JP2010111708A - Colored composition containing azo metal complex pigment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an azo metal complex pigment used for a color filter, inkjet and the like, finely divided, and excellent in fluidity and dispersion stability, and having high contrast when formed into a coating film. <P>SOLUTION: A colored composition includes: a pigment carrier comprising a transparent resin; its precursor or a mixture thereof; and an azo barbituric acid metal complex melamine clathrate pigment treated with an unsaturated higher fatty acid. In the colored composition after drying, an existence probability of particles with median secondary particle diameter ≤30 μm and ≥100 μm, is ≤1%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  Generally, in various coatings or ink compositions, a practically useful pigment that exhibits a clear color tone and high coloring power is composed of fine particles. However, when fine particles of pigment are dispersed in non-aqueous vehicles such as offset ink, gravure ink, color filter resist ink, inkjet ink, and paint, it is difficult to obtain a stable dispersion. It is known to cause various problems that significantly affect the value of the resulting product.

  For example, dispersions containing pigments consisting of fine particles often exhibit high viscosity, making it difficult not only to remove the product from the disperser and to transfer it from the disperser to a tank, etc. It may become difficult to use due to gelation. In addition, when different types of pigments are mixed and used, phenomena such as color separation and sedimentation due to aggregation of the pigments may cause uneven color and a marked decrease in coloring power in the developed product. In addition, the surface of the coating film of the color-extended product may cause a state failure such as a decrease in gloss and a leveling failure. Although not directly related to the dispersion of the pigment, some organic pigments have a phenomenon accompanied by a change in the crystal state of the pigment. In other words, in the case of offset ink, gravure ink, color filter ink, paint, etc., the pigment crystal particles that were in an unstable state in the vehicle changed their size and form to a stable state. Therefore, the product value may be impaired due to a significant change in hue, a reduction in coloring power, generation of coarse particles, and the like in the developed product.

  In particular, pigments used in the manufacture of color filters must have high heat resistance and weather resistance. The pigments used include phthalocyanine pigments, diketopyrrolopyrrole pigments, quinacridone pigments, isoindoline pigments, and isoindoline pigments. Examples thereof include linone pigments, benzimidazolone pigments, quinophthalone pigments, and azo metal complex pigments. Among them, azobarbituric acid nickel complex, that is, C. I. Pigment Yellow 150, is a colorant with high coloring power and is currently widely used. However, when this pigment does not have a compound to be included, it is difficult to control the particles during the production of the pigment, and the pigment becomes difficult to disperse due to strong aggregation and irregular particles. It is also known to have crystal water and is thermally unstable.

  Therefore, in Patent Document 1 and Patent Document 2, it is proposed to include melamine as a particularly suitable product by inclusion of a compound with an azobarbituric acid metal complex and to improve dispersion by adjusting pH. ing. With this method, weather resistance and heat resistance are improved. However, melamine clathrate pigments are still difficult to disperse pigments, and large quality blurring occurs in batch production. Therefore, in order to disperse the pigment in the vehicle, it is necessary to apply a great deal of energy to mechanically disperse or to add a surfactant. However, in order to obtain the required effect, a considerable amount is required, and when the resist ink for the color filter is used, various characteristics required may be lost. There is an urgent need to obtain a pigment dispersion that is excellent in dispersion without losing various resistances, and for that purpose it has been necessary to improve the dispersibility of the pigment.

Patent Document 3 proposes an approach for improving dispersibility by introducing a basic functional group into a part of melamine to be included. Although this method improves dispersibility, it has a problem of high cost as compared with the case where only melamine is included. In addition, although a pigment exhibiting a high contrast ratio although having excellent dispersion stability cannot be obtained, a pigment having a high contrast ratio and high dispersion stability has been required.
JP 58-52361 A JP 2000-119544 A JP 2006-016506 A

  The problem to be solved by the present invention is to provide an azo metal complex pigment that can be used in color filters, ink jets, etc., and has a high contrast when formed into a coating film that is fine and has excellent fluidity and dispersion stability. .

That is, the present invention is characterized in that it is formed from a pigment carrier comprising a transparent resin, its precursor or a mixture thereof, and an azobarbituric acid metal complex melamine inclusion pigment treated with an unsaturated higher fatty acid. The present invention relates to a coloring composition.
The present invention also relates to a colored composition, wherein the metal is nickel.
The present invention also relates to a coloring composition, wherein the azobarbituric acid metal complex melamine inclusion pigment has an average primary particle size of 20 to 40 nm.

  Furthermore, the present invention is characterized in that, in the azobarbituric acid metal complex melamine inclusion pigment, the median diameter of the secondary particle diameter after drying is 30 μm or less and the existence probability of particles having a particle diameter of 100 μm or more is 1% or less. The present invention relates to a coloring composition.

