WO2018182186A1 - Composition de résine photosensible bleue, ainsi que filtre coloré et dispositif d'affichage d'image fabriqués à l'aide de celle-ci - Google Patents

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

Info

Publication number
WO2018182186A1
WO2018182186A1 PCT/KR2018/002423 KR2018002423W WO2018182186A1 WO 2018182186 A1 WO2018182186 A1 WO 2018182186A1 KR 2018002423 W KR2018002423 W KR 2018002423W WO 2018182186 A1 WO2018182186 A1 WO 2018182186A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
blue
resin composition
photosensitive resin
Prior art date
Application number
PCT/KR2018/002423
Other languages
English (en)
Korean (ko)
Inventor
김형주
김주호
왕현정
Original Assignee
동우화인켐 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020170109531A external-priority patent/KR101980186B1/ko
Priority claimed from KR1020170109532A external-priority patent/KR101998775B1/ko
Application filed by 동우화인켐 주식회사 filed Critical 동우화인켐 주식회사
Priority to JP2019552272A priority Critical patent/JP6876823B2/ja
Priority to CN201880023065.4A priority patent/CN110506235B/zh
Publication of WO2018182186A1 publication Critical patent/WO2018182186A1/fr

Links

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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

Definitions

  • the present invention relates to a blue photosensitive resin composition
  • a blue photosensitive resin composition comprising a specific scattering particle, an alkali-soluble resin and a blue colorant, a color filter and an image display device manufactured using the same.
  • 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.
  • color filters are used in various fields, including various image display devices, not only excellent pattern characteristics but also high color reproducibility and excellent performance such as high brightness and high contrast ratio are required.
  • a color filter manufacturing method using a self-luminous photosensitive resin composition is proposed.
  • Republic of Korea Patent Publication No. 2013-0000506 relates to a display device, a plurality of wavelength conversion particles for converting the wavelength of light; And a color converter including a plurality of color filter particles that absorb light having a predetermined wavelength in the light.
  • the efficiency of the color filter may be somewhat degraded as the efficiency of the quantum dot, in particular, the blue quantum dot is decreased, and in the case of the blue quantum dot, the overall manufacturing cost increases due to the high price.
  • the efficiency of the color filter may be somewhat degraded as the efficiency of the quantum dot, in particular, the blue quantum dot is decreased, and in the case of the blue quantum dot, the overall manufacturing cost increases due to the high price.
  • Patent Document 1 Republic of Korea Patent Publication No. 2013-0000506 (2013.01.03.)
  • An object of this invention is to provide the blue photosensitive resin composition which can prevent the fall of the efficiency of a blue pixel, and can lower manufacturing cost.
  • an object of this invention is to provide the blue photosensitive resin composition which is excellent in heat flow property, suppresses generation of a pattern straightness and reverse taper, and can suppress outgas generation.
  • the present invention is to provide a color filter and an image display device including a blue pixel layer manufactured using the above-described blue photosensitive resin composition.
  • the present invention is to provide a color filter and an image display device excellent in image quality, viewing angle, durability, reliability.
  • Blue photosensitive resin composition according to the present invention for achieving the above object is an alkali-soluble resin; Blue colorants; And scattering particles comprising a metal oxide having an average particle diameter of 30 to 500 nm.
  • the alkali-soluble resin may include a cardo-based binder resin including at least one repeating unit of Formulas 1 to 3 below. do.
  • Y is an acid anhydride residue
  • Z is an acid 2 anhydride residue
  • R1, R1 ', R2, R2', R3, R3 ', R4, R4', R5, R5 ', R6 and R6' are each independently a hydrogen atom or a methyl group
  • R7, R7 ', R8 and R8' are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, and the alkylene group is an ester bond, a cycloalkylene group having 6 to 14 carbon atoms, and an arylene group having 6 to 14 carbon atoms.
  • R9, R9 ', R10, R10', R11, R11 ', R12 and R12' are each independently a hydrogen atom, a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms,
  • n and n are integers satisfying 0 ⁇ m ⁇ 30 and 0 ⁇ n ⁇ 30, respectively.
  • R13 is the same as defined in X and X 'in Formulas 1 and 2,
  • R14 is a methacrylate group, a vinyl group or an acrylate group
  • R15 is a reaction residue derived from a monomer represented by the following formula (4),
  • r is an integer from 1 to 20,
  • the present invention provides a color filter made of the above-described blue photosensitive resin composition and an image display device including the same.
  • the blue photosensitive resin composition of the present invention has the advantage of providing excellent color reproduction characteristics and light efficiency, and no pattern residue occurs, and due to excellent heat flowability, pattern straightness and heat taper are suppressed and outgas generation is minimized. There is an advantage.
  • the color filter made of the blue photosensitive resin composition of the present invention and an image display device including the same can ensure high quality image quality, excellent viewing angle, high durability, and reliability due to excellent antireflection effect, and reduce manufacturing cost. There is a possible advantage.
  • a member when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.
  • alkali-soluble resin a compound selected from the group consisting of: Blue colorants; And scattering particles including a metal oxide having an average particle diameter of 30 to 500 nm; wherein the alkali-soluble resin includes a cardo-based binder resin including at least one repeating unit of Formulas 1 to 3 below. It relates to a composition.
  • Y is an acid anhydride residue
  • Z is an acid 2 anhydride residue
  • R1, R1 ', R2, R2', R3, R3 ', R4, R4', R5, R5 ', R6 and R6' are each independently a hydrogen atom or a methyl group
  • R7, R7 ', R8 and R8' are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, and the alkylene group is an ester bond, a cycloalkylene group having 6 to 14 carbon atoms, and an arylene group having 6 to 14 carbon atoms.
  • R9, R9 ', R10, R10', R11, R11 ', R12 and R12' are each independently a hydrogen atom, a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms,
  • n and n are integers satisfying 0 ⁇ m ⁇ 30 and 0 ⁇ n ⁇ 30, respectively.
  • R13 is the same as defined in X and X 'in Formulas 1 and 2,
  • R14 is a methacrylate group, a vinyl group or an acrylate group
  • R15 is a reaction residue derived from a monomer represented by the following formula (4),
