WO2018182302A1 - Composition de résine photosensible bleue, et filtre coloré et dispositif d'affichage d'image fabriqués à l'aide de celle-ci - Google Patents

Composition de résine photosensible bleue, et filtre coloré et dispositif d'affichage d'image fabriqués à l'aide de celle-ci Download PDF

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Publication number
WO2018182302A1
WO2018182302A1 PCT/KR2018/003623 KR2018003623W WO2018182302A1 WO 2018182302 A1 WO2018182302 A1 WO 2018182302A1 KR 2018003623 W KR2018003623 W KR 2018003623W WO 2018182302 A1 WO2018182302 A1 WO 2018182302A1
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Prior art keywords
group
butyl
formula
carbon atoms
methyl
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PCT/KR2018/003623
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English (en)
Korean (ko)
Inventor
박정효
김형주
Original Assignee
동우 화인켐 주식회사
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Priority claimed from KR1020170041419A external-priority patent/KR102300330B1/ko
Priority claimed from KR1020170041416A external-priority patent/KR102300329B1/ko
Application filed by 동우 화인켐 주식회사 filed Critical 동우 화인켐 주식회사
Priority to CN201880019521.8A priority Critical patent/CN110446977B/zh
Priority to JP2019546854A priority patent/JP6868117B2/ja
Publication of WO2018182302A1 publication Critical patent/WO2018182302A1/fr

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Classifications

    • 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
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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

Definitions

  • the present invention relates to a blue photosensitive resin composition, a color filter manufactured using the same, and an image display device.
  • the color filter is a thin film type optical component that extracts three colors of red, green, and blue from white light and makes them possible in fine pixel units.
  • the size of one pixel is about tens to hundreds of micrometers.
  • Such a color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate to shield the boundary between each pixel, and a plurality of colors (typically red (R), green (G) and The pixel units in which the three primary colors of blue (B) are arranged in a predetermined order are stacked in this order.
  • Korean Patent Publication No. 2007-0094679 suggests that color reproducibility can be improved by having a color filter layer formed of quantum dots, and Korean Patent Publication No. 2009-0036373 uses a conventional color filter as a quantum dot phosphor. It is proposed that the display quality can be improved by improving the luminous efficiency by replacing the light emitting layer.
  • the photosensitive resin composition developed to manufacture a color filter did not sufficiently satisfy the requirements of development speed, excellent pattern characteristics, processability, heat resistance, light resistance, yellowing inhibitory effect, reliability, and the like.
  • An object of the present invention is to provide a blue photosensitive resin composition capable of implementing a color filter, particularly a self-luminous color filter, having excellent process speed, excellent processability, excellent heat resistance and light resistance when formed into a cured film, and excellent reliability. .
  • an object of this invention is to provide the blue photosensitive resin composition which has the outstanding pattern characteristic and yellowing suppression effect.
  • an object of this invention is to provide the blue color filter and image display apparatus manufactured using the above-mentioned blue photosensitive resin composition.
  • the present invention includes a scattering particle, a blue colorant, a binder resin, a cardo-based binder resin, a photopolymerizable compound, a photoinitiator, and a solvent,
  • the photoinitiator is a blue photosensitive resin composition, characterized in that at least one selected from the compounds represented by the following formula (1) to (3):
  • R 1 to R 4 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, a benzyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, or 1 to C atoms. It is a naphthyl group which is unsubstituted or substituted with 12 alkyl groups.
  • R 5 is hydrogen, alkyl of 1 to 20 carbon atoms, 8 cycloalkyl of 3 carbon atoms, or phenyl unsubstituted or substituted with methyl, methoxy, halogen, carboxyl and hydroxy groups
  • N is an integer from 1 to 4 and m is an integer from 1 to 6;
  • R 6 is an alkyl group having 1 to 8 carbon atoms, a phenyl group, a substituted phenyl group, a benzyl group or a substituted benzyl group;
  • R 7 is a diphenyl sulfide group, a methyl group, a methoxy group, a halogen, a carboxyl group and a diphenyl sulfide group substituted with a hydroxy group, a carbazole group, a methyl group, a methoxy group, a halogen, a carboxyl group and a hydroxy group and a carbazole group and a fluorene group Or a substituted fluorene group.
  • R 8 , R 9 and R 10 each independently represent R, OR, COR, SR, CONRR 'or CN;
  • R and R ' represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, which are halogen atoms and / or complexes having 2 to 20 carbon atoms May be substituted by ventilation, of which the alkylene portion of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, an ester bond, and R and R 'together may form a ring And;
  • Y 1 represents an oxygen atom, a sulfur atom or a selenium atom, m represents an integer of 0 to 4, and p represents an integer of 0 to 5;
  • q 0 or 1
  • R 11 , R 12 , R 13 and R 14 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms;
  • X 1 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, which are halogen atoms and / or heterocyclic groups having 2 to 20 carbon atoms. Which may be substituted, wherein the alkylene moiety of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, an ester bond;
  • Y 2 and Y 3 each independently represent an oxygen atom, a sulfur atom or a selenium atom.
  • the present invention provides a color filter comprising a blue pattern layer made of the above-described blue photosensitive resin composition.
  • the present invention is the color filter; And a light source emitting blue light.