  The pigment of the present invention can be easily produced, and further, by using the pigment of the present invention, it is possible to obtain a color filter ink having excellent dispersion stability over time and excellent contrast when formed into a coating film. It becomes possible. Due to the excellent stability over time, productivity can be improved in processes such as ink production and color filter creation.

  In the present invention, azobarbituric acid refers to a compound in which two barbituric acids are bonded via an azo group and their tautomers. Barbituric acid may have a substituent such as an alkyl group having 1 to 6 carbon atoms.

    In the present invention, inclusion of a compound means a state in which the compound interacts with an azobarbituric acid or azobarbituric acid metal complex. In other words, when the compound is included in azobarbituric acid or azobarbituric acid nickel complex, it is not washed away by filtration or the like, unlike powder mixing, and crystal growth and heat resistance are improved. It has a great influence on physical properties. Further, when an azobarbituric acid metal complex and melamine are included, an X-ray diffraction peak different from that of the mixture is shown, so that it is known that a crystal different from the mixture is formed.

  In the present invention, the metal is an alkali metal such as sodium or potassium, an alkaline earth metal such as magnesium or calcium, aluminum and a transition metal such as iron, copper or nickel, and one kind of metal or two or more kinds of metals are mixed. May be used. Preferably, nickel, copper, cesium, cobalt, barium, strontium and manganese can be used alone or in combination. In particular, a pigment having a small particle size can be obtained by mixing and using 0.01 mol% to 1.0 mol% of another metal with respect to nickel.

  In the present invention, the unsaturated higher fatty acid is characterized by having 10 or more carbon atoms and having 1 to 2 or more double bonds in the carbon chain. In order to wet the pigment and exert its effect, it is preferably highly hydrophobic, and preferably has 10 or more carbon atoms, more preferably 16 or more, and oleic acid, linoleic acid, linolene are preferable. Examples include acids. Moreover, you may mix and use 2 or more types of carboxylic acid as needed.

  The unsaturated higher fatty acid of the present invention can be treated in any step during or after pigment synthesis. The treatment is preferably performed while the pigment is being synthesized, and more preferably, the treatment is performed during the complexation reaction.

The pigment of the present invention can be produced by the following steps.
First, an aromatic sulfonic acid hydrazide or aminoguanidine is converted to an azide compound with an alkali metal nitrite, and a diazo transfer reaction is performed on the barbituric acid to produce diazobarbituric acid. Barbituric acid is added without isolation, and an azo coupling reaction is performed. Thereafter, the particles are grown and isolated by pH adjustment and heat treatment until they can be filtered with a filter press. At this time, washing is repeated until no side reaction products and unreacted raw materials can be confirmed, and the cake is stored as a cake.

  The azobarbituric acid stored in the cake is fully dispersed again in water and melamine monomer and unsaturated fatty acid are added. An inorganic acid is added so that melamine is sufficiently dispersed, and the pH is adjusted to a weakly acidic region so as to uniformly disperse. Thereafter, an aqueous solution of metal chloride is dropped, heat treatment is performed, pH is adjusted to a weakly acidic region, and heat treatment is performed again. Thereafter, it is thoroughly washed until there is no unencapsulated melamine monomer, and after an aftertreatment step such as drying and pulverization, an azobarbituric acid metal complex melamine inclusion pigment is obtained.

  Control of the secondary particle size after drying can be obtained by grinding. The pulverization equipment includes pin mills, hammer mills and turbo mills, which are usually used for dry pulverization of pigments, ball mills and vibration mills that use the impact force of media, or jet pulverization. Machine. Among them, it is preferable to use a high-speed rotational impact shearing type pulverizer because a desired pulverized particle diameter can be easily obtained. In addition, it is possible to control the pulverized particle diameter by controlling the conditions of the pulverizer such as the pulverization time (feed amount) and pulverization temperature. Depending on the rotation speed and the mesh size of the screen, it can be within the range of the pulverized particle diameter of the present invention.

  Furthermore, it is preferable to use a dry classifier to reliably remove coarse particles and to obtain a dispersant having a pulverized particle size range of the present invention. As the classifier, a commonly used classifier can be used, and examples thereof include a fluid type and an airflow type. Furthermore, in spray drying in which the drying and pulverization steps are performed at once, the desired pulverized particle diameter can also be obtained by controlling the feed amount of the pigment dispersant slurry, the pigment dispersant concentration, and the temperature of the atomizer part.

