TWI812654B - Blue pigment dispersion composition for color filter of display device and blue pigment dispersion resist composition for color filter of display device - Google Patents

Abstract

The present invention provides a blue pigment dispersion composition for color filters with high tinting power and high brightness that can be used in color filters of display devices that meet new specifications. As a solution, it is to provide a blue pigment dispersion composition for a color filter for a display device, which is a blue pigment dispersion composition for a color filter mainly composed of a colored pigment, a pigment dispersion assistant, a resin and an organic solvent. The coloring pigment includes C.I. Pigment Blue 15:6 and zinc phthalocyanine green pigment.

Description

Blue pigment dispersion composition for color filter of display device and blue pigment dispersion resist composition for color filters of display devices

The present invention relates to a blue pigment dispersion composition for a color filter that can be used to form a color filter for a color display device.

In recent years, almost all display devices such as televisions, computers, and mobile phones have been gradually occupied by liquid crystal color display devices. Color filters used in liquid crystal color display devices generally have a transparent substrate, a coloring layer formed on the transparent substrate and composed of coloring patterns of three primary colors of red pixel areas, green pixel areas, and blue pixel areas, and A light-shielding portion (black matrix) is formed on the transparent substrate by distinguishing each colored pattern. These red pixel areas, green pixel areas, and blue pixel areas have a structure in which a synthetic resin film with excellent heat resistance and light resistance in which organic pigments are dispersed is provided on a substrate. As the organic pigments, red, green, and Blue organic pigments.

As the backlight in this liquid crystal color display device, there are types using cold-cathode tubes (cold-cathode tubes), types using LCDs, and types using white organic Type of EL element, etc. In addition, standards organizations in various countries have adopted the RGBW color specification (BT.2020) for such display devices, and display devices using LCDs are also expected to cope with 4K8K TVs and cope with this new standard. Color filters with expanded color gamut. Furthermore, there is a possibility that conventional blue compositions for color filters cannot adequately cope with blue (B).

Furthermore, even if the color filter composition using a combination of a blue pigment and a violet pigment described in Patent Document 1 is used, sufficient coloring power and high brightness cannot be obtained, and thus the composition is not sufficiently suitable for display devices in new specifications.

existing technical documents

patent documents

Patent Document 1: Japanese Patent Application Publication No. 2013-148872

An object of the present invention is to provide a blue pigment dispersion composition for color filters having high tinting power and high brightness that can be used in color filters of display devices conforming to new standards.

The inventors of the present invention conducted in-depth research to solve the above-mentioned problems, and found that by using C.I. Pigment Blue 15:6 and zinc phthalocyanine green pigments as color pigments, and using a pigment dispersion aid and a resin in combination, an LCD can be obtained. The present invention has been completed by providing a blue pigment dispersion composition for a color filter that has high tinting power and high brightness and has a suitable bluish hue for a color filter of a display device using a light source or a white organic EL light source.

That is, the present invention is as follows:

(1) A blue pigment dispersion composition for color filters of a display device, which is a blue pigment dispersion composition for color filters mainly containing a color pigment, a pigment dispersion assistant, a resin and an organic solvent, said The coloring pigments include C.I. Pigment Blue 15:6 and zinc phthalocyanine green pigments.

(2) The blue pigment dispersion composition for a color filter of a display device according to (1), wherein the resin includes an alkali-soluble resin and a photopolymerizable compound.

(3) The blue pigment dispersion composition for a color filter of a display device according to (1) or (2), wherein the mass ratio of the C.I. Pigment Blue 15:6 to the zinc phthalocyanine-based green pigment It is 99.9:0.1~90.0:10.0.

(4) The blue pigment dispersion composition for a color filter of a display device according to any one of (1) to (3), wherein the zinc phthalocyanine green pigment is C.I. Pigment Green 59 and C.I. Pigment Green 58 1 or more of them.

(5) A blue pigment dispersion resist composition for a color filter of a display device, which is a color filter for a display device that mainly contains a color pigment, a pigment dispersion aid, a resin, a photopolymerizable compound and an organic solvent A blue pigment-dispersed resist composition for tablets, wherein the colored pigment includes C.I. Pigment Blue 15:6 and zinc phthalocyanine green pigment.

(6) The blue pigment-dispersed resist composition for a color filter of a display device according to (5), wherein the resin includes an alkali-soluble resin and a photopolymerizable compound.

(7) The blue pigment-dispersed resist composition for a color filter of a display device according to (5) or (6), wherein the C.I. Pigment Blue 15:6 and the zinc phthalocyanine The mass ratio of green-like pigments is 99.9:0.1~90.0:10.0.

(8) The blue pigment-dispersed resist composition for a color filter of a display device according to any one of (5) to (7), wherein the zinc phthalocyanine green pigment is C.I. Pigment Green 59 and C.I. One or more of Pigment Green 58.

According to the present invention, a blue pigment dispersion composition for color filters that has high coloring power and high brightness and is also excellent in dispersion stability can be obtained.

Hereinafter, each component of the blue pigment dispersion composition for a color filter of a display device of the present invention will be specifically described.

The present invention relates to a blue pigment dispersion composition for a color filter of a display device and a blue pigment dispersion resist composition for a color filter. As the blue pigment dispersion composition for a color filter, A composition other than a resist may be used.

Regardless of the composition, the blue pigment dispersion composition for color filters of display devices of the present invention is a composition that can be used for color filters of display devices, and has high coloration as an effect of the present invention brought about by it. It has strong power and high brightness, and can provide blue pigment-dispersed compositions for color filters of display devices and blue pigment-dispersed resist compositions for color filters.

