TWI600720B - Organic pigment composition for color filter, its manufacturing method, and color filter - Google Patents

Description

Organic pigment composition for color filter, manufacturing method thereof and color filter

The present invention relates to an organic pigment composition for a color filter, a method for producing the same, and a color filter.

When the organic pigment is dispersed in a medium to be colored, the organic pigment is often surface-treated with a surfactant or an organic pigment derivative in order to facilitate the dispersion or to further increase the stability in the medium after dispersion. By this surface treatment, the dispersibility or dispersion stability of the organic pigment which is not subjected to any surface treatment can be improved.

In the case where the medium to be dispersed is a synthetic resin, a synthetic resin is often used in the surface treatment. Specifically, a method of performing Solvent salt milling on an organic pigment in the presence of a nonvolatile component of an acrylic resin is known.

Regarding the surface treatment of synthetic resins of organic pigments, studies on polymers such as (meth)acrylic resins, epoxy resins, polyester resins, and polyurehane resins have been conducted, however, specifically, which type of polymer is concerned. The above-mentioned improvement effect is relatively high in terms of improvement in dispersibility or dispersion stability, and in the polymer of the same type of polymer, and the system has not been systematically studied, and there are many unclear points.

Furthermore, organic pigments for high-performance applications such as inkjet inks or color resists for color filters require high-definition printing compared to general-purpose organic pigments used for coatings or thermoplastic molded plastics. Therefore, it is required to be finer. Organic pigments.

However, fine organic pigments are more agglomerated than general organic pigments, so no matter which synthetic tree is used by the surface treatment of organic pigments used in general use. The surface treatment of the fat does not necessarily achieve the desired improvement effect, and the actual situation is that the synthetic resin of the best type and the optimum structure is selected according to the trial error.

Specifically, for example, as a surface treatment method for preparing an organic pigment for a color resist for a color filter, a method of dissolving salt milling of an organic pigment in the presence of a non-volatile component of a (meth)acrylic resin is known ( Patent Document 1) A method of pressurizing and heating an organic pigment in the presence of a polyurethane resin in a liquid medium (Patent Document 2).

[Patent Document 1] Japanese Patent Laid-Open No. Hei 8-179111

[Patent Document 2] WO10/061830 Gazette

However, the actual situation is that the chroma of the coloring matter obtained by the surface-treated organic pigment by the above-mentioned prior art manufacturing method is not sufficient, and if the heat history is continued for a long time, the hue of the coloring matter changes greatly. Also poor.

Therefore, the present inventors have made an effort to study the surface treatment effect of the organic pigment by using various synthetic resins in order to solve the above problems, and as a result, it has been found that copolymerization of (meth) acrylate having different carbon atoms in two or more kinds of side chains is used. When the object is subjected to a surface treatment, the coloring matter in which the above-mentioned disadvantages are eliminated is obtained, and in particular, the color filter used in the liquid crystal display device which is exposed to a high temperature for a long time in a manufacturing step or a use condition can realize a liquid crystal excellent in heat resistance of brightness. The display is such that the present invention is completed.

In other words, the present invention provides an organic pigment composition characterized by copolymerization of (meth) acrylate having two or more kinds of side chain carbon atoms with respect to 100 parts of the organic pigment (A) in terms of mass. The substance (B) has a nonvolatile content of 0.1 to 15 parts.

Moreover, the present invention provides a method for producing an organic pigment composition which is a non-volatile component of a (meth) acrylate copolymer (B) having two or more different carbon atoms in a side chain in a liquid medium. The organic pigment (A) is heated under pressure in the presence of two or more side chains. The organic pigment (A) is subjected to salt-dissolving in the presence of a non-volatile component of a (meth) acrylate copolymer (B) having a different number of carbon atoms.

Further, the present invention is a color filter comprising any one of the above organic pigment compositions in a pixel portion.

Since the organic pigment composition of the present invention contains the organic pigment (A) and the specific copolymer (B) in a predetermined ratio, it is obtained that the color change of the coloring matter which is subjected to the thermal history for a long period of time is small, that is, the heat resistance of coloring is excellent. A particularly significant technical effect of the coloring matter.

Further, the method for producing an organic pigment composition of the present invention achieves an extremely remarkable technical effect of easily obtaining the above organic pigment composition.

Further, since the color filter of the present invention contains the organic pigment composition or the organic pigment composition obtained by the above-described production method in the pixel portion, it is particularly advantageous to obtain a liquid crystal display which is more excellent in heat resistance of brightness.