  • r is an integer from 1 to 20,
  • the blue photosensitive resin composition of the present invention includes a cardo-based binder resin including at least one repeating unit of Formulas 1 to 3 below.
  • Y is an acid anhydride residue
  • Z is an acid 2 anhydride residue
  • R1, R1 ', R2, R2', R3, R3 ', R4, R4', R5, R5 ', R6 and R6' are each independently a hydrogen atom or a methyl group
  • R7, R7 ', R8 and R8' are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, and the alkylene group is an ester bond, a cycloalkylene group having 6 to 14 carbon atoms, and an arylene group having 6 to 14 carbon atoms.
  • R9, R9 ', R10, R10', R11, R11 ', R12 and R12' are each independently a hydrogen atom, a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms,
  • n and n are integers satisfying 0 ⁇ m ⁇ 30 and 0 ⁇ n ⁇ 30, respectively.
  • R13 is the same as defined in X and X 'in Formulas 1 and 2,
  • R14 is a methacrylate group, a vinyl group or an acrylate group
  • R15 is a reaction residue derived from a monomer represented by the following formula (4),
  • r is an integer from 1 to 20,
  • R7, R7 ', R8 and R8' are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, and the alkylene group is an ester bond, a cycloalkylene group having 6 to 14 carbon atoms, and 6 to 6 carbon atoms.
  • R7, R7 ', R8 and R8' are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, and the alkylene group is an ester bond, a cycloalkylene group having 6 to 14 carbon atoms, and 6 to 6 carbon atoms.
  • R7, R7 ', R8 and R8' are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, and the alkylene group is an ester bond, a cycloalkylene group having 6 to 14 carbon atoms, and 6 to 6 carbon atoms.
  • arylene groups are each independently a linear or branched alkylene group having 1
  • R15 includes the reaction residue derived from the monomer represented by the formula (4), the degree of curing is increased to improve the surface hardness, showing excellent heat resistance, chemical resistance, strength and hardness excellent durability and reliability Enables color filters to be implemented.
  • the repeating unit represented by Formula 3 may be represented by at least any one of the following Formulas 5 to 9, but is not limited thereto, and any one known in the art may be used. It is possible.
  • R13 is the same as defined in Formula 3,
  • R14 is a methacrylate group, a vinyl group or an acrylate group
  • r is an integer from 1 to 20.
  • the repeating units of Chemical Formulas 5 to 9 may be included in an amount of 3 to 80 mol%, more preferably 5 to 5 mol, based on 100 mol% of the total mole of the alkali-soluble binder resin. 70 mol% may be included.
  • the sensitivity and adhesion are excellent, there is no peeling of the pattern during the developing process, and exhibits excellent solvent resistance.
  • the self-luminous blue photosensitive resin composition according to the present invention includes a cardo-based binder resin including at least one repeating unit of the repeating units of Chemical Formulas 1 to 3, the inter-process reliability is excellent.
  • the pattern residue does not occur according to the effect that the development speed can be adjusted quickly.
  • the pattern straightness and the reverse taper do not occur due to the excellent heat flow property. It is possible to provide high quality image quality, excellent heat resistance, chemical resistance, durability, and reliability with an excellent anti-reflection effect without afterimage occurrence.
  • the cardo-based binder resin according to the present invention includes all of the repeating units of Formulas 1 to 3, the molar ratio is not particularly limited, but m / n may be, for example, 1/99 to 90/10, and more. Preferably it is 5/95 to 80/20.
  • the carboxyl group content of the binder resin is appropriately maintained to maintain excellent alkali resistance, and the developing solution does not elute at the exposed portion, and exhibits excellent alkali developability and thus fine patterns. To form.
  • Y in Formula 1 is a residue of an acid anhydride, and may be obtained by reacting a bisphenol epoxy acrylate compound, which is a synthetic intermediate of the cardo-based binder resin of the present invention, with an acid anhydride compound.
  • the acid anhydride compound into which the residue Y can be introduced is not particularly limited, and for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylenetetrahydrophthalic anhydride. , Chlororenic acid anhydride, methyltetrahydrophthalic anhydride, and the like.
  • Z in Chemical Formula 2 is a residue of an acid 2 anhydride, and may be obtained by reacting a bisphenol epoxy acrylate compound, which is a synthetic intermediate of the cardo-based binder resin of the present invention, with an acid 2 anhydride compound.
  • the acid dianhydride compound into which the residue Z can be introduced is not particularly limited, and examples thereof include aromatics such as pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, and bitenyl ether tetracarboxylic dianhydride.
  • single bond means a structure directly connected without other functional groups, for example, in the formula (1), means that the oxyphenyl group is directly connected without X and X '.
  • acid dianhydride means a compound containing two acid anhydride groups in a molecule.
  • the manufacturing method of the cardo-based binder resin is not particularly limited.
  • a bisphenol compound is reacted with an epoxy compound to synthesize a bisphenol epoxy compound, and then a synthesized bisphenol epoxy compound is reacted with an acrylate compound to synthesize a bisphenol epoxy acrylate compound, and then the bisphenol epoxy acrylate compound is an acid anhydride, an acid. It may be prepared by reacting with anhydrides or mixtures thereof, but is not limited thereto.
  • the acid value of the alkali-soluble binder resin may be 20 to 200 mgKOH / g, preferably 30 to 150 mgKOH / g.
  • 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. .
  • acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of an acrylic polymer, and can 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. Alkali-soluble resins are preferred.
  • 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.
  • the said alkali-soluble resin it is preferable that it is 1.0-6.0, and, as for the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the said alkali-soluble resin, it is more preferable that it is 1.5-6.0.
  • the cardo-based binder resin is 1 to 50 parts by weight, preferably 5 to 40 parts by weight, more preferably 5 to 30 parts by weight based on 100 parts by weight of the total blue photosensitive resin composition. May be included.
  • the solubility in a 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 during development. It is preferable because there is an advantage that the omission property tends to be good.
  • the alkali-soluble resin may further include a cardo-based binder resin including at least one repeating unit selected from the group consisting of Formula 10 and Formula 11.