The present invention provides a blue pigment dispersion composition for color filters and a blue pigment for color filters prepared by blending an alkali-soluble resin, a photopolymerizable compound, and the like with the blue pigment dispersion composition for color filters. Dispersed resist composition.

Furthermore, the blue pigment dispersion composition for color filters includes a photocurable type and a non-photocurable type.

[A. Composition of blue pigment dispersion composition for color filter]

The blue pigment dispersion composition for color filters of the present invention mainly includes color pigments, pigment dispersion assistants, resins and organic solvents, and can be formulated with a pigment dispersant.

(pigment)

The blue pigment dispersion composition for a color filter of a display device of the present invention contains C.I. Pigment Blue 15:6 (C.I.PB15:6) and a zinc phthalocyanine-based green pigment as pigments.

The zinc phthalocyanine green pigment refers to a pigment containing a compound with a phthalocyanine structure having zinc as a central metal. In addition, the pigment may be a complex composed of a compound having a phthalocyanine structure with zinc as the central metal and other pigments within the range in which the effect of the present invention can be exerted synergistically with C.I. Pigment Blue 15:6.

As the zinc phthalocyanine-based green pigment, one or more types of C.I. Pigment Green 59 (C.I.PG59) and C.I. Pigment Green 58 (C.I.PG58) can be used. When a pigment having a compound having a zinc phthalocyanine structure is added to prepare a blue pigment dispersion composition for color filters and a blue pigment dispersion resist composition for color filters for display devices, the composition can be improved. The brightness of the object or the brightness and transmittance when forming a film.

In the blue pigment dispersion composition for color filters of the present invention, such as a display device equipped with a white organic EL light source, the total usage amount of the color pigments is preferably 5 to 80 mass in terms of mass ratio relative to the total solid content of the composition. %, more preferably 20 to 50 mass%.

In order to impart high brightness and contrast to the blue pigment dispersion composition for a color filter of the display device of the present invention, it is preferable to use micronized pigments as each of the above-mentioned colored pigments. By micronizing the primary particles of the color pigment, The diameter is finer and more uniform.

As the above-mentioned micronization treatment, for example, it is preferable to perform a micronization treatment including an untreated color pigment and a water-soluble inorganic salt (such as sodium chloride, barium chloride, potassium chloride, etc., preferably sodium chloride). The average particle size of the water-soluble inorganic salt used is preferably 50 μm or less) and a water-soluble dispersion medium (alkoxyalcohols, glycols, ethers, etc.) that does not substantially dissolve the water-soluble inorganic salt is prepared by Kneader, roller mill, ball mill, attritor, sand mill, and TRI-MIX (trademark) manufactured by Inoue Manufacturing Co., Ltd. as a planetary mixer described in Japanese Patent Application Publication No. 2006-192385 After kneading using a kneading device such as Miracle KCK manufactured by Asada Iron Works Co., Ltd., which is a continuous single-shaft kneader, a salt milling process is performed to remove the water-soluble inorganic salt and the water-soluble dispersion medium.

Furthermore, from the viewpoint of suppressing the crystal growth of the color pigment and uniformly miniaturizing it, it is preferable to perform the micronization process in the presence of a pigment dispersion aid described below. The usage amount of the pigment dispersion aid at this time is 0.5 to 30 parts by mass, preferably 3 to 10 parts by mass, based on 100 parts by mass of the colored pigment.

In addition to C.I. Pigment Blue 15:6, well-known blue colors such as C.I. Pigment Blue 15:3 (C.I.Pigment Blue 15:3) and C.I. Pigment Blue 16 (C.I.PB16) can be used together within the scope that does not impair the effect of the present invention. Pigments. In addition, as the green pigment, for example, C.I. Pigment Green 7 (C.I.PG7), C.I. Pigment Green 36 (C.I.PG36), etc. can be used as long as the effect of the present invention is not impaired and the brightness and contrast are not reduced.

However, it is better not to use purple pigments.

(Pigment dispersion additive)

As the pigment dispersion aid of the blue pigment dispersion composition for color filters used in the display device of the present invention, it is preferable that the base material has the same or similar molecular structure as C.I. Pigment Blue 15:6 (epsilon phthalocyanine copper pigment) A pigment dispersion aid that is a pigment dispersant containing an acidic group by introducing an acidic group into the skeleton to improve affinity with organic solvents. In the steps of micronizing and dispersing the pigment, such a pigment dispersion aid has the ability to disperse the pigment in fine particles because the basic skeleton is adsorbed on the surface of the pigment and the acidic group increases the affinity with the organic solvent and the pigment dispersant. It has the effect of improving the dispersion stability over time after dispersion and dispersion. In addition, the pigment dispersion aid itself is in a state of being dissolved or dispersed in fine particles in the organic solvent, and can be adsorbed over a wider range of the pigment surface, which is more preferable.

Among them, good results can be obtained by using a pigment dispersion aid having a sulfonic acid group as an acidic group.

In the blue pigment dispersion composition for color filters of the display device of the present invention, the usage amount of the pigment dispersion assistant having an acidic group is 0.5 to 30 parts by mass relative to 100 parts by mass of the colored pigment. When the content of the above-mentioned pigment dispersion aid having an acidic group is less than 0.5 parts by mass, the pigment dispersion effect decreases, on the other hand, when it exceeds 30 parts by mass, the pigment dispersion effect is not further improved.