The organic pigment composition of the present invention is characterized in that a copolymer of (meth) acrylate having two or more kinds of carbon atoms having different side chains is contained in 100 parts by mass of the organic pigment (A). Non-volatile content of 0.1 to 15 parts.

The organic pigment (A) may be any of conventionally known ones, and examples thereof include an anthraquinone pigment, a quinacridone pigment, an azo pigment, and two or two. Pigments, anthraquinone pigments, diketopyrrolopyrrole pigments, organometallic complex pigments, and the like.

The organic pigment (A) in the present invention may be any particle size. When the colorant is a dry powder, if the average particle diameter of the primary particles is 100 nm or less, it is easy to obtain a more vivid color, and therefore it is preferred. . On the other hand, the smaller the particle size, the lower the heat resistance of the organic pigment (A). There are many cases, so it is necessary to improve the heat resistance by using some methods without loss of sharpness.

In the present invention, the average particle diameter of the primary particles is measured as follows. First, the particles in the field of view are taken using a transmission electron microscope or a scanning electron microscope. Then, the longest length (maximum length) of the inner diameter of each particle is obtained for the 50 primary particles constituting the aggregate on the two-dimensional image. The average value of the maximum length of each particle is taken as the average particle diameter of the primary particles.

Further, as the copolymer (B) of the (meth) acrylate having two or more kinds of side chain carbon atoms, it is also possible to use any of the known ones. The (meth) acrylate is a compound containing an ester bond formed of (meth)acrylic acid and various other alcohols, and a carbon atom chain is contained at the terminal of the ester bond COO derived from the above alcohol. Typically, the above carbon chain is referred to as an alkyl (meth) acrylate. By alkyl (meth)acrylate, it is meant that the side chain is an alkyl group. In the field of the present invention, not only a (meth)acrylic acid alkyl ester, but also a compound other than the above-mentioned carbon chain is an alkyl group, and therefore, in the present invention, not only an alkyl (meth)acrylate but also The carbon chain is a compound other than an alkyl group and is called a (meth) acrylate.

Examples of the (meth) acrylate include alkyl (meth) acrylate, that is, methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl (meth) acrylate. Isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (methyl) ) n-octyl acrylate, dodecyl (meth)acrylate [lauryl (meth)acrylate], octadecyl (meth)acrylate [stearyl (meth) acrylate], etc. Alkyl (meth)acrylate; cyclohexyl (meth)acrylate, (meth)acrylic acid An alicyclic group-containing (meth) acrylate such as an ester, an adamantyl (meth) acrylate or a dicyclopentanyl (meth) acrylate; methoxy triethylene glycol (meth) acrylate, methoxy Polyethylene glycol #400 (meth) acrylate, methoxy dipropylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, Ethyl carbitol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy Diethylene glycol (meth) acrylate, p-nonyl phenoxyethyl (meth) acrylate, p-nonyl phenoxy polyethylene glycol (meth) acrylate, etc. ) an acrylate; a (meth) acrylate containing an aromatic ring such as benzyl (meth) acrylate;

In the present invention, the copolymer (B) of (meth) acrylate having two or more kinds of side chain carbon atoms is different, and means that two kinds of (meth) acrylates are selected from the above (meth) acrylates. A polymer obtained by combining the carbon atoms of the above side chains and copolymerizing them.

As the copolymer (B), the glass transition temperature (Tg) is as high as possible, and it is excellent in heat resistance. However, when it is used in combination with the organic pigment (A), it is excellent in heat resistance. A copolymer having a Tg of 0 to 150 ° C is preferred.

As the copolymer (B), any molecular weight can be used. Specifically, a copolymer having a weight average molecular weight of 5,000 to 100,000 has a large affinity for the organic pigment (A) and an effect of improving heat resistance is also greater. Preferably.

The copolymer (B) can be synthesized by various reaction methods known in the art such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and the like. In this case, a conventionally known polymerization initiator, a surfactant, and an antifoaming agent may be used in combination.

The copolymer (B) may be one in which two or more kinds of (meth) acrylates having different carbon atoms in the side chain are used as an essential monomer, and other copolymerizable monomers copolymerizable with the above may be used and copolymerized. Adult.