  • R19 and R20 are each independently hydrogen, hydroxy group, thiol group, amino group, nitro group or halogen atom,
  • Ar1 is each independently a C6 to C15 aryl group
  • A is O, S, N, Si or Se
  • a and b are each independently an integer of 1 to 6,
  • p and q are each independently an integer of 0 to 30,
  • the halogen atom is F, Cl, Br or I.
  • the aryl group may be a C6 to C15 monocyclic aryl group, or a polycyclic aryl group.
  • the monocyclic aryl group may be a phenyl group, biphenyl group, terphenyl group, stilbenyl group and the like, but is not limited thereto.
  • the polycyclic aryl group may be naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.
  • Y ′ in Formula 10 is a residue of an acid anhydride, and an acid anhydride capable of introducing residue Y ′ may be applied to the above-described content of Y.
  • Z ′ in Formula 11 is a residue of acid 2 anhydride, and the acid 2 anhydride compound to which residue Z ′ may be introduced is not particularly limited, and the above-described contents of Z may be applied.
  • the cardo-based binder resin according to the present invention is included in the blue photosensitive resin composition, there is an advantage that the light emission intensity, the diffusion rate, and the external light reflectance can be more excellent.
  • the alkali-soluble resin further comprises a cardo-based binder resin including at least one repeating unit selected from the group consisting of Formula 10 and Formula 11, the cardo-based binder resin is 100 parts by weight of the total alkali-soluble resin. 1 to 50 parts by weight, preferably 5 to 40 parts by weight, and more preferably 5 to 30 parts by weight.
  • the cardo-based binder resin which may be further included, is included in the above range, the light emission intensity, the diffusion rate, and the external light reflectance may be more excellent.
  • the cardo-based binder resin including at least one repeating unit of Formula 10 and Formula 11 may be prepared by, for example, the following method.
  • a cardo-based binder resin including at least one repeating unit of Formulas 10 and 11 may be obtained by polymerizing a compound represented by Formulas 17 to 21 with carboxylic dianhydride.
  • Ar 1, R 19 and R 20 are as defined in Chemical Formulas 10 and 11.
  • carboxylic dianhydride examples include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, and 2,3,3', 4'-biphenyltetracarboxylic dianhydride , 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2 ', 3,3'-benzo Phenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis ( 3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphen
  • the polymerization reaction may be performed at 100 to 130 ° C., or 110 to 120 ° C. for 2 hours to 24 hours, or 4 hours to 12 hours.
  • the carboxylic dianhydride may be added in an amount of 5 to 40 parts by weight, 10 to 30 parts by weight, or 10 to 20 parts by weight based on 100 parts by weight of the monomer represented by Formula 17 to 21, for example.
  • a method for preparing a cardo-based binder resin including at least one repeating unit of Formulas 10 and 11 may include, for example, adding a terminal capping agent after the start of the polymerization reaction. have.
  • the end capping reaction may be performed at 100 to 130 ° C., or 110 to 120 ° C. for 30 minutes to 4 hours, or 1 hour to 3 hours, for example.
  • the end capping agent may be added in an amount of 2 to 10 parts by weight, 2 to 5 parts by weight, or 3 to 5 parts by weight based on 100 parts by weight of the monomer represented by Formula 17 to 21, for example.
  • the end capping agent is preferably aromatic carboxylic anhydride, for example, phthalic anhydride, and the like, and in this case, excellent heat resistance, high permeability, and high refractive properties.
  • the weight average molecular weight of the cardo-based binder resin including at least one repeating unit of Formula 10 and Formula 11 is, for example, 1,000 to 100,000 g / mol, preferably 2,000 to 50,000 g / mol, more preferably 3,000 to It may be 10,000 g / mol, it is excellent in heat resistance within this range and the development speed of the photosensitive material and the development by the developing solution is suitable, there is an effect that the pattern formation is good.
  • the weight average molecular weight can be measured by gel permeation chromatography (GPC) method.
  • the degree of dispersion of the cardo-based binder resin resin including at least one repeating unit of Formula 10 and Formula 11 may be, for example, in the range of 1.0 to 5.0, preferably 1.5 to 4.0, and excellent heat resistance within this range. And the development speed of the photosensitive material and the development by the developer is suitable, there is an effect that the pattern formation is good.
  • the dispersion degree of this description can be measured by GPC measuring method.
  • the alkali-soluble resin may further include an acrylic binder resin.
  • the alkali-soluble resin further includes the acrylic binder resin, it is preferable because the size of the minimum pattern that can be formed without loss of the pattern is small, which has advantages of high resolution pattern implementation and pattern straightness.
  • acrylic binder resin examples include a carboxyl group-containing monomer and a copolymer with another monomer copolymerizable with the monomer.
  • unsaturated carboxylic acids such as unsaturated monocarboxylic acid, unsaturated polyhydric carboxylic acid, such as unsaturated polycarboxylic acid which has 1 or more carboxyl groups in molecules, such as unsaturated dicarboxylic acid and unsaturated tricarboxylic acid, are mentioned, for example.
  • 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. .
  • These 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 glycidyl ether and indene; Methyl acrylate, methyl methyl styrene, o-vinyl toluene, m-
  • 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 acrylic binder resin may be included, for example, in an amount of 10 to 90 parts by weight, preferably 20 to 80 parts by weight, more preferably 30 to 70 parts by weight, based on 100 parts by weight of the alkali-soluble resin in total, in this case a high resolution pattern Fairness, such as implementation and pattern straightness, is advantageous.
  • the content of the alkali-soluble resin is usually 1 to 50 parts by weight, preferably 3 to 40 parts by weight, still more preferably 5 to 30 parts by weight based on 100 parts by weight of the total blue photosensitive resin composition.
  • the solubility in a developing solution is sufficient so that development residues are less likely to occur on the substrate of the non-pixel portion, and the film portion of the pixel portion of the exposed portion is less likely to occur during development. Since the omission of a part tends to be good, it is preferable.
