JP5662847B2 - Color filter correcting ink composition and color filter corrected using the ink composition - Google Patents

Description

  The present invention relates to an ink composition for correcting a color filter used for correcting a color filter pixel defect, and a color filter corrected using the ink composition.

  A color filter used in a color liquid crystal display device has a fine band (stripe) filter segment of two or more different hues arranged in parallel or intersecting on the surface of a transparent substrate such as glass, or a fine filter The filter segments are arranged in a constant arrangement. The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

  In recent years, color liquid crystal display devices equipped with such color filters have been used for liquid crystal color televisions, car navigation systems, monitors, mobile devices, etc., so the color characteristics of liquid crystal display devices have been determined. The demand for high color reproducibility, high brightness, and high contrast is increasing for color filters.

  Moreover, in the color filter, the size of the segment is as small as several microns to several hundred microns, and even if it is a minute foreign matter or defect caused by the color filter manufacturing process or the material of the color filter coloring composition It becomes a defect that cannot reproduce the hue.

  Further, as the mother glass size of the color filter of the liquid crystal display is increased, the coating area is increased, and the probability of occurrence of the above-described defects per sheet is increased. Therefore, the necessity for correction is also increased. As a correction method, for example, a method of cutting and applying a correction ink composition such as a square shape so as to surround a foreign matter portion or a defect portion, or a method of applying a correction ink composition as it is to a defect portion is performed. It has been broken. As the application method of the correction ink composition, there are a needle method, a tampo padding method, an ink jet method, a dispenser method, an electrostatic method, a thermal transfer ribbon method, and the like. The needle method is Patent Document 1, and the ink jet method is Patent Document 2. In addition, as for the dispenser method, Patent Document 3 discloses respective correction devices and correction methods.

  The ink composition used in such a correction device needs to be adapted to each coating method.

  For example, the performance required for a needle-type ink composition is that the ink composition does not dry and harden on the needle as described in Patent Document 4 and Patent Document 5, and the ink composition does not spread too much. The residual solvent does not bleed out, there are few steps (physical and hue) with respect to normal pixels, and the amount of solvent, drying property, viscosity, etc. of the ink composition are adjusted within a certain range.

  In addition, the performance required for nozzle-type (inkjet or dispenser) type ink compositions is that clogging due to drying of volatile components does not occur at the nozzle outlet, the ink composition does not spread too much, and the residual This means that the solvent does not bleed out, there are few steps (physical and hue) with respect to normal pixels, and the amount of solvent, drying property, viscosity, etc. of the ink composition are adjusted within a certain range.

  After being applied, it is necessary to cure and fix the pixels to the glass. If classified according to the curing method, there are a thermosetting ink composition and an active energy ray curable ink composition. Patent Document 6 discloses a thermosetting ink composition used for a dispenser method and a tampo padding method. Patent Document 4 discloses a thermosetting ink composition containing a specific solvent used for a needle type.

An active energy ray-curable ink composition is disclosed in Patent Document 7.
Patent Document 8 discloses a thermosetting ink composition used in a dispenser system.

JP 08-182949 A JP 2006-030283 A JP 2006-068627 A JP 2005-292306 A JP 11-142635 A JP 2006-018252 A JP 2004-067777 A JP 2009-204701 A

  The present invention is a coating method of a color filter correcting ink composition such as a dispenser method, an ink jet method, a needle method, etc., which is applied to a correction location without causing clogging due to drying on a coating medium or a nozzle portion. An object of the present invention is to provide an ink composition for correcting a color filter that does not spread and has excellent solvent resistance.

［一般式（１）中、Ａ₁は、−Ｈまたは−ＣＨ₃であり、Ａ₂は、炭素数２または３のアルキレン基であり、Ａ₃は、−Ｈ、またはベンゼン環を含んでいてもよい炭素数１〜２０のアルキル基であり、ｎは、１〜４の整数である。］
一般式（２）：

［一般式（２）中、Ｄ₁〜Ｄ₆は、独立した置換基であり、−ＣＨ₂ＯＣＨ₃、または−ＣＨ₂ＯＣ₄Ｈ₉である。］
The ink composition of the present invention comprises an organic pigment (A), a monofunctional monomer (B) having one ethylenically unsaturated double bond represented by the following general formula (1), and the following general formula (2). A melamine compound (C) comprising a thermosetting melamine compound [C1] or a mixture [C2] thereof, and an organic solvent (D) of 10% by weight or less based on the total amount of the ink composition; It contains a polyfunctional monomer (E) and a photopolymerization initiator (F), and the content of the melamine compound (C) has one ethylenically unsaturated double bond represented by the general formula (1). The amount is 2.3 parts by weight or more and less than 10 parts by weight with respect to 100 parts by weight of the monofunctional monomer (B) .
General formula (1):