Examples of the comonomer include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl tricarboxylate; heterocyclic vinyl compounds such as vinylpyrrolidone; vinyl chloride and vinylidene chloride; Halogenated olefins such as vinylidene fluoride; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; vinyl ethers such as ethyl vinyl ether and isobutyl vinyl ether; and ketenes such as methyl vinyl ketone ; α-olefins such as ethylene and propylene; dienes such as butadiene and isoprene; A styrene monomer such as a vinyl group, a vinyl toluene, an α-methyl styrene, a dimethyl styrene, a t-butyl styrene or a chlorostyrene.

The present inventors have found that the copolymer (B) is a copolymer containing not only a side chain having a different number of carbon atoms derived from two or more (meth) acrylates but also an epoxy group, and only a carbon atom. Compared with the copolymers of different side chains, the color history is more difficult to change when subjected to a heat history, and the heat resistance is excellent.

The method of introducing the epoxy group into the copolymer is not particularly limited, and the radical polymerizable monomer containing an epoxy group may be polymerized as an essential component, or the previously synthesized copolymer may be subjected to epoxy modification. In order to facilitate the introduction, it is preferred to polymerize a (meth) acrylate having two or more kinds of side chain carbon atoms and a monomer having an epoxy group as essential components.

Examples of the epoxy group-containing monomer include epoxy group-containing monomers such as glycidyl (meth)acrylate, allyl glycidyl ether, and 4-hydroxybutyl glycidyl (meth)acrylate. .

The copolymer (B) is preferably a copolymer obtained by polymerizing two or more kinds of (meth) acrylates having different carbon atoms in the side chain and an epoxy group-containing monomer as essential components. When the total monomer constituting the copolymer (B) is 100% by mass, the epoxy group-containing monomer is 3 to 35% by mass of the total monomer, and the carbon containing only two or more kinds of side chains It is preferable to obtain a higher heat resistance than a copolymer of a (meth) acrylate having a different number of atoms, and to have a good dispersibility in a colored medium to be colored.

In the copolymer in which the epoxy group-containing monomer is from 3 to 35% by mass of the total monomer, the greater the amount of the epoxy group-containing monomer, the greater the chroma or chromaticity change when subjected to the thermal history. The smaller the tendency.

Some or all of the epoxy groups in the copolymer (B) may react with a nucleophile to form a ring-opening functional group. For example, by reacting all of the epoxy groups in the copolymer with hydrochloric acid to form α-chloride When the alcohol group is used as the copolymer (B), it also has the same heat resistance improving effect as when the original epoxy group-containing copolymer is used.

In the organic pigment composition of the present invention, the (V) non-volatile component (B) of the (meth) acrylate having a difference in the number of carbon atoms of two or more kinds of side chains in terms of mass ratio of 100 parts by mass of the organic pigment (A) is 0.1. The copolymer (B) may be contained in a form of ~15 parts, and if it is 0.5 to 12 parts, particularly 1 to 10 parts, per 100 parts of the organic pigment (A), by containing the copolymer (B), It is preferable because it can be an organic pigment composition having the most balanced effects such as the technical effects of the present invention, dispersibility or dispersion stability in a colored medium, and the like.

The above organic pigment composition of the present invention can be produced by mixing the organic pigment (A) and the copolymer (B) in an arbitrary manner. As a simple preparation method, for example, a method of mixing a non-volatile component of the organic pigment (A) and the copolymer (B) is carried out, and the organic pigment (A) is mixed in a liquid medium solution of the copolymer (B), and stirred and filtered. Drying method, etc.

However, the inventors of the present invention have found for the first time that a stronger interaction between the organic pigment (A) and the copolymer (B) can be expected than in the above simple preparation method, specifically, in a liquid medium. Two or more kinds of (meth) acrylate copolymers having different carbon atoms in the side chain (B), the organic pigment (A) is heated under pressure in the presence of a nonvolatile component, or two or more kinds of side chain carbon atoms The organic pigment (A) is dissolved and salt-milled in the presence of a non-volatile component of a (meth) acrylate copolymer (B), whereby the prepared organic pigment composition is prepared by the above simple method Compared with the organic pigment composition, a greater heat resistance improvement effect is obtained. Hereinafter, the preparation method of the former is referred to as a pressurized heating method, and the preparation method of the latter is referred to as a dissolved salt milling method.