  • the blue photosensitive resin composition of this invention contains a blue coloring agent. Since the blue photosensitive resin composition according to the present invention further includes a blue colorant, the light of the light source reflected by the scattering particles, which will be described later, may be prevented from being reflected back by external light such as sunlight, thereby realizing high quality images. There is an advantage.
  • the blue colorant may specifically include a blue pigment, and the blue pigment may specifically include a compound classified as a pigment in the color index (published by The society of Dyers and Colourists). Although the pigment of the same color index (CI) number is mentioned, It is not necessarily limited to these.
  • the blue colorant is C.I. Pigment Blue 15: 3, 15: 4, 15: 6, 16, 21, 28, 60, 64, 76 and at least one blue pigment selected from the group consisting of a combination thereof; may include.
  • C.I. Pigment Blue 15: 3 C.I. Pigment Blue 15: 4, Pigment Blue 15: 6, C.I. It is preferable to include at least one member selected from the group consisting of Pigment Blue 16 in view of the effect of suppressing external reflection and high color reproducibility.
  • the blue colorant may further include one or more selected from the group consisting of dyes and purple pigments.
  • the purple pigment is not limited thereto, for example, C.I. Pigment violet 1, 14, 19, 23, 29, 32, 33, 36, 37, 38, and combinations thereof, and at least one selected from the group consisting of C.I. It is preferable to use Pigment Violet 23 in terms of high color reproducibility and reliability even through low color content.
  • the dye may include a compound classified as a dye in the color index (Published by The Society of Dyers and Colourists) or a known blue or purple dye described in a dye note (color dyed yarn).
  • C.I. Solvent blue 35, 36, 44, 45 and 70; And C.I. It is preferred to include at least one member selected from the group consisting of solvent violet 13.
  • the said dye can be used individually or in combination of 2 or more types, respectively.
  • the blue colorant is included in an amount of 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, and more preferably 1 to 20 parts by weight, based on 100 parts by weight of the total blue photosensitive resin composition. Can be.
  • the content of the blue colorant is less than the above range, it may be difficult to secure the external light reflection suppression effect to be obtained, on the contrary, when the content exceeds the above range, the increase in luminescence intensity may be slightly lowered, and the problem of lowering the viscosity stability of the composition may occur. Since it arises, it uses suitably within the said range.
  • the blue photosensitive resin composition according to the present invention includes scattering particles containing a metal oxide having an average particle diameter of 30 to 500 nm.
  • 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, It may include one or more oxides selected from the group consisting of Ti, Sb, Sn, Zr, Nb, Ce, Ta, In and combinations thereof.
  • the metal oxide is 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 It may include one or more selected from the group consisting of -Al, Nb 2 O 3 , SnO, MgO and combinations thereof, and a material surface-treated with a compound having an unsaturated bond such as acrylate may be used if necessary. .
  • the scattering particles limit the content in the average particle diameter and the total composition to maximize the light emission intensity of the color filter.
  • the "average particle diameter” may be a number average particle diameter, and can be obtained from an image observed by, for example, a field emission runner electron microscope (FE-SEM) or a transmission electron microscope (TEM). Specifically, several samples can be extracted from the observed images of FE-SEM or TEM, and the diameters of these samples can be measured to obtain arithmetic mean values.
  • FE-SEM field emission runner electron microscope
  • TEM transmission electron microscope
  • the metal oxide has an average particle diameter of 30 to 500 nm, preferably 30 to 300 nm.
  • the average particle diameter of the metal oxide satisfies the above range, the scattering effect is increased, and even though the blue photosensitive resin composition including the scattering particles does not include blue quantum dots, the blue light source may serve as a blue pixel.
  • the phenomenon of sinking in the composition can be prevented and the surface of the blue pattern layer of uniform quality can be obtained, it can be used by appropriately adjusting the above range.
  • the scattering particles may be included in an amount of 0.1 to 50 parts by weight, preferably 5 to 30 parts by weight, and more preferably, based on 100 parts by weight of the total blue photosensitive resin composition. It may be included in 10 to 20 parts by weight.
  • the scattering particles are included in the above range, there is an advantage in that a color filter having excellent emission intensity can be manufactured.
  • the scattering particles when the scattering particles are included in the above range, it may be easy to ensure the emission intensity to be obtained, there is an advantage that can suppress the degradation of the composition stability.
  • the blue photosensitive resin composition is a photopolymerizable compound; Photopolymerization initiator; solvent; And it may further include one or more selected from the group consisting of additives.
  • the photopolymerizable compound contained in the blue photosensitive resin composition of this invention is a compound which can superpose
  • monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl py. A ralidone etc. are mentioned.
  • polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate and the like.
  • bifunctional or higher polyfunctional monomers are preferably used.
  • the photopolymerizable compound is used in the range of 1 to 30 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the entire blue photosensitive resin composition.
  • the photopolymerizable compound satisfies the above range, the intensity and smoothness of the pixel portion tend to be good, which is preferable.
  • the said photoinitiator used by this invention contains an acetophenone type compound.
  • acetophenone type compound diethoxy acetophenone, 2-hydroxy-2- methyl-1- phenyl propane- 1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- ( 2-hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl [4- (1-methylvinyl) phenyl] propane-1 Oligomer of -one, etc. are mentioned, Preferably 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one etc. are mentioned.
  • Photoinitiators other than the said acetophenone series can be used in combination.
  • Photopolymerization initiators other than the acetophenone series include active radical generators, sensitizers, and acid generators that generate active radicals by irradiation with light.
  • a benzoin type compound As said active radical generating agent, a benzoin type compound, a benzophenone type compound, a thioxanthone type compound, a triazine type compound, etc. are mentioned, for example.