[In General Formula (1), A ₁ is —H or —CH ₃ , A ₂ is an alkylene group having 2 or 3 carbon atoms, and A ₃ includes —H or a benzene ring. Or an alkyl group having 1 to 20 carbon atoms, and n is an integer of 1 to 4. ]
General formula (2):

[In General Formula (2), D _{1 to} D ₆ are independent substituents, and are —CH ₂ OCH ₃ or —CH ₂ OC ₄ H ₉ . ]

Also, the present invention, the total amount of melamine compound (C) and polyfunctional monomer (E) is, based on the total amount of the ink composition, the color filter repair ink composition, characterized in that at least 15% by weight Related to things.
The present invention also relates to a color filter in which a defective portion of a filter segment of a color filter is corrected using the color filter correcting ink composition.

  The color filter correcting ink composition of the present invention comprises an organic pigment, a specific monofunctional monomer, a specific melamine compound, an organic solvent of 10% by weight or less based on the total amount of the ink, a polyfunctional monomer, and a photopolymerization. Incorporation of an initiator makes it possible to apply corrections without causing clogging due to drying on the application medium or nozzle part in the application method of color filter correction ink compositions such as the dispenser method, ink jet method, and needle method. Thus, it is possible to form a fine correction colored film excellent in solvent resistance, in which the coating liquid does not spread at the correction location.

Glass micropipette used for evaluation in Examples and Comparative Examples of the present invention

［一般式（１）中、Ａ₁は、−Ｈまたは−ＣＨ₃であり、Ａ₂は、炭素数２または３のアルキレン基であり、Ａ₃は、−Ｈ、またはベンゼン環を含んでいてもよい炭素数１〜２０のアルキル基であり、ｎは、１〜４の整数である。］
一般式（２）：

［一般式（２）中、Ｄ₁〜Ｄ₆は、独立した置換基であり、−ＣＨ₂ＯＣＨ₃、または−ＣＨ₂ＯＣ₄Ｈ₉である。］


First, the color filter correcting ink composition in the present invention will be specifically described.
The color filter correcting ink composition of the present invention comprises an organic pigment (A), a monofunctional monomer (B) having one ethylenically unsaturated double bond represented by the general formula (1), and the following general formula: A melamine compound (C) containing the thermosetting melamine compound [C1] represented by (2) or a mixture [C2] thereof, and an organic solvent (D) of 10% by weight or less based on the total amount of the ink; The polyfunctional monomer (E) and the photopolymerization initiator (F), and the content of the melamine compound (C) is one ethylenically unsaturated double bond represented by the general formula (1). It is 2.3 parts by weight or more and less than 10 parts by weight with respect to 100 parts by weight of the monofunctional monomer (B) .
General formula (1):

[In General Formula (1), A ₁ is —H or —CH ₃ , A ₂ is an alkylene group having 2 or 3 carbon atoms, and A ₃ includes —H or a benzene ring. Or an alkyl group having 1 to 20 carbon atoms, and n is an integer of 1 to 4. ]
General formula (2):

[In General Formula (2), D _{1 to} D ₆ are independent substituents, and are —CH ₂ OCH ₃ or —CH ₂ OC ₄ H ₉ . ]

[Organic pigment (A)]
Examples of the organic pigment (A) include pigments used in color filter ink compositions, such as diketopyrrolopyrrole pigments, anthraquinone pigments, quinophthalone pigments, isoindoline and isoindolinone pigments, azo pigments, copper phthalocyanine Pigments, and carbon black pigments. These pigments are excellent in resistance, luminance, contrast characteristics or coloring power, and are preferably used.

  Examples of the diketopyrrolopyrrole pigment include C.I. I. Pigment Red254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264, and C.I. I. Pigment Red 272 and the like. Examples of anthraquinone pigments include C.I. I. Pigment Red177 and the like. Examples of quinophthalone pigments include C.I. I. Pigment Yellow138 etc. are mentioned. Examples of isoindoline and isoindolinone pigments include C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 185, and the like. The azo pigment is preferably a metal complex in the present invention. I. Pigment Yellow 150 and the like. Examples of the copper phthalocyanine pigment include C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, and Pigment Blue 15: 6. Examples of the halogenated phthalocyanine pigment include C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, 37, and C.I. I. Pigment Green 58 and the like. Examples of the carbon black pigment include C.I. I. Pigment Black7 etc. are mentioned.