  In the present invention, the average primary particle diameter is the average of the particle diameters determined with a transmission electron microscope. The primary particle size of the pigment is determined by a general method for directly measuring the size of primary particles from a transmission electron micrograph. Specifically, the minor axis diameter and major axis diameter of each primary particle are measured, and the average is taken as the particle diameter of the particle. Next, for 100 or more particles, the volume (weight) of each particle is obtained by approximating it to a rectangular parallelepiped having the obtained particle size, and the volume average particle size is obtained and used as the average primary particle size.

  In the present invention, the dry pulverized particle size distribution is determined as follows. First, a laser analysis / scattering method is used as a measuring instrument, and the refractive index of the particles is defined as 2.00-0.2i, and the measurement is performed on a volume basis. The median diameter indicates 50% particle size in the dry pulverized particle size distribution thus determined.

  In the present invention, the transparent resin includes a photosensitive transparent resin and a non-photosensitive transparent resin, and the transmittance is preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. is there.

  The photosensitive transparent resin is a resin having an ethylenically unsaturated double bond, for example, a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, an amino group, an isocyanate group, an aldehyde group, an epoxy group, A functional group having an ethylenically unsaturated double bond such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a reactive substituent such as a carboxyl group or cinnamic acid. Resin. Specifically, a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated double bond are added to a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group and another ethylenically unsaturated monomer. Some of them are obtained by reacting the compounds they have. Examples of the functional group capable of reacting with a hydroxyl group include an isocyanate group and a carboxyl group, but an isocyanate group is particularly preferred in terms of reactivity, and specifically, a compound having an isocyanate group and an ethylenically unsaturated double bond. , 2-acryloyl ethyl isocyanate, 2-methacryloyl ethyl isocyanate and the like. In addition, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  The non-photosensitive transparent resin is a resin that does not have an ethylenically unsaturated double bond, and includes a thermoplastic resin and a thermosetting resin. Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, styrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a phenol resin, a melamine resin, and a urea resin.

  In order to improve dispersibility, a resin-type dispersion material or a pigment derivative can be added to the colored composition of the present invention. 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 photosensitive transparent resin and the non-photosensitive transparent resin. It functions to stabilize dispersion in the resin composition. 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, 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, and salts thereof Used. In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, and water-soluble Polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and the like are also used. These can be used alone or in admixture of two or more.

  Commercially available resin-type pigment dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, manufactured by Big Chemie. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen SOLSPERSE-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 320 manufactured by Abyssia 0, 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, etc., EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402 manufactured by Efka Chemicals 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503, and the like.

  A pigment derivative is a compound in which a substituent is introduced into an organic pigment. Organic dyes include light yellow cyclic compounds such as naphthalene, anthraquinone, and barbituric acid that are not generally called dyes. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used singly or in combination of two or more.

  In the coloring composition of the present invention, the azobarbituric acid metal complex melamine inclusion pigment is sufficiently dispersed in the photosensitive resin composition and applied onto a transparent substrate such as a glass substrate to form a filter segment. A solvent can be included for ease. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n-amyl ketone, propylene glycol monomethyl ether toluene, Examples include methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like. These may be used alone or in combination. The solvent can be used in an amount of preferably 800 to 4000 parts by weight, more preferably 1000 to 2500 parts by weight with respect to 100 parts by weight of the colored composition.

  When the composition is cured by irradiation with light such as ultraviolet rays, a photopolymerization initiator or the like is added to the colored composition of the present invention. Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane Acetophenone photopolymerization initiators such as -1-one, benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4 Benzophenone photopolymerization initiators such as phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2 Thioxanthone photopolymerization initiators such as 2,4-diisopropylthioxanthone, 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, 2,4-bis (tri (Loromethyl) -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. A polymerization initiator, a borate photopolymerization initiator, a carbazole photopolymerization initiator, an imidazole photopolymerization initiator, or the like is used. The photopolymerization initiator can be used in an amount of preferably 5 to 20 parts by weight, more preferably 10 to 150 parts by weight with respect to 100 parts by weight of the colored composition.

  These photopolymerization initiators are used alone or in admixture of two or more. As a sensitizer, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl-9,10-phenanth Such as lenquinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. A compound can also be used in combination. The sensitizer can be used in an amount of preferably 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

  The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust.

  Next, the color filter will be described. The color filter includes an additive color mixture comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and at least one magenta filter segment, at least one cyan filter segment, And a subtractive color mixture type having at least one yellow filter segment, and the colored composition of the present invention can be used for a red filter segment, a green filter segment, a yellow filter segment, and the like. As each color coloring composition, it can form using each color pigment, the said non-photosensitive transparent resin, and the usual each color coloring composition containing the said polyfunctional monomer.