  • the blue photosensitive resin composition of the present invention comprises at least one or more photoinitiators selected from the compounds represented by the formulas (1) to (3) in the blue photosensitive resin composition, thereby having excellent development speed, excellent processability, and excellent formation when formed into a cured film. It is possible to implement a color filter, particularly a self-luminous color filter having excellent reliability, excellent heat resistance and light resistance.
  • the blue photosensitive resin composition of the present invention may provide an excellent pattern characteristic and yellowing inhibitory effect by including at least one antioxidant selected from phosphorus antioxidants, sulfur antioxidants and phenolic antioxidants.
  • the blue photosensitive resin composition of this invention can be usefully used for manufacture of a color filter and an image display apparatus.
  • the blue photosensitive resin composition of the present invention includes the blue photosensitive agent by including a blue colorant, a cardo-based binder resin, a photopolymerizable compound, at least one photoinitiator selected from a compound represented by Formulas 1 to 3 as a binder resin, and a solvent.
  • the resin composition may have excellent development speed, excellent processability, and excellent color resistance, particularly self-luminous color filter, having excellent heat resistance and light resistance when formed into a cured film.
  • the scattering particles of the present invention may be a metal oxide having an average particle diameter of 10 to 1000 nm, more preferably when the average particle diameter is in the range of 30 to 300 nm. If the average particle diameter of the scattering particles satisfies the above range, a sufficient scattering effect of the light emitted from the quantum dots can be expected, and the scattering particles may sink in the blue photosensitive composition, or a problem may occur in which the surface of the light emitting layer may be uneven. Lowers.
  • the metal oxide is 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, It may be an oxide including one metal selected from the group consisting of Ce, Ta, In, and combinations thereof.
  • Al 2 O 3 , SiO 2 , ZnO, ZrO 2 , BaTiO 3 , TiO 2 , Ta 2 O 5 , Ti 3 O 5 , ITO, IZO, ATO, ZnO-Al, Nb 2 O 3 , SnO, MgO And combinations thereof may be one or more selected from the group consisting of. If necessary, a material surface-treated with a compound having an unsaturated bond such as acrylate may be used.
  • the scattering particles may be appropriately adjusted as necessary to the average particle diameter and the content in the entire composition to sufficiently improve the light emission intensity of the color filter.
  • the scattering particles may be included in 0.1 to 50% by weight, preferably 5 to 30% by weight based on the total weight of solids in the blue photosensitive resin.
  • the content of the scattering particles satisfies the above range, while achieving the desired emission intensity, it is possible to lower the possibility of a problem of deterioration in stability of the blue photosensitive resin composition.
  • examples of the blue pigment include compounds classified as pigments in the color index (Published by The society of Dyers and Colourists), and more specifically, the color index (CI) as follows.
  • pigment of number is mentioned, It is not necessarily limited to these.
  • Blue pigments are specifically described, for example, in C.I. Pigment blue 15: 3, 15: 4, 15: 6, 16, 21, 28, and 76, and the like.
  • Pigment Blue 15: 3, Pigment Blue 15: 6, Pigment Blue 16 It is preferable to include at least 1 type selected from the group which consists of.
  • the blue colorant of the present invention may further comprise a blue dye, which is a known dye which is described in a compound or dyeing note (color dyed yarn) classified as a dye in the color index (published by The Society of Dyers and Colourists). And dyes.
  • a blue dye which is a known dye which is described in a compound or dyeing note (color dyed yarn) classified as a dye in the color index (published by The Society of Dyers and Colourists). And dyes.
  • the said blue dye can be used individually or in combination of 2 or more types, respectively.
  • the blue colorant of the present invention may further include a purple colorant as an additional colorant.
  • the purple coloring agent may comprise at least one of a purple pigment and a purple dye, wherein the purple pigment is specifically C.I. Pigment violet 1, 14, 19, 23, 29, 32, 33, 36, 37 and 38, among which C.I. It is more preferred to include pigment violet 23.
  • Purple dyes are specifically, C.I. Solvent violet, C.I. acid violet, C.I. Direct violet, C.I. modanto violet, and the like, but are not limited thereto.
  • the C.I. Solvent violet is C.I. Solvent violet 8, 9, 13, 14, 36, 37, 47 and 49, and the like. More preferably, solvent violet 13 is included.
  • C.I. acid violet includes C.I. Acid violet 6B, 7, 9, 17, 19 and 66, and the like. More preferably, acid violet 66 is included.
  • CI direct violet includes CI direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104. .
  • the blue colorant may be included in an amount of 0.1 to 50% by weight based on the total weight of solids in the blue photosensitive resin, and preferably 0.5 to 30% by weight. It may be included in 0.1 to 50% by weight based on 100% by weight of the blue photosensitive resin composition, preferably 0.5 to 30% by weight, more preferably 1 to 20% by weight.
  • the content of the blue colorant satisfies the above range, it is advantageous to achieve the effect of suppressing the external light reflection and is advantageous because it is less likely to cause a problem of lowering the luminescence intensity or a problem of lowering the viscosity stability of the blue photosensitive resin composition.
  • the blue colorant and the scattering particles are included even though the blue quantum dots are not included, thereby reducing the efficiency of the blue pixel of the color filter, particularly the self-luminous color filter.
  • the binder resin of this invention contains cardo system binder resin.
  • the cardo-based binder resin has reactivity and alkali solubility due to the action of light or heat and acts as a dispersion medium of the coloring material.