  From the viewpoint of obtaining sufficient color reproducibility, the content of the organic pigment (A) contained in the ink composition is more preferably 5% by weight or more based on the total amount of the ink composition (100% by weight). Is 10% by weight or more. In addition, 90% by weight or less is preferable and 80% by weight or less is more preferable because the stability of the ink composition is improved.

［一般式（１）中、Ａ₁は、−Ｈまたは−ＣＨ₃であり、Ａ₂は、炭素数２または３のアルキレン基であり、Ａ₃は、−Ｈ、またはベンゼン環を含んでいてもよい炭素数１〜２０のアルキル基であり、ｎは、１〜４の整数である。］ [Monofunctional monomer (B)]
The monofunctional monomer (B) is a compound represented by the following general formula (1). Since this compound has a high transmittance and a low viscosity in the entire wavelength region of 400 to 700 nm in the visible light region, it can be used as a pigment carrier for dispersing a pigment, and has a good pigment dispersibility and is suitable. is there. Furthermore, compared with the case where only a solvent is used for pigment dispersion, the drying property is low, and drying of the discharge portion can be prevented. From the viewpoint of pigment dispersibility, n is preferably 1 to 4, and more preferably n is 1.
General formula (1):

[In General Formula (1), A ₁ is —H or —CH ₃ , A ₂ is an alkylene group having 2 or 3 carbon atoms, and A ₃ includes —H or a benzene ring. Or an alkyl group having 1 to 20 carbon atoms, and n is an integer of 1 to 4. ]

Monofunctional monomer As the (B), for example, A ₁ and A ₃ is -H, a product A ₂ is the -C ₂ H _4, n is 1, (manufactured by Osaka Organic Chemical Industry) Viscoat # 192, SR- 339A (manufactured by Kayaku Sartomer), Light acrylate PO-A (manufactured by Kyoeisha Chemical Co., Ltd.), NK ester AMP-10G (manufactured by Shin-Nakamura Chemical Co., Ltd.), New Frontier PHE (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and Photomer 4035 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) San Nopco Co., Ltd.), a ₁ and a ₃ is -H, a product of a ₂ is -C ₂ H _4, n is 2, Aronix M-101 (manufactured by Toagosei Co., Ltd.), Viscoat # 193 (Osaka organic chemical Co. NK ester AMP-20G (manufactured by Shin-Nakamura Chemical Co., Ltd.), light acrylate P-200A (manufactured by Kyoeisha Chemical Co., Ltd.), and New Frontier PHE-2 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), A ₁ and A ₃ As a product in which A is -H, A ₂ is -C ₂ H ₄ , and n is 4, Aronix M-102 (manufactured by Toagosei Co., Ltd.) and the like can be mentioned.

  The monofunctional monomer (B) is preferably 50 parts by weight or more, more preferably 80 parts by weight or more in order to obtain the stability of the ink composition with respect to 100 parts by weight of the organic pigment (A). Moreover, it is 1000 weight part or less from a viewpoint of obtaining sufficient color reproducibility, More preferably, it is 900 weight part or less.

