JP2007187884A - Manufacturing method of color filter, color filter and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color filter which is excellent in productivity and also excellent in display quality, to provide a manufacturing method of the color filter, and also to provide a display device provided with the color filter which is excellent in productivity and also excellent in display quality without irregularity. <P>SOLUTION: The manufacturing method of color filter has a heat treatment process after forming pixels on a substrate by using an active-energy ray curable inkjet ink which contains pigments, a mono-functional monomer having one ethylenic unsaturated double bond and a multi-functional monomer having at least two ethylenic unsaturated double bonds, and after irradiating active-energy rays. The color filter manufactured by the manufacturing method and the display device provided with the color filter are also provided in the invention. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a color filter that is manufactured at high speed and at low cost by an inkjet method, and in particular, a pixel is formed at a corresponding position on a color filter substrate using an active energy ray-curable inkjet ink, and then the active energy ray is used. The present invention relates to a color filter manufacturing method for curing the pixels.

  The full-color color filter has a configuration in which a large number of pixels composed of the three primary colors RGB are repeatedly arranged on a transparent substrate. Currently, color filters are produced by repeating a process of applying a pigment-dispersed photoresist solution on a transparent substrate, drying, exposing, developing, and curing. Therefore, productivity is low and the demand for cost reduction is high.

  In accordance with the above requirements, the manufacturing method and manufacturing equipment are reviewed. In particular, a method for manufacturing a color filter by an ink jet method, which can easily reduce the size of the manufacturing apparatus and has high productivity, has attracted attention. In addition, due to recent advances in head and ink technology, pigments have begun to be used in colorants used in ink-jet inks. As a result, light resistance and fastness have been improved, and the expected color filter The possibility of applying the inkjet method to the application has begun to appear.

  For example, by specifying the ratio of pigment to resin in the ink, the ratio of colored pigment to extender pigment in the pigment, and the solid content in the ink, the color material layer thickness of the color filter can be controlled to an arbitrary thickness or the surface It is described that smoothness and adhesion with a substrate can be improved (for example, Patent Document 1). Further, a method for obtaining ink ejection stability by using a specific pigment dispersant in a pigment-dispersed water-based ink is disclosed (for example, see Patent Document 2). However, in any case, it is still difficult to completely prevent coalescence and settling of pigments, and the light transmittance inside the pixel or for each pixel cannot be made constant.

On the other hand, for the purpose of obtaining improved adhesion and heat resistance between the cured ink layer and the substrate, utilizing the fact that the carboxylic acid compound, which is a pigment dispersant, reacts with the monomer or oligomer by light or heat. Ink that uses a monomer or oligomer that cures even under light as a binder is disclosed (for example, Patent Document 3).
However, since the ink contains about 70% by mass of water as a solvent and the amount of monomers and oligomers as crosslinkable compounds is 1% by mass or less of the entire ink, instantaneous curing by light is not possible. Unexpectedly, new problems have arisen regarding the dispersion stability of pigments.

Moreover, although the manufacturing method of the color filter using the active energy ray hardening-type inkjet ink whose total amount of a monofunctional monomer and a polyfunctional monomer is 50-95 mass% in the total solid content mass of ink is described (for example, It has been found that when an LCD is produced using a color filter manufactured by this method, unevenness occurs and the display quality is remarkably inferior.
JP-A-9-132740 Japanese Patent Laid-Open No. 11-84123 JP-A-11-124528 JP 2002-372615 A

  An object of the present invention is to provide a method for producing a color filter having excellent productivity and display quality. Another object of the present invention is to provide a color filter produced by a method for producing a color filter having excellent productivity and excellent display quality without unevenness, and a display device including the color filter.

In view of the above circumstances, the present inventors conducted extensive research, and after forming pixels using an active energy ray-curable inkjet ink for producing a color filter by an inkjet method and irradiating active energy rays, It has been found that performing the heat treatment process can solve the above-mentioned problems, and the present invention has been completed.
That is, it is possible to provide a method for producing a color filter that is excellent in productivity and excellent in display quality without unevenness.
That is, the present invention is achieved by the following means.

<1> An active energy ray-curable inkjet ink containing a pigment, a monofunctional monomer having one ethylenically unsaturated double bond and a polyfunctional monomer having two or more ethylenically unsaturated double bonds on a substrate is used. A color filter manufacturing method comprising: forming a pixel, irradiating active energy rays, and then performing a heat treatment step.
<2> The method for producing a color filter according to claim 1, wherein the heat treatment step is performed at a temperature of 150C to 300C.

<3> The above <1> or <2>, wherein the total content of the monomers contained in the active energy ray-curable inkjet ink is 50 to 95% by mass based on the total mass of the ink. The manufacturing method of the color filter of description.
<4> The method for producing a color filter according to any one of <1> to <3>, wherein the active energy ray-curable inkjet ink contains a pigment dispersant.

<5> The method for producing a color filter according to any one of <1> to <4>, wherein the active energy ray-curable inkjet ink contains an organic solvent.
<6> The method for producing a color filter according to any one of <1> to <5>, wherein the active energy ray is ultraviolet light.

<7> The active energy ray-curable inkjet ink contains a photopolymerization initiator that initiates curing of a monofunctional monomer and a polyfunctional monomer by irradiation with the active energy ray, and the content of the photopolymerization initiator is The method for producing a color filter according to any one of <1> to <6>, wherein the content is 8% by mass or less based on the total mass of the ink.
<8> The above <1> to <7, wherein a black matrix is formed on a substrate in advance, and the active energy ray-curable inkjet ink is supplied to an opening of the black matrix to form the pixel. The manufacturing method of the color filter of any one of>.

<9> A color filter produced by the method for producing a color filter according to any one of <1> to <8>.
<10> A display device comprising the color filter according to <9>.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the color filter excellent in productivity and excellent in display quality can be provided.
In addition, according to the present invention, it is possible to provide a color filter produced by a method for producing a color filter that is excellent in productivity and excellent in display quality without unevenness. In particular, it is possible to provide a color filter which is less colored due to decomposition of a photopolymerization initiator or resin due to heat treatment and has excellent color purity, and a method for producing the same.
In addition, according to the present invention, it is possible to provide a display device including the color filter that is excellent in productivity and excellent in display quality without unevenness.

The method for producing a color filter of the present invention comprises at least a pigment, a monofunctional monomer having one ethylenically unsaturated double bond, and a polyfunctional monomer having two or more ethylenically unsaturated double bonds (active energy ray curable). Monomer) and an inkjet ink for curing active energy rays (hereinafter, also simply referred to as “ink”) onto a color filter substrate by an inkjet method, and then irradiating the ink with active energy rays. A heat treatment step is performed after curing.
With the configuration of the present invention, it is possible to provide a color filter manufacturing method capable of manufacturing a color filter excellent in display quality with high productivity.
Hereinafter, the components of the ink used in the method for producing a color filter of the present invention, the method for producing the color filter, and the display device will be described in detail.

