metering system acid diesters) fluorenes (9,9-bis (3,4-methacrylic diester) of 9,9- fluorene Fluorene) at least one of the group formed with selected from by the maleic anhydride, succinic anhydride, itaconic acid as anhydride compound Acid anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic tetrahydrophthalic acid Acid anhydride, chlorendic anhydride, methyl tetrahydrophthalic anhydride composition group or selected from by pyromellitic dianhydride, the hexichol as acid dianhydride In the group of the aromatic polycarboxylic acids acid anhydrides such as ketone tetracarboxylic acid dianhydride, bibenzene tetracarboxylic dianhydride, Biphenyl Ether tetracarboxylic acid dianhydride composition At least one is reacted and is manufactured, and but not limited thereto.
It, can be together with above-mentioned Cardo system resin and with acrylic acid series alkali solubility tree as adhesive resin in the present invention Rouge.That is, above-mentioned blue-sensitive resin combination of the invention can also include acrylic acid other than above-mentioned Cardo system resin It is alkali soluble resins.
The other monomers that acrylic acid series alkali soluble resins can enumerate carboxyl group-containing monomer and can be copolymerized with the monomer are total to Polymers etc..As carboxyl group-containing monomer, can enumerate in the molecules such as unsaturated monocarboxylic or unsaturated dicarboxylic, unsaturated tricarboxylic acids Unsaturated carboxylic acids such as the unsaturated polybasic carboxylic acid with more than one carboxyl etc..It here, can example as unsaturated monocarboxylic Lift acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, meat silicic acid etc..As unsaturated dicarboxylic, Malaysia can be enumerated Acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc..Unsaturated polybasic carboxylic acid may be acid anhydrides, can specifically enumerate Malaysia Acid anhydrides, itaconic anhydride, citraconic anhydride etc..In addition, unsaturated polybasic carboxylic acid can be its single (2- methacryloxyalkyl) Ester can enumerate mono succinate (2- acryloyl-oxyethyl) ester, mono succinate (2- methacryloxyethyl) ester, adjacent benzene Diformate mono (2- acryloyl-oxyethyl) ester, phthalic acid list (2- methacryloxyethyl) ester etc..It is unsaturated more First carboxylic acid may be list (methyl) acrylate of its two ends dicarboxyl based polyalcohol, can enumerate ω-carboxy-polycaprolactone Mono acrylic ester, ω-carboxy-polycaprolactone monomethacrylates etc..These carboxyl group-containing monomers can be respectively individually or by two kinds It is used in mixed way above.As the other monomers that can be copolymerized with above-mentioned carboxyl group-containing monomer, 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 base ether, vinylbenzyl glycidyl base ether, to vinylbenzyl glycidyl base The aromatic ethenyl compounds such as ether, indenes；Methyl acrylate, methyl methacrylate, ethyl acrylate, methacrylic acid second Ester, n-propyl, n propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, The secondary butyl ester of n-BMA, isobutyl acrylate, Isobutyl methacrylate, sec-butyl acrylate, methacrylic acid, Tert-butyl acrylate, Tert-butyl Methacrylate, acrylic acid 2- hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid 2- Hydroxy propyl ester, methacrylic acid 2- hydroxy propyl ester, acrylic acid 3- hydroxy propyl ester, methacrylic acid 3- hydroxy propyl ester, acrylic acid 2- Hydroxybutyl, methacrylic acid 2- hydroxybutyl, acrylic acid 3- hydroxybutyl, methacrylic acid 3- hydroxybutyl, acrylic acid 4- Hydroxybutyl, methacrylic acid 4- hydroxybutyl, allyl acrylate, allyl methacrylate, benzyl acrylate, methyl-prop Olefin(e) acid benzyl ester, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, acrylic acid 2- methoxy Base ethyl ester, methacrylic acid 2- methoxy acrylate, acrylic acid 2- phenoxy ethyl, methacrylic acid 2- phenoxy ethyl, methoxy Base diethylene glycol acrylate, methoxyl group diethylene glycol methacrylate, methoxy triethylene acrylate, methoxyl group three Glycolmethacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxyl group dipropyl two Alcohol acrylate, methoxyl group dipropylene glycol methyl acrylate, isobornyl acrylate, isobornyl methacrylate, propylene Sour bicyclopentadiene ester, methacrylic acid bicyclopentadiene ester, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (methyl) acrylic acid norborneol It is ester, acrylic acid 2- hydroxyl -3- phenoxy-propyl, methacrylic acid 2- hydroxyl -3- phenoxy-propyl, glycerol mono-acrylate, sweet The unsaturated carboxylate types such as oily monomethacrylates；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, methyl The unsaturation carboxylic such as acrylic acid 3- amino propyl ester, acrylic acid 3- dimethylamino propyl ester, methacrylic acid 3- dimethylamino propyl ester Sour aminoalkyl esters；The esterification of the unsaturated carboxylic acids glycidol such as glycidyl acrylate, glycidyl methacrylate Close species；The vinyl esters of carboxylic acids class such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate；Vinyl first The unsaturated ethers such as base ether, vinyl ethyl ether, allyl glycidyl ether；Acrylonitrile, methacrylonitrile, α-chloropropene The vinyl cyanides based compounds such as nitrile, double cyanogen Asias ethylene；Acrylamide, Methacrylamide, α-chloroacrylamide, N-2- ethoxy The unsaturated acyls amines such as acrylamide, N-2- hydroxyethyl methacrylamide；Maleimide, benzyl maleimide, N- benzene The unsaturated acyls imines such as base maleimide, N- N-cyclohexylmaleimide；1,3- butadiene, isoprene, chlorobutadiene Equal aliphatic conjugated dienes class；With polystyrene, polymethyl acrylate, polymethyl methacrylate, polyacrylic acid N-butyl, poly- N-BMA, polysiloxanes the end of polymer molecular chain there is single acryloyl group or monomethacrylate acyl group Polymeric monomer class.These monomers can respectively individually or be use mixing two or more.In particular, as it is above-mentioned can with contain carboxyl The other monomers of monomer copolymerization, the monomer with norborny skeleton, the monomer with adamantane framework, with rosin skeleton The large volumes monomer such as monomer has the tendency for reducing relative dielectric constant, therefore preferably.