  Examples of the green coloring composition include C.I. I. Pigment Green 7, 10, 36, 37, green pigments such as chlorinated brominated compounds of metal phthalocyanines can be used, the coloring composition of the present invention, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 It can be used in combination with the yellow pigments such as 182,185,187,188,193,194,198,199,213,214.

  Examples of the red coloring composition include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 81: 4, 146, 168, 177, 178, 184, Red pigments such as 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, and 279 can be used. I. Pigment Orange 43, 71, 73 and the like, the colored composition of the present invention, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 It can be used in combination with the yellow pigments such as 182,185,187,188,193,194,198,199,213,214.

  Examples of the blue coloring composition include C.I. I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. are used. Blue coloring compositions include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination.

  Examples of cyan coloring compositions include C.I. I. Blue pigments such as Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, and 81 are used.

  Examples of the magenta coloring composition include C.I. I. Pigment Violet 1, 19, C.I. I. Pigment Red 81, 122, 144, 146, 169, 177, 207 and the like violet pigments and red pigments are used.

  Further, the yellow coloring composition includes the coloring composition of the present invention or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 It can be used yellow pigments such 182,185,187,188,193,194,198,199,213,214.

A color filter can be manufactured by forming a filter segment of each color on a substrate using each color coloring composition by a photolithography method.
As the substrate, a glass plate having a high transmittance with respect to visible light, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.

  The formation of each color filter segment by photolithography is performed by the following method. That is, each color-colored photosensitive composition prepared as a color resist material of the above-mentioned solvent development type or alkali development type that is cured by light irradiation is applied to a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. To apply a dry film thickness of 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, “parts” means “parts by weight”.

(Synthesis Example 1 of Ligand)
A separable four-necked flask was equipped with a thermometer, a condenser tube, a nitrogen gas inlet tube, and a stirrer and charged with 150 parts of water. Further, 63 parts of 35% hydrochloric acid was dissolved to prepare a hydrochloric acid solution. While stirring the hydrochloric acid solution, attention was given to foaming, and 30 parts of aminoguanidine bicarbonate was dissolved. After confirming dissolution, the liquid temperature was lowered to 0 ° C. with an ice bath, and 19 parts of sodium nitrite was charged over 30 minutes. After stirring for 30 minutes between 0 ° C. and 15 ° C., sulfamic acid was charged until no coloration was observed on the potassium iodide starch paper. Furthermore, after adding 25.6 parts of barbituric acid, it heated up to 55 degreeC and stirred as it was for 2 hours. Further, 25.6 parts of barbituric acid was added, the temperature was raised to 80 ° C., and then sodium hydroxide was added until the pH became 5. The mixture was further stirred at 80 ° C. for 3 hours, then lowered to 70 ° C., filtered, washed with warm water, and dried at 80 ° C. to obtain 61.4 parts of disodium azobarbituric acid.

(Ligand synthesis example 2)
A separable four-necked flask was equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device, and 150 parts of water was charged, and 63 parts of 35% hydrochloric acid was charged while stirring to prepare a hydrochloric acid solution. While paying attention to foaming, 38.7 parts of benzenesulfonyl hydrazide was added to the hydrochloric acid solution, and ice was added until the liquid temperature became 0 ° C. or lower. After confirming cooling, 19 parts of sodium nitrite was charged over 30 minutes. After stirring for 30 minutes between 0 ° C. and 15 ° C., sulfamic acid was charged until no coloration was observed on the potassium iodide starch paper. Thereafter, the pH was adjusted to 7.0 to 9.0 with sodium hydroxide, 25.6 parts of barbituric acid was added, the temperature was raised to 50 ° C., and the mixture was stirred for 2 hours. Further, 25.6 parts of barbituric acid was added, the temperature was raised to 80 ° C., and hydrochloric acid was added until the pH reached 5. Furthermore, after stirring at 80 degreeC for 3 hours, it lowered to 70 degreeC, and filtered and washed with warm water. The obtained press cake was reslurried in 1200 parts of warm water, and then stirred at 80 ° C. for 2 hours. Thereafter, filtration was carried out at the same temperature, followed by washing with 2000 parts of 80 ° C. water, and it was confirmed that benzenesulfonamide had migrated to the filtrate side. The press cake obtained after reslurry was dried at 80 ° C. to obtain 61.0 parts of azobarbituric acid disodium salt.