(Pigment)
Since the pigment used in the ink of the present invention is required to have sufficient transmission density, light resistance, adhesion to a substrate, and other various resistances, various organic pigments are suitable. Specifically, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60, C.I. I. Pigment Violet 19, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 29, C.I. I. Pigment Violet 30, C.I. I. Pigment Violet 37, C.I. I. Pigment Violet 40, C.I. I. Pigment Violet 50, C.I. I. Pigment Red 7, C.I. I. Pigment Red 9, C.I. I. Pigment Red 14, C.I. I. Pigment Red 41, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 48: 2, C.I. I. Pigment Red 48: 3, C.I. I. Pigment Red 48: 4, C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 146, C.I. I. Pigment Red 149, C.I. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 180, C.I. I. Pigment Red 184, C.I. I. Pigment Red 185, C.I. I. Pigment Red 187, C.I. I. Pigment Red 192, C.I. I. Pigment Red 200, C.I. I. Pigment Red 202, C.I. I. Pigment Red208, C.I. I. Pigment Red209, C.I. I. Pigment Red 210, C.I. I. Pigment Red 216, C.I. I. PigmentRed 220, C.I. I. Pigment Red 221, C.I. I. Pigment Red 223, C.I. I. Pigment Red 226, C.I. I. Pigment Red 227, C.I. I. Pigment Red 240, C.I. I. Pigment Red 246, C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264, C.I. I. Pigment Red 272, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36 can be used. In addition, C.I. I. Pigment Red 254 and C.I. I. Pigment Red 177 mixture, C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 139 or C.I. I. A mixture of Pigment Yellow 13 can also be used. Carbon black, C.I. I. Pigment black 1, C.I. I. Pigment Black 7, titanium carbon, iron oxide, titanium oxide, graphite and the like can also be used.
The content of the pigment in the present invention is not particularly limited, but from the viewpoint of obtaining a desired hue and density, it is preferably 5 to 70% by mass, more preferably 10 to 60% by mass with respect to the total mass of the ink. 15 to 50% by mass is preferable.

In the present invention, the combination of the above-described pigments preferably used in combination is C.I. I. In pigment red 254, C.I. I. Pigment red 177, C.I. I. Pigment red 224, C.I. I. Pigment yellow 139 or C.I. I. A combination with Pigment Violet 23; I. In Pigment Green 36, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 138 or C.I. I. A combination with CI Pigment Yellow 180, and C.I. I. In Pigment Blue 15: 6, C.I. I. Pigment violet 23 or C.I. I. A combination with Pigment Blue 60 is mentioned.
C. in the pigment when used together in this way. I. Pigment red 254, C.I. I. Pigment green 36, C.I. I. The content of Pigment Blue 15: 6 is C.I. I. The pigment red 254 is preferably 80% by mass or more, particularly preferably 90% by mass or more. C. I. The pigment green 36 is preferably 50% by mass or more, particularly preferably 60% by mass or more. C. I. Pigment Blue 15: 6 is preferably 80% by mass or more, and particularly preferably 90% by mass or more.

  The pigment used in the present invention preferably has a number average particle size of 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm. When the number average particle diameter of the pigment is less than 0.001 μm, the particle surface energy is increased and the particles are easily aggregated, so that it is difficult to disperse the pigment and it is difficult to keep the dispersion state stable. On the other hand, if the number average particle diameter of the pigment exceeds 0.1 μm, the polarization is canceled by the pigment, and the contrast is lowered. The “particle diameter” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle diameter” is the above-mentioned particle diameter for a number of particles, The average value of 100 is said.

  The pigment is desirably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the pigment and a pigment dispersant described later to a monomer described later. The disperser used for dispersing the pigment is not particularly limited. For example, the kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, first edition, Asakura Shoten, 2000, 438, Known dispersing machines such as a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, fine grinding may be performed using frictional force by mechanical grinding described in Item 310 of the document.

(Pigment dispersant)
In order to obtain pigment dispersion stability, it is preferable to add a pigment dispersant to the ink of the present invention.
The amount used is preferably 0.1 to 10% by weight, more preferably 0.1 to 9% by weight, and more preferably 0.1 to 8% by weight based on the total weight of the ink. Is particularly preferred.
Examples of the pigment dispersant include a hydroxyl group-containing carboxylic acid ester, a salt of a long chain polyaminoamide and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a salt of a long chain polyaminoamide and a polar acid ester, a high molecular weight unsaturated ester, Polymer copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester, polyoxyethylene nonyl Phenyl ether, stearylamine acetate, pigment derivatives and the like can be used.

  Specific examples of the dispersant include “Anti-Terra-U (polyaminoamide phosphate)”, “Anti-Terraa-203 / 204 (high molecular weight polycarboxylate)” manufactured by BYK Chemie, “Disperbyk-101 ( Polyaminoamide phosphate and acid ester), 107 (hydroxyl group-containing carboxylic acid ester), 110 (copolymerization product containing acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (respectively Polymer copolymer) ”,“ 400 ”,“ Bykumen ”(high molecular weight unsaturated ester),“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ P104S, 240S (high molecular weight unsaturated poly) Carboxylic acid and silicon system "," Lactimon (long chain amine and unsaturated polycarbonate) Bonn acid and silicon) "and the like.

  Furthermore, “Fuka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766” manufactured by Efka CHEMICALS, “Efka Polymer 100 (modified polyacrylate), 150 (aliphatic) System modified polymer), 400, 401, 402, 403, 450, 451, 452, 453 (modified polyacrylate), 745 (copper phthalocyanine system) ", Kyoeisha Chemicals" Floren TG-710 (urethane oligomer), KS860, 873SN " , 874 (polymer dispersant), # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyether ester type) ”and the like.

  Furthermore, “Demol RN, N (Naphthalenesulfonic acid formalin condensate sodium salt), MS, C, SN-B (aromatic sulfonic acid formalin condensate sodium salt), EP”, “Homogenol L-18 (polycarboxylic acid) Acid type polymer) "," Emulgen 920, 930, 931, 935, 950, 985 (polyoxyethylene nonylphenyl ether) "," Acetamine 24 (coconut acetate), 86 (stearylamine acetate) "," Geneca " Solspers 5000 (phthalocyanine ammonium salt type), 17000 (aliphatic amine type), 13940 (polyesteramine type), 20000, 22000, 24000, 32000, Nikko Chemical's "Nikkor T106 (polyoxyethylene monostearate), Hex" gline4-0 (hexa glyceryl Rute Huwei rate) "and the like.

(Monofunctional monomer and polyfunctional monomer)
Monofunctional monomers having one ethylenically unsaturated double bond, which is a curing component of the active energy ray-curable ink used in the present invention, include butanediol monoacrylate, N, N-dimethylaminoethyl acrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, 2-methoxyethyl acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, acryloylmorpholine, N-vinylformamide, cyclohexyl acrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, Glycidyl acrylate, isobornyl acrylate, isodecyl acrylate, phenoxy methacrylate, stearyl acrylate, tetrahydrofurfuryl acrylic 2-phenoxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, isobornyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, Examples include tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, benzyl acrylate, ethoxyethoxyethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydipropylene glycol acrylate, methylphenoxyethyl acrylate, and dipropylene glycol acrylate. It is not a thing.
These compounds may be used alone or in combination of two or more as required.