  • the cardo-based binder resin contained in the blue photosensitive resin composition of the present invention is not limited as long as it is a resin that acts as a binder resin for scattering particles and is soluble in an alkaline developer used in the developing step for producing a color filter.
  • the cardo-based binder resin of the present invention may include one or more of the compounds represented by Formulas 4-1 and 4-2.
  • R 15 , R 16 , R 17 and R 18 are each independently, Is;
  • X is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyl group
  • R 19 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • the compound represented by Chemical Formula 4-1 may be synthesized by the compound represented by Chemical Formula 5-1, and the compound represented by Chemical Formula 4-2 may be synthesized using the compound represented by Chemical Formula 5-2. .
  • the compound represented by Formula 4-1 may be at least one of the compounds represented by Formula 6 or 7, and the compound represented by Formula 4-2 may be at least one of the compounds represented by Formula 8 or Formula 9.
  • the cardo-based binder resin is 9,9-bis (3-cinnamic diester) fluorene (9,9-bis (3-cinnamic diester) fluorene), 9,9-bis (3- cinnamoyl, 4-hydride Hydroxyphenyl) fluorene (9,9-bis (3-cinnamoyl, 4-hydroxyphenyl) fluorene), 9,9-bis (glycidyl methacrylate ether) fluorene (9,9-bis (glycidyl methacrylate ether) fluorene), 9,9-bis (3,4-dihydroxyphenyl) fluorene dinamic ester (9,9-bis (3,4-dihydroxyphenyl) fluorene dicinnamic ester), 3,6-diglycidyl meta Acrylate ether spiro (3,6-diglycidyl methacrylate ether spiro (fluorene-9,9-xantene)), 9,9-bis (3-
  • acrylic alkali-soluble resin may be used together with the cardo-based resin. That is, the blue photosensitive resin composition may further include acrylic alkali-soluble resin in the cardo-based resin.
  • acrylic alkali-soluble resin examples include carboxyl group-containing monomers and copolymers with other monomers copolymerizable with this monomer.
  • carboxyl group-containing monomer unsaturated carboxylic acids, such as unsaturated monocarboxylic acid, unsaturated polycarboxylic acid, such as unsaturated polyhydric carboxylic acid which has one or more carboxyl groups in molecules, such as unsaturated dicarboxylic acid and unsaturated tricarboxylic acid, are mentioned, for example. have.
  • unsaturated monocarboxylic acid acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example.
  • unsaturated dicarboxylic acid a maleic acid, a fumaric acid, itaconic acid, a citraconic acid, a mesaconic acid, etc. are mentioned, for example.
  • the unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride and citraconic anhydride.
  • the unsaturated polyhydric carboxylic acid may be mono (2-methacryloyloxyalkyl) ester thereof, for example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl ), Mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, etc. are mentioned.
  • the unsaturated polyhydric carboxylic acid may be mono (meth) acrylate of the sock end dicarboxy polymer, and examples thereof include? -Carboxypolycaprolactone monoacrylate and? -Carboxypolycaprolactone monomethacrylate. .
  • carboxyl group-containing monomers can be used individually or in mixture of 2 or more types, respectively.
  • styrene (alpha) -methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, p-chloro styrene, o-methoxy styrene, m-meth Oxy styrene, p-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p- Aromatic vinyl compounds such as vinyl benzyl
  • Unsaturated carboxylic acid esters 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate Acid aminoalkyl esters; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Un
  • Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; And monoacryloyl or monomethacryloyl groups at the terminal of the polymer molecular chain of polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, polysiloxane. And macromonomers to have. These monomers can be used individually or in mixture of 2 or more types, respectively.
  • bulky monomers such as monomers having a norbornyl skeleton, monomers having an adamantane skeleton, and monomers having a rosin skeleton as the other monomers copolymerizable with the carboxyl group-containing monomer are preferable because they tend to lower the dielectric constant.
  • the acid value is preferably in the range of 20 to 200 (KOH mg / g). If the acid value is in the above range, the solubility in the developing solution is improved, so that the non-exposed part is easily dissolved and the sensitivity is increased, and as a result, the pattern of the exposed part remains at the time of development to improve the film remaining ratio.
  • the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can usually be obtained by titration using an aqueous potassium hydroxide solution.
  • the polystyrene reduced weight average molecular weight (hereinafter, simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; tetrahydrofuran as an eluting solvent) is 2,000 to 200,000, preferably 3,000 to 100,000.
  • GPC gel permeation chromatography
  • Cardo binder resin or acrylic resin is preferable.
  • the molecular weight is in the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the non-exposed portion in the developer is excellent and the resolution tends to be improved, which is preferable.
  • molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of cardo type binder resin and / or acrylic resin it is more preferable that it is 1.5-6.0. If molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is 1.5-6.0, since developability is excellent, it is preferable.
  • the binder resin of the present invention may be included in 5 to 85% by weight, preferably 5 to 60% by weight based on the total weight of solids in the blue photosensitive resin.
  • the solubility in the developing solution is sufficient, so that development residues are less likely to occur on the substrate of the non-pixel portion, and it is difficult to reduce the film portion of the pixel portion of the exposed portion at the time of development. It is preferable because omission tends to be good.
  • the photopolymerizable compound contained in the blue photosensitive resin composition of this invention is a compound which can superpose
  • bifunctional monomer examples include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.
  • polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol penta (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate etc. are mentioned. Of these, bifunctional or higher polyfunctional monomers are preferably used.
  • the photopolymerizable compound may be included in 5 to 50% by weight, preferably 5 to 30% by weight based on the total weight of solids in the blue photosensitive resin. When the content of the photopolymerizable compound satisfies the above range, the intensity and smoothness of the pixel portion tend to be good, which is preferable.
  • the photopolymerization initiator used in the present invention serves to improve productivity by improving the sensitivity of the photosensitive resin composition, and the photoinitiator may be at least one or more selected from compounds represented by the following Chemical Formulas 1 to 3.
  • R 1 to R 4 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, a benzyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, or 1 to C atoms. It is a naphthyl group which is unsubstituted or substituted with 12 alkyl groups.
  • R 5 is hydrogen, alkyl of 1 to 20 carbon atoms, 8 cycloalkyl of 3 carbon atoms, or phenyl unsubstituted or substituted with methyl, methoxy, halogen, carboxyl and hydroxy groups.
  • N is an integer from 1 to 4 and m is an integer from 1 to 6;
  • R 6 is an alkyl group having 1 to 8 carbon atoms, a phenyl group, a substituted phenyl group, a benzyl group or a substituted benzyl group;
  • R 7 is a diphenyl sulfide group, a methyl group, a methoxy group, a halogen, a carboxyl group and a diphenyl sulfide group substituted with a hydroxy group, a carbazole group, a methyl group, a methoxy group, a halogen, a carboxyl group and a hydroxy group and a carbazole group and a fluorene group Or a substituted fluorene group.
  • R 8 , R 9 and R 10 each independently represent R, OR, COR, SR, CONRR 'or CN;
  • R and R ' represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, which are halogen atoms and / or complexes having 2 to 20 carbon atoms May be substituted by ventilation, of which the alkylene portion of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, an ester bond, and R and R 'together may form a ring And;
  • Y 1 represents an oxygen atom, a sulfur atom or a selenium atom, m represents an integer of 0 to 4, and p represents an integer of 0 to 5;
  • q 0 or 1
  • R 11 , R 12 , R 13 and R 14 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms;
  • X 1 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, which are halogen atoms and / or heterocyclic groups having 2 to 20 carbon atoms. Which may be substituted, wherein the alkylene moiety of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, an ester bond;
  • Y 2 and Y 3 each independently represent an oxygen atom, a sulfur atom or a selenium atom.
  • alkyl group represented by R and R ' for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl , Octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, vinyl, aryl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propyoxyethyl, Methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoro
  • heterocyclic group represented by R and R ' a heterocyclic group with 5-7 carbon atoms, such as pyridyl, pyrimidyl, furyl, and thiophenyl, is mentioned preferably, for example.
  • the C5-C7 ring such as a piperidine ring and a morpholine ring, is mentioned preferably, for example.
  • R and R ' may also be substituted with halogen elements such as fluorine, chlorine, bromine, iodine or pyridyl, pyrimidyl, furyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, Dazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxoxazolidyl, piperidyl, piperidyl It may be substituted with a heterocyclic group having 5 to 7 carbon atoms, such as dill (piperadyl), morpholinyl.
  • halogen elements such as fluorine, chlorine, bromine, iodine or pyridyl, pyrimidyl, furyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, Dazolidyl, pyrazolidyl, thiazo
  • alkyl group represented by X 1 for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl , Isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, vinyl, aryl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propyoxyethyl, methoxy Ethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, diflu
  • Examples of the aryl group represented by X 1 include phenyl, tril, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl, and the like. An aryl group of ⁇ 12 is preferred.
  • As the aralkyl group represented by X 1 for example, aralkyl groups having 7 to 13 carbon atoms such as benzyl, chlorobenzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl, and phenylethenyl are preferable.
  • Examples of the heterocyclic group represented by X 1 include heterocyclic groups having 5 to 7 carbon atoms such as pyridyl, pyrimidyl, furyl, and thiophenyl.
  • halogen atom represented by X 1 examples include fluorine, chlorine, bromine and iodine.
  • the alkyl group represented by X 1 is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl unsubstituted or substituted with a halogen atom. Isooctyl, 2-ethylhexyl, and tert-octyl.
  • Examples of the halogen atom represented by R 11 , R 12 , R 13 and R 14 include fluorine, chlorine, bromine and iodine.
  • the alkyl groups represented by R 11 , R 12 , R 13 and R 14 are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, Octyl, isooctyl, 2-ethylhexyl, tert-octyl.
  • the compound represented by Formula 3 may be the following compound.
  • the compound represented by the formula (1) is 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-2-amino (4-morpholinophenyl) ethane- 1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl- 2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl-2-amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholi Nophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one , 2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one
  • the compound represented by the formula (2) may be at least one selected from the group consisting of Irgacure OXE-01 (BASF) and TR-PBG-305 (Trony) as a commercially available product.
  • the compound represented by the formula (3) may be N-1919 (Adeca Co.) as a commercial item.
  • the blue photosensitive resin composition of the present invention comprises at least one or more photoinitiators selected from the compounds represented by the formulas (1) to (3) in the blue photosensitive resin composition, thereby having excellent development speed, excellent processability, and excellent formation when formed into a cured film. It is possible to implement a color filter, particularly a self-luminous color filter having excellent reliability, excellent heat resistance and light resistance.
