JP2009204701A - Heat curable ink composition for color filter modification - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat curable ink for color filter modification, having high solvent resistance which is applied on a part to be modified, without causing clogging due to drying on an application medium or in a nozzle part, in an application system of color filter modification ink, such as, a dispenser system, an inkjet system or a needle system, and which is heat-cured on the part to be modified without spreading of the application liquid. <P>SOLUTION: There is provided a heat curable ink composition for color filter modification, which comprises (A) an organic pigment; (B) a monofunctional monomer having a single ethylenically unsaturated double bond, represented by general formula (1); (C) a mixture of a thermosetting melamine compound; represented by general formula (2) and/or its partial condensate; (D) ≤10 wt.% of an organic solvent, based on the total amount of the ink; and preferably, (E) a polyfunctional monomer having two or more ethylenically unsaturated double bonds. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a color filter correcting thermosetting ink composition used for correcting color filter pixel defects.

  In color filters used in liquid crystal displays, the segment size is as small as several microns to hundreds of microns, and there are minute foreign objects and defects caused by the color filter manufacturing process and the color filter coloring composition material. Even if it exists, it becomes the defect which cannot reproduce 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, so that the necessity for correction is also increasing. As a correction method, for example, a method of cutting and applying correction ink such as a square shape so as to surround a foreign matter portion or a defect portion, or a method of applying correction ink to a defect portion as it is is performed. The correction ink application method includes a needle method, a tampo padding method, an ink jet method, a dispenser method, an electrostatic method, a thermal transfer ribbon method, etc. The needle method is disclosed in Patent Document 1, the ink jet method is disclosed in Patent Document 2, and the dispenser. Japanese Patent Application Laid-Open No. H10-228561 discloses a correction device and a correction method.

  The correction ink used in such a correction apparatus needs to be adapted to each application method.

  For example, the performance required for the needle type correction ink is that the correction ink does not dry and harden on the needle, the correction ink does not spread too much, and the residual solvent as described in Patent Document 4 and Patent Document 5. The amount of solvent, the drying property, the viscosity, etc. of the correction ink are adjusted within a certain range.

  The performance required for nozzle-type (inkjet and dispenser) type correction inks is that clogging due to drying of volatile components does not occur at the nozzle discharge port, correction ink does not spread too much, and residual solvent For example, it does not bleed out, and there are few steps (physical and hue) from normal pixels, and the amount of solvent, dryability, viscosity, etc. of the correction ink are adjusted within a certain range.

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

An active energy curing type correction fluid is disclosed in Patent Document 7.
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

  The subject of the present invention is a dispenser method, an ink jet method, an application method of a color filter correction ink such as a needle type, which is applied to a correction portion 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 for correcting a thermosetting color filter having a high solvent resistance, which is thermally cured without spreading the coating liquid.

  The subject is represented by the organic pigment (A), the monofunctional monomer (B) having one ethylenically unsaturated double bond represented by the following general formula (1), and the following general formula (2). A thermosetting ink composition for correcting color filters, comprising a mixture (C) of a thermosetting melamine compound and / or a partial condensate thereof, and an organic solvent (D) of 10% by weight or less based on the total amount of the ink. Solved by things.

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 is hydrogen or carbon that may contain a benzene ring. (It is the alkyl group of number 1-20, and n is an integer of 1-4.)

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. )

  In a preferred embodiment of the thermosetting ink composition for correcting a color filter of the present invention, it further contains a polyfunctional monomer (E) having two or more ethylenically unsaturated double bonds.

  In a preferred embodiment of the thermosetting ink composition for correcting a color filter of the present invention, the content of the thermosetting melamine compound and / or its partial condensate (C) is 10 based on the monofunctional monomer (B). ~ 100% by weight.

  In a preferred embodiment of the thermosetting ink composition for correcting color filters of the present invention, the total content of the thermosetting melamine compound and / or its partial condensate (C) and polyfunctional monomer (E) is the total amount of ink. Is 15% by weight or more based on

  The thermosetting ink composition for correcting color filters 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 A mixture (C) of a thermosetting melamine compound represented by the following general formula (2) and / or a partial condensate thereof, and 10% by weight or less of an organic solvent (D) based on the total amount of the ink. Preferably, it further contains a polyfunctional monomer (E) having two or more ethylenically unsaturated double bonds, so that a color filter correction ink such as a dispenser method, an ink jet method, a needle method, etc. In the coating method, it is applied to the corrected part without causing clogging due to drying on the coating medium or the nozzle, and the coating liquid is thermally cured without spreading at the corrected part, resulting in high solvent resistance. It is possible to form a micro-modified colored film.