The above-mentioned pigment dispersion aids with acidic groups are as follows:

(1) When using a colored pigment that has been micronized without the presence of a pigment dispersion aid having an acidic group, when dispersing the micronized colored pigment, use an acidic pigment based on 100 parts by mass of the colored pigment. Pigment dispersion of groups The additive is 0.5 to 30 parts by mass, preferably 3 to 15 parts by mass.

(2) When using a colored pigment that has been micronized in the presence of a pigment dispersing aid having an acidic group, use 0.5 to 30 parts by mass of the pigment dispersing assistant based on 100 parts by mass of the colored pigment during the micronizing process. parts, preferably 3 to 15 parts by mass, when dispersing the micronized colored pigment, use 0 to 29.5 parts by mass of a pigment dispersion aid with an acidic group relative to 100 parts by mass of the colored pigment, preferably 0 to 12 parts by mass.

Moreover, the usage amount of the pigment dispersion aid having an acidic group used in the micronization process is different from the usage amount of the pigment dispersion aid having an acidic group used in the pigment dispersion of the micronized colored pigment. The total amount of the pigment dispersion aid having an acidic group is 0.5 to 30 parts by mass, preferably 3 to 15 parts by mass, based on 100 parts by mass of the colored pigment.

More specifically, the case of using a pigment dispersion aid having a sulfonic acid group as a pigment dispersion aid having an acidic group will be described.

When dispersing C.I. Pigment Blue 15:6 as a blue pigment, as described above, a pigment and/or a sulfonated product of a pigment having an anthraquinone skeleton that is the same as C.I. Pigment Blue 15:6 as an epsilon phthalocyanine copper pigment is used. As a pigment dispersion aid.

(polymer pigment dispersant)

A polymer pigment dispersant can be blended in the blue pigment dispersion composition for color filters of the display device of the present invention. As such a polymer pigment dispersant, a polymer pigment dispersant having a basic group that has been conventionally used in the field of color filters can be used.

In the blue pigment dispersion composition for color filters of the display device of the present invention, when using a polymer pigment dispersant, the usage amount is preferably 1 to 100 parts by mass, and more preferably 1 to 60 parts by mass relative to 100 parts by mass of the colored pigment. share. When the content of the polymeric pigment dispersant is less than 1 part by mass, the pigment dispersing effect may be reduced. On the other hand, when it exceeds 100 parts by mass, the developability may be reduced.

Examples of the polymer pigment dispersant having a basic group include the following.

(1) The amine group and/or imine group of the polyamine compound (such as polyallylamine, polyvinylamine, poly(ethylenepolyimine), poly(lower)alkyleneamine, etc.) and polyamine groups having free carboxyl groups are A reaction product of at least one kind from the group consisting of ester, polyamide and polyesteramide.

(2) Carbodioxide having at least one side chain selected from the group consisting of polyester side chain, polyether side chain and polyacrylic acid side chain and a basic nitrogen-containing group in the molecule Amine compounds.

(3) A reaction product of a low molecular weight amine compound such as poly(lower)alkyleneimine or methyliminobispropylamine and a polyester having a free carboxyl group.

(4) The isocyanate group of the polyisocyanate compound is sequentially reacted with alcohols such as methoxy polyethylene glycol, polyesters having one hydroxyl group such as caprolactone polyester, and 2 to 3 isocyanate group reactive functional groups. A reaction product obtained by reacting a compound, an aliphatic or heterocyclic hydrocarbon compound having an isocyanate reactive functional group and a tertiary amine group.

(5) Combining an acrylate polymer having an alcoholic hydroxyl group with a polyisocyanate and the reaction product of a hydrocarbon compound having an amine group.

(6) A reaction product obtained by adding a low molecular weight amine compound to a polyether chain.

(7) A reaction product obtained by reacting a compound having an isocyanate group and a compound having an amine group.

(8) A reaction product obtained by reacting a polyepoxy compound with a linear polymer having a free carboxyl group and an organic amine compound having one secondary amine group.

(9) A reaction product of a polycarbonate compound and a polyamine compound having a functional group capable of reacting with an amine group at one end.

(10) Selected from methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, At least one of methacrylates or acrylic esters such as propyl acrylate, butyl acrylate, stearyl acrylate, benzyl acrylate, etc. and acrylamide, methacrylamide, N-hydroxymethylamide, ethylene At least one of basic group-containing polymerizable monomers such as imidazole, vinylpyridine, and a monomer having an amine group and a polycaprolactone skeleton, as well as styrene, styrene derivatives, and other polymerizable monomers. A copolymer of at least one of the following.

(11) Acrylic block copolymers composed of blocks having basic groups such as tertiary amine groups and quaternary ammonium bases and blocks having no basic functional groups.

(12) A pigment dispersant obtained by subjecting polyallylamine and a polycarbonate compound to Michael addition reaction.

(13) Carbodiimide compounds each having at least one polybutadiene chain and a basic nitrogen-containing group.

(14) A carbodiimide compound having at least one side chain having a amide group and a basic nitrogen-containing group in the molecule.

(15) A polyurethane compound having a structural unit containing an ethylene oxide chain and a propylene oxide chain and having an amine group quaternized by a quaternary agent.

(16) Compounds obtained by reacting the isocyanate group of an isocyanate compound having an isocyanurate ring in the molecule and the active hydrogen group of a compound having an active hydrogen group in the molecule and having a carbazole ring and/or an azobenzene skeleton. , relative to the total amount of isocyanate groups derived from an isocyanate compound having an isocyanurate ring and urethane bonds and urea bonds generated by the reaction of isocyanate groups and active hydrogen groups in the molecule of the compound, carbazole The number of rings and azobenzene skeleton is 15~85%.