  • benzoin type compound benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoisobutyl ether, etc. are mentioned, for example.
  • benzophenone type compound for example, benzophenone, methyl o-benzoyl benzoate, 4-phenylzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethyl benzophenone, etc. are mentioned.
  • thioxanthone type compound 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro, for example 4-propoxy city oxanthone etc. are mentioned.
  • Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2, -bis (o-chlorophenyl) -4,4 ', 5,5'-tetra Phenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene Compounds and the like can be used.
  • Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate and 4-acetoxyphenyldimethylsulfonium p-toluenesulfo.
  • a triazine photopolymerization initiator is also used as an acid generator.
  • Content of the said photoinitiator used for the blue photosensitive resin composition which concerns on this invention is 0.1-40 weight part normally with respect to the total amount of the said alkali-soluble resin and the said photopolymerizable compound based on 100 weight part of total solids, Preferably it is 1- 30 parts by weight.
  • photoinitiator start adjuvant can be used.
  • the said photoinitiator adjuvant may be used in combination with the said photoinitiator, and is a compound used in order to accelerate superposition
  • An amine compound, an alkoxy anthracene type compound, a thioxanthone type compound etc. are mentioned as said photoinitiator starting adjuvant.
  • 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.
  • photoinitiators (D) 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.
  • EAB-F manufactured by Hodogaya Chemical Co., Ltd.
  • the amount thereof is usually 10 mol or less, preferably 0.01 to 5 mol, per mol of the photopolymerization initiator.
  • the sensitivity of the said blue photosensitive resin composition becomes higher and the productivity of the color filter formed using this composition tends to improve, it is preferable.
  • 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, and 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, and 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, methoxy butyl acetate and methoxy pentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methyl ethyl ketone, acetone , Ketones such as methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cycl
  • 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.
  • the said solvent can be used individually or in mixture of 2 or more types, respectively.
  • Content of the said solvent in the blue photosensitive resin composition of this invention is 40-90 weight part normally with respect to 100 weight part of all the said blue photosensitive resin compositions containing it, Preferably it is 70-85 weight part.
  • a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, or the like. It is preferable because there is.
  • a filler In the blue photosensitive resin composition of this invention, a filler, another high molecular compound, a pigment dispersant as needed. It is also possible to use additives, such as an adhesion promoter, an antioxidant, a ultraviolet absorber, and an aggregation inhibitor.
  • the filler include glass, silica, alumina and the like.
  • the other polymer compound 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.
  • 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.
  • 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 Co., Ltd.), Florard (manufactured by Sumitomo 3M Inc.), Asahi guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Sol SLSPERSE (made by Genka Corporation), EFKA (made by EFKA Chemicals), PB 821 (made by Ajinomoto Co., Ltd.), etc
  • 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.
  • antioxidant examples include 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like.
  • 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 additive may be used by those skilled in the art in addition to an appropriate amount within the scope that does not impair the effects of the present invention.
  • the manufacturing method of the blue photosensitive resin composition is not limited thereto, but may be prepared, 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 30 to 500 nm.
  • a dispersing agent can be further used as needed, and a part or all of a blue coloring agent and alkali-soluble resin may be mix
  • the remainder of alkali-soluble resin, a photopolymerizable compound, a photoinitiator, the other components used as needed, and the additional solvent as needed are further added to the obtained dispersion liquid (henceforth a mill base) so that it may become a predetermined concentration.
  • the desired blue photosensitive resin composition can be obtained.
  • it is preferable that the blue colorant has an average particle diameter of 0.2 ⁇ m or less through a bead mill.
  • Another aspect of the present invention relates to a self-luminous pixel-containing color filter comprising a blue pattern layer containing a cured product of the blue photosensitive resin composition described above.
  • the blue photosensitive resin composition may be a blue photosensitive resin composition for forming a blue pattern layer.
  • the said blue photosensitive resin composition does not contain a quantum dot.
  • the color filter according to the present invention is made of the above-described blue photosensitive resin composition instead of blue quantum dots, the manufacturing cost can be lowered, and there is an advantage of having an excellent viewing angle.
  • the blue photosensitive resin composition according to the present invention has excellent heat flowability, the color filter and the image display device manufactured using the same do not generate pattern straightness and reverse taper, and suppress the outgas generation during the manufacturing process. There is no afterimage during operation, and excellent anti-reflection effect has the advantages of high quality image quality, excellent heat resistance, chemical resistance as well as durability 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 and exposing, developing, and thermosetting in a predetermined pattern, and the pattern layer is conventional in the art. It can be formed by performing a method known as.
  • 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 color filter according to the present invention may include the above-described blue pattern layer, and may further include a self-luminous pixel further comprising at least one selected from the group consisting of a red pattern layer and a green pattern layer.
  • the red pattern layer or the green pattern layer may include quantum dots and 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 may include a metal oxide having an average particle diameter of 30 to 500nm, the content of the scattering particles and the metal oxide is applied to the content of the scattering particles and the metal oxide contained in the blue photosensitive resin composition according to the present invention. can do.