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 is hydrogen or carbon that may contain a benzene ring. (It is the alkyl group of number 1-20, and n is an integer of 1-4.)

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. )

  First, the thermosetting ink composition for color filter correction according to the present invention will be specifically described with reference to preferred embodiments.

  The modified thermosetting ink composition for color filters 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 A mixture (C) of the thermosetting melamine compound represented by the general formula (2) and / or a partial condensate thereof, an organic solvent (D) of 10% by weight or less based on the total amount of the ink, preferably, It contains a polyfunctional monomer (E) having two or more ethylenically unsaturated double bonds.

[Organic pigment (A)]
Examples of organic pigments include pigments used in color filter ink compositions, such as diketopyrrolopyrrole pigments, anthraquinone pigments, isoindoline and isoindolinone pigments, azo pigments, copper phthalocyanine pigments, and carbon black pigments. Pigments can be used. These pigments are excellent in contrast characteristics or coloring power as compared with other organic pigments, and are preferably used for color filter applications.

  Examples of the diketopyrrolopyrrole pigment include C.I. Pigment Red254, C.I. Pigment Red 255, C.I. Pigment Red 264, and C.I. Pigment Red 272. Examples of anthraquinone pigments include C.I. Pigment Red177. Examples of isoindoline and isoindolinone pigments include C.I. Pigment Yellow 139, C.I. Pigment Yellow 185, and C.I. Pigment Yellow 199. The azo pigment is preferably a metal complex in the present invention, and examples thereof include C.I. Pigment Yellow 150. Examples of the copper phthalocyanine pigment include CI Pigment Blue 15, CI Pigment Blue 15: 1, CI Pigment Blue 15: 2, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI and Pigment Blue 15: 6. Etc. Examples of the halogenated phthalocyanine pigment include C.I. Pigment Green 7, C.I. Pigment Green 36, 37, C.I. Pigment Green 58, and the like. Examples of carbon black pigments include C.I. Pigment Black7.

[Monofunctional monomer (B)]
A monofunctional monomer (B) having one ethylenically unsaturated double bond represented by the following general formula (1) (hereinafter abbreviated as monofunctional monomer (B)) is 400 to 700 nm in the visible light region. Since the transmittance is high in all wavelength regions and the viscosity is low, it can be used as a pigment carrier for dispersing the pigment, and the pigment dispersibility is good, which is preferable. Furthermore, compared with the case where 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 is hydrogen or carbon that may contain a benzene ring. (It is the alkyl group of number 1-20, and n is an integer of 1-4.)
Examples of the monofunctional monomer (B) include the following commercially available products. As products in which A ₁ and A ₃ are H, A ₂ is C ₂ H ₄ , and n is 1, biscort # 192 (manufactured by Osaka Organic Chemical Co., Ltd.), 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 San Nopco). As products in which A ₁ and A ₃ are H, A ₂ is C ₂ H ₄ and n is 2, Aronix M-101 (manufactured by Toagosei Co., Ltd.), Biscote # 193 (manufactured by Osaka Organic Chemical Co., Ltd.), NK ester AMP-20G (Shin Nakamura Chemical Co., Ltd.), Light Acrylate P-200A (Kyoeisha Chemical Co., Ltd.), New Frontier PHE-2 (Daiichi Kogyo Seiyaku Co., Ltd.) and the like. Aronix M-102 (manufactured by Toagosei Co., Ltd.) is a product in which A ₁ and A ₃ are H, A ₂ is C ₂ H ₄ , and n is 4.

[Thermosetting melamine mixture (C)]
A mixture (C) of a thermosetting melamine compound represented by the following general formula (2) and / or a partial condensate thereof (hereinafter abbreviated as a thermosetting melamine mixture (C)) is low in viscosity and stable at room temperature. Because there are few volatile components, clogging does not occur in the ink composition coating medium and at the discharge port, and it does not spread at minute correction points, and furthermore, it forms a micro colored film with excellent resistance by thermosetting. 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. )

  The thermosetting melamine mixture (C) is a mixture of a thermosetting melamine compound represented by the following general formula (2) and / or a partial condensate thereof, and examples thereof include the following commercially available products.