Bifunctional or higher polyfunctional monomers and oligomers that are another curing component of the ink used in the present invention include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, ethoxylated 1,6-hexanediol diacrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) Acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol diacrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol diacrylate, tetraethylene Recall diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, dimethylol-tricyclodecane diacrylate, hydroxypivalate neopentyl glycol diacrylate, 1,3-butylene glycol di (meth) acrylate , Ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, dimethylol dicyclopentane diacrylate, trimethylol propane triacrylate, ethoxylated trimethylol propane tri Acrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylolpropane triacrylate, Tramethylol methane triacrylate, pentaerythritol tetraacrylate, caprolactone-modified trimethylolpropane triacrylate, ethoxylated isocyanuric acid triacrylate, tri (2-hydroxyethyl isocyanurate) triacrylate, propoxylate glyceryl triacrylate, tetramethylol methane tetraacrylate , Pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, neopentyl glycol oligoacrylate, 1,4-butanediol oligoacrylate, 1,6-hexanediol oligoacrylate, tri Methylolpropane oligoacrylate Rate, pentaerythritol oligoacrylate, urethane acrylate, epoxy acrylate, polyester acrylate, and the like are not limited thereto.
These compounds such as monomers and oligomers may be used alone or in combination of two or more as required.

When the component having curability by irradiation with these active energy rays is 50% by mass or less of the total amount of ink, the curability tends to be insufficient with the intensity of general active energy rays. You may need to take action.
From the above, the amount of the component having curability (the total content of the two or more monomers and oligomers) is preferably 50 to 95% by mass, more preferably 60 to 95% by mass, particularly in the total mass of the ink. Preferably it has 60 to 90 mass%. If it is less than 50% by mass, the ink may not be cured sufficiently, and if it exceeds 95% by mass, other materials such as a pigment, a pigment dispersant, and if necessary, a photopolymerization initiator are required. Therefore, it is virtually impossible.

  In the monomer and oligomer which are the active energy ray-curable components of the ink used in the present invention, radicals are generated by the active energy rays and a polymerization reaction occurs. In order to generate radicals, for example, (1) UV irradiation to a photopolymerization initiator, (2) monomer chain and oligomer chain cleavage by electron beam irradiation, etc., electron beam irradiation is generally high in energy, Coloring due to decomposition of resin components by irradiation is inevitable. Moreover, since electron beam irradiation becomes large as an apparatus and is not practically used in many cases, it is preferable to irradiate ink containing a photopolymerization initiator with ultraviolet rays to cause a polymerization reaction.

As described above, the present invention preferably contains a photopolymerization initiator in the ink of the present invention.
Specific examples of these photopolymerization initiators include the following.

As benzophenone series, benzophenone, benylbenzoic acid, 4-phenylbenzophenone, 4,4-diethylaminobenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide and the like are thioxanthone series. Thioxanthone, 2-chlorooxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone and the like are 2-methyl-1- (4-methylthio) phenyl-2-morpholines as acetophenone series. Linopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxy Cyclohex Ruphenyl ketone, 2,2-dimethyl-2-hydroxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 4-phenoxydichloroacetophenone, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, etc. Methyl ether, benzoin isobutyl ether, benzyl methyl ketal, etc. are acylphosphine oxides, such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) acylphosphine oxide, etc. Can be mentioned.
These photopolymerization initiators may be used singly or in combination, as long as the effects of the present invention are not impaired.

In the present invention, the content of the photopolymerization initiator that can be used is preferably 8% by mass or less, more preferably 1 to 8% by mass, and further preferably 2 to 7% by mass based on the total mass of the ink.
By making content of a photoinitiator into the range of the said 8 mass% or less, it is preferable from a viewpoint which can prevent the color purity fall of the color filter resulting from coloring derived from a photoinitiator beforehand.

In the present invention, a surfactant or an organic solvent (water-soluble or non-aqueous solvent) can be contained as an ink component in order to improve the wettability of the ink to the base (for example, a substrate such as a glass substrate). . A precaution when selecting a surfactant or organic solvent is that compatibility with other ink components is required.
There are various types of surfactants such as anionic, cationic, amphoteric and nonionic, and a suitable one may be selected.
As the organic solvent, water-soluble organic solvents such as alcohols such as methanol, ethanol and isopropyl alcohol, and ketones such as acetone and MEK are preferable in terms of the effect of reducing the surface tension. There is no need to limit the solvent as long as it is effective.

  In addition, the ink used in the present invention is not activated by ultraviolet rays as other additives by itself, but is used as a photoinitiator (or sensitizer) as an agent that promotes the initiation reaction in combination with a photopolymerization initiator. It can be used in the name of an agent). For example, triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone, ethyl 2,2-dimethylaminobenzoate, ethyl 4,4-dimethylaminobenzoate (n-butoxy), and the like aliphatic and aromatic Such as amines.

  You may add the thermal-polymerization inhibitor which is another additive to the ink used for this invention. The effect of this additive is to make the ink stability over time and the stability on the substrate more reliable. Examples of those that can be added include hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, 2,6-t-butyl-p-cresol, 2,3-dimethyl-6-t-butylphenol, and anthraquinone. A desired effect can be obtained by adding 0.01 to 5 mass% of these in the total amount of ink.

  Furthermore, for the purpose of improving the adhesion of the ink used in the present invention to the color filter substrate, an active energy ray-curable monomer, a prepolymer, and other resins soluble in the liquid to be added can be added. Specific examples of resins that can be added are polyvinyl chloride, poly (meth) acrylic acid ester, epoxy, polyurethane, cellulose derivatives, vinyl chloride-vinyl acetate copolymer, polyamide, polyvinyl acetal, diallyl phthalate, butadiene-acrylonitrile copolymer. , Acrylic, styrene-acrylic, styrene-maleic acid, rosin, rosin ester, ethylene-vinyl acetate, petroleum resin, coumarone indene, terpene phenol, phenol, melamine, urea, vinyl chloride, xylene, alkyd, aliphatic hydrocarbon , Butyral, silicon, maleic acid, fumaric acid and the like.

A dilution solvent can be added to the ink of the present invention as long as the gist of the present invention is not impaired. That is, as a physical property of the ink for ink for curing active energy rays used in the present invention, the viscosity of the ink is preferably 50 mPa · s or less at 25 ° C., and the monofunctional and bifunctional or higher monomers and oligomers are appropriately selected. The viscosity can be obtained by selecting a suitable combination.
On the other hand, when a pigment, if necessary, a pigment dispersant, a photopolymerization initiator, or the like is used as an ink component, when the viscosity of the ink may exceed 50 mPa · s, at most 15% by mass of the ink component The viscosity can be adjusted by using a dilution solvent in an amount not exceeding. In this case, the dilution solvent used is preferably compatible with the ink component.

  Examples of solvents that can be used as dilution solvents include water (ion exchange water), alcohols such as methanol and ethanol, ketones such as acetone and MEK, amides such as dimethylformamide and dimethylacetamide, and other glycols and hydrocarbon solvents ( Aliphatic hydrocarbon solvents).