(resin)

As a resin used in the blue pigment dispersion composition for color filters such as a display device equipped with a white organic EL light source of the present invention, a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm in the visible light region can be used , preferably more than 95% resin. As these resins, thermosetting resins, thermoplastic resins, and alkali-soluble resins can be used.

The total amount of such a resin used is preferably 5 to 94 mass % in terms of mass fraction relative to the total solid content of a blue pigment dispersion composition for a color filter such as a display device equipped with a white organic EL light source. The range of 20-50 mass % is more preferable.

Examples of thermosetting resins and thermoplastic resins include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, and vinyl chloride. Ethylene-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, phenolic resin, polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, ring Chemical rubber, epoxy resin, cellulose, polybutadiene, polyimide resin, benzoguanamine resin, melamine resin, urea resin, etc.

In addition, in some cases, a photopolymerizable resin described below may be blended in the blue pigment-dispersed resist composition for a color filter of a display device.

(Alkali-soluble resin as resin)

The alkali-soluble resin can be blended with the blue pigment dispersion composition for the color filter of the display device of the present invention. There is no particular requirement as long as such a resin functions as a binder for pigments and is soluble in a developer used in the development step when manufacturing a color filter, particularly preferably an alkali developer. Conventionally used developers can be used. Among these, an alkali-soluble resin having a carboxyl group is preferred, and a copolymer of an ethylenically unsaturated monomer having one or more carboxyl groups and other copolymerizable ethylenically unsaturated monomers is particularly preferred.

Specific examples include an ethylenically unsaturated monomer having a carboxyl group such as acrylic acid and methacrylic acid, and styrene, 2-hydroxyethyl acrylate, and methyl group selected from the group consisting of copolymerizable ethylenically unsaturated monomers having a carboxyl group. 2-hydroxyethyl acrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glyceryl monoacrylate, methacrylic acid Monomers and oligomers such as glyceryl ester, N-phenylmaleimide, polystyrene macromonomer, polymethyl methacrylate macromonomer, carbonyl epoxy diacrylate, etc. composed of A copolymer of at least one ethylenically unsaturated monomer from the group.

The acid value of the alkali-soluble resin in the present invention is preferably 50 to 300 mgKOH/g from the viewpoint of development characteristics. In addition, in the present invention, the above-mentioned acid value is a theoretical acid value, which is a value calculated arithmetic based on the ethylenically unsaturated monomer having a carboxyl group and its content.

In general, the weight average molecular weight of the alkali-soluble resin in the present invention is preferably 1,000 to 100,000 from the viewpoint of development characteristics and solubility in organic solvents. In the present invention, the weight average molecular weight of the alkali-soluble resin is the weight average molecular weight in terms of polystyrene obtained by GPC. In the present invention, Waters 2690 (manufactured by Waters Co., Ltd.) was used as the device, and PLgel 5 μ MIXED-D (manufactured by Polymer Laboratories Co., Ltd.) was used as the column.

The usage amount of the alkali-soluble resin in the present invention is 1 to 300 parts by mass, preferably 10 to 200 parts by mass relative to 100 parts by mass of the colored pigment used. At this time, if the usage amount of the alkali-soluble resin is less than 1 part by mass, the development characteristics may be reduced. On the other hand, when it exceeds 300 parts by mass, the colorant concentration is relatively reduced, so that it may be difficult to achieve the target color density as a film.

(barium sulfate)

In order to improve the heat resistance (brightness) of the blue pigment dispersion composition for color filters of the present invention, barium sulfate with a primary particle size of 5 to 20 nm can be used.

The usage amount of barium sulfate is in the range of 0 to 25 parts by mass, preferably 5 to 20 parts by mass based on 100 parts by mass of the color pigment.

The above-mentioned barium sulfate is used during or after the dispersion of the micronized colored pigment. use.

(organic solvent)

As the organic solvent used in the blue pigment dispersion composition for color filters of the display device of the present invention, organic solvents conventionally used in the field of liquid crystal color filter resists can be suitably used. Specifically, they are ester organic solvents, ether organic solvents, ether ester organic solvents, ketone organic solvents, and aromatic hydrocarbon organic solvents with a boiling point of 100 to 220°C under normal pressure (1.013×10 ² kPa). Solvents, nitrogen-containing organic solvents, etc. When a large amount of an organic solvent with a boiling point exceeding 220°C is contained, the organic solvent is not fully evaporated when the coating film coated with the blue pigment dispersion composition for color filters or a composition containing the composition is pre-baked. However, it remains in the dried coating film, thereby possibly reducing the heat resistance of the dried coating film. In addition, when a large amount of an organic solvent having a boiling point of less than 100° C. is contained, it is difficult to apply uniformly without unevenness, and there is a possibility that a coating film with excellent surface smoothness cannot be obtained.

Specific examples of the organic solvent used in the blue pigment dispersion composition for color filters of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monoisopropyl. Ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol Ether organic solvents such as diethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, etc.; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetic acid Ester ester organic solvents such as ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc.; methyl isobutyl ketone, cyclohexanone, 2 -Ketone organic solvents such as heptanone and δ-butyrolactone; 2-hydroxypropionic acid methyl ester, 2- Ethyl hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutylpropionate, methyl 3-methoxypropionate, 3-methoxy Ester organic solvents such as ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethoxyethyl acetate, ethyl glycolate, n-pentyl formate, etc.; methanol , alcoholic solvents such as ethanol, isopropanol, butanol, etc.; nitrogen-containing organic solvents such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. . These can be used individually or in mixture of 2 or more types.