The above two organic pigment compositions of the present invention are produced by, for example, obtaining, for example, CI Pigment Blue 15:6 (ε-type copper phthalocyanine pigment), CI Pigment Green 36 (copper halide indigo pigment), and CI Pigment Green 58. The anthraquinone pigment of the (zirconium halide phthalocyanine pigment) is particularly excellent as a method for producing an organic pigment composition of the organic pigment (A).

First, the pressurized heating method will be described. According to the pressure heating method, for example, the organic pigment (A) and the solution or dispersion in which the copolymer (B) is dissolved or dispersed in a liquid medium are mixed and stirred, and heated, thereby not heating. In contrast, the copolymer (B) can be more uniformly and surely coated on the surface of the organic pigment (A). Further, by performing pressure heating, not only the coating of the copolymer (B) onto the surface of the organic pigment (A) particles but also the copolymer (B) to the organic pigment (A) particles can be promoted. If the void portion of the pores penetrates, the effect of coating is further improved.

In this case, if only a liquid medium (referred to as an aqueous medium) containing water-soluble organic solvent as a main component is used as the liquid medium, the organic heating is performed using only the organic solvent as the liquid medium. The change in the crystal shape or the like of the pigment (A) itself is small, and the change in hue is small, which is preferable.

Examples of the water-soluble organic solvent include propylene glycol monomethyl ether acetate, ethanol, isopropyl alcohol, and isobutanol.

The aqueous medium used for the pressure heating is preferably excessively large relative to the organic pigment (A), so that the effect by pressurization heating is maximized, and the added copolymer (B) is further increased to participate in the organic pigment ( The amount of coating of A), the reduction of the outflow of the copolymer (B) in the filtration step described below or the time for further shortening the step is more preferably 15 parts by mass relative to the organic pigment (A). ~100 copies.

In the case of preparing an organic pigment composition from the organic pigment (A) and the copolymer (B) by a pressure heating method, the organic pigment composition finally obtained is 100 parts by mass relative to the organic pigment (A). The copolymer (B) is added in such a manner that it is 0.5 to 12 parts, and since the adsorption interaction between the organic pigment (A) and the copolymer (B) is strong, the copolymer (B) added is not volatile. It does not flow out, and at least 70% of the non-volatile component remains in the organic pigment (A) in terms of mass conversion.

The heating of the organic pigment (A) and the copolymer (B) can be carried out after mixing the two In a closed system, the mixture is stirred at a temperature of 100 to 150 ° C for 30 minutes to 5 hours. By heating in a sealed system as described above, a pressurized state is formed. As described above, the copolymer (B) penetrates into the voids of the pigment particles, and exhibits an even more excellent effect than the surface of the particles alone.

Next, the dissolved salt milling method will be explained. According to the dissolved salt milling method, for example, the organic pigment (A) and the copolymer (B) are kneaded by applying mechanical stress to the water-soluble inorganic salt and the hydrophilic organic solvent, whereby the particle diameter of the organic pigment (A) is fine. At the same time, the particle shape is made into a substantially cubic shape, and the copolymer (B) can be uniformly and surely coated on the surface of the organic pigment (A).

Specifically, the dissolved salt mill is obtained by adding an organic pigment, a water-soluble inorganic salt, and a hydrophilic organic solvent insoluble thereto to a kneading machine, and kneading and kneading therein. In the above kneading, when it is not intended to convert the crystal form of the raw material, as the organic pigment (A), a commercially available ε-type copper phthalocyanine pigment can be used as a raw material for kneading. On the other hand, when it is intended to be a conversion of a crystalline form or the like, as the organic pigment (A), a crude organic pigment having a different crystal form and after kneading may be used as a raw material for kneading. Specifically, the ε-type copper phthalocyanine pigment can be obtained by kneading the crude α-type copper phthalocyanine pigment as a raw material.

In the case of preparing an organic pigment composition from the organic pigment (A) and the copolymer (B) by a dissolved salt milling method, the copolymer is obtained in an organic pigment composition finally obtained in an amount of 100 parts relative to the organic pigment (A) ( B) When the organic pigment (A) and the copolymer (B) have a strong adsorption interaction by adding 0.5 to 12 parts, the copolymer to be added is the same as the pressure heating method ( B) The non-volatile component does not substantially flow out, and at least 70% of the non-volatile component remains in the organic pigment (A) in terms of mass conversion.