(Pigment Synthesis Example 1)
A separable four-necked flask was equipped with a thermometer, a condenser tube, a nitrogen gas inlet tube, and a stirring device, charged with 600 parts of water, and further stirred with the disodium azobarbituric acid disodium salt obtained in Synthesis Example 1 of the ligand. Dispersion was confirmed by charging 25.0 parts of powder and 0.5 part of oleic acid. After uniformly dispersing, the pH was adjusted to 1.0, the solution was heated to 95 ° C., and 19.2 parts of melamine was added. A green solution obtained by dissolving 18.6 parts of nickel chloride hexahydrate in 115 parts of water was added dropwise over 5 minutes. After completion of the dropwise addition, complexation was performed at 90 ° C. for 1.5 hours. Thereafter, the pH was adjusted to 5.5, and the mixture was further heated and stirred for 4 hours. Filtration was quickly performed, and washing with warm water was repeated until inorganic salts and excess melamine could be washed. After completion, the film was dried at 80 ° C. until the water content became 1.5% or less. . The mixture was pulverized by a pulverizer equipped with a classifier to obtain 42 parts of a metal complex pigment having a median diameter of 22.3 μm and particles of 100 μm or more being 0.1% or less. The average primary particle size was 28 nm.

(Pigment synthesis example 2)
Pigment Synthesis A dry pigment was obtained in the same manner except that oleic acid in Example 1 was changed to linoleic acid. The mixture was pulverized by a pulverizer equipped with a classifier to obtain 41.8 parts of a metal complex pigment having a median diameter of 21.8 μm and particles having a particle size of 100 μm or more being 0.1% or less. The average primary particle size was 35 nm.
(Pigment Synthesis Example 3)
Pigment Synthesis A dry pigment was obtained in the same manner except that oleic acid in Example 1 was changed to linolenic acid. The mixture was pulverized by a pulverizer equipped with a classifier to obtain 40.9 parts of a metal complex pigment having a median diameter of 25.4 μm and particles having a particle size of 100 μm or more being 0.1% or less. The average primary particle size was 30 nm.
(Pigment Synthesis Example 4)
A dry pigment was obtained in the same manner except that the ligand synthesis example 1 in the pigment synthesis example 1 was changed to the ligand synthesis example 2. The mixture was pulverized by a pulverizer equipped with a classifier to obtain 41.4 parts of a metal complex pigment having a median diameter of 21.2 μm and particles having a particle size of 100 μm or more being 0.1% or less. The average primary particle size was 24 nm.

(Pigment Comparative Synthesis Example 1)
A separable four-necked flask was equipped with a thermometer, a condenser tube, a nitrogen gas inlet tube, and a stirring device, charged with 600 parts of water, and further stirred with the disodium azobarbituric acid disodium salt obtained in Synthesis Example 1 of the ligand. 25.0 parts of the powder was charged and dispersion was confirmed. After uniformly dispersing, the pH was adjusted to 1.0, the solution was heated to 95 ° C., and 19.2 parts of melamine was added. After confirming sufficient dispersion, a green solution prepared by dissolving 18.6 parts of nickel chloride hexahydrate in 115 parts of water was added dropwise over 5 minutes. After completion of the dropwise addition, complexation was performed at 90 ° C. for 1.5 hours. Thereafter, the pH was adjusted to 5.5, and the mixture was further heated and stirred for 4 hours. After cooling to 80 ° C., it was quickly filtered and washed with warm water until inorganic salts and excess melamine could be washed. After completion, the film was dried at 80 ° C. until the water content became 1.5% or less. The mixture was pulverized by a pulverizer equipped with a classifier to obtain 42 parts of a metal complex pigment having a median diameter of 22.3 μm and particles of 100 μm or more being 0.1% or less. The average primary particle diameter of the pigment was 32 nm.
(Comparative Synthesis Example 2 of Pigment)
A separable four-necked flask was equipped with a thermometer, a condenser tube, a nitrogen gas inlet tube, and a stirring device, charged with 600 parts of water, and further stirred with the disodium azobarbituric acid disodium salt obtained in Synthesis Example 1 of the ligand. 25.0 parts of the powder was charged and dispersion was confirmed. After uniformly dispersing, the pH was adjusted to 1.0, the solution was heated to 95 ° C., and 19.2 parts of melamine was added. After confirming sufficient dispersion, a green solution prepared by dissolving 18.6 parts of nickel chloride hexahydrate in 115 parts of water was added dropwise over 5 minutes. After completion of the dropwise addition, complexation was performed at 90 ° C. for 1.5 hours. Thereafter, the pH was adjusted to 5.5, and the mixture was further heated and stirred for 4 hours. After cooling to 80 ° C., it was quickly filtered and washed with warm water until inorganic salts and excess melamine could be washed. After completion, the film was dried at 80 ° C. until the water content became 1.5% or less. The mixture was pulverized with a hammer mill to obtain 39.5 parts of a metal complex pigment having a median diameter of 65.2 μm and 25.4% of particles having a particle size of 100 μm or more. The average primary particle diameter of the pigment was 32 nm.
(Comparative Synthesis Example 3 of Pigment)
A separable four-necked flask was equipped with a thermometer, a condenser tube, a nitrogen gas inlet tube, and a stirring device, charged with 600 parts of water, and further stirred with the disodium azobarbituric acid disodium salt obtained in Synthesis Example 1 of the ligand. 25.0 parts of the powder was charged and dispersion was confirmed. After being uniformly dispersed, the solution was heated to 95 ° C. and 19.2 parts of melamine was added. After confirming sufficient dispersion, a green solution prepared by dissolving 18.6 parts of nickel chloride hexahydrate in 115 parts of water was added dropwise over 5 minutes. After completion of the dropwise addition, complexation was performed at 90 ° C. for 1.5 hours. Thereafter, the pH was adjusted to 5.5, and the mixture was further heated and stirred for 4 hours. After cooling to 80 ° C., it was quickly filtered and washed with warm water until inorganic salts and excess melamine could be washed. After completion, the film was dried at 80 ° C. until the water content became 1.5% or less. By pulverizing with a hammer mill, 39.8 parts of a metal complex pigment having a median diameter of 68.2 μm and 18.4% of particles having a particle size of 100 μm or more were obtained. The average primary particle size was 80 nm.

