WO2010137702A1 - Encre pour jet d'encre thermodurcissable pour un filtre de couleur - Google Patents

Encre pour jet d'encre thermodurcissable pour un filtre de couleur Download PDF

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Publication number
WO2010137702A1
WO2010137702A1 PCT/JP2010/059135 JP2010059135W WO2010137702A1 WO 2010137702 A1 WO2010137702 A1 WO 2010137702A1 JP 2010059135 W JP2010059135 W JP 2010059135W WO 2010137702 A1 WO2010137702 A1 WO 2010137702A1
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WIPO (PCT)
Prior art keywords
meth
ink
acrylate
monomer
acrylic copolymer
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Application number
PCT/JP2010/059135
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English (en)
Japanese (ja)
Inventor
浩明 木田
克巳 渡部
祐二 牧本
修 清家
文 山田
恭一 飯島
克 大河原
Original Assignee
株式会社Ｄｎｐファインケミカル
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Application filed by 株式会社Ｄｎｐファインケミカル filed Critical 株式会社Ｄｎｐファインケミカル
Priority to JP2011516077A priority Critical patent/JPWO2010137702A1/ja
Priority to CN2010800027517A priority patent/CN102165339A/zh
Publication of WO2010137702A1 publication Critical patent/WO2010137702A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G02F1/133516—Methods for their manufacture, e.g. printing, electro-deposition or photolithography

Definitions

  • the present invention relates to a thermosetting inkjet ink for a color filter used for forming pixels having a predetermined pattern using an inkjet method.
  • a water-soluble polymer material which is a dyeing material
  • a photolithography process patterned into a desired shape by a photolithography process, and then the obtained pattern is immersed in a dyeing bath.
  • a dyeing bath To get a colored pattern.
  • R, G, and B pixels are formed.
  • Another method is a pigment dispersion method.
  • a photosensitive resin layer in which a pigment is dispersed is first formed on a substrate, and this is patterned to obtain a monochromatic pattern. Further, by repeating this process three times, R, G, and B pixels are formed.
  • Still other methods include an electrodeposition method, a method in which a pigment is dispersed in a thermosetting resin, R, G, and B are printed three times, and then the resin is thermoset.
  • Patent Document 1 describes that a pixel portion is formed by spraying a colored ink containing a thermosetting resin onto a substrate by an inkjet method and heating. Has been.
  • the first object of the present invention is to provide a thermosetting inkjet ink for a color filter, which can realize a color filter having excellent storage stability and curability, excellent chemical resistance after thermosetting, and good color gamut reproducibility. It is to be.
  • the second object of the present invention is to provide a thermosetting inkjet ink for a color filter which is excellent in adhesion, surface hardness and flatness after thermosetting even when the pigment concentration is increased. is there.
  • thermosetting binder component of an ink-jet ink for a color filter a polyfunctional monomer having an ethylenically unsaturated bond, an epoxy group-containing monomer, and an alicyclic hydrocarbon-containing monomer.
  • the present inventors have found that the above object can be solved by using in combination with an acrylic copolymer obtained by copolymerizing a monomer group containing at least a monomer group, and have completed the present invention.
  • a polyfunctional monomer having an ethylenically unsaturated bond is used as a thermosetting binder component, and when the inkjet ink is cured, the polyfunctional monomer is polymerized and / or crosslinked by heat.
  • the first thermosetting inkjet ink for a color filter is a thermosetting inkjet ink for a color filter containing a polyfunctional monomer, a binder resin, a pigment, a pigment dispersant, and a solvent.
  • the polyfunctional monomer is a compound having 4 or more ethylenically unsaturated bonds in one molecule
  • the binder resin is (A) an epoxy group-containing monomer having an epoxy group and an ethylenically unsaturated bond; (B) It is an acrylic copolymer obtained by copolymerizing a monomer group containing at least an alicyclic hydrocarbon-containing monomer having an alicyclic hydrocarbon group and an ethylenically unsaturated bond.
  • the (A) epoxy group-containing monomer is 20% by weight to 80% by weight in the total copolymerization component, and (B) the alicyclic hydrocarbon It is preferable that the contained monomer is 20% by weight to 80% by weight in the total copolymerization components from the viewpoint of storage stability and viscosity reduction of the ink, chemical resistance of the cured film, and color gamut reproducibility.
  • the (B) alicyclic hydrocarbon-containing monomer has a bridged alicyclic hydrocarbon group, so that the cured film has chemical resistance and color gamut reproduction.
  • the bridged alicyclic hydrocarbon group means a polycyclic aliphatic hydrocarbon group having a crosslinked structure in the alicyclic hydrocarbon group and having a polycyclic structure in the molecule.
  • the second thermosetting inkjet ink for a color filter is a thermosetting inkjet ink for a color filter containing a polyfunctional monomer, a binder resin, a pigment, a pigment dispersant, and a solvent.
  • the polyfunctional monomer is a compound having 4 or more ethylenically unsaturated bonds in one molecule
  • the binder resin is (A) an epoxy group-containing monomer having an epoxy group and an ethylenically unsaturated bond; (B) an acrylic copolymer obtained by copolymerizing a monomer group containing at least an alicyclic hydrocarbon-containing monomer having an alicyclic hydrocarbon group and an ethylenically unsaturated bond, and the acrylic copolymer And an epoxy resin different from the above.
  • the acrylic copolymer is a copolymer obtained by copolymerizing a monomer group containing at least the (A) epoxy group-containing monomer and (B) the alicyclic hydrocarbon-containing monomer. It is preferable that it is an acryl-type copolymer formed by making the carboxyl group-containing monomer (C) which has a carboxyl group and an ethylenically unsaturated bond react with one or more of the epoxy groups which have.
  • the side chain of the acrylic copolymer has an ethylenically unsaturated bond and can be cross-linked with the polyfunctional monomer, adhesion after thermosetting, surface hardness, and flatness It is preferable from the point that it is excellent in the properties and further becomes excellent in the ITO resistance.
  • the (A) epoxy group-containing monomer is 20% by weight to 80% by weight in the total copolymerization component, and (B) the alicyclic hydrocarbon
  • the contained monomer is preferably 20% by weight to 80% by weight in the total copolymerization components.
  • the (B) alicyclic hydrocarbon-containing monomer preferably has a bridged alicyclic hydrocarbon group from the viewpoint of surface hardness after heat curing of the ink and solvent resistance.
  • the weight of the epoxy resin relative to the sum of the polyfunctional monomer and the acrylic copolymer in the content ratio of the polyfunctional monomer, the acrylic copolymer, and the epoxy resin is 0.25 to 4, and the weight ratio of the acrylic copolymer to the polyfunctional monomer (acrylic copolymer) / Polyfunctional monomer) is preferably from 0.125 to 8 from the viewpoint of excellent adhesion after heat curing of the ink, surface hardness, and flatness.
  • thermosetting ink jet ink for color filter of the present invention can realize a color filter having excellent storage stability and curability, excellent chemical resistance after thermosetting, and good color gamut reproducibility. Moreover, the thermosetting inkjet ink for 2nd color filters of this invention is excellent in the adhesiveness after heat curing, surface hardness, and flatness.
  • a first thermosetting inkjet ink for a color filter according to the present invention is a thermosetting inkjet ink for a color filter containing a polyfunctional monomer, a binder resin, a pigment, a pigment dispersant, and a solvent.