  • the photopolymerization initiator used in the blue photosensitive resin composition according to the present invention may be included in an amount of 0.1 to 30% by weight, preferably 0.3 to 20% by weight, based on the total weight of solids in the blue photosensitive resin.
  • the coloring photosensitive resin composition becomes highly sensitive and the intensity
  • photoinitiator start adjuvant can be used.
  • a photoinitiator adjuvant may be used in combination with a photoinitiator, and is a compound used in order to accelerate superposition
  • photopolymerization start adjuvant an amine compound, an alkoxy anthracene type compound, a thioxanthone type compound, etc. are mentioned.
  • Examples of the amine compound include triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylamino benzoic acid.
  • Ethyl, 2-ethylhexyl 4-dimethylaminobenzoic acid, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzphenone (commonly known as Michler's ketone), 4,4'-bis (diethyl Amino) benzophenone, 4, 4'-bis (ethylmethylamino) benzophenone, etc. are mentioned, Among these, 4,4'-bis (diethylamino) benzophenone is preferable.
  • an alkoxy anthracene type compound 9,10- dimethoxy anthracene, 2-ethyl-9,10- dimethoxy anthracene, 9,10- diethoxy anthracene, 2-ethyl-9, 10- diethoxy anthracene, for example.
  • Etc. can be mentioned.
  • a thioxanthone type compound 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro- 4-propoxy city oxanthone etc. are mentioned.
  • Such photopolymerization initiators may be used alone or in combination of a plurality thereof.
  • a commercially available thing can be used as a photoinitiator starter,
  • brand name "EAB-F” manufactured by Hodogaya Chemical Co., Ltd.] etc. are mentioned, for example.
  • the amount thereof is usually 10 mol or less, preferably 0.01 to 5 mol, per mol of the photopolymerization initiator.
  • the sensitivity of a blue photosensitive resin composition becomes higher and the productivity of the color filter formed using this composition tends to improve, it is preferable.
  • the antioxidant used in the present invention captures radicals generated by heat at the time of postbaking, so that the radicals react with fluorescent dyes to effectively suppress and prevent a decrease in fluorescence efficiency, and even when used in a small amount because of excellent radical trapping effect. Sufficient effect can be expected.
  • the antioxidant is at least one selected from phosphorus antioxidants, sulfur antioxidants and phenolic antioxidants.
  • the fluorescence efficiency is lowered by radicals generated in the photopolymerization initiator, and there is a possibility of causing yellowing by the baking process performed in the manufacturing process.
  • at least one or more antioxidants selected from phosphorus antioxidants, sulfur antioxidants and phenolic antioxidants with at least one photopolymerization initiator selected from compounds represented by Formulas 1 to 3, the phosphorus antioxidants and sulfur-based At least one or more antioxidants selected from antioxidants and phenolic antioxidants can suppress yellowing generation caused by the photopolymerization initiator by using an antioxidant to solve the problem of lowering fluorescence efficiency. Also taper and straightness can be excellent.
  • Antioxidants may include one or more selected from the group consisting of phenolic compounds, phosphorus compounds and sulfur compounds, which are phenol-phosphorus compounds, phenol-sulfur compounds, phosphorus-sulfur compounds, or phenol-phosphorus- It can be used as a combination of sulfur-based compounds.
  • the kind of the phenolic antioxidant is not particularly limited, but specific examples thereof include 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1. , 1-dimethylethoxy] -2,4,8,10-tetraoxaspiro [5.5] undecane, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxy Phenyl) propionate], 1,3,5, -trimethyl-2,4,6, -tris (3'5'-di-t-butyl-4-hydroxybenzyl) benzene, triethylene glycol-bis [ 3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-t-butyl-3-methylphenol), tris- (3,5 -Di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-tris (4
  • Irganox 1010 made by BASF
  • Sumilizer BBM-S made by Sumitomo Chemical
  • ADK STAB AO-80 made by ADEKA
  • Sumilizer GP made by Sumitomo Chemical
  • Irganox 1035 made by BASF
  • the kind of phosphorus antioxidant is not particularly limited, but specific examples thereof include 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa- 3,9-diphosphaspiro [5.5] undecane, diisodecylpentaerythritoldiphosphite, bis (2,4-di-t-butylphenyl) pentaerythritoldiphosphite, 2,2'-methylenebis (4 , 6-di-t-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy]- 2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphine, triphenylphosphite, diphenylisodecylphosphite,
  • the type of sulfur-based antioxidant is not particularly limited, but specific examples thereof include 2,2-bis ( ⁇ [3- (dodecylthio) propionyl] oxy ⁇ methyl) -1,3-propanediyl-bis [3- (Dodecylthio) propionate], 2-mercaptobenzimidazole, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl -3,3'- thiodipropionate, a pentaerythryl- tetrakis (3-lauryl thio propionate), 2-mercapto benzimidazole, etc. are mentioned.
  • the antioxidant may be included in 0.1 to 30% by weight, preferably 0.5 to 20% by weight based on the total weight of solids of the blue photosensitive resin composition of the present invention.
  • content of the antioxidant satisfies the above range, it is advantageous in terms of solving a problem of lowering fluorescence efficiency.
  • the solvent contained in the blue photosensitive resin composition of this invention is not specifically limited, Various organic solvents used in the field of a blue photosensitive resin composition can be used. Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene.
  • ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene.