(Production example of non-photosensitive transparent resin solution 1)
A separable four-necked flask was equipped with a thermometer, a condenser tube, a nitrogen gas inlet tube, and a stirrer, charged with 70.0 parts of cyclohexanone, heated to 80 ° C. and purged with nitrogen in the reaction vessel. 13.3 parts of butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), 2, 2 A mixed solution of 0.4 part of '-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26000. After cooling to room temperature, a part of the resin solution is sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone is added to the previously synthesized resin solution so that the nonvolatile content is 30%. Thus, a non-photosensitive transparent resin solution 1 was prepared.

(Production example of photosensitive transparent resin solution 1)
480 parts of cyclohexanone is put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 32.0 parts of methacrylic acid, 224.0 parts of methyl methacrylate, 16.0 parts of n-butyl methacrylate at the same temperature, 29.0 parts of benzyl methacrylate, 19.0 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) as monomer (a), 15.0 parts of glycerol monomethacrylate, 2,2′- A mixture of 4.0 parts of azobisisobutyronitrile was added dropwise over 1 hour to conduct a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 80 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin copolymer solution was obtained.
Next, with respect to 445 parts of the obtained transparent resin copolymer solution, a mixture of 14.0 parts of 2-methacryloylethyl isocyanate, 0.4 part of dibutyltin laurate and 55.0 parts of cyclohexanone was added at 70 ° C. It dripped over time and the photosensitive transparent resin solution was obtained. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The previously synthesized photosensitive transparent resin solution has a non-volatile content of 20% by weight. Thus, cyclohexanone was added to prepare a photosensitive transparent resin solution 1. The obtained photosensitive transparent resin 1 had a weight average molecular weight Mw of 21000 and a double bond equivalent of 1000.

Example 1
After the mixture having the following composition is uniformly stirred and mixed, the mixture is dispersed for 2 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 dispersion was prepared.
Green pigment: C.I. I. Pigment Green 36 7.5 parts ("Rionol Green 6YK" manufactured by Toyo Ink Manufacturing Co., Ltd.)
Yellow pigment: Metal complex pigment obtained in Pigment Synthesis Example 7.5 7.5 parts Dispersant: Resin-type dispersant 3.4 parts (Ajinomoto Fine Chemical Co., Ltd. “Ajisper PB-821”)
Resin: Non-photosensitive transparent resin solution 1 20.3 parts Solvent: Cyclohexanone 56.5 parts

(Production Example 1 of photosensitive coloring composition)
Next, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a green colored composition having photosensitivity.
Pigment dispersion prepared in Example 1 67.0 parts Photosensitive transparent resin 1 solution 5.0 parts Dipentaerythritol hexaacrylate 4.0 parts Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Specialty Chemicals) 1.4 Part sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.) 0.2 part cyclohexanone 22.4 parts

(Examples 2 to 4)
A pigment dispersion was prepared by replacing the metal complex pigment obtained in Synthesis Example 1 of Example 1 with Pigment Synthesis Example 2, Pigment Synthesis Example 3, and Pigment Synthesis Example 4, respectively. Using the obtained pigment dispersion, green colored compositions were obtained.
(Comparative Examples 1-3)
A pigment dispersion was prepared by replacing the metal complex pigment obtained in Synthesis Example 1 of the pigment of Example 1 with Comparative Synthesis Example 1 of Pigment, Comparative Synthesis Example 2 of Pigment, and Comparative Synthesis Example 3 of Pigment, respectively. Using the obtained pigment dispersion, green colored compositions were obtained.