The ink used in the present invention is the above-mentioned components, two or more essential monomers or oligomers, pigments, and, if necessary, pigment dispersants, photopolymerization initiators, photopolymerization aids, thermal polymerization prohibited An agent, a resin, and the like are put into a normal disperser and dispersed until a desired average particle size and particle size distribution are obtained.
These materials may be mixed and dispersed all at once, or may be mixed and dispersed separately in consideration of the characteristics and economics of each material. At that time, when the ink viscosity is too high and dilution is necessary, it is possible to obtain a desired ink by adding water for dilution, a water-soluble solvent or a hydrocarbon solvent to the ink stock solution and stirring uniformly.

  As the disperser, a sand mill, a bead mill, an agitator mill, a dyno mill, a covol mill, and the like are suitable. If each of the dispersers has a viscosity range suitable for pigment dispersion, there is a method of obtaining an ink by adjusting the ratio of the monomer or oligomer to the pigment. After obtaining the dispersion liquid, it is desirable to filter by a filter or a centrifugal method for the purpose of removing coarse particles and foreign matters.

The method for producing a color filter of the present invention is characterized in that a pixel is formed on a substrate using the active energy ray-curable inkjet ink, and after the irradiation with active energy rays, a heat treatment step is included.
In the present invention, by performing the heat treatment in the heat treatment step, the curing reaction of the pixels of the obtained color filter can be ensured. Moreover, when the said ink contains a photoinitiator, the addition amount of the photoinitiator which affects the color purity of a color filter can be reduced by providing the said heat processing process.

The temperature of the heat treatment is preferably in the range of 150 ° C. to 300 ° C., more preferably 170 ° C. to 280 ° C., and still more preferably 200 ° C. to 250 ° C., from the viewpoint of display unevenness of the color filter and color purity. If it is less than 150 ° C., a sufficient effect of improving display unevenness may not be obtained, and if it is 300 ° C. or more, the resin may be colored and the color purity may be deteriorated. The heat treatment time is not particularly limited but is preferably 10 minutes to 150 minutes. If it is less than 10 minutes, the effect may not be sufficiently exhibited, and if it is 150 minutes or more, the resin may be colored and the color purity may be deteriorated.
Among these, a preferable combination of temperature and time is 200 to 250 ° C. and 20 to 130 minutes.

  As the heat treatment means, it is preferable to heat a color filter in which a black matrix is formed on a substrate and a pixel at the opening thereof in an electric furnace, a dryer, or to irradiate an infrared lamp.

The pixel is preferably formed by supplying the ink to an opening of a black matrix previously formed on a substrate.
As a method for supplying the ink to the opening, an inkjet method is preferable in terms of cost because the manufacturing apparatus can be easily downsized and no development process is required.

The shape of the pixel formed in this manner is not particularly limited as long as the effect of the present invention is not impaired, and a general rectangular shape or the like can be adopted.
As the dose of the active energy ray is not particularly limited, as long as the atmosphere 10~15000mJ / cm ^2, preferably 50~1000mJ / cm ^2.

In the method for producing a color filter of the present invention, elements other than those described above can be appropriately used as elements of known production methods, and are not particularly limited.
In addition, the color filter of the present invention is a color filter in which pixels are formed by an inkjet method using the method for producing a color filter of the present invention, and is a three-color color filter that is the RGB three-color ink. It is preferable.

Hereinafter, the black matrix in the present invention will be described in detail.
(Deep color composition)
The black matrix is formed from a dark color composition containing a colorant (dark color body). Here, the dark color composition is a composition having a high optical density, and its value is preferably 2.0 to 10.0 when the black matrix is formed. The optical density of the dark color composition is more preferably 2.5 to 6.0, and particularly preferably 3.0 to 5.0. Further, since this dark color composition is preferably cured by a photoinitiating system as described later, the optical density with respect to the exposure wavelength (generally the ultraviolet region) is also important. That is, the value is 2.0 to 10.0, preferably 2.5 to 6.0, and most preferably 3.0 to 5.0. If it is less than 2.0, the shape of the black matrix may not be as desired, and if it exceeds 10.0, the polymerization cannot be started and it is difficult to produce the black matrix itself. As long as it has such properties, the dark body in the composition may be an organic substance (various dyes such as dyes and pigments), or each form of carbon. May be. Such a dark body is not particularly limited, but a black body is most often used.

  Specific examples of the dark color used in the present invention include pigments and dyes described in JP-A-2005-17716 [0038] to [0054], and JP-A-2004-361447 [0068] to [0072]. And the colorants described in JP-A-2005-17521 [0080] to [0088] can be suitably used.

  In addition to the above colorants, in addition to the light-shielding agent such as carbon black, titanium oxide, iron oxide, and other metal oxide powders, metal sulfide powders, and metal powders, red, Mixtures of pigments such as blue and green can be used. Known colorants (dyes and pigments) can be used. Among the known colorants, when a pigment is used, it is preferably dispersed uniformly in the dark color composition.

From the viewpoint of sufficiently shortening the development time, the ratio of the dark color body in the solid content of the dark color composition is preferably 30 to 70% by mass, more preferably 40 to 60% by mass, More preferably, it is 50-55 mass%.
Further examples of the dark black colored body include carbon black, titanium carbon, iron oxide, titanium oxide, and graphite. Among these, carbon black is preferable.

The pigment is desirably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the pigment and the pigment dispersant in an organic solvent (or vehicle) described later. The vehicle refers to a portion of a medium in which the pigment is dispersed when the paint is in a liquid state. The portion is a liquid that binds to the pigment and hardens the coating film (binder), and a component that dissolves and dilutes the portion. (Organic solvent).
The disperser used for dispersing the pigment is not particularly limited. For example, the kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, first edition, Asakura Shoten, 2000, 438, Known dispersing machines such as a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, fine grinding may be performed using frictional force by mechanical grinding described in Item 310 of the document.
The dark color body (pigment) used in the present invention preferably has a number average particle diameter of 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm, from the viewpoint of dispersion stability. The “particle diameter” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle diameter” is the above-mentioned particle diameter for a number of particles, This 100 average value is said.

  The dark color composition preferably contains at least a polymerization initiator and a polyfunctional monomer in addition to the dark color body. Further, if necessary, a known additive such as a plasticizer, a filler, a stabilizer, a polymerization inhibitor, a surfactant, a solvent, an adhesion promoter, and the like can be further contained. Furthermore, the dark color composition is preferably softened or tacky at a temperature of at least 150 ° C., and is preferably thermoplastic. From such a viewpoint, it can be modified by adding a compatible plasticizer.

As a method for curing the dark color composition, a thermal initiation system using a thermal initiator and a photoinitiation system using a photoinitiator are common, but in the present invention, the cured black matrix has a shape as described later. It is important to use a photoinitiating system. The photopolymerization initiator used here generates an active species that initiates polymerization of a polyfunctional monomer, which will be described later, upon irradiation (also referred to as exposure) of radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray. It is a compound to be obtained and can be appropriately selected from known photopolymerization initiators or photopolymerization initiator systems.
For example, trihalomethyl group-containing compounds, acridine compounds, acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds Compound, etc. can be mentioned.