As the water-soluble inorganic salt, an inorganic salt such as sodium chloride, potassium chloride or sodium sulfate is preferably used. Further, it is more preferred to use an inorganic salt having an average particle diameter of 0.5 to 50 μm. The above inorganic salt can be easily obtained by finely pulverizing a usual inorganic salt.

Further, the amount of the inorganic salt used is preferably in terms of mass relative to the organic pigment. (A) 1 part is set to 8 to 20 parts, more preferably 10 to 15 parts.

As the water-soluble organic solvent, those capable of suppressing crystal growth can be preferably used, and for example, diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2-(methoxy group) can be used. Methoxy)ethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Alcohol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, two Propylene glycol monomethyl ether, dipropylene glycol, triethylene glycol, polyethylene glycol, 1,2-propylene glycol, 1-methoxy-2-propanol or the like is preferably ethylene glycol or diethylene glycol.

The amount of the water-soluble organic solvent to be used is not particularly limited, and is preferably 0.01 to 5 parts by weight based on 1 part by mass of the organic pigment (A).

The kneading temperature is preferably between 60 and 150 °C. In the case where the organic pigment (A) is a copper phthalocyanine pigment, if the temperature is between 80 and 120 ° C, the ε-type ε-type bismuth blue crystallization rate can be improved (the ε-type crystallization ratio contained in the copper phthalocyanine) Further, the reduction in heat resistance, contrast, and the like described below can be reduced, and thus the organic pigment composition thus obtained is preferably used as a color filter.

As a device to be used for the kneading, a mixer, a kneading machine, a planetary mixer described in Japanese Laid-Open Patent Publication No. 2007-100008, or a Trimix (trade name) manufactured by Inoue Seisakusho Co., Ltd., or a special Japanese Kaiping 4- The continuous twin-screw extruder described in the publication No. 122778 or the continuous single-axis kneading machine described in JP-A-2006-306996, namely, Miracle KCK manufactured by Asada Iron Works Co., Ltd., and the like.

In the case where an anthraquinone pigment is used as the organic pigment (A), as a method of preparing the organic pigment composition, a pressure heating method or a dissolved salt milling method may be employed to obtain a metal indigo pigment as an organic pigment. In the case of the organic pigment composition of (A), it is preferred to use a dissolved salt milling method, and in the case of obtaining an organic pigment composition containing a halogenated metal indigo pigment as the organic pigment (A), it is preferred to use a pressurization. Heating method.

Heating in a liquid medium by means of pressurized heating or dissolved salt milling or The mixture obtained by heating and kneading is, for example, cooled, and the liquid medium is removed therefrom, and the solid matter is washed, filtered, dried, pulverized, etc. as needed, whereby the organic pigment (A) and the copolymer (B) are obtained. A powder of the organic pigment composition of the present invention having a volatile component.

As the washing, either water washing or hot water washing can be used. The number of cleanings can also be repeated within 1 to 5 times. The copolymer (B) which is not adsorbed on the organic pigment (A) can be easily removed by washing. If necessary, acid cleaning, alkali cleaning, and solvent cleaning may be performed without changing the crystal state. The amount of the non-volatile component (the so-called yield) of the active ingredient contained in the organic pigment composition, that is, the copolymer (B), for example, may be based on the solvent extraction amount of the organic pigment composition, or the copolymer (B) may be added to the filtrate. Calculated by the amount of outflow.

Examples of the filtration and separation and the drying after the cleaning include batchwise or continuous drying in which the pigment is dehydrated and/or desolventized by heating at 80 to 120 ° C of a heating source provided in a dryer. As the dryer, there are usually a box dryer, a belt dryer, a spray dryer, and the like. In particular, the spray dryer is preferably dried when it is dried to form a slurry. Further, the pulverization after drying is not an operation for increasing the specific surface area or reducing the average particle diameter of the primary particles, but is, for example, a case where the pigment is formed in a slope shape, such as in the case of drying using a box dryer or a belt dryer. In the case of the block, the pigment is decomposed and pulverized, and examples thereof include pulverization using a mortar, a hammer mill, a disk mill, a pin mill, a jet mill, and the like. Thus, a dry powder containing the organic pigment composition containing the organic pigment (A) and the copolymer (B) as a main component can be obtained.

The organic pigment composition of the present invention may contain impurities such as a free metal or a source of free metal ions, but when it is used for coloring of a pixel portion of a color filter, the above impurities are preferably as small as possible. For example, when the organic pigment (A) is an anthraquinone pigment, the organic pigment composition is such that a metal ion source such as copper, zinc or copper ions or zinc ions is as small as possible, and it is difficult to adversely affect liquid crystal display characteristics. Therefore, it is preferred. The free metal contained may be a case of a free metal remaining when the metal is indigo, or a case where it is formed by decomposition of the synthesized metal indigo.