  Next, the obtained pigment dispersion and evaluation were performed. First, the obtained pigment dispersion was stored in a thermostatic bath at 25 ° C. for 30 minutes or more, then measured at 6 rpm and 60 rpm with a BM viscometer, and the 6 rpm viscosity was divided by the 60 rpm viscosity to obtain a thixo index (TI). Asked. Moreover, it stored for 1 week in a 40 degreeC thermostat, and measured the viscosity of 60 rpm with the BM type | mold viscosity meter. The photosensitive coloring composition was applied to a glass plate with a spin coater so as to have a target chromaticity, and was exposed, developed and baked at 230 ° C. to obtain a colored glass plate. Thereafter, brightness and contrast were determined. The brightness was calculated from a spectral curve obtained from a spectrophotometer “U-3100” manufactured by Hitachi, Ltd.

Contrast is measured using a brightness meter manufactured by TOPCON, with the colored glass plate sandwiched between two polarizing plates, and the luminance when the polarizing plates are parallel and perpendicular to each other is measured. It was calculated as the ratio of luminance when orthogonal.
The film was formed so that the target chromaticity was y = 0.57 in the xy color coordinates using a C light source as the light source.
The obtained results are shown in Table 1.

  The obtained results show that the pigments obtained in Pigment Synthesis Examples 1 to 4 are superior in dispersion stability and the coating contrast ratio is improved as compared with the pigments obtained in Comparative Synthesis Examples 1 and 2. It was.

(Example 5)
After the mixture having the following composition is uniformly stirred and mixed, the mixture is dispersed for 2 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 dispersion was prepared.
Red pigment: C.I. I. Pigment Red 254 6.0 parts ("Irgafoa Red BT-CF" manufactured by Ciba Specialty Chemicals)
Red pigment: C.I. I. Pigment Red 177 6.0 parts ("Chromophthaled Red A3B" manufactured by Ciba Specialty Chemicals)
Yellow pigment: Metal complex pigment obtained in Pigment Synthesis Example 1 3.0 parts Resin-type dispersion material 3.4 parts ("Ajisper PB-821" manufactured by Ajinomoto Fine Chemical Co., Ltd.)
Resin: Transparent resin solution 1 20.3 parts Solvent: 56.5 parts of cyclohexanone

(Method for producing photosensitive red coloring composition)
Next, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a green colored composition having photosensitivity.
Pigment dispersion prepared in Example 1 67.0 parts Photosensitive transparent resin 1 solution 5.0 parts Dipentaerythritol hexaacrylate 4.0 parts Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Specialty Chemicals) 1.4 Part sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.) 0.2 part cyclohexanone 22.4 parts

(Example 6)
After the mixture having the following composition is uniformly stirred and mixed, the mixture is dispersed for 2 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 dispersion was prepared.
Red pigment: C.I. I. Pigment Red 177 10.5 parts (“Chromophthaled Red A3B” manufactured by Ciba Specialty Chemicals)
Yellow Pigment: Metal Complex Pigment Obtained in Pigment Synthesis Example 4.5 4.5 parts Resin Type Dispersant 3.4 parts (“Ajisper PB-821” manufactured by Ajinomoto Fine Chemical Co., Ltd.)
Resin: Transparent resin solution 1 20.3 parts Solvent: 56.5 parts of cyclohexanone

(Method for producing photosensitive red coloring composition)
Next, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a green colored composition having photosensitivity.
Pigment dispersion prepared in Example 1 67.0 parts Photosensitive transparent resin 1 solution 5.0 parts Dipentaerythritol hexaacrylate 4.0 parts Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Specialty Chemicals) 4 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts cyclohexanone 22.4 parts

(Comparative Example 4)
The metal complex pigment obtained in the pigment synthesis example 1 of Example 5 was replaced with the pigment comparison synthesis example 1, and thereafter, the same pigment dispersion was prepared in the same manner. A red colored composition was obtained using the obtained pigment dispersion.
(Comparative Example 5)
A pigment dispersion was prepared by replacing the metal complex pigment obtained in Synthesis Example 1 of the pigment of Example 6 with Comparative Synthesis Example 1 of Pigment, and performing the same process thereafter. A red colored composition was obtained using the obtained pigment dispersion.