［一般式（２）中、Ｄ₁〜Ｄ₆は、独立した置換基であり、−ＣＨ₂ＯＣＨ₃、または−ＣＨ₂ＯＣ₄Ｈ₉である。］
具体的には、例えば以下の市販品が挙げられる。
メラミン化合物（Ｃ）としては、Ｄ₁〜Ｄ₆が−ＣＨ₂ＯＣＨ₃の製品として、ニカラックＭＷ−３０Ｍ、ニカラックＭＷ−３０、ニカラックＭＷ−２２、およびニカラックＭＷ−２１（以上日本カーバイド工業社製）、並びに、サイメル３００、サイメル３０１、サイメル３０３、およびサイメル３５０（以上日本サイテックインダストリーズ社製）等、Ｄ₁〜Ｄ₆が−ＣＨ₂ＯＣＨ₃および−ＣＨ₂ＯＣ₄Ｈ₉の製品として、ニカラックＭＸ−４５、ニカラックＭＸ−５００、ニカラックＭＸ−５２０、およびニカラックＭＸ−４３（以上日本カーバイド工業社製）、並びに、サイメル２３２、サイメル２３５、サイメル２３６、およびサイメル２３８（以上日本サイテックインダストリーズ社製）等、Ｄ₁〜Ｄ₆が−ＣＨ₂ＯＣ₄Ｈ₉の製品として、マイコート５０６（以上日本サイテックインダストリーズ社製）等のヘキサメチロールメラミンのフルアルキルエーテル化合物および／またはその部分縮合物の混合物（平均重合度が１〜３）が挙げられる。 [Melamine compound (C)]
The melamine compound (C) is a melamine compound (C) containing a thermosetting melamine compound [C1] represented by the following general formula (2) or a mixture [C2] thereof, and the thermosetting melamine compound The case where both [C1] and a mixture [C2] of the partial condensate thereof are included is also included. This compound is low-viscosity and stable at room temperature, and has few volatile components, so it does not clog in the coating medium and discharge port of the ink composition, does not spread at minute correction points, and has various resistances due to thermal curing. Can be used suitably. Further, the compatibility with the monofunctional monomer (B) is good, and the pigment dispersion stability can be maintained.
General formula (2):

[In General Formula (2), D _{1 to} D ₆ are independent substituents, and are —CH ₂ OCH ₃ or —CH ₂ OC ₄ H ₉ . ]
Specific examples include the following commercially available products.
As the melamine compound (C), D _{1 to} D ₆ are products of —CH ₂ OCH ₃ , Nicarak MW-30M, Nicarak MW-30, Nicarac MW-22, and Nicarac MW-21 (manufactured by Nippon Carbide Industries Co., Ltd.) ), And Cymel 300, Cymel 301, Cymel 303, Cymel 350 (manufactured by Nippon Cytec Industries, Inc.) and the like, D _{1 to} D ₆ are products of —CH ₂ OCH ₃ and —CH ₂ OC ₄ H ₉ , MX-45, Nikarak MX-500, Nikarak MX-520, and Nikarak MX-43 (manufactured by Nippon Carbide Industries Co., Ltd.), and Cymel 232, Cymel 235, Cymel 236, and Cymel 238 (manufactured by Nippon Cytec Industries, Inc.) etc., D ₁ to D ₆ are manufactured of -CH ₂ OC ₄ H ₉ As a mixture of Mycoat 506 (Nippon Cytec Industries Inc.) Full alkyl ether compound of hexamethylol melamine and the like and / or partial condensate thereof (average degree of polymerization 1-3) can be mentioned.

D ₁ to D one or more of _6, Iminotaipu and is -H, methylol type and a -CH ₂ OH, among more than one one of D ₁ to D ₆ is H and D ₁ to D ₆ The imino-methylol type in which one or more is —CH ₂ OH is not preferable because it has high reactivity and the viscosity of the ink increases with time, and the discharge port of a coating medium such as a dispenser may be clogged.

  The average degree of polymerization of the melamine compound (C) is the weight average molecular weight of the melamine compound (C) including the mixture [C2] of the thermosetting melamine compound [C1] represented by the general formula (2) and its partial condensate. The value divided by the weight average molecular weight of the thermosetting melamine compound [C1] represented by the general formula (2). The average degree of polymerization is more than 1.05 and less than 2.60, more preferably 1.2 to 2.3. When it is 1.05 or less, the purity of the hexaalkylol melamine fluoralkyl ether compound is too high, resulting in crystals, and the compatibility with the monofunctional monomer (B) is deteriorated. When it is larger than 2.60, the viscosity becomes high, and the discharge port of the application medium such as a dispenser may be clogged, which is not preferable.

  The melamine compound (C) is preferably 0.1 parts by weight or more and less than 10 parts by weight with respect to 100 parts by weight of the monofunctional monomer (B). When the melamine compound (C) is less than 0.1 parts by weight, the curability by heating becomes insufficient. On the other hand, when the melamine compound (C) is 10 parts by weight or more, the reaction of the photopolymerization initiator by ultraviolet rays becomes insufficient.

[Organic solvent (D)]
As an organic solvent (D), what is generally used for the ink composition for color filters can be included. For example, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3 -Propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy -3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N -Dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butyl Rubenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ -Butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene Glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene Glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether , Cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol mono Chill ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene Glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl Black hexanol, acetate n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters, and the like, used these alone or in mixtures.