The source of the free metal or the free metal ion can be washed with an acid as described in JP-A-2008-308605. The acid to be used is, for example, preferably hydrochloric acid, sulfuric acid, hydrochloric acid or sulfuric acid, and the concentration is preferably 0.5% to 4%. Further, the temperature during cleaning is preferably 50 to 90 °C. Also, it can be washed with water.

In the case where the heat resistance of the color filter is less reduced, in the case of the organic pigment composition of the present invention containing the metal phthalocyanine pigment as the organic pigment (A), the content of the free metal is preferably in mass conversion. It is 900 ppm or less in the organic pigment composition.

The organic pigment composition of the present invention has high dispersibility and dispersion stability in a liquid medium, and the following pigment dispersion has a low viscosity and is dispersed into fine particles, so that Newtonian fluidity is also kept high and stable, for example, In the case where the color filter pixel portion is thus manufactured, a homogeneous coating film can be formed to obtain a color filter having high brightness, contrast, and light transmittance.

When the organic pigment composition of the present invention obtained as described above is colored, the coloring matter is sharp and excellent in chroma, and even if it is subjected to a heat history for a long period of time, the hue of the coloring matter does not largely change, and the heat resistance is excellent. Therefore, it is also representative of the coloring of the pixel portion of the color filter, and is also suitable for the coloring of paints, plastics, printing inks, rubber, leather, dyeing, electrophotographic toners, inkjet inks, thermal transfer inks, and the like.

When the organic pigment composition of the present invention is used for forming a pixel portion of a color filter, the organic pigment composition of the present invention containing a metal indigo pigment as the organic pigment (A) may be further contained as needed. pigment. The organic pigment composition of the present invention containing a diketopyrrolopyrrole pigment as the organic pigment (A) may contain an anthracene pigment as needed. The organic pigment composition of the present invention containing a halogenated metal indigo pigment as the organic pigment (A) may contain a quinophthalone pigment or an organometallic complex pigment as needed.

Further, the organic pigment composition of the present invention may contain a sulfonic acid derivative of the organic pigment (A), an N-(dialkylamino)methyl derivative of the organic pigment (A), and an organic pigment (A), if necessary. N-(dialkylaminoalkyl)sulfonamide derivative, adjacent to organic pigment (A) Organic pigment derivatives such as benzoquinone imine alkyl derivatives; or DISPERBYK 130, DISPERBYK 161, DISPERBYK 162, DISPERBYK 163, DISPERBYK 170, DISPERBYK 171, DISPERBYK 174, DISPERBYK 180, DISPERBYK 182 of BYK-Chemie DISPERBYK 183, DISPERBYK 184, DISPERBYK 185, DISPERBYK 2000, DISPERBYK 2001, DISPERBYK 2020, DISPERBYK 2050, DISPERBYK 2070, DISPERBYK 2096, DISPERBYK 2150, DISPERBYK LPN21116, DISPERBYK LPN6919, EFKA 46 from EFKA, EFKA 47, EFKA 452, EFKA LP4008 EFKA 4009, EFKA LP4010, EFKA LP4050, LP4055, EFKA 400, EFKA 401, EFKA 402, EFKA 403, EFKA 450, EFKA 451, EFKA 453, EFKA 4540, EFKA 4550, EFKA LP4560, EFKA 120, EFKA 150, EFKA 1501 EFKA 1502, EFKA 1503, Lubrizol Solsperse 3000, Solsperse 9000, Solsperse 13240, Solsperse 13650, Solsperse 13940, Solsperse 17000, 18000, Solsperse 20000, Solsperse 21000, Solsperse 20000, Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000 , Solsperse 32000, Solspers e 36000, Solsperse 37000, Solsperse 38000, Solsperse 41000, Solsperse 42000, Solsperse 43000, Solsperse 46000, Solsperse 54000, Solsperse 71000, Ajisper PB711, Ajisper PB821, Ajisper PB822, Ajisper PB814, Ajisper PN411, Ajisper Dispersing agent such as PA111; or acrylic resin, amine ester resin, alkyd resin, natural rosin such as wood rosin, rosin gum, tall oil rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, oxidized rosin, maleic acid Modified rosin such as rosin, rosin amine, lime rosin, rosin alkylene oxide adduct, rosin alkyd adduct, rosin modified phenol and other rosin derivatives are equivalent to a liquid and water-insoluble synthetic resin at room temperature. The addition of the dispersant or the resin contributes to a reduction in flocculation, an improvement in dispersion stability of the pigment, and an increase in viscosity characteristics of the dispersion.