As products in which D _{1 to} D ₆ are CH ₂ OCH ₃ , Nikarak MW-30M, Nikarak MW-30, Nikarak MW-22, and Nikarak MW-21 (manufactured by Nippon Carbide Industries Co., Ltd.), Cymel 300, Cymel 301 , Cymel 303, Cymel 350 (manufactured by Nippon Cytec Industries, Inc.), etc., where D _{1 to} D ₆ are CH ₂ OCH ₃ and CH ₂ OC ₄ H ₉ products, such as Nikarak MX-45, Nikarak MX-500, Nikarak MX -520, Nikarak MX-43 (Nippon Carbide Industries Co., Ltd.), Cymel 232, Cymel 235, Cymel 236, and Cymel 238 (Nippon Cytec Industries, Inc.), etc., D _{1 to} D ₆ are CH ₂ OC as a product of ₄ H _9, CYMEL 506 (Nippon Cytec Industries Inc.) full alkyl ether compound of hexamethylol melamine and the like, and / or The mixture of partial condensate (the average polymerization degree of 1-2) can be mentioned.

D ₁ to D one or more of _6, Iminotaipu and is H, or a methylol type is CH2 OH, D ₁ one or more of to D ₆ are one or more of H and D ₁ to D ₆ The imino-methylol type that is CH ₂ OH is not preferable because it has high reactivity and the viscosity of the ink increases with time, which may clog the discharge port of a coating medium such as a dispenser.

  The average degree of polymerization of the thermosetting melamine mixture (C) was obtained by dividing the weight average molecular weight of the thermosetting melamine mixture (C) by the weight average molecular weight of the thermosetting melamine compound represented by the general formula (2). Value. The average degree of polymerization is more than 1.05 and less than 2.00, more preferably 1.2 to 1.6. 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. If it is larger than 2.00, the viscosity becomes high, and the discharge port of the application medium such as a dispenser may be clogged.

  The thermosetting melamine mixture (C) is preferably 10 to 100% by weight based on the monofunctional monomer (B). When the thermosetting melamine mixture (C) is less than 10% by weight, the curability is insufficient. Moreover, when a thermosetting melamine mixture (C) exceeds 100 weight%, the influence of the film contraction by condensation is large and formation of a cured coating film is difficult.

[Organic solvent (D)]
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. In consideration of an organic solvent contained in an additive such as a resin-type dispersant and a leveling agent and an organic solvent as a viscosity modifier, it can be contained up to 10% by weight based on the total amount of the ink composition.

  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-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o- L-toluene, 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, ethyl 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 monobutyl 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 cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, acetic acid Isobutyl Propyl acetate, and dibasic acid esters, and the like, used alone or in combination.

[Polyfunctional monomer (E)]
The ink composition of the present invention is further added with a polyfunctional monomer (E) having two or more ethylenically unsaturated double bonds for the purpose of increasing the crosslinking density of the coating film and increasing various resistances of the cured coating film. Can do.

  Examples of the polyfunctional monomer (E) having two or more ethylenically unsaturated double bonds (hereinafter abbreviated as polyfunctional monomer (E)) include polyethylene glycol di (meth) acrylate and neopentyl glycol di (meth). Acrylate, trimethylolpropane (PO-modified) tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol Examples include various acrylic esters and methacrylic esters such as penta (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate. It can be used, not necessarily limited thereto. These may be used alone or in combination.

  The total of the thermosetting melamine mixture (C) and the polyfunctional monomer (E) contained in the ink is preferably 15% by weight or more based on the total amount of the ink. When the total of the thermosetting melamine mixture (C) and the polyfunctional monomer (E) is less than 15% by weight, sufficient effects for improving fluidity and curability cannot be obtained.

〔dispersion〕
The correction ink composition for a color filter of the present invention comprises an organic pigment (A), a monofunctional monomer (B), a thermosetting melamine compound (C), if necessary, a polyfunctional monomer (E), and an organic solvent. It can manufacture by disperse | distributing to (D). The dispersion of the organic pigment in the monomer can be performed using various dispersing means such as a three roll mill, a two roll mill, a sand mill, a kneader, and an attritor.

  When dispersing the pigment in the pigment carrier, organic pigment derivatives, dispersion aids such as resin-type pigment dispersants, surfactants and the like can be used as appropriate. 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. The dispersing aid can be used in an amount of 0.1 to 30% by weight, based on the total weight of the pigment.