  Since the organic solvent (D) has high volatility, if it is contained in a large amount in the ink composition of the present invention, a rapid increase in viscosity due to drying, shrinkage, poor pigment dispersion, etc. cause a dispenser or the like. There are problems such as clogging of the discharge port of the coating medium, contraction of the corrected portion, and generation of cracks. Therefore, it is desirable to reduce the content of the organic solvent in the ink composition as much as possible, but when adding a high-boiling organic solvent to adjust the ink viscosity or when using raw materials containing the organic solvent. Therefore, it is difficult to make it 0% by weight. Therefore, in consideration of the organic solvent contained in additives such as resin-type dispersants and leveling agents, and the organic solvent as a viscosity modifier, the total amount of the ink composition is 100% by weight, up to 10% by weight. Can be contained.

[Polyfunctional monomer (E)]
Polyfunctional monomers (E) include polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane (PO-modified) tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tri ( Various acrylic acid esters and methacrylic acid esters such as (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like, and urethane (meth) acrylate Polyester (meth) acrylate, epoxy (meth) acrylate, and the like can be used, but are not necessarily limited thereto. These may be used alone or in combination.

  The amount of the polyfunctional monomer (E) contained in the ink composition is preferably 5% by weight or more and 80% by weight or less based on the total amount of the ink composition (100% by weight). If the amount of the polyfunctional monomer (E) is less than 5% by weight, it is difficult to obtain a sufficient effect for improving fluidity and curability, and if it exceeds 80% by weight, sufficient color reproducibility is hardly obtained.

  The total of the melamine compound (C) and the polyfunctional monomer (E) contained in the ink composition is preferably 15% by weight or more and 85% by weight or less based on the total amount of the ink (100% by weight). If the total of the melamine compound (C) and the polyfunctional monomer (E) is less than 15% by weight, it is difficult to obtain a sufficient effect for improving fluidity and curability, and if it exceeds 85% by weight, sufficient color reproduction is achieved. It is difficult to obtain sex.

[Photopolymerization initiator (F)]
By including the photopolymerization initiator (F), the color filter correcting ink composition of the present invention can be cured by active energy rays such as ultraviolet rays. Such curing by an active energy ray has an advantage that curing in a short time is possible as compared with curing by heat.

  As the photopolymerization initiator (F), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one Acetophenone compounds such as 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Benzoin compounds such as ether and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-ben Benzophenone compounds such as yl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, Thioxanthone compounds such as 2,4-diisopropylthioxanthone and 2,4-diethylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2 -(P-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4, 6-bis (trichloromethyl) -s-triazine, 2, -Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-) Yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, etc. 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), O- (acetyl) -N- (1-phenyl-2-oxo- Oxime ester compounds such as 2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine, bis (2,4,6-trimethylbenzoyl) phenylphos Phosphine compounds such as fin oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, borate compounds, carbazole compounds, imidazole compounds Compounds, titanocene compounds and the like are used. These photopolymerization initiators can be used alone or in combination.

Of these photopolymerization initiators (F), acetophenone compounds and oxime ester compounds are particularly preferred from the viewpoint of achieving both solvent resistance of the coating film and ink stability.
As for content of a photoinitiator (F), 5-200 weight part is preferable with respect to 100 weight part of organic pigments (A), More preferably, it is 10-150 weight part.

A sensitizer can be used in combination with the photopolymerization initiator (F). Examples of the sensitizer include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 2-dimethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethylamino) ) Amine-based compounds such as benzophenone. These sensitizers can be used alone or in combination.
The content of the sensitizer is preferably 0.1 to 60 parts by weight with respect to 100 parts by weight of the organic pigment (A).

[Method for producing ink composition]
In the color filter correcting ink composition of the present invention, the organic pigment (A) is dispersed in the monofunctional monomer (B), the melamine compound (C), the organic solvent (D), and the polyfunctional monomer (E). After being dispersed with the partial component, the dispersion can be produced by mixing and stirring the remaining component and the photopolymerization initiator (F). The organic pigment can be dispersed using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor.

  When the organic pigment (A) is dispersed in the pigment carrier, a dispersion aid such as a dye derivative, a resin-type pigment dispersant, or a surfactant can be appropriately used. The dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, when an ink composition in which an organic pigment is dispersed using a dispersion aid is used, the dispersion aid is transparent. A color filter having excellent properties can be obtained.