  Specifically, a trihalomethyloxazole derivative or s-triazine derivative substituted with a trihalomethyl group described in JP-A No. 2001-117230, a trihalomethyl-s-triazine compound described in US Pat. No. 4,239,850, Trihalomethyl group-containing compounds such as the trihalomethyloxadiazole compounds described in US Pat. No. 4,221,976;

9-phenylacridine, 9-pyridylacridine, 9-pyrazinylacridine, 1,2-bis (9-acridinyl) ethane, 1,3-bis (9-acridinyl) propane, 1,4-bis (9-acridinyl) ) Butane, 1,5-bis (9-acridinyl) pentane, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane 1,9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, 1,12-bis (9-acridinyl) dodecane, etc. Acridine compounds such as bis (9-acridinyl) alkane;

6- (p-methoxyphenyl) -2,4-bis (trichloromethyl) -s-triazine, 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis ( Triazine compounds such as trichloromethyl) -s-triazine; 9,10-dimethylbenzphenazine, Michler's ketone, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, benzyldimethyl ketal, thioxanthone / amine, 2,2 ′ -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

Among the above, at least one selected from a trihalomethyl group-containing compound, an acridine compound, an acetophenone compound, a biimidazole compound, and a triazine compound is preferable, and particularly selected from a trihalomethyl group-containing compound and an acridine compound. It is preferable to contain at least one kind. Trihalomethyl group-containing compounds and acridine compounds are also useful in that they are versatile and inexpensive.
Particularly preferred as the trihalomethyl group-containing compound is 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, and as the acridine compound, 9-phenylacridine is preferred. Further, 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -5 Trihalomethyl group-containing compounds such as trichloromethyl-1,3,4-oxadiazole, and Michler's ketone, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl- 1,2'-biimidazole.

  The said photoinitiator may be used independently and may use 2 or more types together. The total amount of the photopolymerization initiator in the dark color composition is preferably from 0.1 to 20% by weight, particularly preferably from 0.5 to 10% by weight, based on the total solid content (mass) of the dark color composition. When the total amount is less than 0.1% by mass, the photocuring efficiency of the composition is low and exposure may take a long time. When it exceeds 20% by mass, an image pattern formed during development is formed. May be lost or the pattern surface may be rough.

  The photopolymerization initiator may be configured using a hydrogen donor in combination. The hydrogen donor is preferably a mercaptan compound or an amine compound as defined below from the viewpoint that sensitivity can be further improved. The “hydrogen donor” herein refers to a compound that can donate a hydrogen atom to a radical generated from the photopolymerization initiator by exposure.

  The mercaptan-based compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “ A mercaptan-based hydrogen donor). The amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, and more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “the amine compound”). , Referred to as “amine-based hydrogen donor”). These hydrogen donors may have a mercapto group and an amino group at the same time.

  Specific examples of the mercaptan hydrogen donor include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-2. , 5-dimethylaminopyridine, and the like. Of these, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

  Specific examples of the amine-based hydrogen donor include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl. Examples include -4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like. Of these, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone are preferable, and 4,4'-bis (diethylamino) benzophenone is particularly preferable.

  The hydrogen donor can be used alone or in admixture of two or more, and the formed image is difficult to drop off from the permanent support during development, and can be improved in strength and sensitivity. It is preferable to use a combination of one or more mercaptan hydrogen donors and one or more amine hydrogen donors.

  Specific examples of the combination of the mercaptan hydrogen donor and the amine hydrogen donor include 2-mercaptobenzothiazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4′-. Examples thereof include bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone. More preferred combinations are 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone and 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzobenzone. Thiazole / 4,4′-bis (diethylamino) benzophenone.

  When the mercaptan hydrogen donor and the amine hydrogen donor are combined, the mass ratio (M: A) of the mercaptan hydrogen donor (M) to the amine hydrogen donor (A) is usually 1: 1-1: 4 is preferable, and 1: 1-1: 3 is more preferable. The total amount of the hydrogen donor in the dark color composition is preferably from 0.1 to 20% by weight, particularly preferably from 0.5 to 10% by weight, based on the total solid content (mass) of the dark color composition.

  As the polyfunctional monomer of the dark color composition, the following compounds can be used alone or in combination with other monomers. Specifically, t-butyl (meth) acrylate, ethylene glycol di (meth) acrylate, 2-hydroxypropyl (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 2- Ethyl-2-butyl-propanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, polyoxy Ethylated trimethylolpropane tri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, 1,4-diisopropenylbenzene, 1,4-dihydroxy Nzenji (meth) acrylate, decamethylene glycol di (meth) acrylate, styrene, diallyl fumarate, triallyl trimellitate, lauryl (meth) acrylate, (meth) acrylamide, xylylenebis (meth) acrylamide, and the like.

Reaction of compounds having hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and polyethylene glycol mono (meth) acrylate with diisocyanates such as hexamethylene diisocyanate, toluene diisocyanate and xylene diisocyanate Things can also be used.
Of these, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and tris (2-acryloyloxyethyl) isocyanurate are particularly preferable.

  As content in the dark composition of a polyfunctional monomer, 5-80 mass% is preferable with respect to the total solid (mass) of a dark color composition, and 10-70 mass% is especially preferable. When the content is less than 5% by mass, the resistance to an alkaline developer at the exposed portion of the composition may be inferior, and when it exceeds 80% by mass, the tackiness of a dark color composition increases. Therefore, the handleability may be inferior.

(Black matrix)
The black matrix of each pixel is formed from the dark color composition. The black matrix separates two or more pixel groups and is generally black in many cases, but is not limited to black. The dark colored product is preferably an organic material (various dyes such as dyes and pigments). The black matrix is preferably formed by exposing the dark color composition in an oxygen-poor atmosphere and then developing it.
Under an oxygen-poor atmosphere when photocuring such a dark-colored composition means an inert gas, a reduced pressure, or a protective layer that can block oxygen, and these are described in detail below. .

The inert gas refers to a general gas such as N ₂ , H ₂ , CO ₂ , or a rare gas such as He, Ne, Ar. Among these, N ₂ is preferably used because of safety, availability, and cost.

  Under reduced pressure refers to a state of 500 hPa or less, preferably 100 hPa or less.

Examples of the protective layer capable of blocking oxygen include, for example, polyvinyl ether / maleic anhydride polymers, water-soluble salts of carboxyalkyl cellulose described in JP-A Nos. 46-2121 and 56-40824. Water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinyl alcohol, polyvinylpyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various starches And a group of water-soluble salts thereof, styrene / maleic acid copolymers, maleate resins, and combinations of two or more thereof. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable. The polyvinyl alcohol preferably has a saponification rate of 80% or more, and the content of polyvinyl pyrrolidone is preferably 1 to 75% by mass, more preferably 1 to 50% by mass, and still more preferably the alkali-soluble resin layer solid content. It is 10-40 mass%.
In addition, various films can be used as the layer capable of blocking oxygen. For example, polyesters such as PET, polyamides such as nylon, and ethylene-vinyl acetate copolymers (EVAs) are also preferably used. be able to. These films may be stretched as necessary, and the thickness is suitably 5 to 300 μm, preferably 20 to 150 μm. When the black matrix is produced using a transfer material, the temporary support described below can be suitably used as a layer capable of blocking oxygen.