  • the functional monomer is a compound having 4 or more ethylenically unsaturated bonds in one molecule
  • the binder resin is (A) an epoxy group-containing monomer having an epoxy group and an ethylenically unsaturated bond
  • the polyfunctionality having 4 or more ethylenically unsaturated bonds in one molecule without using conventional epoxy resin and acid component as thermosetting binder components.
  • thermosetting resin since a thermosetting resin is used, there is an advantage that a special incidental equipment such as light irradiation is not required and productivity is high.
  • thermosetting binder component a polyfunctional monomer having 4 or more ethylenically unsaturated bonds in one molecule is copolymerized with a monomer group containing at least an epoxy group-containing monomer and an alicyclic hydrocarbon-containing monomer.
  • the reason why the above-described effects are exhibited by using the acrylic copolymer in combination is estimated as follows.
  • a conventional epoxy resin and an acid component are mainly used as a thermosetting binder component, the reactivity between the acid component and the epoxy resin is very high, so that the viscosity gradually increases with time, and there is a problem in storage stability. It was. Moreover, there existed a problem that chemical resistance was inadequate.
  • an acrylic copolymer having an epoxy group and an alicyclic hydrocarbon in the side chain without using polymerization and / or crosslinking reaction of a conventional epoxy resin and an acid component as a thermosetting binder component.
  • a polyfunctional monomer having 4 or more ethylenically unsaturated bonds in one molecule in combination, polymerization of ethylenically unsaturated bonds and / or crosslinking reaction by heat, and polymerization of epoxy groups by heat and / or A cross-linking reaction is used.
  • the reaction between the epoxy group and the acid component is not essentially used and the acid component is not allowed to coexist with the epoxy group, the epoxy group hardly reacts and the storage stability is excellent.
  • An acrylic copolymer having an epoxy group and an alicyclic hydrocarbon in the side chain is excellent in curability because the epoxy group reacts by heat to polymerize and / or crosslink, and has an alicyclic hydrocarbon. Since it has an alicyclic hydrocarbon, it is difficult to undergo yellowing due to thermal history, and therefore color gamut reproducibility is good.
  • a polyfunctional monomer having four or more ethylenically unsaturated bonds in one molecule can be thermally polymerized to obtain a high hardness coating film having a high crosslinking density.
  • thermosetting inkjet ink for color filter of the present invention contains at least a polyfunctional monomer, a binder resin, a pigment, a pigment dispersant, and a solvent, and may contain other components as necessary. It is. Hereinafter, each component used for the thermosetting inkjet ink for color filters of this invention is demonstrated.
  • a compound having 4 or more ethylenically unsaturated bonds in one molecule is used as the polyfunctional monomer.
  • the ethylenically unsaturated bond refers to a double bond between carbon atoms capable of radical polymerization, and examples of the functional group having such an ethylenically unsaturated bond include a vinyl group (CH 2 ⁇ CH—).
  • the polyfunctional monomer used in this invention may be used individually by 1 type or in combination of 2 or more types.
  • the ethylenically unsaturated bond preferably has four or more (meth) acryloyloxy groups and / or (meth) acryloyl groups from the viewpoint of curability of the cured film by thermal polymerization and / or crosslinking.
  • acrylic ester and methacrylic ester are collectively referred to as “(meth) acrylate”. Others are the same.
  • the molecular weight of the polyfunctional monomer is preferably 2000 or less, more preferably 1000 or less, from the viewpoint of ink viscosity.
  • Examples of the compound having 4 or more ethylenically unsaturated bonds in one molecule include tetramethylol methane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and ditrimethylolpropane tetra.
  • Method acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol Penta (meth) acrylate, urethane hexa (meth) acrylate, polyester hexa (meth) acrylate, succinic acid modified dipentaerythritol Penta (meth) acrylate.
  • pentaerythritol tetracaprolactonate tetra (meth) acrylate diglycerin tetra (meth) acrylate, ditrimethylolpropane tetracaprolactonate tetra (meth) acrylate, ditrimethylolethane tetra (meth) acrylate, Ditrimethylolbutanetetra (meth) acrylate, ditrimethylolhexanetetra (meth) acrylate, ditrimethyloloctanetetra (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa ( (Meth) acrylates, tripentaerythritol polyalkylene oxide hepta (meth) acrylates and their ethylene oxides Id a
  • ethoxylated pentaerythritol tetra (meth) acrylate neopentyl glycol oligoacrylate, 1,4-butanediol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol oligoacrylate, urethane
  • examples include acrylate and epoxy acrylate.
  • hexakis (methacryloyloxyethyl) cyclotriphosphazene for example, “PPZ” manufactured by Kyoeisha Chemical Co., Ltd.
  • dipentaerythritol pentaacrylate hexamethylene diisocyanate / urethane prepolymer for example, “UA-510H” manufactured by Kyoeisha Chemical Co., Ltd.
  • the content of the polyfunctional monomer having 4 or more ethylenically unsaturated bonds in one molecule is preferably in the range of 5 to 80% by weight, more preferably 10% by weight, based on the solid content of the ink. It is preferably in the range of% to 60% by weight. If the amount is less than the above range, the cured film may have insufficient curability and chemical resistance. Further, if the amount is larger than the above range, a desired color may not be reproduced.
  • the content of the polyfunctional monomer having 4 or more ethylenically unsaturated bonds in one molecule is preferably 10 to 90% by weight in the solid content other than the pigment and the pigment dispersant described later.
  • solid content includes all the components except a solvent, and a liquid compound etc. are also contained in solid content.
  • the polyfunctional monomer a compound having 4 or more ethylenically unsaturated bonds in one molecule is used.
  • a compound having 2 to 3 ethylenically unsaturated bonds in the molecule may be used in combination.
  • the compound having 4 or more ethylenically unsaturated bonds in one molecule is preferably contained in 50% by weight or more, more preferably 70% by weight or more in the total amount of the polyfunctional monomer. .
  • the compound which has 4 or more of ethylenically unsaturated bonds in 1 molecule is 100 weight% in the polyfunctional monomer whole quantity.
  • the compound having 2 to 3 ethylenically unsaturated bonds in the molecule that may be used in combination is preferably a compound having 2 to 3 (meth) acryloyl groups.
  • the binder resin used in the present invention includes (A) an epoxy group-containing monomer having an epoxy group and an ethylenically unsaturated bond, and (B) an alicyclic carbonization having an alicyclic hydrocarbon group and an ethylenically unsaturated bond.
  • the acrylic copolymer used in the present invention includes (A) an epoxy group-containing monomer having an epoxy group and an ethylenically unsaturated bond, and (B) a fat having an alicyclic hydrocarbon group and an ethylenically unsaturated bond. If a monomer group containing at least a cyclic hydrocarbon-containing monomer is copolymerized, each monomer is copolymerized at random, even if the monomers are randomly copolymerized. Also good.
  • the acrylic copolymer contains an epoxy group.
  • the reactivity by heat improves and brings about the effect
  • the epoxy group-containing monomer having an epoxy group and an ethylenically unsaturated bond include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4 -Epoxycyclohexylmethyl (meth) acrylate and the like. Among them, glycidyl (meth) acrylate can be preferably used in the present invention.