Among these organic solvents, in terms of solubility, dispersibility, coating properties, etc., diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, and Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutylpropionate , ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, n-amyl formate, etc., and propylene glycol monomethyl ether acetate is more preferred.

The blue pigment dispersion composition for color filters of display devices of the present invention mainly includes colored pigments, pigment dispersion assistants, resins and organic solvents. The total of these components in the blue pigment dispersion composition of color filters for display devices Accounting for 90~100% by mass. In addition, a polymeric pigment dispersing agent may be further added. As such a polymeric pigment dispersing agent, any of the above-mentioned materials may be used.

In addition, the blue pigment dispersion composition for color filters of the display device of the present invention may be used as a resist composition in a state that does not have photocurability.

(Additives can be added as needed)

According to the manufacturing method of the blue pigment dispersion composition for a color filter of a display device, a photopolymerization initiator, a thermal polymerization inhibitor, an ultraviolet absorber, and an antioxidant can be appropriately used. Various additives such as chemical agents. Examples of the photopolymerization initiator include those mentioned below.

(Method for manufacturing blue pigment dispersion composition for color filter of display device of the present invention)

A method of manufacturing a blue pigment dispersion composition for a color filter of a display device using the above raw materials will be described. Furthermore, when the blue pigment-dispersed resist composition for a color filter of a display device is not a photocurable display device, it is not necessary to prepare a photopolymerizable compound.

Therefore, first, a pigment dispersion composition containing C.I. Pigment Blue 15:6 and a zinc phthalocyanine-based green pigment dispersion composition were prepared as follows.

Pigment dispersion composition containing C.I. Pigment Blue 15:6

Obtained by micronization treatment in the presence or absence of a pigment dispersion aid with an acidic group (preferably a pigment with an anthraquinone skeleton having the same skeleton as C.I. Pigment Blue 15:6 and/or a sulfonated product of the pigment) A mixture of C.I. Pigment Blue 15:6, resin, polymer pigment dispersant as needed, organic solvent, barium sulfate as needed, and further other additives as needed. The obtained mixture is kneaded and dispersed using various dispersing machines such as roller mills, kneaders, high-speed stirring devices, bead mills, ball mills, sand mills, ultrasonic dispersers, and high-pressure dispersers to obtain C.I. Pigment blue 15:6 pigment dispersion composition.

Zinc phthalocyanine green pigment dispersion composition

Obtained by the presence or absence of a pigment dispersion aid having an acidic group (preferably a sulfonate of a pigment having the same skeleton as a zinc phthalocyanine green pigment) or the like. Micronized zinc phthalocyanine-based green pigment, pigment dispersion aid (preferably a sulfonate of a pigment having the same skeleton as the zinc phthalocyanine-based green pigment), resin, polymer pigment dispersant if necessary, organic solvent, sulfuric acid A mixture of barium and other additives as needed. The obtained mixture is kneaded and dispersed using various dispersing machines such as roller mills, kneaders, high-speed stirring devices, bead mills, ball mills, sand mills, ultrasonic dispersers, and high-pressure dispersers to obtain phthalocyanine. Zinc green pigment dispersion composition.

The pigment dispersion composition containing C.I. Pigment Blue 15:6 obtained as described above and the zinc phthalocyanine green pigment dispersion composition can be used, for example, by the following production methods (1) and (2) to obtain a white organic A blue pigment dispersion composition for a color filter of a display device using an EL light source.

At this time, the following pigment dispersion composition containing a complementary color pigment may be used together as necessary. Pigment dispersion composition containing complementary color pigments: If necessary, the complementary color pigments may also be micronized in the presence or absence of a pigment dispersion aid having an acidic group, so as to be compatible with the above-mentioned C.I. Pigment Blue 15: A pigment dispersion composition was obtained in the same manner as the pigment dispersion composition of 6.

(1) A pigment dispersion composition containing C.I. Pigment Blue 15:6 and a zinc phthalocyanine-based green pigment dispersion composition are mixed in advance with a required complementary color pigment in a predetermined ratio, and then resin is added as necessary. , barium sulfate, organic solvents, and other additives to produce a blue pigment dispersion composition for a color filter of a display device equipped with a white organic EL light source of the present invention.

(2) Pigments containing C.I. Pigment Blue 15:6 produced in advance A step of mixing the complementary color pigment in the dispersion composition to a predetermined ratio as necessary, and then adding resin, barium sulfate, organic solvent, and other additives as necessary to produce a color filter blue containing C.I. Pigment Blue 15:6 On the other hand, as for the zinc phthalocyanine-based green pigment dispersion composition, a blue pigment dispersion composition for color filters containing a zinc phthalocyanine-based green pigment is also produced and mixed. steps to produce the blue pigment dispersion composition for color filters of the present invention.

To the pigment dispersion composition containing C.I. Pigment Blue 15:6 and the zinc phthalocyanine green pigment dispersion composition obtained by the above method, resin, barium sulfate, organic solvent, and other additives are added as necessary to prepare a color filter. Disperse the composition with blue pigment.

Next, in the prepared blue pigment dispersion composition for color filters, a complementary color pigment is mixed with C.I. Pigment Blue 15:6 and a zinc phthalocyanine-based green pigment in a predetermined ratio to obtain the white organic compound of the present invention. A blue pigment dispersion composition for a color filter of a display device using an EL light source.