  • Diethylene glycol dialkyl ethers such as glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol Alkylene glycol alkyl ether acetates such as monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, methyl Ketones such as methyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, propanol, butanol, hexanol, cyclohexanol, alcohol
  • organic solvents having a boiling point of 100 ° C. to 200 ° C. in the coating properties and drying properties are preferable, and alkylene glycol alkyl ether acetates, ketones, and 3-ethoxy are more preferable.
  • Ester such as ethyl propionate and the methyl 3-methoxy propionate, is mentioned, More preferably, propylene glycol monomethyl ether acetate, a propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy propionate, 3- Methyl methoxy propionate etc. are mentioned.
  • These solvents can be used individually or in mixture of 2 or more types, respectively.
  • Content of the solvent in the blue photosensitive resin composition of this invention can be contained 50-90 mass%, Preferably it is 55-85 mass% with respect to the whole blue photosensitive resin composition containing it.
  • Applicability when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, if the solvent content is in the range of 50 to 90% by mass based on the above criteria. This is preferable because it tends to be good.
  • the blue photosensitive resin composition which concerns on this invention is a filler, another high molecular compound, a pigment dispersant as needed.
  • Additives such as an adhesion promoter, antioxidant, a ultraviolet absorber, and an aggregation inhibitor, can be further included.
  • the filler examples include glass, silica, alumina and the like.
  • the other polymer compound examples include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. Can be.
  • surfactants can be used as the pigment dispersant, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic and amphoteric. These can be used individually or in combination of 2 types or more, respectively.
  • polyoxyethylene alkyl ether For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl peer ether, polyethyleneglycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane , Polyethylenimine, etc.
  • trade names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), MEGAFAC (manufactured by Dainippon Ink Chemical Industries, Ltd.), Florard (manufactured by Sumitomo 3M), Asahi guard, Surflon (above, manufactured by Asahi Glass), Sol SLSPERSE (made by Genka Corporation), EFKA (made by EFKA Chemicals), PB 821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.
  • adhesion promoter for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminoprotriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane etc. are mentioned. Specific examples of the antioxidant include 2,2'-
  • ultraviolet absorber examples include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone and the like.
  • aggregation inhibitor examples include sodium polyacrylate and the like.
  • the additives can be used by those skilled in the art as appropriate without departing from the effect of the present invention.
  • the additive may be used in an amount of 0.05 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total blue photosensitive resin composition, but is not limited thereto.
  • the blue photosensitive resin composition which concerns on this invention can be manufactured, for example by the following method.
  • the scattering particles are mixed with the solvent in advance and dispersed using a bead mill or the like until the average particle diameter becomes 10 to 1000 nm.
  • a dispersing agent can be further used as needed, and some or all of binder resin (cardo resin or mixture of cardo resin and acrylic alkali-soluble resin) may be mix
  • the remainder of the binder resin (a mixture of cardo resin or cardo resin and acrylic alkali soluble resin) in the obtained dispersion (hereinafter sometimes referred to as mill base), represented by a blue colorant, a photopolymerizable compound, and the formulas (1) to (3) At least one selected from the group of compounds, at least one selected from phosphorus antioxidants, sulfur antioxidants, and phenolic antioxidants, and other components to be used if necessary, and additional solvents as necessary. It can be added further and the desired blue photosensitive resin composition can be obtained.
  • Another aspect of the present invention relates to a color filter comprising a blue pattern layer containing a cured product of the blue photosensitive resin composition for forming a blue pattern layer described above.
  • the color filter according to the present invention is made of the blue photosensitive resin composition for forming the blue pattern layer instead of the blue quantum dots, there is an advantage of lowering the manufacturing cost.
  • the blue photosensitive resin composition of the present invention includes at least one or more photoinitiators selected from the compounds represented by the formulas (1) to (3), thereby having excellent development speed and excellent processability, and excellent heat resistance and light resistance when formed into a cured film. It is possible to implement a color filter having excellent reliability, particularly a self-luminous color, in particular a self-luminous color filter.
  • the blue photosensitive resin composition of the present invention may further include at least one or more selected from phosphorus antioxidants, sulfur antioxidants, and phenolic antioxidants, thereby ensuring excellent processability and reliability.
  • the color filter includes a substrate and a blue pattern layer formed on the substrate.
  • the substrate may be the substrate of the color filter itself, or may be a portion where the color filter is positioned in a display device or the like, and is not particularly limited.
  • the substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).
  • the blue pattern layer is a layer including the blue photosensitive resin composition of the present invention, and may be a layer formed by applying the blue photosensitive resin composition for forming a blue pattern layer and exposing, developing and thermosetting in a predetermined pattern. Can be formed by carrying out methods commonly known in the art.
  • the color filter may further include one or more selected from the group consisting of a red pattern layer and a green pattern layer.
  • the red pattern layer or green pattern layer may include a quantum dot and / or scattering particles.
  • the color filter according to the present invention may include a red pattern layer including a red quantum dot or a green pattern layer including a green quantum dot, and the red pattern layer or the green pattern layer may include scattering particles.
  • the red pattern layer or the green pattern layer may emit red light or blue light, respectively, by a light source emitting blue light, which will be described later.
  • the scattering particles included in the red pattern layer or the green pattern layer may include a metal oxide having an average particle diameter of 10 to 1000nm, the details of the scattering particles and the metal oxide The content of the scattering particles and the metal oxide contained in the blue photosensitive resin composition according to the invention can be applied.