  • 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 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 a color filter including a blue pattern layer and the light source according to the present invention
  • a color filter including a blue pattern layer and the light source according to the present invention there is an advantage of having excellent light emission intensity or viewing angle.
  • 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, a reflux condenser, a dropping lot, and a nitrogen introduction tube was prepared, and as a monomer dropping lot, 74.8 g (0.20 mole) of benzylmaleimide, 43.2 g (0.30 mole) of acrylic acid, and vinyltoluene 118.0 g (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.
  • PGMEA propylene glycol monomethyl ether acetate
  • n-dodecanethiol 6g and PGMEA24g were 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 weight average molecular weight (Mw) measurement of binder resin was performed on condition of the following using GPC method.
  • 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).
  • Table 1 shows scattering particles
  • Table 2 shows blue and purple colorants
  • Tables 3 to 8 are Examples.
  • Blue photosensitive resin composition according to, Table 9 shows the configuration and content of the photosensitive resin composition according to the comparative example).
  • Photopolymerizable Compound (C) dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
  • Photopolymerizable Compound (C) dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
  • Photopolymerizable Compound (C) dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
  • Photopolymerizable Compound (C) dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
  • Photopolymerizable Compound (C) dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
  • Photopolymerizable Compound (C) dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
  • Photopolymerizable Compound (C) dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
  • the color filter was manufactured using the photosensitive resin composition manufactured according to the said Example and the comparative example. That is, each of the photosensitive resin composition was applied 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 transmissive pattern of 20 mm by 20 mm square and a line / space pattern of 1 to 100 ⁇ m was placed on the thin film and irradiated with ultraviolet rays at 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.
  • Sensitivity The degree of formation of a flawless thin film of the sensitivity mask fine pattern (1 to 60) (the lower the value, the better the sensitivity).
  • Pattern Stability Pattern error after exposure of pattern mask at low exposure amount (20-100mJ)
  • Solvent resistance evaluation The color filter prepared above is immersed in solvent NMP (1-methyl- 2-pyrrolidinone) for 30 minutes, and the color change before and after evaluation is calculated and compared.
  • the equation used at this time is calculated by the following equation (1) representing the color change in the three-dimensional colorimeter defined by L * , a * , b * .
  • Heat resistance evaluation The color filter manufactured by the above method was calculated by Equation (1) to measure color change before and after heating after heating for 2 hours in a heating oven at 230 °C.
  • the outgas measurement of the color filter made of the photosensitive resin composition according to the Examples and Comparative Examples was performed through the following method.
  • Each of the photosensitive resin compositions was coated on a glass substrate by spin coating, then placed on a heating plate and maintained at 100 ° C. for 3 minutes to form a thin film.
  • a photomask ⁇ pattern area: 3 ⁇ 3 cm> was placed on the thin film, and the ultraviolet rays were irradiated with a distance of 100 ⁇ m from the test photo mask.
  • the ultraviolet light source was irradiated with luminous intensity of 100mJ / cm 2 using a 1kW high-pressure mercury lamp containing all g, h, and i rays, and no special optical filter was used.
  • the UV-irradiated thin film was immersed in a KOH aqueous solution developing solution of pH 10.5 for 2 minutes and then developed.
  • the thin film coated glass plate was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 200 ° C. for 30 minutes.
  • the pattern shape (film) thickness of the color filter obtained through this is 1-5 micrometers, More preferably, it is about 2-4 micrometers.
  • the formed thin substrate was pyrolyzed at 230 ° C. for 30 minutes through Py-GC / FID to analyze the collected compounds.
  • the analysis criteria are as follows.
  • Outgas measurement value The value of Comparative Example 1 was expressed as a percentage based on 100%. The lower the value, the better.
  • the size of the pattern which was obtained through a line / space pattern mask designed to 100 ⁇ m among color filters manufactured using the photosensitive resins according to the above examples and comparative examples, was measured by OM equipment (ECLIPSE LV100POL Nikon). . The measurement results are shown in Table 10.
  • a negative value means a threshold value that causes a process defect.
  • Example 1 25 9 ⁇ 13 ⁇ ⁇ 5%
  • Example 2 23 8 ⁇ 11 ⁇ ⁇ 13%
  • Example 3 22 8 ⁇ 10 ⁇ ⁇ 15%
  • Example 4 24 7 ⁇ 5 ⁇ ⁇ 18%
  • Example 5 24 11 ⁇ One ⁇ ⁇ 12%
  • Example 6 21 13 ⁇ 11 ⁇ ⁇ 16%
  • Example 7 17 11 ⁇ 9 ⁇ ⁇ 10%
  • Example 8 13 10 ⁇ 12 ⁇ ⁇ 17%
  • Example 9 19 8 ⁇ 7 ⁇ ⁇ 28%
  • Example 10 15 11 ⁇ 10 ⁇ ⁇ 3%
  • Example 12 23 7 ⁇ 9 ⁇ ⁇ 34%
  • Example 13 19 11 ⁇ 7 ⁇ ⁇ 36%
  • Example 14 17 8 ⁇ 5 ⁇ ⁇ 31%
  • Example 15 15 12 ⁇ 9 ⁇ ⁇ 25%
  • Example 16 10 13 ⁇ 8 ⁇ ⁇ 19%
  • Example 17 22 8 ⁇ 7 ⁇ ⁇ 23%
  • Example 18 21
  • I means light intensity measured at the viewing angle.
  • Spectrophotometer CM-3600A Konica Minolta Co., Ltd.
  • CM-3600A Konica Minolta Co., Ltd.
  • Part of a color filter manufactured using the photosensitive resin composition prepared according to the above Examples and Comparative Examples was formed in a pattern of 20 ⁇ 20 mm square through a 365 nm Tube type 4 W UV irradiator (VL-4LC, VILBER LOURMAT). The light-converted region was measured, and Examples and Comparative Examples measured the emission intensity in the 450 nm region using a Spectrum meter (Ocean Optics). The measurement results are shown in Table 11.
  • Example 1 28500 21.53 2.64
  • Example 2 34700 45.68 3.23
  • Example 3 31800 82.22 2.38
  • Example 4 29800 82.01 2.21
  • Example 5 28200 88.52 2.3
  • Example 6 31300 56.18 3.06
  • Example 7 26500 82.85 3.23
  • Example 8 23900 51.03 2.64
  • Example 9 36500 51.03 1.79
  • Example 10 28500 86.21 2.13
  • Example 11 34800 35.28 2.47
  • Example 12 30800 82.01 2.64
  • Example 13 27800 86.21 3.23
  • Example 14 34200 53.87 3.06
  • Example 15 31300 76.23 2.72
  • Example 16 26500 78.65 2.47
  • Example 17 21900 45.68 1.79
  • Example 18 36500 52.19 1.62
  • Example 19 39770 89.03 1.23
  • Example 20 41250 91.2 1.19
  • Example 21 40540 90.01 1.2
  • Example 22 40805 90.88 1.17