As Cardo system adhesive resin and/or acrylic acid series alkali soluble resins of the invention, acid value be preferably 20 to The range of 200 (KOH ㎎/g).If acid value is in above range, the dissolubility in developer solution is improved, and non-exposed portion is easy molten Solution, clever density increase, and as a result the pattern of exposure portion leaves in development and improves membrane left rate (film remaining ratio), Thus preferably.Here, so-called acid value is surveyed as the amount (mg) of required potassium hydroxide when neutralizing acrylic acid series polymeric compounds 1g Fixed value usually can be used potassium hydroxide aqueous solution and be titrated and be found out.Furthermore it is preferred that by gel permeation chromatography (GPC； Using tetrahydrofuran as eluting solvent) measurement polystyrene convert weight average molecular weight (hreinafter referred to as " weight average molecular weight ") Cardo system adhesive resin and/or acrylic acid series alkali solubility tree for 2,000 to 200,000, preferably 3,000 to 100,000 Rouge.If molecular weight is in above range, there are the raising of the hardness of coated film, membrane left rate is high, the non-exposed portion in developer solution The tendency that dissolubility is excellent and resolution ratio improves, thus preferably.
Cardo system adhesive resin and/or acrylic acid series 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 feline amount in blue-sensitive resin combination, the content of adhesive resin of the invention It can be 5 to 85 weight %, preferably can be 5 to 60 weight %.The case where the content of adhesive resin is in above range Under, deposit in developer solution dissolubility sufficiently and non-pixel portion is not easy to generate development residue on substrate, when development, is not easy to send out The film of the pixel portion of raw exposure portion is reduced, and the deciduous of non-pixel portion becomes good tendency, therefore preferably.
Photopolymerizable compound
Photopolymerizable compound contained by blue-sensitive resin combination of the invention is can be by light and aftermentioned Photoepolymerizationinitiater initiater effect and the compound that polymerize, monofunctional monomer, two functional monomers, other multifunctional lists can be enumerated Body etc..As the concrete example of monofunctional monomer, nonyl phenyl carbitol acrylate, acrylic acid 2- hydroxyl -3- benzene can be enumerated Oxygroup propyl ester, 2- ethylhexyl carbitol acrylate, acrylic acid 2- hydroxy methacrylate, 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 Pentanediol 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, trihydroxy methyl third can be enumerated Alkane three (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, pentaerythrite Five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc..It is wherein, it is preferable to use more than two functions multifunctional Monomer.
Relative to the feline amount in blue-sensitive resin combination, the content of above-mentioned photopolymerizable compound It can be 5 to 50 weight %, preferably can be 5 to 30 weight %.Meet above-mentioned model in the content of above-mentioned photopolymerizable compound In the case where enclosing, there are the intensity of pixel portion or flatness to become good tendency, therefore preferably.
Photoinitiator
Photoepolymerizationinitiater initiater used in the present invention, which plays, makes the clever density of photosensitive polymer combination be promoted and be improved The effect of productivity preferably comprises acetophenone based compound.As acetophenone based compound, diethoxybenzene second can be enumerated Ketone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, benzil dimethyl ketal, 2- hydroxyl -1- [4- (2- hydroxyl-oxethyl) Phenyl]-2- methylpropane-1- ketone, 1- hydroxycyclohexylphenylketone, 2- methyl-1-(4- methylthiophenyi)-2- morpholino third Alkane -1- ketone, 2- benzyl -2- dimethylamino -1- (4- morphlinophenyl) butane -1- ketone, 2- hydroxy-2-methyl [4- (1- methyl Vinyl) phenyl] propane-1- ketone etc., it can preferably enumerate 2- methyl-1-(4- methylthiophenyi)-2- morpholino propane-1- Ketone, 2- benzyl -2- dimethylamino -1- (4- morphlinophenyl) butane -1- ketone etc..Furthermore, it is possible to by above-mentioned acetophenone system with Outer Photoepolymerizationinitiater initiater is applied in combination.Photoepolymerizationinitiater initiater other than acetophenone system can enumerate irradiation light and generate activity certainly By the living radical producing agent of base, sensitizer, acid agent etc..As living radical producing agent, benzoin system can be enumerated Compound, benzophenone based compound, thioxanthones based compound, triazine based compound etc..It, can be with as benzoin based compound Enumerate benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether etc..As hexichol Ketone based compound can enumerate benzophenone, methyl o-benzoylbenzoate, 4- phenyl benzophenone, 4- benzoyl -4'- Dimethyl diphenyl sulfide, 3,3', 4,4'- tetra- (tert-butyl hydroperoxide carbonyl) benzophenone, 2,4,6- tri-methyl benzophenone etc.. As thioxanthones based compound, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- diethyl thioxanthone, 2 can be enumerated, Chloro- 4- propoxythioxanthone of bis- clopenthixal ketone of 4-, 1- etc..As triazine based compound, 2,4- bis- (trichloromethyls)-can be enumerated 6- (4- methoxyphenyl) -1,3,5- triazine, 2,4- bis- (trichloromethyl) -6- (4- methoxyl group naphthalene) -1,3,5- triazine, 2,4- Bis- (trichloromethyl) -6- (4- methoxyl-styrene) -1,3,5- triazines, 2,4- bis- (trichloromethyl) -6- [2- (5- methyl furan Mutter -2- base) ethylidene] -1,3,5- triazine, bis- (the trichloromethyl) -6- of 2,4- [2- (furans -2- base) ethylidene] -1,3,5- three Bis- (the trichloromethyl) -6- of piperazine, 2,4- [2- (4- diethylamino -2- aminomethyl phenyl) ethylidene] -1,3,5- triazine, 2,4- are bis- (trichloromethyl) -6- [2- (3,4 Dimethoxyphenyl) ethylidene] -1,3,5- triazine etc..It is generated as above-mentioned living radical Agent, it is, for example, possible to use 2,4,6- trimethylbenzoyl diphenyl phosphine oxides, 2,2,-bis- (Chloro-O-Phenyl) -4,4', 5,5'- tetra- Phenyl -1,2'- bisglyoxaline, 10- butyl -2- chloro-acridine ketone, 2- ethyl hydrazine, benzil, 9,10- phenanthrenequione, camphorquinone, phenyl second Aldehydic acid methyl esters, titanocenes compound etc..As above-mentioned acid agent, 4- hydroxy phenyl dimethyl sulfonium p-methyl benzenesulfonic acid can be enumerated Salt, 4- hydroxy phenyl dimethyl sulfonium hexafluoro antimonate, 4- acetoxyl group phenyl dimethyl sulfonium tosilate, 4- acetoxyl group Phenylmethyl benzyl sulfonium hexafluoro antimonate, triphenylsulfonium tosilate, triphenylsulfonium hexafluoro antimonate, diphenyl iodine Tosilate, diphenyl iodineHexafluoro antimonate etc.Salt or nitrobenzyl tosylat class, benzoin toluene Sulfonic acid esters etc..In addition, also have in above compound as living radical producing agent while generating living radical and acid Compound, for example, triazine system Photoepolymerizationinitiater initiater also serves as acid agent.