  • the shape, configuration, and content of the quantum dots included in the red pattern layer or the green pattern layer are not limited, and quantum dots commonly used in the art may be applied.
  • the color filter including the substrate and the pattern layer may further include a partition formed between each pattern, and may further include a black matrix, but is not limited thereto.
  • the color filter may be a self-luminous color filter.
  • the above-described color filter And a light source emitting blue light.
  • the image display apparatus includes a color filter including a blue pattern layer including a cured product of the above-described blue photosensitive resin composition and a light source emitting blue light.
  • the color filter of the present invention can be applied to various image display devices such as electroluminescent display devices, plasma display devices, field emission display devices, as well as ordinary liquid crystal display devices.
  • the image display device includes the color filter including the blue pattern layer and the light source according to the present invention
  • the blue pattern layer included in the color filter according to the present invention does not include blue quantum dots, there is an advantage in that an image display device having low manufacturing cost can be manufactured.
  • a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, and as a monomer dropping lot, 74.8 g (0.20 mol) of benzylmaleimide, 43.2 g (0.30 mol) of acrylic acid, and 118.0 g of vinyltoluene (0.50 mol), 4 g of t-butylperoxy-2-ethylhexanoate and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were added thereto, followed by stirring and mixing. As a chain transfer agent dropping tank, 6 g of n-dodecanethiol was added.
  • PGMEA propylene glycol monomethyl ether acetate
  • PGMEA 24g was added and the thing mixed with stirring was prepared. Thereafter, 395 g of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was carried out for 2 h each while maintaining 90 ° C., and after 1 h, the temperature was raised to 110 ° C. and maintained for 3 h. Started.
  • the temperature was melt
  • the temperature was heated to 120 ° C. to completely dissolve it.
  • the acid value was measured and stirred until the acid value was less than 1.0 mgKOH / g. It took 11 hours to reach the target (0.8).
  • the temperature of the reactor was lowered to room temperature to obtain a colorless transparent compound of formula (8).
  • the temperature was melt
  • the temperature was heated to 120 ° C. to completely dissolve it.
  • the acid value was measured and stirred until the acid value was less than 1.0 mgKOH / g. It took 11 hours to reach the target (0.8).
  • the temperature of the reactor was lowered to room temperature to obtain a colorless transparent compound of formula (9).
  • HLC-8120GPC manufactured by Tosoh Corporation
  • the ratio of the weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution (Mw / Mn).
  • V-1 Fastogen Super Violet 140V (DIC): C.I. Pigment Violet 23
  • A-1 cardo-type resin of manufacture example 6,
  • Acrylic resin Acrylic alkali-soluble resin of Preparation Example 1
  • Photopolymerizable compound dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
  • Antioxidant A 4,4'-butylidenebis (6-tert-butyl-3-methylphenol) (Sumitomo Chemical-BBM-S): Phenolic antioxidant
  • Antioxidant B bis [3- (dodecylthio) propionic acid] 2,2-bis [[3- (dodecylthio) -1-oxopropyloxy] methyl] -1,3-propanediyl (Sumitomo Chemical, trade name) : Smolizer TP-D: Sulfur Antioxidant
  • Antioxidant C Irgafos® 126 (BASF): Phosphorus-based antioxidant
  • V-1 Fastogen Super Violet 140V (DIC): C.I. Pigment Violet 23
  • A-1 cardo-type resin of manufacture example 6,
  • Acrylic resin Acrylic alkali-soluble resin of Preparation Example 1
  • Photopolymerizable compound dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
  • Antioxidant A 4,4'-butylidenebis (6-tert-butyl-3-methylphenol) (Sumitomo Chemical-BBM-S): Phenolic antioxidant
  • Antioxidant B bis [3- (dodecylthio) propionic acid] 2,2-bis [[3- (dodecylthio) -1-oxopropyloxy] methyl] -1,3-propanediyl (Sumitomo Chemical, trade name) : Smolizer TP-D: Sulfur Antioxidant
  • Antioxidant C Irgafos® 126 (BASF): Phosphorus-based antioxidant
  • V-1 Fastogen Super Violet 140V (DIC): C.I. Pigment Violet 23
  • A-1 cardo-type resin of manufacture example 6,
  • Acrylic resin Acrylic alkali-soluble resin of Preparation Example 1
  • Photopolymerizable compound dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
  • Antioxidant A 4,4'-butylidenebis (6-tert-butyl-3-methylphenol) (Sumitomo Chemical-BBM-S): Phenolic antioxidant
  • Antioxidant B bis [3- (dodecylthio) propionic acid] 2,2-bis [[3- (dodecylthio) -1-oxopropyloxy] methyl] -1,3-propanediyl (Sumitomo Chemical, trade name) : Smolizer TP-D: Sulfur Antioxidant
  • Antioxidant C Irgafos® 126 (BASF): Phosphorus-based antioxidant
  • Color filters were prepared using the blue photosensitive resin compositions prepared in Examples 1 to 25 and Comparative Examples 1 to 6. That is, each of the blue photosensitive resin compositions was coated on a glass substrate by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film.
  • test photomask having a transverse x vertical (20 mm x 20 mm) square transmission pattern and a line / space pattern of 1 to 100 ⁇ m was placed on the thin film, and ultraviolet rays were irradiated with a distance of 100 ⁇ m from the test photomask.