[Organic dye derivative]
The organic dye derivative is a compound represented by the following general formula (3), and there are those having a basic substituent and those having an acidic substituent.

General formula (3):
P-Lm (3)
{In General Formula (3), P is an m-valent organic dye residue, m is an integer of 1 to 4, and L is an organic substituent having a basic substituent or an acidic substituent. . )
In the general formula (3), the organic pigment constituting the organic dye residue of P includes diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, and polyazo, copper phthalocyanine, halogenated copper phthalocyanine, halogenated Phthalocyanine pigments such as zinc phthalocyanine and metal-free phthalocyanine, anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone pigment, dioxazine pigment, Examples thereof include perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, and metal complex pigments.

  In the general formula (3), examples of L include basic substituents represented by the following general formula (4), general formula (5), general formula (6), and general formula (7). Examples of the substituent include substituents represented by the following general formula (10), general formula (11), and general formula (12).

General formula (4):

General formula (5):

General formula (6):

General formula (7):
[In the general formulas (4) to (7),
X is —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ —, or a direct bond;
n is an integer of 1 to 10,
R ₁ and R ₂ are each independently an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, an optionally substituted phenyl group, R ₁ and R ₂ form together, heterocyclic ring which may be substituted or R ₁ and and R ₂ form together, further nitrogen, an oxygen or sulfur atom, substituted A heterocyclic ring which may be
R ₃ is an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group;
R ₄ , R ₅ , R ₆ , and R ₇ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, or an optionally substituted alkenyl group having 2 to 36 carbon atoms. Or an optionally substituted phenyl group,
Y is —NR ₈ —Z—NR ₉ — or a direct bond;
R ₈ and R ₉ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted group. A good phenyl group,
Z is an optionally substituted alkylene group having 1 to 36 carbon atoms, an optionally substituted alkenylene group having 2 to 36 carbon atoms, or an optionally substituted phenylene group,
R is a substituent represented by the general formula (8) or a substituent represented by the general formula (9);
Q is a hydroxyl group, an alkoxyl group, a substituent represented by the following general formula (8), or a substituent represented by the following general formula (9).

General formula (8):

General formula (9):
(In the general formulas (8) and (9), R _{1 to} R ₇ and n are as defined in the general formulas (4) to (7).)]
General formula (10):
-SO ₃ M / i
General formula (11):
-COOM / i

Formula (12):
[In the general formulas (10) to (12),
M is a hydrogen atom, calcium atom, barium atom, strontium atom, manganese atom, or aluminum atom;
i is the valence of M;
R ₁₀ , R ₁₁ , R ₁₂ , and R ₁₃ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, or an optionally substituted alkenyl group having 2 to 36 carbon atoms. , An optionally substituted phenyl group. ]}

  Examples of the amine component used to form the substituents represented by the formulas (4) to (9) include dimethylamine, diethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine , Disec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, didecylamine Diallylamine, N, -Ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamyl Amine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopro Ruamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecholine, 3-pipecholine, 4 -Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-piperidinemethanol, Pipecolic acid, Isonipecotate, Methyl isonipecotate, Ethyl isonipecotate, 2-Piperidinethanol, Pyrrolidine, 3-hydroxy Pyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecholine, N-aminopropyl Examples include propylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, and 1-cyclopentylpiperazine.

  The amine component used to form the sulfonic acid amine salt of formula (12) may be any of primary, secondary, tertiary and quaternary amines. For example, primary amines have side chains. Hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, And amines such as eocosylamine, and unsaturated amines corresponding to the respective carbon number.

  Secondary amine, tertiary amine, and quaternary ammonium salts include dioleylamine, distearylamine, dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylstearylamine, dilaurylmonomethylamine, trioctylamine, dimethyldiamine. Dodecyl ammonium chloride, dimethyl dioleyl ammonium chloride, dimethyl didecyl ammonium chloride, dimethyl dioctyl ammonium chloride, trimethyl stearyl ammonium chloride, dimethyl distearyl ammonium chloride, trimethyl decyl ammonium chloride, trimethyl hexadecyl ammonium chloride, trimethyl octadecyl ammonium chloride, dimethyl dodecyl Tetradecyl ammonium chloride, and di Chill hexadecyl ammonium chloride, and the like.