In the production methods of the above (1) and (2), when a micronized pigment that has been micronized in the presence of a pigment dispersion aid having an acidic group is used, the micronized pigment does not contain an acidic pigment during dispersion. Pigment dispersing aids based on groups can also be manufactured.

In addition, in the manufacturing methods of the above (1) and (2), the resin and barium sulfate may be added during the preparation of the pigment dispersion composition and/or after the preparation of the pigment dispersion composition.

In addition, in the manufacturing methods (1) and (2) above, high tinting strength can be obtained from From the viewpoint of high brightness and high brightness, it is preferable to use a pigment that has been micronized in the presence of a pigment dispersion aid having an acidic group.

Currently, as a method for manufacturing color filters using a blue pigment-dispersed resist composition for color filters, the main method is the photoresist method using a photocurable composition. Hereinafter, it is divided into photoresists The components contained in the photocurable blue pigment dispersion composition for color filters used in the method and the non-photocurable blue pigment dispersion composition for color filters different from the above are described below. .

The total amount of the resin used in mass fraction is preferably 5 to 94% by mass, more preferably 20 to 94% by mass relative to the total solid content of the blue pigment dispersion composition for color filters in display devices equipped with white organic EL light sources. 50 mass% range.

[B. When the blue pigment-dispersed resist composition for color filters of display devices is photocurable]

Next, a case in which the blue pigment-dispersed resist composition for a color filter of a display device of the present invention is photocurable will be described.

When the blue pigment-dispersed resist composition for color filters of the display device of the present invention is photocurable, the composition has active energy ray curability and is a resist composition capable of alkali development, and mainly contains pigments. , pigment dispersion aid, resin and organic solvent, including barium sulfate, as the photopolymerizable compound of the resin, and may further include an alkali-soluble resin.

The types and amounts of pigments, pigment dispersion aids, polymer pigment dispersants, resins other than photopolymerizable compounds, barium sulfate, and organic solvents are to be used according to the instructions for the blue pigment dispersion composition for color filters mentioned above. .

Furthermore, the organic solvent is preferably used in the blue pigment-dispersed resist composition for the color filter of the display device of the present invention from the viewpoints of solubility of the alkali-soluble resin, dispersibility of the color pigment, coating properties, etc. Containing 50 mass% or more, more preferably 70 mass% or more.

(photopolymerizable compound)

As the photopolymerizable compound used in the blue pigment-dispersed resist composition for color filters of the display device of the present invention, monomers, oligomers, and oligomers having one or more photopolymerizable unsaturated bonds in the molecule can be used. The photopolymerizable resin and other photopolymerizable compounds are the same as those described in the blue pigment dispersion composition for color filters. Monomers, oligomers, etc. having a photopolymerizable unsaturated bond refer to the action of free radicals and cations generated when the photopolymerization initiator described below is decomposed by active energy rays such as ultraviolet rays and electron rays. Monomers and oligomers with unsaturated bonds that are polymerized and resinized.

As the photopolymerizable compound, examples of monomers having one photopolymerizable unsaturated bond in the molecule include methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and methyl acrylate. , alkyl methacrylates or acrylates such as butyl acrylate, 2-ethylhexyl acrylate, etc.; aralkyl methacrylates or acrylates such as benzyl methacrylate, benzyl acrylate, etc.; butoxy methacrylate Alkoxyalkyl methacrylate or acrylate such as ethyl acrylate, butoxyethyl acrylate; N,N-dimethylaminoethyl methacrylate, N,N-dimethylamine acrylate Aminoalkyl methacrylate or acrylate such as ethyl ester; methyl ether of polyalkylene glycol alkyl ether such as diethylene glycol ethyl ether, triethylene glycol butyl ether, dipropylene glycol methyl ether, etc. acrylate or propylene Acid ester; methacrylate or acrylate of polyalkylene glycol aryl ether such as hexaethylene glycol phenyl ether; isobornyl methacrylate or acrylate; glyceryl methacrylate or acrylate; 2-hydroxyethyl acrylate or acrylate, etc.

Examples of the monomer having two or more photopolymerizable unsaturated bonds in the molecule of the photopolymerizable compound include bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, and 1,3- Butylene glycol dimethacrylate, diethylene glycol dimethacrylate, glyceryl dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate Methacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol Hexamethacrylate, dipentaerythritol pentamethacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, diethylene glycol diacrylate , Glyceryl diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc. These monomers can be used individually or in combination of 2 or more types.

In addition, an oligomer obtained by polymerizing a photopolymerizable compound can be used.

As the photopolymerizable compound, a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, an amine group, or the like, and (meth)acrylic acid introduced thereto via an isocyanate group, an aldehyde group, an epoxy group, etc., can be used. Resin with photo-crosslinkable groups such as compounds and cinnamic acid. Styrene-maleic anhydride copolymers, alpha-olefin-male A polymer such as an acid anhydride copolymer is a polymer in which a linear polymer containing an acid anhydride is half-esterified with a (meth)acrylic compound having a hydroxyl group such as hydroxyalkyl (meth)acrylate.

The photopolymerizable compound which can form the said resin can be used individually or in combination of 2 or more types. In the present invention, the usage amount of the photopolymerizable compound is preferably in the range of 3 to 50 mass % in terms of mass fraction relative to the total solid content in the blue pigment-dispersed resist composition for color filters of display devices. .