  • an epoxy group containing monomer it may be used individually by 1 type, and may be used in mixture of 2 or more types.
  • the content of the (A) epoxy group-containing monomer is not limited as long as the binder resin can be cured to have a desired cured film. %, Preferably 30 to 70% by weight, more preferably 40 to 60% by weight. It is because it can be made excellent in sclerosis
  • the acrylic copolymer contains an alicyclic hydrocarbon group. become. Thereby, the sclerosis
  • Examples of the alicyclic hydrocarbon-containing monomer having an alicyclic hydrocarbon group and an ethylenically unsaturated bond include cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, 3-cyclohexenylmethyl (meth) acrylate, 4-isopropylcyclohexyl (meth) acrylate, 1-methylcyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, 3-methylcyclohexyl (meth) acrylate, 4-methylcyclohexyl (meth) acrylate, 1-ethylcyclohexyl ( (Meth) acrylate, 4-ethylcyclohexyl (meth) acrylate, 2-tert-butylcyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, methyl ( )
  • alicyclic hydrocarbon-containing monomer in particular, a fat having a bridged alicyclic hydrocarbon group and an ethylenically unsaturated bond from the viewpoint of suppressing yellowing due to thermal history and not reducing color gamut reproducibility.
  • a cyclic hydrocarbon-containing monomer is preferred.
  • Examples of the alicyclic hydrocarbon-containing monomer having a bridged alicyclic hydrocarbon group and an ethylenically unsaturated bond include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, From dicyclopentenyloxy (meth) acrylate, adamantyl (meth) acrylate, 2-alkyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, and 1-perfluoroadamantyl (meth) acrylate It is preferable that it is 1 or more types selected from the group which consists of a point which suppresses yellowing by a heat history and does not reduce color gamut reproducibility.
  • dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, and 2-alkyl-2-adamantyl (meth) acrylate can be preferably used in the present invention.
  • the content of the (B) alicyclic hydrocarbon-containing monomer is not limited as long as the binder resin can have a desired cured film curing ability. It is preferably -80% by weight, more preferably 30-70% by weight, and further preferably 40-60% by weight. It is because it can be made excellent in sclerosis
  • the (A) epoxy group-containing monomer and the above ( B) may be a copolymer obtained by further using a copolymerizable monomer other than the alicyclic hydrocarbon-containing monomer.
  • Such monomers include, for example, methyl (meth) acrylate, n-butyl (meth) acrylate, allyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, 2-hydroxylethyl (meth) acrylate, etc .; N-substituted maleimides such as N-methylmaleimide, N-cyclohexylmaleimide and the like can be exemplified.
  • the content of the copolymerizable monomer other than the (A) epoxy group-containing monomer and the (B) alicyclic hydrocarbon-containing monomer is 0% by weight to 50% by weight in the total copolymerization component. It is preferably 0% by weight to 30% by weight, and more preferably 0% by weight to 20% by weight.
  • an aromatic ring is not included from the viewpoint of suppressing yellowing.
  • an acid component such as a structural unit derived from (meth) acrylic acid is not substantially contained.
  • the phrase “substantially free of an acid component” means an acrylic copolymer that does not intentionally use a monomer containing an acid component such as a carboxyl group as the copolymer component.
  • the weight average molecular weight of the acrylic copolymer is not particularly limited, but is preferably 1,000 to 30,000, and more preferably 3000 to 20,000. If the weight average molecular weight of the acrylic copolymer is less than 1,000, physical properties such as strength and solvent resistance required for the cured layer as the details of the color filter may be insufficient. On the other hand, if the weight average molecular weight of the acrylic copolymer is more than 30,000, there is a fear that the viscosity is likely to increase, and the stability of the discharge amount and the discharge direction when discharging from the discharge head by the ink jet method are likely to occur. This is because there is a possibility that straightness may deteriorate and stability of long-term storage may deteriorate.
  • the weight average molecular weight can be determined as a standard polystyrene equivalent value by gel permeation chromatography (GPC).
  • any copolymerization method may be used as long as it is a copolymerization method so that each monomer is contained in a desired ratio, and a general polymerization method can be used. Specifically, a method of polymerizing after dissolving or dispersing each of the monomers and the polymerization initiator in a solvent can be mentioned.
  • the content of the acrylic copolymer is preferably in the range of 5% by weight to 80% by weight, more preferably in the range of 10% by weight to 60% by weight, based on the solid content of the ink. . This is because if it is less than the above range, the cured film has poor curability and is likely to crack. Also, if the amount is larger than the above range, the viscosity may be easily increased, the stability of the discharge amount when discharging from the discharge head by the ink jet method, the straightness of the discharge direction may be deteriorated, and the long-term storage stability. Because there is a risk of getting worse.
  • the content of the acrylic copolymer is preferably 10 to 90% by weight, and more preferably 20 to 80% by weight in solids other than the pigment and pigment dispersant described later. Is preferable from the viewpoints of heat resistance, cured film curability, chemical resistance, and color gamut reproducibility.
  • the content ratio of the polyfunctional monomer used in the present invention to the binder resin may be any ratio that can achieve desired ink suitability and cure suitability of the cured film.
  • the weight ratio of polyfunctional monomer and binder resin (polyfunctional monomer / binder resin) contained in the curable inkjet ink is preferably in the range of 10/90 to 90/10, and in particular, 20/80 to It is preferably within the range of 80/20 from the viewpoints of ink viscosity reduction, storage stability, ejection stability in inkjet, cured film curability, chemical resistance, and color gamut reproducibility.
  • ⁇ Pigment> As the pigment used in the present invention, a known pigment can be used. Specific examples of organic pigments that can be used in the present invention are shown in Tables 1 and 2 below.
  • inorganic pigments examples include titanium oxide, zinc white, lead sulfate, yellow lead, zinc yellow, bengara, cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium black, and synthetic iron black. And carbon black.
  • these pigments may be used independently and may mix and use 2 or more types.
  • the dispersion average particle diameter of the pigment used in the present invention is particularly selected so long as a desired color can be formed when the color filter colored layer is formed using the thermosetting inkjet ink for color filter. It is not limited, but usually it is preferably in the range of 0.01 ⁇ m to 0.30 ⁇ m, and particularly preferably in the range of 0.01 ⁇ m to 0.10 ⁇ m. This is because when the colored layer of the color filter is formed using the thermosetting inkjet ink for a color filter of the present invention, a colored layer having excellent luminance and contrast can be obtained.
  • the dispersion average particle diameter of the pigment can be measured by a light scattering type particle size distribution measuring apparatus.
  • the content of the pigment is not particularly limited as long as a desired color can be developed when the colored layer of the color filter is formed, and depending on the type of pigment used. It is different and is not particularly limited.
  • the pigment content is preferably in the range of 5 wt% to 70 wt% in the solid content of the ink, and more preferably in the range of 10 wt% to 60 wt%. This is because, if the content of the pigment is larger or smaller than the above range, the viscosity of the ink-jet ink may lack stability or the dispersed particle size may not be in an appropriate range.