[Dye derivative]
Examples of the dye derivative include a compound in which a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic pigment, anthraquinone, acridone, or triazine.
In the present invention, a pigment derivative is particularly preferable, and the structure thereof is a compound represented by the following general formula (3).
General formula (3):
P-Lm
[However,
P: Organic pigment residue L: Basic substituent, acidic substituent, compound having a phthalimidomethyl group which may have a substituent, etc. m: an integer of 1 to 4]
Examples of the dye derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, or JP-B-5-9469. What is currently used can be used, These can be used individually or in mixture of 2 or more types.

  The blending amount of the pigment derivative is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, and most preferably 5 to 25 parts by weight with respect to 100 parts by weight of the organic pigment (A). When the pigment derivative is less than 1 part by weight with respect to 100 parts by weight of the organic pigment (A), the dispersibility may be deteriorated, and when it exceeds 50 parts by weight, the heat resistance and light resistance may be deteriorated.

In the general formula (3), examples of the organic pigment constituting the organic pigment residue of P include the following.
For example,
Diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, and polyazo;
Phthalocyanine pigments such as copper phthalocyanine, copper halide phthalocyanine, and metal-free phthalocyanine;
Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyrantrone, and violanthrone;
Quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; isoindoline pigments; isoindolinone pigments; quinophthalone pigments; selenium pigments; and metal complex pigments.

(Resin type pigment dispersant)
Resin-type pigment dispersants include polyurethanes, polyacrylates such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polycarboxylic acid esters Siloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amide formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, its salt, etc. In addition, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct-based, and can include aqueous dispersants such as phosphate ester-based, they can be used alone or in admixture of two or more.

[Surfactant]
Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, monododecyl sulfate. Anions such as ethanolamine, triethanolamine dodecyl sulfate, ammonium dodecyl sulfate, monoethanolamine stearate, sodium stearate, sodium dodecyl sulfate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate Surfactants: polyoxyethylene oleyl ether, polyoxyethylene dodecyl ether, polyoxyethylene nonyl pheny Nonionic surfactants such as ethers, polyoxyethylene alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic properties such as alkyl quaternary ammonium salts and their ethylene oxide adducts Surfactants; alkylbetaines such as alkyldimethylaminoacetic acid betaines; and amphoteric surfactants such as alkylimidazolines can be used, and these can be used alone or in admixture of two or more.

  When adding a resin type dispersing agent and a surfactant, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the organic pigment (A). When the blending amount of the resin-type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the blending amount is more than 55 parts by weight, the dispersion is affected by an excessive dispersant. May affect.

[Color filter correction method]
Next, a method for correcting a color filter using the ink composition of the present invention will be described. In order to correct the defect of the color filter, the ink composition of the present invention is attached to the tip of the needle to contact the defective part, or the ink composition filled in the dispenser or the dispenser with a fine tip is extruded to the defective part, This is done by coating the defective part. The defect correction of the color filter can also be performed by applying the ink composition after removing the coating film including the defective part. The ink composition of the present invention can be cured by ultraviolet irradiation. Such curing by ultraviolet irradiation has an advantage that curing in a short time is possible as compared with curing by heat. Further, in order to increase the solvent resistance, heat curing may be further performed using a convection oven, an IR lamp, a halogen lamp, a hot plate, or the like.

  Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

[Example 1]
After uniformly stirring and mixing a mixture having the following composition, the mixture was dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A pigment composition 1 was prepared.
23.0 parts of red pigment (CI Pigment Red 177) (“Chromophthal Red A2B” manufactured by Ciba Japan)
7.0 parts of yellow pigment (CI Pigment Yellow 139) ("PALIOTOL YELLOW D1819" manufactured by BASF)
Resin-type pigment dispersant 3.0 parts ("Disperbyk-111" manufactured by Big Chemie)
Monofunctional monomer 67.0 parts (Osaka Organic Chemical Co., Ltd. “Biscoat # 192”)

Next, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a color filter correcting ink composition 1 of Example 1.
Pigment composition 1 40.0 parts Melamine compound 1.0 part ("Nikarak MW-30" manufactured by Sanwa Chemical Co., Ltd.)
Multifunctional monomer 49.0 parts ("Aronix M-400" manufactured by Toagosei Co., Ltd.)
3.0 parts of photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan)
7.0 parts of organic solvent (cyclohexanone)

[Examples 2-7 and Comparative Examples 1-7]
Except for setting the composition and blending amount of the pigment composition to Table 1, and setting the composition and blending amount of the color filter correcting ink composition to Table 2, Examples 2 to 7 and Comparative Examples 1 to 1 were the same as Example 1. A color filter correcting ink composition No. 7 was prepared.