Relative to the feline amount in blue-sensitive resin combination, blue-sensitive resin group of the invention The content for closing above-mentioned Photoepolymerizationinitiater initiater used in object can be 0.1 to 30 weight %, preferably can be 0.3 to 20 weight Measure %.If being in above range, have the high spirit of photosensitive composition densification and formed using the composition Pixel portion or the flatness on surface of the pixel portion become good tendency, therefore preferably.
Further, photopolymerization initiator can be used in the present invention.Photopolymerization initiator causes with photopolymerization sometimes Agent is applied in combination, and is the change used to promote the polymerization for the photopolymerizable compound for causing polymerization due to Photoepolymerizationinitiater initiater Close object.As photopolymerization initiator, amine compound, alkoxy anthracene based compound, thioxanthones based compound etc. can be enumerated.
As amine compound, triethanolamine, methyl diethanolamine, triisopropanolamine, 4- dimethylamino can be enumerated Methyl benzoate, ethyl 4-dimethylaminobenzoate, 4- dimethylaminobenzoic acid isopentyl ester, benzoic acid 2- dimethylamino Ethyl ester, 4- dimethylaminobenzoic acid 2- ethylhexyl, N, bis- (dimethylamino) hexichol of N- dimethyl-p-toluidine, 4,4'- Ketone (common name Michler's keton), bis- (diethylamino) benzophenone of 4,4'-, bis- (ethylmethylamino) benzophenone of 4,4'- etc., Wherein, bis- (diethylamino) benzophenone of preferably 4,4'-.As alkoxy anthracene based compound, 9,10- diformazan can be enumerated Oxygroup anthracene, 2- ethyl -9,10- dimethoxy anthracene, 9,10- diethoxy anthracene, 2- ethyl -9,10- diethoxy anthracene etc..As thiophene Ton ketone based compound, can enumerate 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- diethyl thioxanthone, 2,4- dichloro Chloro- 4- propoxythioxanthone of thioxanthones, 1- etc..Such Photoepolymerizationinitiater initiater (D) can be used alone, and multiple combinations are used Even.In addition, commercially available product can be used as photopolymerization initiator, it, can example as commercially available photopolymerization initiator Lift trade name " EAB-F " [manufacturer: Baotugu Chemical Industrial Co., Ltd] etc..
Using these photopolymerization initiators, usage amount is usual in terms of every 1 mole of Photoepolymerizationinitiater initiater For 10 moles hereinafter, preferably 0.01~5 mole.If being in above range, with photosensitive composition Clever density more improves, the tendency that the productivity of the colour filter formed using the composition is improved, therefore preferably.
Solvent
Solvent contained by blue-sensitive resin combination of the invention is not particularly limited, and blue-sensitive can be used Various organic solvents used in resin combination field.As its concrete example, ethylene glycol single methyl ether, second two can be enumerated The ethylene glycol monoalkyl ethers classes such as alcohol list ethylether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, Diethylene glycol dialkyl ethers class, the methyl such as diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether are molten The ethylene glycol alkyl ethers acetate esters such as fine agent acetic acid esters, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol The alkylenes such as single monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, methoxybutyl acetic acid esters and methoxypentyl acetic acid esters Base glycol alkyl ether acetate esters, benzene,toluene,xylene, mesitylene etc. are aromatic hydrocarbon, methyl ethyl ketone, acetone, methyl The ketones such as amyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, the alcohol such as ethyl alcohol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol Class, 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 the aspect of coating, drying property, it is preferable that can enumerate boiling point in above-mentioned solvent is 100 DEG C to 200 DEG C organic molten Agent can more preferably enumerate aklylene glycol alkylether acetates class, ketone, 3- ethoxyl ethyl propionate or 3- methoxypropionic acid The esters such as methyl esters can further preferably enumerate propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, hexamethylene Ketone, 3- ethoxyl ethyl propionate, 3- methoxy methyl propionate etc..These solvents can be mixed respectively alone or in any combination to be made With.
The content of solvent in blue-sensitive resin combination of the invention is with 100 weight of blue-sensitive resin combination It can be 50 to 90 quality % on the basis of amount %, preferably can be 55 to 85 quality %.If the content of solvent is with said reference It is calculated as the range of 50 to 90 quality %, then (otherwise referred to as using roll coater, spin coater, slit spin coater, slit coater Die coating machine), the apparatus for coating such as flush coater are when being coated, there is coating to become good tendency, therefore preferably.