  • the blending weight ratio (P / V) of the pigment (P) and the solid content (V) other than the pigment is 0.25 to 1.2, particularly 0.5 to 1.2. It is preferable from the viewpoint of the balance between ink ejection performance, prevention of ink breakage, and film properties obtained. If the P / V ratio is too low, in order to obtain sufficient coloring power, it is necessary to increase the amount of ink droplets that adhere to the pixel formation region, which causes problems such as ink breaking from the pixel formation region. There is a case. On the other hand, if the P / V ratio is too high, there may be a problem that the ejection performance such as clogging or flight bending occurs in the ejection head or the film surface becomes rough.
  • a pigment dispersant is blended in the thermosetting inkjet ink for color filter of the present invention in order to disperse the pigment satisfactorily.
  • the pigment dispersant that can be used include cationic, anionic, nonionic, amphoteric, and silicone surfactants.
  • the surfactants polymer surfactants (polymer dispersants) as exemplified below are preferable.
  • a dispersion auxiliary resin such as a special acrylic polymer may be further used.
  • polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether
  • Polymeric surfactants such as polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes are preferably used.
  • the content of the pigment dispersant is preferably 5 to 50% by weight based on the total solid content of the ink, and more preferably 10 to 30% by weight based on the total solid content.
  • thermosetting inkjet ink for a color filter of the present invention is mixed with a solvent in order to prepare the ink so that the ink can be discharged from a high concentration liquid or immediately from the head.
  • the solvent is particularly limited as long as it is a solvent that suitably dissolves and disperses solid components. Not.
  • the solvent examples include glycol ethers such as ethylene glycol monoethyl ether and diethylene glycol diethyl ether; glycol ether esters such as ethylene glycol monomethyl ether acetate; glycol oligomer ethers such as diethylene glycol monomethyl ether; diethylene glycol monomethyl ether acetate Glycol oligomer ether esters such as diethylene glycol monobutyl ether acetate; aliphatic or aromatic esters such as ethyl acetate, propyl benzoate; dicarboxylic acid diesters such as diethyl carbonate; and methyl 3-methoxypropionate Alkoxycarboxylates; ketocarboxylates such as ethyl acetoacetate; Alcohols or phenols such as ethanol, isopropanol and phenol; aliphatic or aromatic ethers such as diethyl ether and anisole; alkoxy alcohols such as 2-ethoxyethanol and 1-methoxy-2
  • thermosetting inkjet ink for color filters according to the present invention contains a pigment
  • a solvent that does not contain a hydroxyl group from the viewpoint of the dispersibility and dispersion stability of the pigment.
  • Preferred solvents include ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethyl adipate, dibutyl oxalate, dimethyl malonate, diethyl malonate, succinic acid Examples thereof include dimethyl and diethyl succinate.
  • solvents are mixed with or without mixing with highly dispersible solvents conventionally used for preparing pigment dispersions such as 3-methoxybutyl acetate and propylene glycol monomethyl ether acetate (PGMEA). It can be used as a solvent to prepare a pigment dispersion.
  • highly dispersible solvents conventionally used for preparing pigment dispersions such as 3-methoxybutyl acetate and propylene glycol monomethyl ether acetate (PGMEA). It can be used as a solvent to prepare a pigment dispersion.
  • the solubility of the solvent for preparing the ink-jet ink in water is preferably 20 parts by weight or less with respect to 100 parts by weight of water having a liquid temperature of 20 ° C.
  • diethylene glycol monobutyl ether acetate does not have a hydroxyl group, and its solubility in 100 parts by weight of water at a liquid temperature of 20 ° C. is low at 6.5 parts by weight. Is particularly preferable.
  • the solvent is usually used at a ratio of 40 to 95% by weight with respect to the total amount of the ink-jet ink containing the solvent to prepare the ink-jet ink.
  • the amount of the solvent is too small, the viscosity of the inkjet ink is high, and in the case of the inkjet ink, it becomes difficult to discharge from the inkjet head.
  • the ink will break from the predetermined ink layer formation site, the amount of ink that can be deposited on the ink layer formation site will be insufficient, the film thickness after drying will be too thin, Accordingly, a sufficient transmission density cannot be obtained.
  • thermal polymerization initiator in order to harden
  • thermal polymerization initiators that thermally cure ethylenically unsaturated bonds include various peroxides such as benzoyl peroxide, azo compounds such as azobisbutyronitrile, onium salts, and triazine compounds having a trihalomethyl group. , Azide compounds, quinonediazides, oxime ester compounds, triarylmonoalkylborate compounds, and the like can be used.
  • the above thermal polymerization initiators can be used singly or in combination of two or more.
  • the amount of the thermal polymerization initiator used in the present invention is usually in the range of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight per 100 parts by weight of the polyfunctional monomer. If the blending amount of the thermal polymerization initiator is less than 0.1 part by weight, curing may be insufficient and a tough coating film may not be formed. Moreover, when the compounding quantity of a thermal-polymerization initiator exceeds 10 weight part, there exists a possibility that the storage stability of an ink may be inferior.
  • an epoxy curing agent / accelerator may be contained for the purpose of efficiently reacting the epoxy group in the acrylic copolymer.
  • epoxy curing agents / accelerators unmodified aliphatic polyamines, modified aliphatic polyamines, unmodified aromatic polyamines, modified aromatic polyamines, modified alicyclic polyamines, unmodified alicyclic polyamines, unmodified polyaminoamides, modified Polyaminoamide, tertiary amine, acid anhydride, hydrazide derivative, dicyandiamide and its derivative, boron halide complex, organometallic complex, onium salt, polythiol, phenol formaldehyde condensate, phenol and its derivative, other compound having hydroxyl group, isocyanate, Blocked isocyanate, ketimine, imidazole and derivatives thereof can be used.
  • the above curing agents / accelerators can be used singly or in combination of two or more.
  • the amount of the curing agent / accelerator used in the present invention is usually in the range of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the acrylic copolymer. is there. If the blending amount of the curing agent / accelerator is less than 0.1 part by weight, curing may be insufficient and a tough coating film may not be formed. Moreover, when the compounding quantity of a hardening
  • thermosetting inkjet ink for color filters of this invention can mix
  • the following can be illustrated as such an additive.
  • Leveling agents For example, vinyl polymers such as polyoxyalkylene surfactants, fatty acid ester surfactants, special acrylic polymers, vinyl ether polymers, and the like.
  • Anti-aggregation agent for example, sodium polyacrylate.
  • the thermosetting inkjet ink for a color filter of the present invention may be produced by adding and mixing each component into a solvent and dissolving or dispersing the solid component.
  • the pigment is directly put into the whole solvent together with other components such as a resin and mixed with stirring, the pigment is often not sufficiently dispersed in the solvent. Therefore, usually, a solvent having good dispersibility and dispersion stability of the pigment is prepared, and the pigment is added thereto together with the dispersant, and sufficiently stirred with a dissolver or the like to prepare a pigment dispersion. Then, the obtained pigment dispersion is put into a solvent together with components other than the pigment, and sufficiently stirred and mixed with a dissolver or the like, whereby the ink-jet ink according to the present invention can be obtained.
  • an inkjet ink having a composition obtained by subtracting the amount of the solvent used for preparing the pigment dispersion from the final composition of the entire solvent is diluted to the final concentration. May be completed.
  • a high-concentration inkjet ink may be prepared by introducing the pigment dispersion into a relatively small amount of solvent. The high-concentration ink-jet ink can be stored as it is and diluted to the final concentration just before use and used in the ink-jet method.