Here, C.I. I. The Pigment number is as follows.
“CROMOPHTAL RED A2B” manufactured by Ciba Japan Co., Ltd .: C.I. I. Pigment Red 177
“PALIOTOL YELLOW D1819” manufactured by BASF: C.I. I. Pigment Yellow 139
LANXESS "E4GN": C.I. I. Pigment Yellow 150
“LIONOL GREEN 6YK” manufactured by Toyo Ink Co., Ltd .: C.I. I. Pigment Green 36
“LIONOL BLUE ES” manufactured by Toyo Ink Co., Ltd .: C.I. I. Pigment Blue 15: 6
“Printex 75” manufactured by Degussa Co., Ltd. I. Pigment Black 7
The monofunctional monomers in Table 1 are as follows.
“Biscoat # 192” manufactured by Osaka Organic Chemical Co., Ltd .: a monomer represented by the general formula (1), wherein A ₁ and A ₃ are —H, A ₂ is —C ₂ H ₄ , and n is 1.
“Aronix M-101” manufactured by Toa Gosei Co., Ltd .: a monomer represented by the general formula (1), wherein A ₁ and A ₃ are —H, A ₂ is —C ₂ H ₄ , and n is 2.
“NK ester AMP-60G” manufactured by Shin-Nakamura Chemical Co., Ltd .: a monomer represented by the general formula (1), wherein A ₁ and A ₃ are —H, A ₂ is —C ₂ H ₄ , and n is 6.

（＊１）Ｃ／Ｂ重量部
単官能モノマー（Ｂ）１００重量部に対するメラミン化合物（Ｃ）の含有量（重量部）
（＊２）Ｃ＋Ｅ重量％
インキ組成物全量中の、メラミン化合物（Ｃ）および多官能モノマー（Ｅ）の合計量（重量％）

(* 1) Content of melamine compound (C) with respect to 100 parts by weight of C / B monofunctional monomer (B) (parts by weight)
(* 2) C + E wt%
Total amount (% by weight) of melamine compound (C) and polyfunctional monomer (E) in the total amount of the ink composition

Here, the melamine compounds in Table 2 are as follows.
“Nicalak MW-30” manufactured by Nippon Carbide Industries Co., Ltd .: In the thermosetting melamine compound represented by the general formula (2), D _{1 to} D ₆ are —CH ₂ OCH ₃ .
“Nicarac MX-45” manufactured by Nippon Carbide Industries Co., Ltd .: In the thermosetting melamine compound represented by the general formula (2), D _{1 to} D ₆ are —CH ₂ OCH ₃ and —CH ₂ OC ₄ H ₉ .
“My Coat 506” manufactured by Mitsui Cytec Co., Ltd .: In the thermosetting melamine compound represented by the general formula (2), D _{1 to} D ₆ are —CH ₂ OC ₄ H ₉ .
“Nicarac MS-11” manufactured by Nippon Carbide Industries Co., Ltd .: In the thermosetting melamine compound represented by the general formula (2), D _{1 to} D ₆ are —CH ₂ OCH ₃ and —CH ₂ OH, and the solvent is 40 %include.

Moreover, the polyfunctional monomer (E) of Table 2 is as follows.
“Aronix M400” manufactured by Toagosei Co., Ltd .: Dipentaerythritol penta and hexaacrylate

Moreover, the organic solvent (D) of Table 2 is as follows.
Cyclohexanone DEDG: Diethylene glycol diethyl ether The photopolymerization initiator (F) in Table 2 is as follows.
“Irgacure 907” manufactured by Ciba Japan Co., Ltd .: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (acetophenone photopolymerization initiator)
“Irgacure 379” manufactured by Ciba Japan Co., Ltd .: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (acetophenone photopolymerization) Initiator)
“Irgacure OXE02” manufactured by Ciba Japan Co., Ltd .: ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime) ( Oxime ester photoinitiator)
“Biimidazole” manufactured by Kurokin Kasei Co., Ltd .: 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole (imidazole photopolymerization initiator)

  The ink compositions obtained in the examples and comparative examples were filled in a glass micropipette (FIG. 1: pipe inner diameter 260 μm, discharge tip inner diameter 5 μm), and extruded and applied to the part where the pixels were removed squarely for correction. The coated film was exposed for 10 seconds using a spot UV irradiator (“EXECRE 4000” manufactured by HOYA) to obtain a coating film. Evaluation methods and evaluation ranks are as follows. The results are shown in Table 3.