The oxygen permeability coefficient of the protective layer capable of blocking oxygen produced in this manner is preferably 2000 cm ³ / (m ² · day · atm) or less, but 100 cm ³ / (m ² · day · atm) or less. Is more preferably 50 cm ³ / (m ² · day · atm) or less.
When the oxygen permeability is higher than 2000 cm ³ / (m ² · day · atm), the oxygen cannot be effectively blocked, and the exposure sensitivity may be lowered.

(Photosensitive transfer material)
As a technique for realizing such a black matrix shape easily and at low cost, there is a method of using a photosensitive transfer material having a layer made of at least a dark color composition on a temporary support. The photosensitive transfer material may further have an oxygen barrier layer. When a material having such an oxygen blocking layer is used, the layer made of the photosensitive dark color composition is protected by the oxygen blocking layer, and thus automatically becomes in an oxygen-poor atmosphere. Therefore, there is no need to carry out the exposure process under an inert gas or under reduced pressure, so that there is an advantage that the current process can be used as it is.
Alternatively, a photosensitive transfer material having at least a layer made of a dark color composition on a temporary support may be used, and the temporary support may be used as a “protective layer capable of blocking oxygen”. In this case, it is not necessary to provide the oxygen barrier layer, and the number of steps can be reduced.

  The photosensitive transfer material may have a thermoplastic resin layer as necessary. Such a thermoplastic resin layer is alkali-soluble and includes at least a resin component, and the resin component preferably has a substantial softening point of 80 ° C. or less. By providing such a thermoplastic resin layer, good adhesion to the permanent support can be exhibited in the black matrix forming method described later.

  Examples of alkali-soluble thermoplastic resins having a softening point of 80 ° C. or lower include saponified products of ethylene and acrylate copolymers, saponified products of styrene and (meth) acrylate copolymers, vinyltoluene and (meth) acrylic. Examples thereof include saponification products of acid ester copolymers, saponification products such as poly (meth) acrylic acid esters, and (meth) acrylic acid ester copolymers such as butyl (meth) acrylate and vinyl acetate.

  For the thermoplastic resin layer, at least one of the above-mentioned thermoplastic resins can be appropriately selected and used. Further, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, Of those organic polymers having a softening point of about 80 ° C. or lower, issued on October 25, 1968), those soluble in an alkaline aqueous solution can be used.

  In addition, for an organic polymer substance having a softening point of 80 ° C. or higher, by adding various plasticizers compatible with the polymer substance to the organic polymer substance, the substantial softening point is 80 ° C. or lower. It can also be used by lowering. In addition, these organic polymer substances include various polymers, supercooling substances, adhesion improvers or interfaces within the range where the substantial softening point does not exceed 80 ° C. for the purpose of adjusting the adhesive force with the temporary support. Activators, mold release agents, etc. can also be added.

  Specific examples of preferable plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, and biphenyl diphenyl phosphate.

The temporary support in the photosensitive transfer material can be appropriately selected from those that are chemically and thermally stable and composed of a flexible substance. Specifically, a thin sheet such as Teflon (registered trademark), polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, polyester, or a laminate thereof is preferable. As thickness of the said temporary support body, 5-300 micrometers is suitable, Preferably it is 20-150 micrometers. If the thickness is less than 5 μm, the temporary support tends to be easily broken when peeled off, and if the exposure is performed via the temporary support, the resolution tends to be lowered if the thickness exceeds 300 μm.
Among the above specific examples, a biaxially stretched polyethylene terephthalate film is particularly preferable.

(substrate)
As the substrate (permanent support) constituting the color filter, a metallic support, a metal bonded support, glass, ceramic, a synthetic resin film, or the like can be used. Particularly preferred are transparent glass and synthetic resin film having good dimensional stability.

(Formation of black matrix)
Hereinafter, a case where a black matrix is formed using the photosensitive transfer material will be described. A photosensitive transfer material having an oxygen blocking layer and a dark color composition layer on a temporary support and a cover sheet provided on the dark color composition layer is prepared. First, after removing and removing the cover sheet, the surface of the exposed dark color composition layer is bonded onto a permanent support (substrate) and laminated by heating and pressing through a laminator or the like (laminate). As the laminator, those appropriately selected from conventionally known laminators, vacuum laminators and the like can be used, and an auto-cut laminator can also be used in order to further increase the productivity.

Subsequently, it peels between a temporary support body and an oxygen barrier layer, and a temporary support body is removed. Subsequently, in a state where a desired photomask (for example, quartz exposure mask) is vertically set above the removal surface after the temporary support is removed, an appropriate distance between the exposure mask surface and the oxygen blocking layer (for example, 200 μm) for exposure. Next, after the irradiation, development processing is performed using a predetermined processing solution to obtain a patterning image, and subsequently, water washing processing is performed as necessary to obtain a black matrix.
When the temporary support is used as a protective layer capable of blocking oxygen, a desired photomask (for example, a quartz exposure mask) is provided above the temporary support while leaving the temporary support (without peeling). In a state in which is vertically set, the distance between the exposure mask surface and the temporary support is appropriately set (for example, 200 μm) and exposed. Next, the temporary support is removed, and after irradiation, development processing is performed using a predetermined processing solution to obtain a patterning image. Subsequently, if necessary, the substrate is washed with water to obtain a black matrix.
The exposure is performed, for example, with a proximity type exposure machine (for example, manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp, and the exposure amount may be appropriately selected (for example, 300 mJ / cm ² ). it can.
After irradiation, development processing is performed using a predetermined processing solution. As the developer used in the development process, a dilute aqueous solution of an alkaline substance is used, but it may be further added with a small amount of an organic solvent miscible with water. Examples of the light source used for the light irradiation include medium to ultrahigh pressure mercury lamps, xenon lamps, metal halide lamps, and the like.

  Prior to the development, it is preferable to spray pure water with a shower nozzle or the like to uniformly wet the surface of the dark color photosensitive resin layer. As the developer used in the development process, a dilute aqueous solution of an alkaline substance is used, but it may be further added with a small amount of an organic solvent miscible with water.

  Suitable alkaline substances include alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg, sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate). , Potassium bicarbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicates (eg, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, Examples include morpholine, tetraalkylammonium hydroxides (for example, tetramethylammonium hydroxide), trisodium phosphate, and the like. The concentration of the alkaline substance is preferably 0.01 to 30% by mass, and the pH is preferably 8 to 14.

  Examples of the “water-miscible organic solvent” include, for example, methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether. Benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like are preferable. . The concentration of the organic solvent miscible with water is preferably 0.1 to 30% by mass. Furthermore, a known surfactant can be added, and the concentration of the surfactant is preferably 0.01 to 10% by mass.