  • thermosetting inkjet ink for color filter of the present invention can be used for forming a colored layer of a color filter by an inkjet method. Among them, the color gamut reproducibility is good and the luminance is high. Is preferably used for forming a colored layer.
  • the present invention is not limited to the above embodiment.
  • the above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.
  • the second thermosetting inkjet ink for color filters is a thermosetting inkjet ink for color filters containing a polyfunctional monomer, a binder resin, a pigment, a pigment dispersant, and a solvent
  • the functional monomer is a compound having 4 or more ethylenically unsaturated bonds in one molecule
  • the binder resin is (A) an epoxy group-containing monomer having an epoxy group and an ethylenically unsaturated bond
  • B) An acrylic copolymer obtained by copolymerization containing at least an alicyclic hydrocarbon-containing monomer having an alicyclic hydrocarbon group and an ethylenically unsaturated bond is different from the acrylic copolymer.
  • thermosetting inkjet ink for color filter of the present invention contains an epoxy resin.
  • a thermosetting binder component a polyfunctional monomer having four or more ethylenically unsaturated bonds in one molecule, an epoxy group-containing monomer, and an alicyclic carbonization Even when the pigment concentration is increased by using a combination of an acrylic copolymer obtained by copolymerization containing at least a hydrogen-containing monomer and an epoxy resin different from the acrylic copolymer, A color filter having a colored layer excellent in adhesion, surface hardness, and flatness after thermosetting can be realized. Further, in the present invention, since a thermosetting resin is used, there is an advantage that a special incidental equipment such as light irradiation is not required and productivity is high.
  • thermosetting binder component an acrylic prepared by copolymerizing at least a polyfunctional monomer having four or more ethylenically unsaturated bonds in one molecule, an epoxy group-containing monomer, and an alicyclic hydrocarbon-containing monomer.
  • the surface hardness and solvent resistance of the cured film become superior due to the alicyclic hydrocarbon introduced into the acrylic copolymer.
  • a polyfunctional monomer having 4 or more ethylenically unsaturated bonds in one molecule the crosslink density of the cured film is increased, and the surface hardness is further improved. Wet spreadability is improved and flatness is improved. And it is estimated that the colored layer excellent in the adhesiveness after heat curing, surface hardness, and flatness is realizable even if it is a case where the pigment density
  • the second inkjet ink contains at least a polyfunctional monomer, an acrylic copolymer and an epoxy resin as a binder resin, a pigment, a pigment dispersant, and a solvent. And may contain other components.
  • a polyfunctional monomer an acrylic copolymer and an epoxy resin as a binder resin
  • a pigment a pigment dispersant
  • a solvent a solvent
  • each component used for the second inkjet ink will be described. Description of matters similar to those of the first ink-jet ink will be omitted, and matters different from those of the first ink-jet ink will be described with emphasis. Matters described with respect to the first ink-jet ink are cited for the description of the second ink-jet ink unless the difference described below applies.
  • the same polyfunctional monomer used in the first inkjet ink is used. Also in the second inkjet ink, it is preferable from the viewpoint of surface hardness and adhesion that the ethylenically unsaturated bond has 4 or more (meth) acryloyloxy groups and / or (meth) acryloyl groups.
  • the molecular weight of the polyfunctional monomer is preferably in the same range as in the first inkjet ink in the second inkjet ink. That is, the molecular weight of the polyfunctional monomer is preferably 2000 or less, more preferably 1000 or less, from the viewpoint of the ink viscosity and the flatness of the cured film.
  • the content of the polyfunctional monomer having 4 or more ethylenically unsaturated bonds in one molecule is in the range of 0.5 wt% to 30 wt% with respect to the solid content of the ink. It is preferable that it is in the range of 5.0% by weight to 20% by weight. This is because if it is less than the above range, there is a risk of deterioration of flatness due to a decrease in wettability and surface hardness. Further, if the amount is larger than the above range, the solvent resistance of the ink cured film may be deteriorated due to the balance with the acrylic copolymer content.
  • the binder resin used in the second ink-jet ink is an acrylic copolymer obtained by copolymerizing a monomer group containing at least an (A) epoxy group-containing monomer and (B) an alicyclic hydrocarbon-containing monomer, It contains an epoxy resin different from the acrylic copolymer.
  • Acrylic copolymer In the second inkjet ink, the same acrylic copolymer used in the first inkjet ink is used. Since the acrylic copolymer contains an epoxy group, the adhesiveness to the ink adhesion surface is improved and the compatibility with other components is improved. In addition, since the acrylic copolymer contains an alicyclic hydrocarbon group, the curability of the cured film is improved, the surface hardness is improved, and the solvent resistance is improved.
  • alicyclic hydrocarbon-containing monomers having a bridged alicyclic hydrocarbon group and an ethylenically unsaturated bond from the viewpoint of the surface hardness and solvent resistance of the cured film, among others. It is preferable that As the alicyclic hydrocarbon-containing monomer having a bridged alicyclic hydrocarbon group and an ethylenically unsaturated bond, preferred for the first ink-jet ink are the flatness of the cured film, the surface hardness and the resistance to resistance. It is also preferable from the viewpoint of solvent properties. In particular, in the second inkjet ink, dicyclopentanyl (meth) acrylate, 1-adamantyl (meth) acrylate, and 2-adamantyl (meth) acrylate can be preferably used.
  • the content of the (B) alicyclic hydrocarbon-containing monomer is not limited as long as the binder resin can have the desired surface hardness and solvent resistance of the cured film.
  • the binder resin As in the case of the inkjet ink, it is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, and further preferably 40 to 60% by weight in the total copolymer components.
  • an epoxy group-containing monomer having an epoxy group and an ethylenically unsaturated bond (A) an epoxy group-containing monomer having an epoxy group and an ethylenically unsaturated bond, and (B) an alicyclic hydrocarbon having an alicyclic hydrocarbon group and an ethylenically unsaturated bond. It is formed by reacting a carboxyl group-containing monomer (C) having a carboxyl group and an ethylenically unsaturated bond with one or more epoxy groups of a copolymer obtained by copolymerizing a monomer group containing at least a monomer containing An acrylic copolymer is preferred.
  • the acrylic copolymer has an ethylenically unsaturated bond in the side chain, and the acrylic copolymer is polymerized and / or crosslinked by the ethylenically unsaturated bond with the polyfunctional monomer. Therefore, the adhesiveness after heat curing, the surface hardness, and the flatness are excellent, and further, the ITO forming resistance is excellent.
  • the ITO resistance is the formation of a cured layer such as a colored layer (hereinafter referred to as a cured layer) using the ink when forming a transparent electrode film (for example, ITO), so that wrinkles and cracks are less likely to occur. , A characteristic that hardly causes wrinkles and cracks in adjacent layers.
  • a protective film is formed thereon, and then a transparent electrode film is formed.
  • a transparent electrode film is formed.
  • wrinkles are generated on the surface of the transparent electrode film when the electrode film is formed.
  • a method for forming the transparent electrode film it is necessary to heat the substrate under a reduced pressure atmosphere such as a vacuum deposition method, a sputtering method, or an ion plating method.
  • a vacuum deposition method such as a sputtering method, or an ion plating method.
  • a typical ITO film is vacuum-deposited as a transparent electrode film, the underlying colored layer or protective film is exposed to a high temperature and an ultra-low pressure due to vacuum.