(Photopolymerization initiator)

As the photopolymerization initiator used in the blue pigment-dispersed resist composition for color filters of the display device of the present invention, as long as it can generate radicals and cations by irradiation with active energy rays such as ultraviolet rays and electron rays, It is not particularly limited, and examples thereof include benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, and 4-methoxy-4'-dimethylaminodiphenyl. Methyl ketone, benzoyl, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylbenzophenone, thiophene Anthraquinone, 2-chlorothioxanthone, 1-hydroxycyclohexylphenone, tert-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2-methyl-1[4-( Methylthio)phenyl]-2-morpholinylpropan-1-one, triazine photopolymerization initiator, etc. These photopolymerization initiators can be used individually or in combination of 2 or more types.

In the present invention, the content of the photopolymerization initiator is preferably 1 to 20 mass % in terms of mass fraction relative to the total solid content in the blue pigment-dispersed resist composition for the color filter of the display device. range.

Blue pigment dispersed resist set for color filter of display device of the present invention The finished product mainly contains colored pigments, pigment dispersion aids, polymer pigment dispersants, alkali-soluble resins, photopolymerizable compounds, photopolymerization initiators, barium sulfate and organic solvents. The total of the above ingredients is used in blue color filters. The pigment dispersion resist composition accounts for 90 to 100% by mass.

(Additives can be added as needed)

When the blue pigment-dispersed resist composition for color filters of the display device of the present invention is photocurable, various additives such as thermal polymerization inhibitors, ultraviolet absorbers, and antioxidants can be appropriately used as needed.

[C. When the blue pigment-dispersed resist composition for color filters of display devices is non-photocurable]

When the blue pigment-dispersed resist composition for color filters of display devices is non-photocurable, the above B. The blue pigment-dispersed resist composition for color filters of display devices is photocurable. The photopolymerizable compound and photopolymerization initiator used may be further blended with a resin other than the photopolymerizable compound shown in the composition description of the blue pigment dispersion composition for a color filter of a display device as needed.

(Additives can be added as needed)

When the blue pigment-dispersed resist composition for color filters of the display device of the present invention is non-photocurable, various additives such as ultraviolet absorbers and antioxidants can be appropriately used as needed.

(Method for manufacturing blue pigment-dispersed resist composition for color filter of display device of the present invention)

A method of manufacturing a blue pigment-dispersed resist composition for a color filter of a display device using the above materials will be described. When the blue pigment-dispersed resist composition for color filters of display devices is photopolymerizable, a photopolymerizable compound, light A polymerization initiator, an alkali-soluble resin if necessary, barium sulfate, an organic solvent, and other additives are used to obtain a blue pigment-dispersed resist composition for a color filter of a display device of the present invention.

In addition, when it is non-photopolymerizable, any one of alkali-soluble resin, barium sulfate, organic solvent, other additives, etc. can be further added to obtain a blue pigment-dispersed resist composition for a color filter of a display device of the present invention. things. The same applies to the following manufacturing method.

Specifically, it can be obtained by the following manufacturing methods (1) and (2), for example.

(1) The above-mentioned pigment dispersion composition containing C.I. Pigment Blue 15:6, zinc phthalocyanine-based green pigments, and complementary color pigments as needed are prepared in advance so that they are in prescribed ratios. To the blue pigment dispersion composition for color filters of display devices obtained by mixing the green pigment dispersion composition, a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin, barium sulfate, and an organic solvent are further added as necessary. , other additives, etc., thereby obtaining a blue pigment-dispersed resist composition for a color filter of a display device of the present invention.

(2) To the above-mentioned pigment dispersion composition containing C.I. Pigment Blue 15:6 and the zinc phthalocyanine green pigment dispersion composition, add polymerizable compounds, photopolymerization initiators, alkali-soluble resin, barium sulfate, Organic solvents, others Additives are added to obtain a blue pigment-dispersed resist composition for color filters of display devices.

Thereafter, the blue pigment-dispersed resist composition for a color filter of a display device is mixed, thereby producing a blue pigment-dispersed resist composition for a color filter of a display device of the present invention.

To the blue pigment-dispersed resist composition for a color filter of a display device obtained by the methods (1) and (2), a photopolymerizable compound and a photopolymerization initiator are further added as necessary. , alkali-soluble resin, barium sulfate, organic solvent, and other additives as required to prepare a pigment-dispersed resist composition for each color filter. Next, each of the prepared pigment-dispersed resist compositions for color filters is mixed so that C.I. Pigment Blue 15:6, zinc phthalocyanine-based green pigment and, if necessary, a complementary color pigment are in a predetermined ratio, thereby obtaining the present invention. A blue pigment dispersed resist composition is used for a color filter of a display device.

In addition, as a method of manufacturing a color filter of a display device using the blue pigment dispersion composition for a color filter of a display device of the present invention, a configuration other than the pigment dispersion composition including necessary devices and the manufactured by known methods.

The blue pigment dispersion composition for color filters having a specific composition of the present invention preferably has a chromaticity x of 0.125 to 0.135 as its color characteristics (x, y, Y). Preferably y is 0.040~0.121, particularly preferably 0.044~0.100.

[Example]

The following examples are enumerated to further illustrate the present invention in detail, but the present invention It is not limited only to these Examples. In addition, unless otherwise stated, "%" means "mass %" and "part" means "mass part".

<Pigment dispersion aid>

Phthalocyanine derivatives: DISPER BYK-2100 (manufactured by BYK Chemical Co., Ltd.)