  • the ultraviolet light source was irradiated with an exposure amount (365 nm) of 200 mJ / cm 2 under an atmospheric atmosphere using an ultra high pressure mercury lamp (trade name USH-250D) manufactured by Ushio Denki Co., Ltd., and no special optical filter was used.
  • an ultra high pressure mercury lamp (trade name USH-250D) manufactured by Ushio Denki Co., Ltd., and no special optical filter was used.
  • the thin film irradiated with ultraviolet rays was developed by soaking for 80 seconds in a KOH aqueous solution developing solution of pH 10.5.
  • the thin film coated glass plate was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 150 ° C. for 10 minutes to prepare a color filter pattern.
  • the film thickness of the color pattern prepared above was 5.0 ⁇ m.
  • Heat resistance was measured by using a colorimeter (Olympus, OSP-200) and chromaticity of the substrate produced in the manufacturing of the color filter and the substrate after the color coordinate measurement is completed for 120 minutes at 230 °C Color and transmittance were remeasured with a colorimeter (Olympus, OSP-200). The heat resistance was evaluated by measuring the color change value ( ⁇ Eab) after heating at 230 ° C. for 120 minutes. ⁇ Eab is a value required by the following saturation formula by the CIE 1976 (L *, a *, b *) spatial colorimeter (New Color Science Handbook (Showa 60) p. 266).
  • Light resistance was measured by using a colorimeter (Olympus, OSP-200) and chromaticity of the substrate produced in the color filter manufacturing and 200hr irradiated to the light-resistant equipment (ATLAS CPS + equipment) after measuring the color coordinates to measure the color and transmittance Remeasurement was carried out with a colorimeter (Olympus, OSP-200).
  • ⁇ Eab is the value required by the following saturation formula by the CIE 1976 (L *, a *, b *) spatial colorimeter.
  • Each of the blue photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 2 was applied on a glass substrate by spin coating, and then placed on a heating plate and held at a temperature of 100 ° C. for 3 minutes to form a thin film. After irradiating 50mJ / cm ⁇ 2> ultraviolet-rays by the front exposure, the film thickness of the pattern was measured using the film thickness measuring apparatus (DEKTAK 6M; Veeco company make). After the substrate having been measured for thickness was developed by soaking again in a KOH aqueous solution developing solution of pH 10.5 for 80 seconds, the presence of a blue photosensitive resin composition was confirmed in the non-exposed part.
  • Example 1 Heat resistance Light resistance Developing speed Taper Straightness Luminous intensity
  • Example 2 ⁇ ⁇ 14 - - - Example 3 ⁇ ⁇ 16 - - - Example 4 ⁇ ⁇ 18 - - - Example 5 ⁇ ⁇ 16 - - - Example 6 ⁇ ⁇ 17 - - - Example 7 ⁇ ⁇ 11 - - - Example 8 ⁇ ⁇ - ⁇ ⁇ 28500
  • Example 9 ⁇ ⁇ - ⁇ ⁇ 34700
  • Example 10 ⁇ ⁇ - ⁇ ⁇ 31800
  • Example 11 ⁇ ⁇ - ⁇ ⁇ 29800
  • Example 12 ⁇ ⁇ - ⁇ ⁇ 28200
  • Example 13 ⁇ ⁇ - ⁇ ⁇ 31300
  • Example 14 ⁇ ⁇ - ⁇ ⁇ 26500
  • Example 15 ⁇ ⁇ - ⁇ ⁇ 23900
  • Example 16 ⁇ ⁇ - ⁇ ⁇ 36500
  • Example 17 ⁇ ⁇ - ⁇ ⁇ 28
  • Comparative Examples 1 and 2 the development speed was slower than the examples, and the results were not excellent in heat resistance and light resistance.
  • Comparative Examples 3 to 6 the deterioration in processability was confirmed due to the decrease in heat resistance, light resistance, taperness, and straightness, and it was confirmed that the luminous intensity was not excellent.
  • the blue photosensitive resin composition of the present invention comprises at least one or more photoinitiators selected from the compounds represented by the formulas (1) to (3) in the blue photosensitive resin composition, thereby having excellent development speed, excellent processability, and excellent formation when formed into a cured film. It is possible to implement a color filter, particularly a self-luminous color filter having excellent reliability, excellent heat resistance and light resistance.

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Abstract

La présente invention concerne une composition de résine photosensible bleue comprenant : des particules de diffusion ; un colorant bleu ; une résine de liant de cadmium en tant que résine liante ; un composé photopolymérisable ; un photoinitiateur ; et un solvant, le photoinitiateur étant au moins un composé choisi parmi les composés représentés par les formules chimiques 1 à 3.
PCT/KR2018/003623 2017-03-31 2018-03-27 Composition de résine photosensible bleue, et filtre coloré et dispositif d'affichage d'image fabriqués à l'aide de celle-ci WO2018182302A1 (fr)

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JP2019546854A JP6868117B2 (ja) 2017-03-31 2018-03-27 青色感光性樹脂組成物、これを用いて製造されたカラーフィルタおよび画像表示装置

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KR1020170041416A KR102300329B1 (ko) 2017-03-31 2017-03-31 청색 감광성 수지 조성물, 이를 이용하여 제조된 컬러필터 및 화상 표시 장치

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