Additive
Blue-sensitive resin combination of the invention can optionally further include filler, other macromolecule chemical combination The additives such as object, pigment dispersing agent, closely sealed promotor, antioxidant, ultraviolet absorbing agent, anticoagulant.
Concrete example as above-mentioned filler exemplifies glass, silica, aluminium oxide etc..
As other above-mentioned high-molecular compounds, the curability such as epoxy resin, maleimide resin can be specifically enumerated Resin, the thermoplasticity such as polyvinyl alcohol, polyacrylic acid, polyalkylene glycol monoalkyl ether, poly- fluoroalkyl, polyester, polyurethane Resin etc..
As above-mentioned pigment dispersing agent, commercially available surfactant can use, can enumerate organic silicon-type, fluorine system, ester Surfactants such as system, cationic system, anionic system, nonionic system, both sexes etc..They can respectively individually or will be two or more It is applied in combination.
As above-mentioned surfactant, such as there are 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 in addition to this, as trade name, KP (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacture), POLYFLOW (common prosperity society chemistry can be enumerated (strain) manufacture), EFTOP (manufacture of Tohkem Products company), MEGAFAC (big Japanese ink chemical industry (strain) manufacture), Flourad (Sumitomo 3M (strain) manufacture), Asahi guard, Surflon (more than, Asahi Glass's (strain) manufacture), SOLSPERSE (Zeneca (strain) manufacture), EFKA (manufacture of EFKA chemical company), PB 821 (aginomoto (strain) manufacture) etc..
As above-mentioned closely sealed promotor, vinyltrimethoxysilane, vinyltriethoxysilane, ethylene can be enumerated Base three (2- methoxy ethoxy) silane, N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane, N- (2- amino Ethyl) -3- TSL 8330,3-aminopropyltriethoxysilane, 3- glycidoxypropyl trimethoxy silicon Alkane, 3- glycidoxypropyl dimethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 3- chloropropyl Methyl dimethoxysilane, 3- r-chloropropyl trimethoxyl silane, 3- methyl allyl acyloxypropyl trimethoxysilane, 3- sulfydryl third Base trimethoxy silane etc..
As antioxidant, 2,2'- thiobis (4- methyl-6-tert-butylphenol), 2,6- bis--tertiary fourth can be specifically enumerated Base -4- methylphenol etc..
As above-mentioned ultraviolet absorbing agent, 2- (3- tert-butyl -2- hydroxy-5-methyl base phenyl) -5- chlorine can be specifically enumerated Benzotriazole, alkoxy benzophenone etc..
As above-mentioned anticoagulant, Sodium Polyacrylate etc. can be specifically enumerated.
For above-mentioned additive, within the scope of the effect of the invention, those skilled in the art can be fitted It is used when additional.For example, relative to whole 100 parts by weight of above-mentioned blue-sensitive resin combination, above-mentioned additive can be with 0.05 to 10 parts by weight, preferably with 0.1 to 10 parts by weight, more preferably with 0.1 to 5 parts by weight use, but not limited thereto.
Blue-sensitive resin combination of the invention can such as manufacture by the following method.Scattering particles is preparatory It is mixed with solvent, so that it is dispersed to average grain diameter using ball mill becomes 10 until 1000nm.At this point, can optionally add Using dispersing agent, adhesive resin (Cardo system resin or Cardo system resin and acrylic acid series alkali soluble resins can also be cooperated Mixture) part or all.According to as predetermined concentration in resulting dispersion liquid (hereinafter, otherwise referred to as mill base) Mode further add remaining adhesive resin (Cardo system resin or Cardo system resin and acrylic acid series alkali soluble resins Mixture), the mercaptan compound of chemical formula 1, blue colorant, photopolymerizable compound, Photoepolymerizationinitiater initiater, optionally make Other compositions and optionally additional solvent, so as to obtain target blue-sensitive resin combination.
<colour filter and image display device>
Another way again of the invention is related to having comprising above-mentioned blue color patterns layer formation blue-sensitive resin group Close the colour filter of the blue color patterns layer of the solidfied material of object.
Colour filter of the invention is due to using above-mentioned blue color patterns layer formation with blue-sensitive resin combination come generation It is manufactured for blue quantum point, therefore has the advantages that can reduce manufacturing cost.In addition, blue-sensitive tree of the invention Oil/fat composition is by the inclusion of mercaptan compound represented by chemical formula 1, so that above-mentioned blue-sensitive resin combination is formed as Can be realized when cured film solvent resistance, adaptation and the excellent colour filter of patternability (fine pattern formative) and from Shine colour filter.
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 itself substrate of above-mentioned colour filter, or may be in display device etc. locating for colour filter Position is not particularly limited.Aforesaid substrate can be glass, silicon (Si), Si oxide (SiOx) or polymeric substrate, above-mentioned height Molecule substrate can be polyether sulfone (polyethersulfone, PES) or polycarbonate (polycarbonate, PC) etc..
Above-mentioned blue color patterns layer, can be above-mentioned to be coated with as the layer comprising blue-sensitive resin combination of the invention Blue color patterns layer formation blue-sensitive resin combination and be exposed in a predetermined pattern, develop and heat cure and formed Layer, above-mentioned pattern layer can be formed by implementing method commonly known in the art.
In another embodiment of the invention, above-mentioned colour filter can be further included selected from by red pattern layer and green One or more of the 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 the red pattern layer containing red quantum dot or containing 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 red light or blue light by the aftermentioned light source for issuing blue light respectively.
In another embodiment of the invention, scattering particles that above-mentioned red pattern layer or green pattern layer are included can be with The metal oxide for being 10 to 1000nm comprising average grain diameter, the content about above-mentioned scattering particles and metal oxide are applicable The content of scattering particles and metal oxide included in blue-sensitive resin combination of the invention.
In the present invention, form, composition and its content of the quantum dot that above-mentioned red pattern layer or green pattern layer are included It does not limit, the commonly used quantum dot in this field can be used.