The developer can be used as a bath solution or a spray solution. When removing the uncured portion of the photosensitive resin layer, methods such as rubbing with a rotating brush or wet sponge in the developer can be combined. The liquid temperature of the developer is usually preferably from about room temperature to 40 ° C.
The development time is usually about 10 seconds to 2 minutes, depending on the composition of the photosensitive resin layer, the alkalinity and temperature of the developer, and the type and concentration when an organic solvent is added. If it is too short, the development of the non-exposed area may be insufficient, and the absorbance of ultraviolet rays may be insufficient, and if it is too long, the exposed area may be etched. In either case, it is difficult to make the black matrix shape suitable. It is also possible to put a water washing step after the development processing. In this development process, the black matrix shape is formed as described above.

(Water repellent treatment)
In the present invention, it is preferable that at least a part of the black matrix is water-repellent by subjecting the black matrix to a water repellent treatment. This is because when a droplet of a colored liquid composition (the active energy ray-curable inkjet ink) is applied between the black matrices by a method such as inkjet after forming the black matrix, the ink gets over the black matrix and is adjacent to the black matrix. This is in order to eliminate inconvenience such as color mixing with the color.

  As the water repellent treatment, a method of applying a water repellent material on the upper surface of the black matrix (for example, see JP-A-10-123500) or a method of newly providing a water-repellent layer (for example, see JP-A-5-241011). ), A method for imparting water repellency by plasma treatment (for example, see JP-A-2002-62420), a method for kneading a water-repellent substance into a black matrix (for example, see JP-A-2005-36160), and the like. .

(Overcoat layer)
After the color filter is manufactured, an overcoat layer may be provided on the entire surface to improve resistance. The overcoat layer can protect the solidified layers of the inks R, G, and B and can flatten the surface, but it is preferably not provided from the viewpoint of increasing the number of steps.

Examples of the resin (OC agent) that forms the overcoat layer include an acrylic resin composition, an epoxy resin composition, and a polyimide resin composition. Above all, it is excellent in transparency in the visible light region, and the resin component of the photocurable composition for color filters (the active energy ray-curable inkjet ink) usually has an acrylic resin as a main component, and the adhesiveness. An acrylic resin composition is desirable because of its excellent resistance.
Examples of the overcoat layer include those described in JP-A No. 2003-287618, paragraphs 0018 to 0028, and commercially available overcoat agents such as “Optomer SS6699G” manufactured by JSR.

[Display device]
The display device of the present invention refers to a display device such as a liquid crystal display device, a plasma display display device, an EL display device, or a CRT display device. For the definition of display devices and explanation of each display device, refer to “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issue)).
Among the display devices of the present invention, a liquid crystal display device is particularly preferable. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”. Among these, the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention can be applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA. These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(issued in 2001 by Toray Research Center Research Division)".

  In addition to the color filter, the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The present invention can be applied to a liquid crystal display device composed of these known members. For example, “'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Kentaro Shima, CMC Co., Ltd., 1994)”, “2003 Liquid Crystal Related Market Status and Future Prospects (Volume 2)” (Table Yoshiyoshi) Fuji Chimera Research Institute, published in 2003) ”.

[Target use]
The color filter of the present invention can be applied to applications such as televisions, personal computers, liquid crystal projectors, game machines, mobile terminals such as mobile phones, digital cameras, car navigation systems, and the like without any particular limitation.

  Hereinafter, the present invention will be described in detail using examples. The part and% in an Example show a mass part and mass%, respectively. The present invention is not limited to these examples.

<Example 1>
[Preparation of active energy ray-curable inkjet ink (1-8)]
In the recording liquids 1, 3, 5, and 7, the pigment, the dispersant, and the diluent shown in Table 1 below were added together with the monomer (1) below in a sand mill and dispersed for 4 hours. A stock solution of ink (hereinafter also simply referred to as “ink”) was obtained.
Next, the photopolymerization initiator (2) below was added to the ink stock solution, mixed gently until the photopolymerization initiator was dissolved in the ink stock solution, and further filtered under pressure with a membrane filter to obtain the ink.

Further, in inks 2, 4, 6, and 8, the pigment and dispersant shown in Table 1 below were dispersed together with the monomer (1) by the method described above to obtain a stock solution of the ink.
Next, the photopolymerization initiator (2) below was added to the ink stock solution, and after gently mixing until the photopolymerization initiator was dissolved in the ink stock solution, the ink was obtained through the aforementioned filtration step.

Inks 1 to 8 are each printed at a predetermined position on a glass substrate for a color filter on which a black matrix is formed in advance by an inkjet printer having a piezo head, and then dried and cured by a UV irradiation device (conditions: high-pressure mercury lamp 1 Lamp: output 120 W, conveyor speed: 20 m / min).
Subsequently, the obtained glass substrate was processed at 230 ° C. for 30 minutes. These are designated as color filters 1 to 8, respectively.

(1) Monomer formulation trimethylolpropane triacrylate (KS-TMPTA, Nippon Kayaku Co., Ltd.)
50 parts N-vinylformamide (Beam Set 770, Arakawa Chemical Co., Ltd.) 40 parts (2) Photopolymerization initiator formulation Irgacure 907 6.5 parts Isopropylthioxanthone 3.5 parts

<Pigment>
-P1-
Crude copper phthalocyanine (“Copper phthalocyanine” manufactured by Toyo Ink Mfg. Co., Ltd.): 250 parts, sodium chloride: 2500 parts, and polyethylene glycol (“Polyethylene glycol 300” manufactured by Tokyo Chemical Industry Co., Ltd.): 160 parts, 1 gallon kneader made of styrene (Inoue Manufacturing Co., Ltd.) And kneaded for 3 hours. Next, this mixture is poured into 2.5 liters of warm water, stirred for about 1 hour with a high speed mixer (Fukae Powtech Co., Ltd.) while being heated to about 80 ° C., and then filtered and washed with water. Repeated 5 times to remove sodium chloride and solvent, then spray dried to obtain a dried treated pigment.

-P2-
Quinacridone red pigment (“Cincacia Magenta RT-355-D” manufactured by Ciba Geigy): 250 parts, sodium chloride: 2500 parts, and “polyethylene glycol 300”: 160 parts made of 1 gallon kneader (manufactured by Inoue Seisakusho) ) And treated pigment was obtained in the same manner as P1.

-P3-
Benzimidazolone yellow pigment ("Hosta Palm Yellow H3G" manufactured by Hoechst): 250 parts, sodium chloride: 2500 parts, and "polyethylene glycol 300": 160 parts were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) made of styrene. A treated pigment was obtained in the same manner as P1.

-P4-
Carbon black pigment “Printex 150 T” (Degussa)

<Monomer>
・ NVF N-vinylformamide ("Beam Set 770" manufactured by Arakawa Chemical Co., Ltd.)
・ TMPTA trimethylolpropane triacrylate (“KS-TMPTA” manufactured by Nippon Kayaku Co., Ltd.)