  Next, the obtained pigment dispersion and evaluation were performed. First, the obtained pigment dispersion was stored in a thermostatic bath at 25 ° C. for 30 minutes or more, then measured at 6 rpm and 60 rpm with a BM viscometer, and the 6 rpm viscosity was divided by the 60 rpm viscosity to obtain a thixo index (TI). Asked. The photosensitive coloring composition was applied to a glass plate with a spin coater so as to have a target chromaticity, and was exposed, developed and baked at 230 ° C. to obtain a colored glass plate. Thereafter, brightness and contrast were determined. The brightness was calculated from a spectral curve obtained from a spectrophotometer “U-3100” manufactured by Hitachi, Ltd.

Contrast is measured using a brightness meter manufactured by TOPCON, with the colored glass plate sandwiched between two polarizing plates, and the luminance when the polarizing plates are parallel and perpendicular to each other is measured. It was calculated as the ratio of luminance when orthogonal.
The film was formed so that the target chromaticity was x = 0.6 in the xy color coordinates using a C light source as the light source.
The obtained results are shown in Table 2.

From the results obtained, the pigment obtained in Pigment Synthesis Example 1 is superior in initial dispersion viscosity and dispersion stability in the red coloring composition as compared with the pigment obtained in Comparative Synthesis Example 1, and the contrast ratio of the coating film. Has been shown to improve.

(Example 7)
After the mixture having the following composition is uniformly stirred and mixed, the mixture is dispersed for 2 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 dispersion was prepared.
Yellow pigment: Metal complex pigment obtained in pigment synthesis example 14.25 parts Dye derivative: Dye derivative of the following formula (1) 0.75 part Resin-type dispersing agent 3.4 parts (Ajinomoto Fine Chemical Co., Ltd. “Ajisper PB -821 ")
Resin: Transparent resin solution 1 20.3 parts Solvent: Cyclohexanone 56.5 parts Formula (1)

(Method for producing photosensitive yellow coloring composition)
Next, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a yellow colored composition having photosensitivity.
Pigment dispersion prepared in Example 1 67.0 parts Photosensitive transparent resin 1 solution 5.0 parts Dipentaerythritol hexaacrylate 4.0 parts Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Specialty Chemicals) 4 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts cyclohexanone 22.4 parts

(Example 8)
Pigment Synthesis Example 1 was replaced with Pigment Synthesis Example 2, and the pigment derivative was changed from Formula (1) to Formula (2) below to obtain a pigment dispersion. A yellow colored composition was obtained using the obtained pigment dispersion.
Formula (2)

(Comparative Example 6, Comparative Example 7)
The pigment synthesis example 1 and pigment synthesis example 1 and pigment synthesis example 2 of Example 7 and Example 8 were replaced with pigment comparative synthesis example 1 and pigment comparative synthesis example 2, respectively. . A yellow colored composition was obtained using the obtained pigment dispersion.

  Next, the obtained pigment dispersion and evaluation were performed. First, the obtained pigment dispersion was stored in a thermostatic bath at 25 ° C. for 30 minutes or more, then measured at 6 rpm and 60 rpm with a BM viscometer, and the 6 rpm viscosity was divided by the 60 rpm viscosity to obtain a thixo index (TI). Asked. The photosensitive coloring composition was applied to a glass plate using a spin coater so as to have a target chromaticity, and a development and baking process was performed to obtain a colored glass plate. Thereafter, brightness and contrast were determined. The brightness was calculated from a spectral curve obtained from a spectrophotometer “U-3100” manufactured by Hitachi, Ltd.

Contrast was measured using a brightness meter manufactured by TOPCON, with the glass plate coated with the pigment dispersion sandwiched between two polarizing plates and the luminance when the polarizing plates were parallel and perpendicular to each other. The ratio of luminance when paralleled / luminance when orthogonalized was calculated.
The target chromaticity was a C light source, and a film was formed so that x = 0.44 in the xy color coordinates.

As shown in Tables 1, 2, and 3, pigments treated with unsaturated higher fatty acids have better dispersion stability, better initial viscosity, and higher contrast ratio when made into a coating than when not treated. It has been found. It was also found that the contrast ratio was further improved by using a specific dry pulverized particle size even when treated with the same unsaturated fatty acid.

Claims (4)

  A coloring composition comprising a pigment carrier comprising a transparent resin, a precursor thereof or a mixture thereof, and an azobarbituric acid metal complex melamine inclusion pigment treated with an unsaturated higher fatty acid.   The coloring composition according to claim 1, wherein the azobarbituric acid metal complex is an azobarbituric acid nickel complex.   The coloring composition according to claim 1 or 2, wherein the average primary particle diameter of the azobarbituric acid metal complex melamine inclusion pigment is 20 to 40 nm. The coloring composition according to any one of claims 1 to 3, wherein the pigment has a median diameter of a secondary particle diameter after drying of 30 µm or less and an existence probability of particles of 100 µm or more is 1% or less.