The colour filter comprising substrate and pattern layer as described above can further include be formed between each pattern every Wall can also further include black matrix, and but not limited thereto.
In the present invention, above-mentioned colour filter can be self-luminous colour filter.
Another mode of the invention is related to the image display device comprising above-mentioned colour filter and the light source for issuing blue light. For example, image display device of the invention includes the blue for having the solidfied material containing above-mentioned blue-sensitive resin combination 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 aobvious applied to electroluminescent The various image display devices such as showing device, plasm display device, field emission display device.
The case where above-mentioned image display device includes the colour filter and above-mentioned light source for having blue color patterns layer of the invention Under, have the advantages that luminous intensity is excellent.In addition, the blue color patterns layer that colour filter of the invention is included does not include blue quantum Point, therefore have the advantages that the low image display device of manufacturing cost can be manufactured.
Embodiment
Hereinafter, enumerating embodiment in order to further illustrate this specification and being described in detail.But this specification Embodiment can be deformed into other various forms, should not be construed as the range of this specification by following detailed description of The restriction of embodiment.The embodiment of this specification is to be more fully explained this explanation to those of ordinary skill in the art Book and provide.In addition, " % " and " part " of following presentation content as long as no it is specifically mentioned then be weight basis.
Synthesis example: the synthesis of adhesive resin
Production Example 1: acrylic acid series alkali soluble resins
Prepare the flask for having blender, thermometer, reflux condensing tube, dropping funel and nitrogen ingress pipe, on the other hand, As monomer dropping funel, benzyl maleimide 74.8g (0.20 mole), acrylic acid 43.2g (0.30 mole), ethylene are put into Base toluene 118.0g (0.50 mole), tert-butyl hydroperoxide -2 ethyl hexanoic acid ester 4g, propylene glycol monomethyl ether (PGMEA) it is stirred and is prepared after 40g, as chain-transferring agent dropwise adding tank, prepare that n-dodecane mercaptan 6g, PGMEA is added 24g and substance made of being stirred.Later, PGMEA 395g is imported into flask, by the atmosphere in flask from air displacement After nitrogen, the temperature of flask is risen to 90 DEG C while stirring.Then, monomer and chain tra nsfer are added dropwise since dropping funel Agent.When dropwise addition, 2h is respectively carried out while maintaining 90 DEG C, after 110 DEG C are warming up to after 1h and maintains 3h, gas are imported and imports 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 put into flask, at 110 DEG C, the reaction was continued 8 hours, obtain solid at Dividing acid value is the Resin A of 70 ㎎ KOH/g.Weight average molecular weight by the polystyrene conversion of GPC measurement is 16,000, molecular weight Being distributed (Mw/Mn) is 2.3.
Production Example 2: the synthesis of the compound of chemical formula 15
By 3', 6'- dihydroxy spiral shell (fluorenes -9,9- xanthene) (3', 6'- in 3000ml three neck round bottom flask Dihydroxyspiro (fluorene-9,9-xantene)) 364.4g and tert-butyl ammonium bromide 0.4159g mixing, be added table chlorine Alcohol 2359g is simultaneously heated to 90 DEG C and is reacted.By liquid-phase chromatographic analysis, if 3,6- dihydroxy spiral shells (fluorenes -9,9- xanthene) are complete It totally disappeared mistake, be then cooled to 30 DEG C, be slowly added 50%NaOH aqueous solution (3 equivalent).By liquid-phase chromatographic analysis, when epichlorohydrin is complete When totally disappeared mistake, after being extracted using methylene chloride, washes 3 times, after then keeping organic layer dry using magnesium sulfate, methylene chloride is subtracted Pressure distillation, is recrystallized using the methylene chloride and methanol of mixing ratio 50:50.
By 1 equivalent of epoxide synthesized in this way and 0.004 equivalent of tert-butyl ammonium bromide, 2,6- diisobutyl phenol After 0.001 equivalent, the mixing of 2.2 equivalent of acrylic acid, solvent propylene glycol monomethyl ether acetate 24.89g is added and is mixed.On one side Air is blown into 25ml/min into the reaction solution temperature is heated to 90~100 DEG C on one side and dissolved.By reaction solution 120 DEG C are heated to from gonorrhoea state, to make it completely dissolved.If solution becomes transparent and viscosity is got higher, acid value is measured, It stirs always to acid value and is less than 1.0mgKOH/g.Acid value reaches target (0.8) and needs 11 hours.After reaction, by reactor Temperature be down to room temperature, obtain the compound of colorless and transparent chemical formula 15.
[chemical formula 15]
Production Example 3: the synthesis of the compound of chemical formula 16
By 3', 6'- dihydroxy spiral shell (fluorenes -9,9- xanthene) (3', 6'- in 3000ml three neck round bottom flask Dihydroxyspiro (fluorene-9,9-xantene)) 364.4g and tert-butyl ammonium bromide 0.4159g mixing, be added table chlorine Alcohol 2359g is simultaneously heated to 90 DEG C and is reacted.By liquid-phase chromatographic analysis, if 3,6- dihydroxy spiral shells (fluorenes -9,9- xanthene) are complete It totally disappeared mistake, be then cooled to 30 DEG C, be slowly added 50%NaOH aqueous solution (3 equivalent).By liquid-phase chromatographic analysis, if epichlorohydrin It completely disappears, then after being extracted using methylene chloride, washes 3 times, after then keeping organic layer dry using magnesium sulfate, by methylene chloride Vacuum distillation, is recrystallized using the methylene chloride and methanol of mixing ratio 50:50.
By 1 equivalent of epoxide synthesized in this way and 0.004 equivalent of tert-butyl ammonium bromide, 2,6- diisobutyl phenol After 0.001 equivalent, the mixing of 2.2 equivalent of methacrylic acid, solvent propylene glycol monomethyl ether acetate 24.89g is added and is mixed. Temperature 90~100 DEG C are heated to while being blown into air into the reaction solution with 25ml/min to dissolve.It will reaction Solution is heated to 120 DEG C from gonorrhoea state, to make it completely dissolved.If solution becomes transparent and viscosity is got higher, measure Acid value stirs always to acid value and is less than 1.0mgKOH/g.Acid value reaches target (0.8) and needs 11 hours.It after reaction, will be anti- It answers the temperature of device to be down to room temperature, obtains the compound of colorless and transparent chemical formula 16.