<Pigment dispersant>

LP21116: BYK Chemical Co., Ltd., acrylic polymer, amine value 29, solid content 40% by mass

<Alkali-soluble resin>

ZAH110: Made by Soken Chemical Co., Ltd., acid value: 100mgKOH/g, weight average molecular weight: about 15000, solid content 35% by mass

<Photopolymerizable compound>

DPHA: dipentaerythritol hexaacrylate

<Organic solvent>

PGMEA: propylene glycol monomethyl ether acetate

PGME: propylene glycol monomethyl ether

Based on the preparation shown in Table 1 below, a blue pigment dispersion composition for color filters was obtained.

[Table 1]

<Blue pigment-dispersed resist composition for color filters>

Each component of the above Examples and Comparative Examples was mixed to have the composition shown in Table 1, and the mixture was kneaded for 6 hours using a paint conditioner using 0.2 mm Φ zirconia beads to obtain a color filter. Blue pigment dispersion composition.

[Table 2]

Next, the blue pigment dispersion composition for color filters described in Table 1 and other materials were uniformly mixed using a high-speed mixer to obtain the composition of Table 2, and then filtered with a membrane filter with a pore size of 3 μm to obtain a color The filter uses a blue pigment dispersed resist composition.

(evaluation)

<Preparation of sample>

The blue pigment-dispersed resist compositions for color filters of Examples and Comparative Examples were coated on a glass substrate using a glue spreader. Next, it was prebaked at 100°C for 3 minutes, exposed with a high-pressure mercury lamp, and post-baked at 230°C for 30 minutes.

<Color characteristics. Contrast>

Regarding the above-mentioned samples of Examples and Comparative Examples, the color characteristics (x, y, Y) of each resist were measured using a spectrophotometer (UV-2500PC, manufactured by Shimadzu Corporation, C light source, 2° field of view). Obtain the brightness Y and contrast under the chromaticity x=0.1332, y=0.120, x=0.1330, y=0.090 and x=0.1337, y=0.090 respectively.

<Film thickness>

Regarding the film thickness, the coating film was cut to approximately 5 mm with a cutter, and measured using a film thickness meter (surface profilometer Alpha-Step IQ, manufactured by KLA-Tencor Corporation).

<viscosity>

The viscosity at 25°C was measured using an E-type viscometer (R100 viscometer model RE100L manufactured by Toki Sangyo Co., Ltd.).

<Dispersion stability>

Regarding the blue pigment-dispersed resist compositions for color filters used in the resist methods of the above examples and comparative examples, they were collected into glass bottles and sealed, and stored at 40°C, 5°C and room temperature. The state after storage at each temperature of (23° C.) for one month was evaluated according to the following evaluation criteria.

○: The viscosity change rate before and after storage is 10% or less

×: The viscosity change rate before and after storage exceeds 10%

According to the above-mentioned Examples and Comparative Examples when preparing the blue pigment-dispersed resist composition for color filters, the dispersion stability was good. Furthermore, according to the embodiment, higher brightness and contrast can be obtained than in the comparative example.

In addition, although the ingredients other than pigments in Examples and Comparative Examples are the same in their formulation amounts, the viscosity of the compositions in Examples is lower.

Claims (6)

A blue pigment dispersion composition for color filters of a display device, which is a blue pigment dispersion composition for color filters that mainly contains a color pigment, a pigment dispersion assistant, a resin and an organic solvent, and the color pigment contains C.I. Pigment Blue 15:6 and zinc phthalocyanine green pigment, the mass ratio of the C.I. Pigment Blue 15:6 to the zinc phthalocyanine green pigment is 99.9:0.1~90.0:10.0, the color filter is The chromaticity x of the coating film of the blue pigment dispersion composition is 0.125~0.135, and the y is 0.040~0.121, wherein the coating film is a film obtained as follows: using a glue leveling machine, the color filter is coated with blue The pigment dispersion composition was coated on a glass substrate, and then prebaked at 100° C., exposed using a high-pressure mercury lamp, and post-baked at 230° C. for 30 minutes. The blue pigment dispersion composition for a color filter of a display device according to claim 1, wherein the resin includes an alkali-soluble resin and a photopolymerizable compound. The blue pigment dispersion composition for a color filter of a display device as described in Item 1 or 2 of the patent application, wherein the zinc phthalocyanine green pigment is one of C.I. Pigment Green 59 and C.I. Pigment Green 58 above. A blue pigment dispersion resist composition for a color filter of a display device, which is a blue pigment dispersion resist composition for a color filter of a display device that mainly contains a color pigment, a pigment dispersion assistant, a resin, a photopolymerizable compound and an organic solvent. Color pigment dispersion resist composition, the color pigment includes C.I. Pigment Blue 15:6 and zinc phthalocyanine green pigment, The mass ratio of the C.I. Pigment Blue 15:6 to the zinc phthalocyanine green pigment is 99.9:0.1~90.0:10.0, and the color of the coating film of the blue pigment dispersed resist composition for the color filter is The degree of The substrate was prebaked at 100°C, exposed using a high-pressure mercury lamp, and post-baked at 230°C for 30 minutes. The blue pigment-dispersed resist composition for a color filter of a display device according to claim 4, wherein the resin includes an alkali-soluble resin and a photopolymerizable compound. The blue pigment-dispersed resist composition for a color filter of a display device as described in item 4 or 5 of the patent application, wherein the zinc phthalocyanine green pigment is C.I. Pigment Green 59 and C.I. Pigment Green 58 More than 1 species.