(Resin type pigment dispersant)
The resin-type pigment dispersant has a pigment affinity part that has the property of adsorbing to the pigment and a part that is compatible with the pigment carrier, and acts to stabilize the dispersion of the pigment on the pigment carrier by adsorbing to the pigment. It is something to do. Specific examples of resin-type pigment dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, and amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups Oily dispersants such as salts thereof;
Water-soluble polymer systems such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, polyester Examples thereof include aqueous dispersants such as a system, a modified polyacrylate system, an ethylene oxide / propylene oxide addition compound system, and a phosphate ester system, and these can be used alone or in admixture of two or more.

  Specific examples of commercially available resin-type pigment dispersants that can be used in the present invention include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110, and 111 (copolymers containing acid groups) manufactured by Big Chemie. Polymer)), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), “BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), manufactured by EFKA “EFKA 4047, 4050, 4010, 4165 (polyurethane type), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 ( Fatty acid polyester) ", Ajinomoto Fan Techno Co., Ltd. “Spar PB821, PB822”, “Floren TG-710 (urethane oligomer)” manufactured by Kyoeisha Chemical Co., Ltd., “Polyflow No. 50E, No. 300 (acrylic copolymer)”, “Disparon KS-860, 873SN” manufactured by Enomoto Kasei , 874, # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyether ester), DA-703-50, DA-705, DA-725 "," Demol RN, N (naphthalenesulfonic acid formalin) manufactured by Kao Corporation Polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) ”,“ homogenol L-18 (polymer polycarboxylic acid) ”,“ Emulgen 920, 930, 935, 985 (polyoxy) Ethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ”, ru “Solsperse 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer)” manufactured by Brisol Co., Ltd., “Nikkor T106 (polyoxyethylene sorbitan mono) manufactured by Nikko Chemical Co., Ltd. Oleate), MYS-IEX (polyoxyethylene monostearate) "and the like.

[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.

[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 is heated and cured by 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, “part” represents “part by weight”.

[Preparation example of correction ink composition for color filter]
In the composition shown in Table 1 below, the mixture was stirred and mixed uniformly, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 1 mm. It filtered with the filter and produced the pigment compositions 1-7. Next, the mixture having the composition shown in Table 2 below was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter. The thermosetting ink compositions 1 for correcting color filters of Examples 1 to 10 and Comparative Examples 1 to 4 were used. ~ 7 were made.

Here, the CIPigment numbers of the organic pigment (A) in Table 1 are as follows.
CibaOPHTAL RED A2B manufactured by Ciba Japan: CIPigment Red 177
・ Toyo Ink Manufacturing “LIONOL GREEN 6YK”: CIPigment Green 36
-LANXESS "E4GN": CIPigment Yellow 150
・ Toyo Ink Manufacturing “LIONOL BLUE ES”: CIPigment Blue 15: 6
・ BASF "PALIOTOL YELLOW D1819": CIPigment Yellow 139
Degussa “Printex 75”: CIPigment Black 7

The structure of the monofunctional monomer (B) in Table 1 is as follows.
“Viscoat # 192” manufactured by Osaka Organic Chemical Co., Ltd .: a monomer represented by the general formula (1), wherein R ₁ and R ₃ are H, R 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 R ₁ and R ₃ are H, R 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 R ₁ and R ₃ are H, R ₂ is C ₂ H ₄ , and n is 6.

  Here, the polyfunctional monomer (E) in Table 2 is as follows.

-"Aronix M400" manufactured by Toagosei Co., Ltd .: Dipentaerythritol penta and hexaacrylate-"Aronix M305" manufactured by Toagosei Co., Ltd .: Pentaerythritol triacrylate The thermosetting melamine mixture (C) in Table 2 is as follows.
-“Nicalak MW-30” manufactured by Nippon Carbide Industries Co., Ltd .: a monomer represented by the general formula (2), wherein D _{1 to} D ₆ are CH ₂ OCH ₃ .
-“Nicalak MX-45” manufactured by Nippon Carbide Industries Co., Ltd .: a monomer represented by the general formula (2), wherein D _{1 to} D ₆ are CH ₂ OCH ₃ and CH ₂ OC ₄ H ₉ .
“Nicarac MS-11” manufactured by Nippon Carbide Industries Co., Ltd .: a monomer represented by the general formula (2), wherein D _{1 to} D ₆ are CH ₂ OCH ₃ and CH ₂ OH, and contain 40% of a solvent. .