[chemical formula 16]
Production Example 4: the synthesis of the compound of chemical formula 17
By 4,4'- (9H- xanthene -9,9- diyl) biphenol (4,4'- (9H- in 3000ml three neck round bottom flask Xanthene-9,9-diyl) diphenol) 364.4g and tert-butyl ammonium bromide 0.4159g mixing, be added epichlorohydrin 2359g simultaneously 90 DEG C are heated to be reacted.By liquid-phase chromatographic analysis, if 4,4'- (9H- xanthene -9,9- diyl) biphenols (4,4'- (9Hxanthene-9,9-diyl) diphenol) it completely disappears, then 30 DEG C are cooled to, 50%NaOH aqueous solution (3 is slowly added Equivalent).By liquid-phase chromatographic analysis, if epichlorohydrin completely disappears, after being extracted using methylene chloride, washes 3 times, utilize sulphur After sour magnesium keeps organic layer dry, methylene chloride is evaporated under reduced pressure, is tied again using the methylene chloride and methanol of mixing ratio 50:50 It is brilliant.1 equivalent of epoxide synthesized in this way is worked as with 0.004 equivalent of tert-butyl ammonium bromide, 2,6- diisobutyl phenol 0.001 After amount, the mixing of 2.2 equivalent of acrylic acid, solvent propylene glycol monomethyl ether acetate 24.89g is added and is mixed.It is anti-to this on one side It answers in solution to be blown into air with 25ml/min temperature is heated to 90~100 DEG C on one side and dissolve.By reaction solution from gonorrhoea State is heated to 120 DEG C, to make it completely dissolved.If solution becomes transparent and viscosity is got higher, acid value is measured, is stirred always It mixes to acid value and is less than 1.0mgKOH/g.Acid value reaches target (0.8) and needs 11 hours.After reaction, by the temperature of reactor It is down to room temperature, obtains the compound of colorless and transparent chemical formula 17.
[chemical formula 17]
Production Example 5: the synthesis of the compound of chemical formula 18
By 4,4'- (9H- xanthene -9,9- diyl) biphenol (4,4'- (9H- in 3000ml three neck round bottom flask Xanthene-9,9-diyl) diphenol) 364.4g and tert-butyl ammonium bromide 0.4159g mixing, be added epichlorohydrin 2359g simultaneously 90 DEG C are heated to be reacted.By liquid-phase chromatographic analysis, if 4,4'- (9H- xanthene -9,9- diyl) biphenols (4,4'- (9Hxanthene-9,9-diyl) diphenol) it completely disappears, then 30 DEG C are cooled to, 50%NaOH aqueous solution (3 is slowly added Equivalent).By liquid-phase chromatographic analysis, if epichlorohydrin completely disappears, after being extracted using methylene chloride, wash 3 times, it is then sharp Keep organic layer dry then with magnesium sulfate, methylene chloride be evaporated under reduced pressure, using mixing ratio 50:50 methylene chloride and methanol into Row recrystallization.By 1 equivalent of epoxide synthesized in this way and t-0.004 equivalent, 0.001 equivalent of 2,6- diisobutyl phenol, After the mixing of 2.2 equivalent of methacrylic acid, solvent propylene glycol monomethyl ether acetate 24.89g is added and is mixed.It is anti-to this on one side It answers in solution to be blown into air with 25ml/min temperature is heated to 90~100 DEG C on one side and dissolve.By reaction solution from gonorrhoea State is heated to 120 DEG C, to make it completely dissolved.If solution becomes transparent and viscosity is got higher, acid value is measured, is stirred always It mixes to acid value and is less than 1.0mgKOH/g.Acid value reaches target (0.8) and needs 11 hours.After reaction, by the temperature of reactor It is down to room temperature, obtains the compound of colorless and transparent chemical formula 1-2-2.
[chemical formula 18]
The synthesis (A-1) of Production Example 6:Cardo system adhesive resin
Production Example 2 manufacture chemical formula 15 compound 307.0g in add propylene glycol monomethyl ether 600g and After dissolution, bibenzene tetracarboxylic dianhydride 78g and teabrom 1g is mixed, is slowly heated up, is reacted 4 hours at 110~115 DEG C. After the disappearance for confirming anhydride group, 1,2,3,6- tetrabydrophthalic anhydride 38.0g is mixed, reacted 6 hours at 90 DEG C and is polymerize At Cardo system adhesive resin.The disappearance of acid anhydrides is confirmed by IR spectrum.Weight average molecular weight: 3500
The synthesis (A-2) of Production Example 7:Cardo system adhesive resin
Production Example 3 manufacture chemical formula 16 compound 307.0g in add propylene glycol monomethyl ether 600g and After dissolution, bibenzene tetracarboxylic dianhydride 78g and teabrom 1g is mixed, is slowly heated up, is reacted 4 hours at 110~115 DEG C. After the disappearance for confirming anhydride group, 1,2,3,6- tetrabydrophthalic anhydride 38.0g is mixed, reacted 6 hours at 90 DEG C and is polymerize At Cardo system adhesive resin.The disappearance of acid anhydrides is confirmed by IR spectrum.Weight average molecular weight: 3800
The synthesis (A-3) of Production Example 8:Cardo system adhesive resin
Production Example 3 manufacture chemical formula 17 compound 307.0g in add propylene glycol monomethyl ether 600g and After dissolution, pyromellitic acid anhydride 78g and teabrom 1g is mixed, is slowly heated up, is reacted 4 hours at 110~115 DEG C. After the disappearance for confirming anhydride group, 1,2,3,6- tetrabydrophthalic anhydride 38.0g is mixed, reacted 6 hours at 90 DEG C and is polymerize At Cardo system adhesive resin.The disappearance of acid anhydrides is confirmed by IR spectrum.Weight average molecular weight: 4500
The synthesis (A-4) of Production Example 9:Cardo system adhesive resin
Production Example 3 manufacture chemical formula 18 compound 307.0g in add propylene glycol monomethyl ether 600g and After dissolution, pyromellitic acid anhydride 78g and teabrom 1g is mixed, is slowly heated up, is reacted 4 hours at 110~115 DEG C. After the disappearance for confirming anhydride group, 1,2,3,6- tetrabydrophthalic anhydride 38.0g is mixed, reacted 6 hours at 90 DEG C and is polymerize At Cardo system adhesive resin.The disappearance of acid anhydrides is confirmed by IR spectrum.Weight average molecular weight: 4900
Device: HLC-8120GPC (Tosoh (strain) manufacture)
Column: TSK-GELG4000HXL+TSK-GELG2000HXL (series connection)
Column temperature: 40 DEG C
Mobile phase solvent: tetrahydrofuran
Flow velocity:/ minute
Injection rate: 50
Detector: RI
Measure sample solution concentration: 0.6 weight % (solvent=tetrahydrofuran)
Correction standard substance: TSK STANDARD POLYSTYRENE the F-40, (east F-4, F-1, A-2500, A-500 Cao's (strain) manufacture)
The ratio between weight average molecular weight and number-average molecular weight derived above are set as molecular weight distribution (Mw/Mn).