  • a hardened layer such as a colored layer formed from ink
  • the hardened layer thermally expands and contracts to generate wrinkles, which distorts adjacent layers such as transparent electrode films. It is thought that wrinkles and cracks occur on the surface. If wrinkles or cracks occur on the surface of the transparent electrode film, the local resistivity is increased at the location where the transparent electrode film is generated, resulting in disconnection, resulting in an afterimage, and in turn causing display defects. Therefore, if the ITO forming resistance is excellent, a high-intensity color filter with reduced display defects can be obtained.
  • carboxyl group-containing monomer (C) having a carboxyl group and an ethylenically unsaturated bond include methacrylic acid, acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, ⁇ - (hydroxymethyl).
  • Acrylic acid, (meth) acryloyloxyethyl succinic acid monoester, (meth) acryloyloxyphthalic acid monoester, and the like acrylic acid, methacrylic acid, and maleic acid can be preferably used in the present invention, and acrylic acid and methacrylic acid can be particularly preferably used.
  • a carboxyl group-containing monomer (C) is reacted with one or more of the epoxy groups of a copolymer obtained by copolymerizing (A) an epoxy group-containing monomer and (B) an alicyclic hydrocarbon-containing monomer.
  • A an epoxy group-containing monomer
  • B an alicyclic hydrocarbon-containing monomer.
  • the acrylic copolymer a part of the epoxy group in the side chain of the copolymer is used for the reaction with the carboxyl group-containing monomer (C), and the side chain has a repeating ethylenically unsaturated bond. Comes with a unit.
  • the content of the repeating unit having an ethylenically unsaturated bond in the side chain is preferably 10 to 80 mol% in all repeating units of the copolymer, and further 20 It is preferably ⁇ 60 mol%. This is because when the content is within the above range, the reactivity with the polyfunctional monomer is improved, and in particular, the ITO forming resistance can be improved.
  • the content of the repeating unit containing an epoxy group in the side chain is 10 to 10 in all repeating units of the copolymer.
  • the content of the repeating unit containing an alicyclic hydrocarbon in the side chain is the total repeating unit in the copolymer. It is preferably 10 to 70 mol%, more preferably 20 to 50 mol%, from the viewpoints of adhesion of the cured film, surface hardness, and ITO resistance.
  • the content of the acrylic copolymer is preferably in the range of 0.5 to 30% by weight, more preferably 1.0% by weight, based on the solid content of the ink. It is preferably in the range of from 15% to 15% by weight. This is because if the amount is less than the above range, the solvent resistance of the ink cured film may be deteriorated. Moreover, it is because there exists a possibility that surface hardness may deteriorate when more than the said range.
  • the content of the acrylic copolymer is preferably 10 to 70% by weight, and more preferably 10 to 40% by weight in the solid content other than the pigment and pigment dispersant described later. It is preferable from the point of hardness.
  • the epoxy resin used together as the binder resin in the present invention is a resin different from the acrylic copolymer having the epoxy group in the side chain.
  • the epoxy resin used in the present invention preferably has two or more epoxy groups in one molecule from the viewpoint of film physical properties such as solvent resistance and adhesion of pixels formed by inkjet ink.
  • an epoxy group what is necessary is just a group which has an epoxide structure, for example, a glycidyl group, an oxyethylene group, an epoxycyclohexyl group etc. can be shown.
  • the epoxy resin preferably has a polystyrene-equivalent weight average molecular weight of 3,000 to 20,000, more preferably 4,000 to 15,000, from the viewpoint of increasing the crosslink density of the cured film and improving the ink jetting performance by lowering the viscosity. It is. If the molecular weight of the epoxy resin is less than 3000, physical properties such as strength and solvent resistance required for the cured layer as the details of the color filter are likely to be insufficient, and if the molecular weight is more than 20000, the viscosity increases. This is because the stability of the discharge amount and the straightness in the discharge direction when discharging from the discharge head by the ink jet method may be deteriorated, and the stability of long-term storage may be deteriorated.
  • the epoxy resin is not particularly limited as long as it contains two or more epoxy groups in one molecule.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S Type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, Trifunctional epoxy resin, tetraphenylolethane type epoxy resin, dicyclopentadienephenol type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A nucleated poly Lumpur type epoxy resins, polypropylene glycol type epoxy resins, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, glyoxal type epoxy resins, alicyclic epoxy resins, and the like heterocyclic epoxy resin.
  • bisphenol A type epoxy resin such as trade name Epicoat 828 (made by Japan Epoxy Resin Co., Ltd.), trade name Epicoat 807 (made by Japan Epoxy Resin Co., Ltd.), trade name YDF-175S (produced by Toto Kasei Co., Ltd.), etc.
  • Bisphenol F type epoxy resin brominated bisphenol A type epoxy resin such as trade name YDB-715 (manufactured by Toto Kasei Co., Ltd.), bisphenol S type epoxy resin such as trade name EPICLON EXA1514 (made by Dainippon Ink and Chemicals, Inc.), trade name Biphenyl such as hydroquinone type epoxy resin such as YDC-1312 (manufactured by Toto Kasei Co., Ltd.), naphthalene type epoxy resin such as brand name EPICLON EXA4032 (manufactured by Dainippon Ink & Chemicals, Inc.), brand name Epicoat YX4000H (made by Japan Epoxy Resin Co., Ltd.) Epoxy resin, bisphenol A type novolak epoxy resin such as trade name Epicoat 157S70 (made by Japan Epoxy Resin), phenol such as trade name Epicoat 154 (made by Japan Epoxy Resin), trade name YDPN-638 (made by Toto Kasei) Novol
  • Hydrogenated bisphenol A type epoxy resin such as trade name Epicoat 190P (Japan Epoxy Resin Co., Ltd.), glycidyl amine type epoxy resin such as trade name YH-434 (manufactured by Toto Kasei Co., Ltd.), trade name YDG- Glyoxal type epoxy resin such as 414 (manufactured by Toto Kasei Co., Ltd.), alicyclic epoxy resin such as brand name EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.), and alicyclic type such as brand name Epollide GT-401 (manufactured by Daicel Chemical Industries, Ltd.)
  • TGIC triglycidyl isocyanate
  • epoxy resins such as trade name EHPE3150 (manufactured by Daicel Chemical Industries) and bisphenol A type novolac epoxy resins such as Epicoat 157S70 (manufactured by Japan Epoxy Resin) are preferable.
  • An alicyclic epoxy resin such as trade name EHPE3150 (manufactured by Daicel Chemical Industries) is preferred.
  • These epoxy resins may be used alone or in combination of two or more.
  • the content of the epoxy resin is preferably 2.0% to 35% by weight, more preferably 5.0% to 30% by weight, based on the solid content of the ink. This is because if the epoxy resin content is too small, sufficient thermosetting may not be obtained. Moreover, when there is too much content of an epoxy resin, it will cause a curing defect.
  • the content ratio of the polyfunctional monomer, the acrylic copolymer, and the epoxy resin used in the present invention it is possible to achieve desired adhesion, surface hardness, and flatness.
  • the weight ratio of the epoxy resin to the sum of the polyfunctional monomer and the acrylic copolymer is 0.25.
  • the weight ratio of the acrylic copolymer to the polyfunctional monomer is 0.125 to 8, the adhesion, surface hardness From the viewpoints of flatness, solvent resistance and storage stability.