<Dispersant>
・ 13940 Polyesteramine dispersant ("Solspers 13940" manufactured by Zeneca)
・ 24000 Aliphatic modified dispersant ("Solspers 24000" manufactured by Zeneca)
-5000 Blue pigment dispersant ("Solspers 5000" manufactured by Zeneca)
・ 22000 Yellow pigment dispersant ("Solspers 22000" manufactured by Zeneca)
L-18 polycarboxylic acid type polymer dispersant ("Homogenol L-18" manufactured by Kao Corporation)
・ Efka 49 modified polyacrylate dispersant ("Efka 49" manufactured by Efka CHEMICAL)

<Diluted solvent>
・ Water Ion-exchanged water ・ Ethyl alcohol Water-soluble solvent ・ Acetone Water-soluble solvent ・ EXXSOL D110 Aliphatic hydrocarbon solvent (Exxon)

<Example 2>
In the photopolymerization initiator formulation of Example 1, except that the amount of Irgacure 907 was changed from 6.5 g to 4.5 g, color filters 9 to 16 corresponding to color filters 1 to 8 were prepared in the same manner as in Example 1. Created.

<Example 3>
(Formation of ITO electrode)
The glass substrates 1 to 16 on which the color filters are formed are put into a sputtering apparatus, and 1300 mm thick ITO (indium tin oxide) is vacuum-deposited on the entire surface at 100 ° C., and then annealed at 240 ° C. for 90 minutes. Crystallized to form an ITO transparent electrode.

(Spacer formation)
A spacer was formed on the ITO transparent electrode produced above by the same method as the spacer forming method described in [Example 1] of JP-A-2004-240335.

(Formation of liquid crystal alignment control protrusions)
A liquid crystal alignment control protrusion was formed on the ITO transparent electrode on which the spacer was formed, using the following positive photosensitive resin layer coating solution.
However, the following methods were used for exposure, development, and baking.
A proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) is arranged so that the predetermined photomask is at a distance of 100 μm from the surface of the photosensitive resin layer, and the irradiation energy is 150 mJ / Proximity exposure was performed at cm ² .
Subsequently, a 2.38% tetramethylammonium hydroxide aqueous solution was developed by spraying it on a substrate at 33 ° C. for 30 seconds in a shower type developing device. In this way, by removing the unnecessary portion (exposed portion) of the photosensitive resin layer by developing and removing the liquid crystal, the liquid crystal alignment control protrusions made of the photosensitive resin layer patterned into a desired shape are formed on the color filter side substrate. A display device substrate was obtained.
Next, the liquid crystal alignment control projection on which the liquid crystal alignment control protrusion was formed was baked at 230 ° C. for 30 minutes to form a cured liquid crystal alignment control protrusion on the liquid crystal display substrate.

<Positive photosensitive resin layer coating solution formulation>
・ Positive resist solution (FH-2413F manufactured by FUJIFILM Electronics Materials Co., Ltd.) 53.3 parts ・ Methyl ethyl ketone 46.7 parts ・ Megafac F-780F (produced by Dainippon Ink & Chemicals, Inc.) 0.04 parts

(Creation of liquid crystal display device)
Using the liquid crystal display device substrate obtained above, liquid crystal display devices 1 to 16 were produced using the methods described in the first examples [0079] to [0082] of JP-A-11-242243. .

<Comparative Example 1>
In Example 1, the color filters 17 to 24 produced in the same manner as in Example 1 except that the heat treatment process was not performed using inks 1 to 8 were processed in the same manner as in Example 3 to obtain liquid crystal display devices 17 to 17. 24 was produced.

(Evaluation)
1) Display unevenness When the obtained liquid crystal display devices 1 to 24 were inputted with a gray test signal, they were observed visually and with a magnifying glass to confirm the presence or absence of unevenness, and judged according to the following criteria.
A: No unevenness at all (very good)
B: Slight unevenness is observed on the edge of the glass substrate, but there is no problem in the display (good)
C: Slight unevenness on the display, but practical level (normal)
D: Display is uneven (somewhat bad)
E: Strong unevenness in display (very bad)

2) Color purity Using a chromaticity meter OSP-200 (Olympus Kogyo Co., Ltd.), the color of each color filter was measured as follows. Microscopically measure red (R), green (G), and blue (B) of each color filter, plot the x and y coordinates of each color on the CIE1931 standard coordinates, and reproduce the triangle that is formed when the RGB points are connected Region S _n was _designated . Here, when the color reproduction region S ₀ defined by the NTSC standard is 100, the measured value ratio [%] of each of the color filters (1) to (24) with respect to S ₀ is the NTSC ratio. It was evaluated according to the evaluation criteria.
<Evaluation criteria>
○: 70 ≦ NTSC ratio (very good level)
Δ: 67 ≦ NTSC ratio <70 (practical level)
×: NTSC ratio <67 (defective level that cannot be practically used)

<Example 4>
Color filters 25 to 34 were produced in the same manner as in Example 2 except that the heat treatment step at 230 ° C. for 30 minutes was changed to the conditions shown in Table 3 below in the production method of the color filter 9 of Example 2.
Next, using the color filters 25 to 34 obtained above, liquid crystal display devices 25 to 34 were produced in the same manner as in Example 3. The same evaluation as above was performed, and the results are shown in Table 3 below.

  As is clear from the above results, in any of the examples, a liquid crystal display device having a color filter excellent in display unevenness and color purity is obtained, and in particular, at a temperature of 200 to 250 ° C., a heat treatment time of 10 to 150 minutes is obtained. You can see that it is most suitable.

Claims (10)

Using an active energy ray-curable inkjet ink containing a pigment, a monofunctional monomer having one ethylenically unsaturated double bond, and a polyfunctional monomer having two or more ethylenically unsaturated double bonds on a substrate, a pixel A method for producing a color filter, characterized by comprising a heat treatment step after forming an active energy ray. The method for producing a color filter according to claim 1, wherein the heat treatment step is performed at a temperature of 150C to 300C. The total content of the monomer contained in the active energy ray-curable inkjet ink is 50 to 95% by mass based on the total mass of the ink, The color filter according to claim 1 or 2, Method. The method for producing a color filter according to claim 1, wherein the active energy ray-curable ink-jet ink contains a pigment dispersant. The method for producing a color filter according to any one of claims 1 to 4, wherein the active energy ray-curable inkjet ink contains an organic solvent. The method for producing a color filter according to claim 1, wherein the active energy rays are ultraviolet rays. The active energy ray-curable inkjet ink contains a photopolymerization initiator that initiates curing of a monofunctional monomer and a polyfunctional monomer upon irradiation with the active energy ray, and the content of the photopolymerization initiator is the total amount of the ink. It is 8 mass% or less in mass, The manufacturing method of the color filter in any one of Claims 1-6 characterized by the above-mentioned. The black matrix is formed in advance on a substrate, and the active energy ray-curable inkjet ink is supplied to the opening of the black matrix to form the pixel. The manufacturing method of the color filter as described in any one of. A color filter produced by the method for producing a color filter according to claim 1. A display device comprising the color filter according to claim 9.