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Nonlinear Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)

Abstract

L'invention concerne une composition de résine photosensible bleue comprenant : une résine soluble en milieu alcalin ; un colorant bleu; et des particules de diffusion ayant un diamètre moyen de particule de 30 à 500 nm et comprenant un oxyde métallique. La résine soluble en milieu alcalin comprend une résine liante à base de cardo comprenant au moins un motif répétitif parmi les formules chimiques (1) - (3). La composition de résine photosensible bleue selon la présente invention présente les avantages suivants en ce qu'elle : fournit d'excellentes propriétés de reproduction de couleurs et une efficacité lumineuse élevée ; montre d'excellentes propriétés d'écoulement de chaleur et donc montre une linéarité de motif améliorée et une efficacité de processus améliorée et ne montre pas de conicité inverse ; ne montre pas de post-image lors du fonctionnement d'un panneau et montre des images de haute qualité, ainsi qu'une résistance à la chaleur, une résistance chimique, une durabilité et une fiabilité, excellentes, au moyen d'excellents effets antireflet.
PCT/KR2018/002423 2017-03-30 2018-02-28 Composition de résine photosensible bleue, ainsi que filtre coloré et dispositif d'affichage d'image fabriqués à l'aide de celle-ci WO2018182186A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2019552272A JP6876823B2 (ja) 2017-03-30 2018-02-28 青色感光性樹脂組成物、これを利用して製造されたカラーフィルターおよび画像表示装置
CN201880023065.4A CN110506235B (zh) 2017-03-30 2018-02-28 蓝色感光性树脂组合物、利用其制造的滤色器及图像显示装置

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
KR10-2017-0040617 2017-03-30
KR20170040618 2017-03-30
KR10-2017-0040618 2017-03-30
KR20170040617 2017-03-30
KR1020170109531A KR101980186B1 (ko) 2017-03-30 2017-08-29 청색 감광성 수지 조성물, 이를 이용하여 제조된 컬러필터 및 화상 표시 장치
KR10-2017-0109531 2017-08-29
KR10-2017-0109532 2017-08-29
KR1020170109532A KR101998775B1 (ko) 2017-03-30 2017-08-29 청색 감광성 수지 조성물, 이를 이용하여 제조된 컬러필터 및 화상 표시 장치

Publications (1)

Publication Number Publication Date
WO2018182186A1 true WO2018182186A1 (fr) 2018-10-04

Family

ID=63678124

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/002423 WO2018182186A1 (fr) 2017-03-30 2018-02-28 Composition de résine photosensible bleue, ainsi que filtre coloré et dispositif d'affichage d'image fabriqués à l'aide de celle-ci

Country Status (1)

Country Link
WO (1) WO2018182186A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1057808A2 (fr) * 1999-06-01 2000-12-06 Mitsui Chemicals, Inc. Composé carboxylique unsaturé contenant du soufre et son utilisation
KR100781823B1 (ko) * 2000-04-05 2007-12-03 다이니폰 인사츠 가부시키가이샤 칼라 필터
KR20110076489A (ko) * 2009-12-29 2011-07-06 제일모직주식회사 신규한 카도계 수지 및 이를 포함하는 컬러필터용 감광성 수지 조성물
KR20150055417A (ko) * 2013-11-13 2015-05-21 동우 화인켐 주식회사 착색 감광성 수지 조성물
KR20150106335A (ko) * 2014-03-11 2015-09-21 동우 화인켐 주식회사 청색 감광성 수지 조성물, 이를 포함하는 청색 컬러필터 및 표시장치
KR20160114292A (ko) * 2015-03-24 2016-10-05 동우 화인켐 주식회사 자발광 감광성 수지 조성물, 이로부터 제조된 컬러필터 및 상기 컬러필터를 포함하는 화상표시장치
KR20170019277A (ko) * 2015-08-11 2017-02-21 동우 화인켐 주식회사 자발광 감광성 수지 조성물, 이로부터 제조된 컬러필터 및 상기 컬러필터를 구비한 화상표시장치
KR20170027916A (ko) * 2015-09-02 2017-03-13 삼성디스플레이 주식회사 색변환 기판의 제조 방법