  • the weight ratio of the epoxy resin to the sum of the polyfunctional monomer and the acrylic copolymer is 0.3 to 1.
  • the weight ratio of the acrylic copolymer to the polyfunctional monomer is preferably 0.15 to 3.
  • the same pigment as that used in the first inkjet ink is used.
  • the content of the pigment is not particularly limited as long as it can produce a desired color when a colored layer of a color filter is formed, and is not particularly limited depending on the type of pigment used.
  • the content is set relatively high in order to achieve the second object of increasing the pigment concentration.
  • the content of the pigment is preferably in the range of 20% by weight to 70% by weight, and more preferably in the range of 30% by weight to 60% by weight, in the solid content of the ink.
  • ⁇ Pigment dispersant> In the second inkjet ink, the same pigment dispersant used in the first inkjet ink is used. ⁇ Solvent> In the second inkjet ink, the same solvent as that used in the first inkjet ink is used.
  • the same ethylenic unsaturated bond as that used in the first ink-jet ink can be used because the ethylenically unsaturated bond is cured by polymerization or crosslinking reaction.
  • the thermal-polymerization initiator in order to harden
  • a thermal polymerization initiator is not particularly limited, but is preferably an acid anhydride from the viewpoint of high storage stability and low calorific value.
  • acid anhydride examples include polyvalent carboxylic acid anhydrides, and specifically include phthalic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride.
  • Aliphatic polycarboxylic dianhydrides such as acids, hexahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hymic anhydride, nadic anhydride, and other aliphatic or alicyclic dicarboxylic dianhydrides; pyromellitic anhydride , Aromatic polycarboxylic acid anhydrides such as trimellitic anhydride and benzophenone tetracarboxylic anhydride; and ester group-containing acid anhydrides such as ethylene glycol bistrimellilate and glyceryl tristrimellate An epoxy resin curing agent made of carboxylic acid anhydride can also be suitably used. .
  • the blending amount of the thermal polymerization initiator used in the second inkjet ink is preferably in the range of 0.1 wt% to 5.0 wt% in the solid content of the ink, and more preferably 0.15 wt%. It is preferably in the range of -3.0% by weight.
  • a thermal-polymerization initiator hardening may become inadequate and there exists a possibility that a tough coating film cannot be formed.
  • storage stability may be inferior.
  • the second ink-jet ink can be produced in the same manner as the method for producing the first ink-jet ink.
  • the application of the second ink-jet ink is also the same as that of the first ink-jet ink, and is particularly preferably used for forming a colored layer that is required to have good color gamut reproducibility and high luminance.
  • Example A series is an experiment on the first inkjet ink.
  • Example B series is an experiment related to the second inkjet ink.
  • Example A series > Examples A1 to A9 and Comparative Examples A1 to A9 were performed according to the following procedure. 1.
  • Preparation of pigment dispersion A pigment, a pigment dispersant, and a solvent are mixed in the following ratio, 200 parts by weight of zirconia beads having a diameter of 0.5 mm are added, and dispersed for 3 hours using a paint shaker (manufactured by Asada Tekko). A pigment dispersion was prepared.
  • an acrylic copolymer was synthesized with 1-adamantyl methacrylate (ADAMA), 2-methyl-2-adamantyl methacrylate (MADAMA), and benzyl methacrylate (BzMA) in the proportions shown in Table 3 below.
  • the weight average molecular weight (Mw) of the obtained acrylic copolymers a-1 to a-5 was measured with a GPC measuring device (HLC-8220 GPC, manufactured by Tosoh Corporation) under the conditions of polystyrene standards.
  • the green ink the green pigment dispersion and the resin composition are sufficiently mixed, and the blending weight ratio (P / V) between the pigment (P) and the solid content (V) other than the pigment is 0.7, and BDGAC was added so that the solid content in the mixed solution was 20% by weight to prepare a thermosetting inkjet ink for a color filter.
  • the blue ink the blue pigment dispersion and the resin composition are sufficiently mixed, and the blending weight ratio (P / V) of the pigment (P) and the solid content (V) other than the pigment is 0.25, and BDGAC was added so that the solid content in the mixed solution was 20% by weight to prepare a thermosetting inkjet ink for a color filter.
  • b-1 a dipentaerythritol hexa and pentaacrylate mixture (product name: Aronix M403, pentaacrylate 50-60%, manufactured by Toa Gosei), b-2: ditrimethylolpropane tetraacrylate (product name) : Aronix M408, manufactured by Toagosei Co., Ltd.).
  • b-3 Isocyanuric acid EO modified di- and triacrylate (product name: Aronix M315, manufactured by Toagosei Co., Ltd.) were used.
  • thermosetting inkjet ink for each color filter was evaluated.
  • the chromaticity, NMP resistance, NaOH resistance, and surface hardness were evaluated by forming a cured resin film as follows.
  • the evaluation results are shown in Table 6.
  • Each inkjet ink was applied onto a 0.7 mm thick glass substrate (Corning Corp., 1737) by spin coating. Thereafter, prebaking was performed on a hot plate at 90 ° C. for 10 minutes. Then, in a clean oven, heating was performed at 200 ° C. for 30 minutes to perform post baking, and heating was further performed at 240 ° C. for 30 minutes to perform post baking, thereby forming a colored layer.
  • NMP resistance The substrate on which the colored layer was formed was immersed in an NMP solution for 30 minutes, and the color difference before and after immersion was measured.
  • ⁇ The color difference was 2 or less before and after the NMP immersion.
  • delta The color difference was 2 excess 5 or less before and behind NMP immersion.
  • X The color difference was more than 5 before and after NMP immersion.
  • the ink-jet ink according to the first invention has excellent storage stability, excellent curability, excellent chemical resistance after heat curing, high brightness, and good color gamut reproducibility. Was confirmed.
  • Examples B1 to B14 and Comparative Examples B1 to B6 were performed according to the following procedure. 1. Preparation of pigment dispersion A pigment, a pigment dispersant, and a solvent are mixed in the following ratio, 200 parts by weight of zirconia beads having a diameter of 0.5 mm are added, and dispersed for 3 hours using a paint shaker (manufactured by Asada Tekko). A pigment dispersion was prepared.
  • a GMA / DCPMA copolymer (main chain) solution was obtained by reacting at 100 ° C. for 3 hours.
  • EADAMA 2-adamantyl methacrylate
  • acrylic copolymers j to l for comparative examples as shown in Table 7, an aromatic ring-containing monomer (benzyl methacrylate; BzMA) and a methyl group-containing monomer (methyl methacrylate; MMA) were used. Polymerization was carried out in the same manner. In addition, the numerical value in Table 7 shows weight%.
  • Thermosetting Inkjet Ink for Color Filter As shown in Table 8 below, the acrylic copolymers (a to l), epoxy resins, polyfunctional monomers, thermal polymerization initiators and solvents (BDGAC) obtained above are shown.
  • the resin composition was prepared by blending with the above. Next, the pigment dispersion and the resin composition are sufficiently mixed, the blending weight ratio (P / V) of the pigment (P) and the solid content (V) other than the pigment is 0.6, and the mixture BDGAC was added so that the solid content was 20% by weight to prepare a thermosetting inkjet ink for color filters.