Moreover, the organic solvent (D) of Table 2 is as follows.
・ Cyclohexanone ・ DEDG: Diethylene glycol diethyl ether

  The ink compositions 1 to 14 obtained in Examples 1 to 10 and Comparative Examples 1 to 4 are filled in a glass micropipette (FIG. 1: tube inner diameter 260 μm, discharge tip inner diameter 5 μm), and pixels are removed in a square for correction. Extrusion was applied to the areas. The coated product was dried at 230 ° C. for 20 minutes to obtain a coating film. Evaluation methods and evaluation ranks are as follows. The results are shown in Table 3.

[Drying resistance]
The correction ink was put in from the side where the tip of the glass micropipette in FIG.
○: Discharged ×: Impossible to discharge due to clogging at the moment when the corrected ink comes out from the tip (liquid spread suppression evaluation and appearance evaluation)
The corrected portion of the above-described extrudable ink was observed with an optical microscope.
A: Corrected ink is completely replenished only to the removed part, and the corrected ink does not overlap the part that has not been removed, and there is little chromaticity difference between the corrected part and the uncorrected part. If the correction ink is completely replenished, the correction ink slightly overlaps the part that has not been removed, but the chromaticity difference between the corrected part and the uncorrected part is small. X: Only the removed part is corrected When ink is completely replenished, the difference in chromaticity between the corrected and uncorrected areas is noticeable.

(Solvent resistance evaluation)
Observe the changes in the coating after immersion of the dried coating in N-methylpyrrolidone for 30 minutes.
○: Insoluble.
X: Swelling, dissolution, or color loss.

  As shown in Table 3, the correction inks obtained in Examples 1 to 8 were evaluated for drying resistance, liquid spread suppression evaluation, even when the tip as shown in FIG. Both the evaluation results of the appearance evaluation and the solvent resistance evaluation were good.

  In Example 9 in which the amount of the solvent (D) is 10% based on the total amount of the ink and the boiling point of the main solvent component is 156 ° C., drying resistance, liquid spread suppression evaluation, appearance evaluation, and solvent resistance evaluation All the evaluation results were good.

  In Example 10 in which the amount of the solvent (D) is 10% based on the total amount of the ink and the boiling point of the main solvent component is 188 ° C., if the correction ink is completely replenished only to the removed portion, it is removed. The correction ink slightly overlapped the part that was not, but it was in a range where it could be used.

  In Comparative Example 1 using the monofunctional monomer (B) having n of 6 in the general formula (1), when the corrected ink is completely replenished only to the removed portion, the difference in chromaticity between the corrected portion and the uncorrected portion. Became prominent.

In Comparative Example 2 using the monomer represented by the general formula (2) of the thermosetting melamine mixture (C) in which D _{1 to} D ₆ are CH ₂ OCH ₃ and CH ₂ OH, the correction ink is at the tip. Discharge became impossible due to clogging at the moment of leaving.

  In Comparative Example 3 not including the thermosetting melamine mixture (C), the thermosetting was insufficient and the solvent resistance was poor.

  In Comparative Example 4 in which the amount of the solvent (D) exceeds 10% based on the total amount of ink, the correction ink cannot be ejected due to clogging at the moment when it comes out from the tip.

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

Explanation of symbols

1: Glass micropipette 2: Ink filling part of glass micropipette 3: Tube inner diameter (260 μm) of glass micropipette
4: Discharge tip inner diameter of glass micropipette (5μm)

Claims (4)

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 thermosetting ink composition for correcting color filters, comprising a mixture (C) of a compound and / or a partial condensate thereof, and 10% by weight or less of an organic solvent (D) based on the total amount of the ink.
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 is hydrogen or carbon that may contain a benzene ring. (It is the alkyl group of number 1-20, and n is an integer of 1-4.)
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 thermosetting ink composition for correcting a color filter according to claim 1, further comprising a polyfunctional monomer (E) having two or more ethylenically unsaturated double bonds.   The color filter correction material according to claim 1 or 2, wherein the content of the mixture (C) of the thermosetting melamine compound and / or its partial condensate is 10 to 100% by weight based on the monofunctional monomer (B). Thermosetting ink composition.   The total content of the mixture (C) of the thermosetting melamine compound and / or its partial condensate and the polyfunctional monomer (E) is 15% by weight or more based on the total amount of the ink. The thermosetting ink composition for color filter correction as described.