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1057808A2 (fr) * 1999-06-01 2000-12-06 Mitsui Chemicals, Inc. Composé carboxylique unsaturé contenant du soufre et son utilisation
KR100781823B1 (ko) * 2000-04-05 2007-12-03 다이니폰 인사츠 가부시키가이샤 칼라 필터
KR20110076489A (ko) * 2009-12-29 2011-07-06 제일모직주식회사 신규한 카도계 수지 및 이를 포함하는 컬러필터용 감광성 수지 조성물
KR20150055417A (ko) * 2013-11-13 2015-05-21 동우 화인켐 주식회사 착색 감광성 수지 조성물
KR20150106335A (ko) * 2014-03-11 2015-09-21 동우 화인켐 주식회사 청색 감광성 수지 조성물, 이를 포함하는 청색 컬러필터 및 표시장치
KR20160114292A (ko) * 2015-03-24 2016-10-05 동우 화인켐 주식회사 자발광 감광성 수지 조성물, 이로부터 제조된 컬러필터 및 상기 컬러필터를 포함하는 화상표시장치
KR20170019277A (ko) * 2015-08-11 2017-02-21 동우 화인켐 주식회사 자발광 감광성 수지 조성물, 이로부터 제조된 컬러필터 및 상기 컬러필터를 구비한 화상표시장치
KR20170027916A (ko) * 2015-09-02 2017-03-13 삼성디스플레이 주식회사 색변환 기판의 제조 방법

Similar Documents

Publication Publication Date Title
WO2017057813A1 (fr) Résine liante et composition de résine photosensible contenant cette dernière
WO2018182136A9 (fr) Composition de résine photosensible bleue, filtre coloré préparé à l'aide de cette dernière et dispositif d'affichage d'image
WO2018080008A1 (fr) Composition de résine photosensible de type à émission spontanée, filtre coloré fabriqué à l'aide de celle-ci, et appareil d'affichage d'images
WO2018182133A1 (fr) Composition de résine photosensible bleue, filtre coloré fabriqué en l'utilisant, et dispositif d'affichage d'image
WO2017052351A1 (fr) Composé ester d'oxime présentant une excellente stabilité de résistance à la chaleur, initiateur de photopolymérisation le contenant, et composition de résine photosensible
WO2018182302A1 (fr) Composition de résine photosensible bleue, et filtre coloré et dispositif d'affichage d'image fabriqués à l'aide de celle-ci
WO2019107685A1 (fr) Procédé de production d'une composition de colorant, et composition de colorant, dispersion de colorant, composition de résine photosensible, filtre coloré et dispositif d'affichage à cristaux liquides produit à l'aide dudit procédé
WO2020050590A1 (fr) Composé, composition colorante, matériau photosensible, filtre coloré et dispositif d'affichage
WO2019132138A1 (fr) Composé à base de xanthène et composition de résine photosensible le comprenant
WO2018182127A1 (fr) Composition de résine photosensible et filtre coloré et dispositif d'affichage d'image fabriqués au moyen de celle-ci
WO2021075740A1 (fr) Points quantiques, composition durcissable les comprenant, film durci fabriqué à l'aide de la composition, et filtre coloré comprenant un film durci
WO2021137466A1 (fr) Couche de résine photosensible, et résine photosensible à film sec et élément photosensible l'utilisant
WO2019164157A1 (fr) Composé, composition colorante le comprenant, et composition de résine le comprenant
WO2018182135A1 (fr) Composition de résine photosensible bleue, filtre coloré produit à l'aide de celle-ci et dispositif d'affichage d'image
WO2021221304A1 (fr) Composé, film antireflet le comprenant, et dispositif d'affichage
WO2018182186A1 (fr) Composition de résine photosensible bleue, ainsi que filtre coloré et dispositif d'affichage d'image fabriqués à l'aide de celle-ci
WO2020197179A1 (fr) Copolymère soluble dans les alcalis, photodurcissable et thermodurcissable, et composition de résine photosensible, film de résine photosensible et filtre coloré l'utilisant
WO2021080267A1 (fr) Copolymère de polysiloxane, procédé de production associé et composition de résine le contenant
WO2018182137A1 (fr) Composition de résine photosensible bleue, et filtre coloré et dispositif d'affichage d'image fabriqués à l'aide de ladite composition
WO2019142956A1 (fr) Composition de résine photosensible, filtre coloré comprenant une matrice noire, espaceur de colonne ou espaceur de colonne noire fabriqués à l'aide de cette dernière, et appareil d'affichage comprenant un filtre coloré
WO2021091222A1 (fr) Composé, résine liante, composition de résine photosensible de type négatif et dispositif d'affichage comprenant un film isolant noir formé par utilisation de cette dernière
WO2017126795A1 (fr) Composition de résine photosensible noire et élément d'espacement de colonne noir préparé à partir de cette dernière
WO2021091223A1 (fr) Résine liante, composition de résine photosensible de type négatif et dispositif d'affichage comprenant un banc noir formé à l'aide de celle-ci
WO2019074262A1 (fr) Résine liante et composition de résine photosensible ou solution de revêtement la contenant
WO2022260283A1 (fr) Composition de résine photosensible, film de résine photosensible l'utilisant, filtre coloré et dispositif d'affichage

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18774489

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019552272

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18774489

Country of ref document: EP

Kind code of ref document: A1