  • an alicyclic epoxy resin having two or more epoxy groups in one molecule (product name: EHPE-3150 (shown as EHPE in Table 8), manufactured by Daicel Chemical Industries, Ltd.), and A bisphenol A type novolak epoxy resin (product name: Epicoat 157S70 (shown as Epicoat in Table 8), manufactured by Japan Epoxy Resin Co., Ltd.) was used.
  • dipentaerythritol hexa and pentaacrylate mixture product name: Aronix M403, pentaacrylate 50-60%, manufactured by Toa Gosei
  • dipentaerythritol hexa and pentaacrylate mixture product name: Aronix M405, penta) Acrylate 10-20%, manufactured by Toagosei Co., Ltd.
  • a thermal polymerization initiator a mixture of glycerin bis (anhydrotrimellitate) monoacetate and an alicyclic dicarboxylic acid anhydride (manufactured by Shin Nippon Rika) was used.
  • thermosetting inkjet ink for color filters the resin cured film was formed as follows, and surface hardness, adhesiveness, and ITO formation resistance were evaluated.
  • a colored layer was formed by an inkjet method to evaluate flatness.
  • Table 8. The evaluation results are also shown in Table 8. (Formation of cured resin film)
  • Each inkjet ink was applied onto a 0.7 mm thick glass substrate (Corning Corp., 1737) by spin coating. Thereafter, prebaking was performed on a hot plate at 90 ° C. for 10 minutes. Then, in a clean oven, heating was performed at 200 ° C. for 30 minutes to perform post baking, and heating was further performed at 240 ° C. for 30 minutes to perform post baking, thereby forming a colored layer.
  • Adhesiveness The adhesiveness between the colored layer and the substrate was evaluated by the “adhesive cross-cut tape method” according to JIS K 5400-1990 8.5.3. In Table 8, the number of grids remaining without peeling off the color filter layer in 100 grids is shown.
  • a black matrix pattern having a line width of 20 ⁇ m and a film thickness of 2.2 ⁇ m is formed on a glass substrate (Corning Corp., 1737) having a thickness of 0.7 mm by a photolithography method using a curable resin composition for black matrix. Formed.
  • the inkjet ink was adhered to the pixel forming portion partitioned by the black matrix of the substrate by an inkjet method. Then, it dried under reduced pressure at 10 Torr for 120 seconds, and further pre-baked for 10 minutes on a 90 degreeC hotplate. Thereafter, the substrate was post-baked by heating at 200 ° C.
  • the substrate on which the cured resin film was formed as described above was immersed in isopropyl alcohol for 5 minutes, then dried with isopropyl alcohol vapor, washed, and then set at a substrate set temperature of 200 ° C.
  • An ITO (indium tin oxide) electrode was formed to a thickness of 120 nm under a vacuum of 6 ⁇ 10 ⁇ 3 Torr and evaluated according to the following criteria. Further, the surface roughness (Ra) of the deposited ITO film was measured by AFM. The AFM used was NanoScope IIIa manufactured by Biko Japan. [Evaluation criteria for ITO resistance] A: No abnormality such as wrinkles or cracks was observed on the ITO electrode. ⁇ : Several abnormalities such as wrinkles and cracks were observed on the ITO electrode. X: Abnormalities such as wrinkles and cracks were observed on the entire surface of the ITO electrode.
  • the ink-jet ink according to the second invention can realize a colored layer having excellent adhesion, surface hardness, and flatness after thermosetting.

Abstract

L'invention concerne une encre pour jet d'encre thermodurcissable destinée à des filtres de couleur qui présente une excellente stabilité au stockage et une excellente aptitude au durcissement, qui offre une excellente résistance chimique après le thermodurcissement, et qui atteint une capacité de reproduction de couleur satisfaisante sur toute la gamme de couleur, ou une encre pour jet d'encre thermodurcissable destinée à des filtres de couleur qui, après le thermodurcissement, présente une excellente adhérence, une excellente dureté de surface et une excellente planéité. L'encre pour jet d'encre thermodurcissable destinée à des filtres de couleur comprend un monomère polyfonctionnel, une résine de liant, un pigment, un dispersant de pigment et un solvant, et est caractérisée en ce que le monomère polyfonctionnel est un composé présentant quatre liaisons éthyléniquement insaturées ou plus par molécule, et en ce que la résine de liant est un copolymère acrylique obtenu par copolymérisation de monomères comprenant (A) un monomère époxydé présentant un groupe époxy et une liaison éthyléniquement insaturée et (B) un monomère contenant un hydrocarbure alicyclique ayant un groupe hydrocarbure alicyclique et une liaison éthyléniquement insaturée.
PCT/JP2010/059135 2009-05-29 2010-05-28 Encre pour jet d'encre thermodurcissable pour un filtre de couleur WO2010137702A1 (fr)

Priority Applications (2)

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JP2011516077A JPWO2010137702A1 (ja) 2009-05-29 2010-05-28 カラーフィルタ用熱硬化性インクジェットインク
CN2010800027517A CN102165339A (zh) 2009-05-29 2010-05-28 滤色片用热固性喷墨墨液

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JP2009130055 2009-05-29
JP2009-130055 2009-05-29
JP2009-134196 2009-06-03
JP2009134196 2009-06-03

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CN (1) CN102165339A (fr)
TW (1) TW201111454A (fr)
WO (1) WO2010137702A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017190393A (ja) * 2016-04-13 2017-10-19 Ｄｉｃグラフィックス株式会社 印刷インキ用ワニス、印刷インキ、及び印刷物

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105683154B (zh) * 2013-10-25 2018-03-16 三菱瓦斯化学株式会社 氰酸酯化合物、包含该化合物的固化性树脂组合物及其固化物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004191680A (ja) * 2002-12-11 2004-07-08 Hitachi Chem Co Ltd 感光性樹脂組成物、感光性エレメント及び積層基材
JP2007328062A (ja) * 2006-06-06 2007-12-20 Dainippon Printing Co Ltd カラーフィルター用インクジェットインク及びその製造方法、カラーフィルターの製造方法、並びに液晶表示装置の製造方法
JP2008191198A (ja) * 2007-02-01 2008-08-21 The Inctec Inc 感光性着色組成物
JP2009036954A (ja) * 2007-08-01 2009-02-19 Sumitomo Chemical Co Ltd 感光性樹脂組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004191680A (ja) * 2002-12-11 2004-07-08 Hitachi Chem Co Ltd 感光性樹脂組成物、感光性エレメント及び積層基材
JP2007328062A (ja) * 2006-06-06 2007-12-20 Dainippon Printing Co Ltd カラーフィルター用インクジェットインク及びその製造方法、カラーフィルターの製造方法、並びに液晶表示装置の製造方法
JP2008191198A (ja) * 2007-02-01 2008-08-21 The Inctec Inc 感光性着色組成物
JP2009036954A (ja) * 2007-08-01 2009-02-19 Sumitomo Chemical Co Ltd 感光性樹脂組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017190393A (ja) * 2016-04-13 2017-10-19 Ｄｉｃグラフィックス株式会社 印刷インキ用ワニス、印刷インキ、及び印刷物

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TW201111454A (en) 2011-04-01
KR20120026021A (ko) 2012-03-16
JPWO2010137702A1 (ja) 2012-11-15

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