Embodiment
As follows, the present invention is described in more detail based on embodiment, but it is only to illustrate, the scope of the present invention is not It is defined in these embodiments.The scope of the present invention has been shown in scope of the claims, and including with scope of the claims It records with being had altered in equivalence and range.In addition, " % " and " part " of following presentation content is as long as no spy It indescribably and is then quality criteria.
Embodiment 1 to 5 and comparative example 1 to 2: the manufacture of blue-sensitive resin combination
According to the composition of following table 1 to 2, the blue-sensitive resin combination of embodiment 1 to 5, comparative example 1 to 2 is manufactured. (table 1 shows scattering particles, and table 2 shows the composition and content of the composition of embodiment and comparative example.)
[table 1]
Type Average grain diameter Product name Manufacturing company
E-1 TiO2 130nm PT-401L Shi Yuan
E-2 TiO2 210nm CR-63 Shi Yuan
E-3 Al2O3 50nm 0.05um alumina powder Allied company
E-4 Al2O3 300nm 0.3um alumina powder Allied company
[table 2]
(unit: weight %)
0) colorant:
B-1:Fastogen Blue EP-7S (DCI company): C.I. pigment blue 15: 6
B-2:Fastogen Blue 5424 (DCI company): C.I. pigment blue 15: 4
V-1:Fastogen Super Violet 140V (DIC company): C.I. pigment Violet 23
1) adhesive resin:
A-1: Production Example 6,
A-2: Production Example 7,
A-3: Production Example 8,
A-4: Production Example 9,
A-5: single (2- methacryl oxyalkyl) ester
2) photopolymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD DPHA；Japanese chemical drug (strain) system It makes)
3) mercaptan compound represented by chemical formula 1:
D-1: trimethylolpropane tris (3-thiopropionate) (Trimethylolpropane tris (3- mercaptopropionate)；TMMP-20P)
D-2: five pentaerythrite four (3-thiopropionate) (Pentaerythritol tetrakis (3- mercaptopropionate)；PEMP)
4) photoinitiator (D):907 (BASF AG's systems)
5) solvent (E): propylene glycol monomethyl ether
The manufacture of colour filter
Colour filter is manufactured using blue-sensitive resin combination manufactured by above-described embodiment 1 to 5 and comparative example 1 to 2. That is, be placed in heating plate after above-mentioned each blue-sensitive resin combination is coated on glass substrate using spin-coating method, It is maintained 3 minutes at a temperature of 100 DEG C and forms film.
Then, on the above-mentioned films place have transverse direction × longitudinal direction 20mm × 20mm regular quadrangle transmission pattern and 1 to 100 μm of lines/space pattern test photomask, and the interval with photomask is set as 100 μm and irradiates ultraviolet light.
At this point, ultraviolet light source utilizes the extra-high-pressure mercury vapour lamp (trade name USH-250D) of oxtail motor (strain) system, big According to 200mJ/cm under gas atmosphere2Light exposure (365nm) carry out light irradiation, not use special optical filter.
The above-mentioned thin film dipped KOH aqueous development solution in pH 10.5 through ultraviolet light irradiation is developed for 80 seconds. The glass plate for being covered with film is washed using distilled water, then nitrogen blowing is dried, in 150 DEG C of heated oven Heating 10 minutes, to manufacture color filter pattern.The film thickness of the multicolour pattern of above-mentioned manufacture is 5.0 μm.
1. solvent resistance of test example
The colour filter of above-mentioned production is impregnated in N-Methyl pyrrolidone solvent 30 minutes, the color difference of evaluation front and back is carried out Comparative evaluation.Specifically, utilizing the above-mentioned filter of colorimeter (Olympus Corp manufactures, OSP-200) measurement about solvent resistance The substrate for completing chromaticity coordinates measurement is impregnated in N-Methyl pyrrolidone by the coloration and transmitance of the substrate made in the manufacture of color device After solvent 30 minutes, colorimeter (Olympus Corp manufactures, OSP-200) measurement coloration and transmitance are utilized again.△ Eab is The value acquired by the saturation degree formula below based on the space CIE 1976 (L*, a*, b*) chromaticity coordinates.(Japanese color science meeting Compile newly organized color science handbook (Showa 60 years) p.266).
About formula used at this time, by the following mathematics for indicating color difference in the three-dimensional colorimeter that is defined by L*, a*, b* Formula (1) calculates, and value of chromatism is smaller, can more manufacture the colour filter of high reliability.As a result it is shown in following Table 3.