[Drying resistance]
The ink composition was introduced from the end of the glass micropipette of FIG. 1 where the tip was not an acute angle, and extrusion evaluation was performed at a discharge pressure of 0.1 MPa.
○: ejected ×: cannot be ejected due to clogging at the moment the ink composition comes out of the tip

[Liquid spreading suppression evaluation and appearance evaluation]
The corrected portion of the above-described extrudable ink was observed with an optical microscope.
○: The ink composition is completely replenished only to the removed part, and the ink composition does not overlap the part that has not been removed, and the chromaticity difference between the corrected part and the uncorrected part is small. When the ink composition is completely replenished to only the areas that have been exposed, the difference in chromaticity between the corrected and uncorrected areas is noticeable.

(Solvent resistance evaluation)
Observe the change of the coating after immersing the dried coating in isopropyl alcohol for 10 minutes.
○: Insoluble.
Δ: Some wrinkles are observed.
X: Swelling, dissolution, or color loss.

表３に示すように、本発明のインキ組成物は、図１に示すような先端が微細なディスペンサに充填して塗布する場合でも、耐乾燥性、液の広がり抑制評価、外観評価、溶剤耐性評価のいずれの評価結果も良好であった。

As shown in Table 3, the ink composition of the present invention has a drying resistance, a liquid spread suppression evaluation, an appearance evaluation, and a solvent resistance even when the tip as shown in FIG. All the evaluation results of the evaluation were good.

In Example 7 using the imidazole-based photopolymerization initiator, some wrinkles were observed in the solvent immersion, but this was in a range that was not problematic in practice.
In Comparative Example 1 in which n is 6 in the monofunctional monomer of the general formula (1), when the ink composition is completely replenished only to the removed portion, the chromaticity difference between the corrected portion and the uncorrected portion is It started to stand out.
In Comparative Example 2 containing no melamine compound (C), Comparative Example 3 containing a large amount of melamine compound (C), and Comparative Example 6 containing no polyfunctional monomer (E), curing was insufficient and solvent resistance was poor. there were.
In Comparative Example 4 in which D _{1 to} D ₆ are —CH ₂ OCH ₃ and —CH ₂ OH in the thermosetting melamine compound of the general formula (2), the ink composition appears at the moment when it comes out from the tip. Discharge became impossible due to clogging.

In Comparative Example 5 in which the amount of the solvent (D) exceeded 10% by weight based on the total amount of the ink, ejection became impossible due to clogging at the moment when the ink composition exited from the tip.
In Comparative Example 7 containing no photopolymerization initiator (F), the curing was insufficient and the solvent resistance was poor.

1: Glass micropipette 2: Glass filling portion of glass micropipette 3: Inner diameter of glass micropipette (260 μm)
4: Discharge tip inner diameter of glass micropipette (5 μm)

Claims (3)

Organic pigment (A), monofunctional monomer (B) having one ethylenically unsaturated double bond represented by the following general formula (1), and thermosetting melamine represented by the following general formula (2) A melamine compound (C) containing compound [C1] or a mixture [C2] thereof, a 10% by weight or less organic solvent (D) based on the total amount of the ink composition, a polyfunctional monomer (E), A photopolymerization initiator (F),
The content of the melamine compound (C) is 2.3 to 10 parts by weight with respect to 100 parts by weight of the monofunctional monomer (B) having one ethylenically unsaturated double bond represented by the general formula (1). An ink composition for correcting a color filter, characterized by being less than a part.
General formula (1):

[In General Formula (1), A ₁ is —H or —CH ₃ , A ₂ is an alkylene group having 2 or 3 carbon atoms, and A ₃ includes —H or a benzene ring. Or an alkyl group having 1 to 20 carbon atoms, and n is an integer of 1 to 4. ]
General formula (2):

[In General Formula (2), D _{1 to} D ₆ are independent substituents, and are —CH ₂ OCH ₃ or —CH ₂ OC ₄ H ₉ . ]   The ink composition for correcting a color filter according to claim 1, wherein the total amount of the melamine compound (C) and the polyfunctional monomer (E) is 15% by weight or more based on the total amount of the ink composition.   A color filter in which a defective portion of a filter segment of a color filter is corrected using the ink composition for correcting a color filter according to claim 1.

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