Mathematical expression (1): △ Eab*=[(△ L*)2+(△a*)2+(△b*)2](1/2)
2. adaptation of test example
When evaluating pattern generated by optical microscopy, commented by the peeling phenomenon degree on following pattern Valence.As a result it is shown in following Table 3.
Zero: not peeled off on pattern
△: there is 1~3 peeling on pattern
×: there are 4 or more to peel off on pattern
[table 3]
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Comparative example 1 Comparative example 2
Solvent resistance 0.87 1.07 0.55 0.85 1.02 4.55 5.46
Adaptation ○ ○ ○ ○ ○ × ×
The measurement of 3. fine pattern of test example
It is manufactured for using blue-sensitive resin combination manufactured by above-described embodiment 1 to 5 and comparative example 1 to 2 Colour filter in by being designed to the size of pattern that 100 μm of lines/space pattern mask obtains, utilize OM equipment (ECLIPSE LV100POL Nikon Corporation) is measured.
[table 4]
Fine pattern (μm)
Embodiment 1 9
Embodiment 2 10
Embodiment 3 10
Embodiment 4 11
Embodiment 5 12
Comparative example 1 -6
Comparative example 2 -5
If the difference of lines/space pattern mask design value and the measured value of obtained fine pattern is 20 μm or more, It is then difficult to realize small pixel, if having negative value, meaning leads to the undesirable critical numerical value of process.
It arrives, feels with the blue of the comparative example 1 for not including mercaptan compound represented by chemical formula 1 or 2 as can be recognized from Table 4 Photosensitive resin composition is compared, the blue-sensitive resin of the embodiment 1 to 5 comprising mercaptan compound represented by chemical formula 1 Composition forms fine pattern well.
Industrial availability
Blue-sensitive resin combination of the invention is by including 1 institute of chemical formula in blue-sensitive resin combination The mercaptan compound of expression, to can be realized solvent resistant when above-mentioned blue-sensitive resin combination is formed as cured film Property, adaptation and the excellent colour filter of patternability (fine pattern formative), more particularly to realize self-luminous colour filter.

Claims (15)

1. a kind of blue-sensitive resin combination, it includes mercaptan compound represented by scattering particles, following chemical formula 1, Blue colorant, Cardo system adhesive resin, photopolymerizable compound, photoinitiator and solvent as adhesive resin,
[chemical formula 1]
In chemical formula 1, Z1For methylene or the alkylidene or alkylmethylene of the linear chain or branched chain of carbon atom number 2 to 10, Y is single Key ,-CO- ,-O-CO- or-NHCO-, the integer that n is 3 to 10, X is the carbon atom number 2 to 70 that can have one or more ehter bonds The alkyl of n valence, alternatively, n is 3 and X is the group of trivalent represented by following chemical formula 2,
[chemical formula 2]
In chemical formula 2, Z2、Z3And Z4It is each independently the alkylidene of methylene or carbon atom number 2 to 6, " * " indicates to combine Key.
2. blue-sensitive resin combination according to claim 1, mercaptan compound packet represented by the chemical formula 1 One or more of the group that compound represented by containing being selected from by chemical formula 5 to 12 forms,
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
[chemical formula 8]
[chemical formula 9]
[chemical formula 10]
[chemical formula 11]
[chemical formula 12]
3. blue-sensitive resin combination according to claim 1, the scattering particles include average grain diameter be 10 to The metal oxide of 1000nm.
4. blue-sensitive resin combination according to claim 1, the scattering particles includes selected from by Al2O3、 SiO2、ZnO、ZrO2、BaTiO3、TiO2、Ta2O5、Ti3O5、ZnO、Nb2O3, SnO and MgO composition one or more of group.
5. blue-sensitive resin combination according to claim 1, the blue-sensitive resin combination also include Violet colorant.
6. blue-sensitive resin combination according to claim 1, the blue colorant includes blue pigment and indigo plant One or more of color dyestuff.
7. blue-sensitive resin combination according to claim 1, Cardo system adhesive resin includes followingization One or more of compound represented by formula 13-1 and chemical formula 13-2,
[chemical formula 13-1]
[chemical formula 13-2]
In the chemical formula 13-1 and 13-2,
R1、R2、R3And R4It is each independently
X is the alkyl or hydroxyl of hydrogen atom, carbon atom number 1 to 5, R5For hydrogen atom or the alkyl of carbon atom number 1 to 5.
8. blue-sensitive resin combination according to claim 7, compound represented by chemical formula 13-1 is chemistry In compound represented by formula 15 or chemical formula 16 it is any more than, compound represented by chemical formula 13-2 be chemical formula 17 or It is more than any in compound represented by chemical formula 18,
[chemical formula 15]
[chemical formula 16]
[chemical formula 17]
[chemical formula 18]
9. blue-sensitive resin combination according to claim 1, the blue-sensitive resin combination also include Acrylic acid series alkali soluble resins is as adhesive resin.
10. blue-sensitive resin combination according to claim 1, which is characterized in that the photoinitiator is benzene second Ketone based compound.
11. blue-sensitive resin combination according to claim 10, the acetophenone based compound is selected from by two 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- methylthiophenyi)- 2- morpholino propane -1- ketone, 2- benzyl -2- dimethylamino -1- (4- morphlinophenyl) butane -1- ketone, 2- hydroxy-2-methyl One or more of the group of [4- (1- methyl ethylene) phenyl] propane -1- ketone composition.
12. a kind of colour filter, it includes the blue-sensitive resin combinations as described in any one of claims 1 to 11 to be formed Blue color patterns layer.
13. colour filter according to claim 12, the colour filter also includes selected from by red pattern layer and green pattern One or more of the group of layer composition,
The red pattern layer or green pattern layer include quantum dot.
14. colour filter according to claim 12, which is characterized in that the colour filter is self-luminous colour filter.
15. a kind of image display device, it includes the light sources of colour filter and sending blue light described in claim 12.
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