The organic pigment composition of the present invention can be used in any of the conventionally known applications, and if it is contained in the pixel portion of the color filter, if the average particle diameter of the primary particles is When 0.01 to 0.10 μm, the pigment aggregation is relatively weak, and the dispersibility in the synthetic resin to be colored or the like is further improved.

The organic pigment composition of the present invention or the organic pigment composition obtained by the production method of the present invention is contained in the pixel portions of the respective colors R, G, and B of the color filter, whereby a color filter can be produced. Specifically, for example, an R pixel may be obtained from the organic pigment composition of the present invention containing a diketopyrrolopyrrole pigment such as CI Pigment Red 254, which may be a metal halide containing a halogenated metal such as CI Pigment Green 36 or CI Pigment Green 58. The organic pigment composition of the present invention of the pigment obtains a G pixel, and the B pixel can be obtained from the organic pigment composition of the present invention containing a metallic indigo pigment such as CI Pigment Blue 15:6.

As described above, the organic pigment composition of the present invention can be used in the formation of a pattern of the pixel portions of the R, G, and B colors of the color filter by a known method. Typically, a photosensitive composition for a color filter pixel portion including the pigment composition for a color filter of the present invention and a photosensitive resin as an essential component can be obtained.

The method for producing a color filter is, for example, a method called photolithography, in which the organic pigment composition of the present invention is dispersed in a dispersion medium composed of a photosensitive resin, and thereafter, by a spin coating method, The roll coating method, the inkjet method, or the like is applied onto a transparent substrate such as glass, and then the coating film is subjected to ultraviolet pattern printing through a photomask, and then the unexposed portions are washed with a solvent or the like to obtain respective color patterns.

Alternatively, a color filter may be produced by forming a pattern of each color pixel portion by a method such as an electrodeposition method, a transfer method, a micelle electrolysis method, or a PVED (Photovoltaic Electrodeposition) method. The organic pigment composition of the present invention has a small hue change even when subjected to a heat history, and thus is extremely useful, for example, in a method of producing a color filter including baking in the step.

When the photosensitive composition for a pixel portion of a color filter is prepared, for example, the organic pigment composition of the present invention, a photosensitive resin, a photopolymerization initiator, and an organic solvent in which the resin is dissolved are mixed as an essential component. As a method of manufacturing the same, the usual method is to use the present invention. After preparing a dispersion liquid from an organic pigment composition, an organic solvent, and an optional dispersing agent, a photosensitive resin or the like is added thereto and prepared.

As the dispersing agent to be used as needed, for example, DISPERBYK (DisperbyK registered trademark) 130, DISPERBYK 161, DISPERBYK 162, DISPERBYK 163, DISPERBYK 170, EFKA 46 of EFKA, EFKA 47, etc. of BYK-Chemie Co., Ltd. may be mentioned. Further, a leveling agent, a coupling agent, a cationic surfactant, or the like may be used in combination.

Examples of the organic solvent include aromatic solvents such as toluene, xylene, and methoxybenzene, and acetate solvents such as ethyl acetate or butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. a propionate solvent such as ethyl ethoxypropionate, an alcohol solvent such as methanol or ethanol, or an ether solvent such as butyl racesu, propylene glycol monomethyl ether, diethylene glycol diethyl ether or diethylene glycol dimethyl ether. a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; an aliphatic hydrocarbon solvent such as hexane; N,N-dimethylformamide, γ-butylimamine, N a solvent such as a methyl compound such as methyl-2-pyrrolidone, aniline or pyridine, or a lactone solvent such as γ-butyrolactone, such as an amine ester of a mixture of methyl carbamate and ethyl urethane 48:52. , water, etc. The organic solvent is preferably a polar solvent such as a propionate type, an alcohol type, an ether type, a ketone type, a nitrogen compound type, a lactone type or water, and is preferably water-soluble.

The organic solvent of 300 to 1000 parts by mass, and optionally 0 to 100 parts by mass of the dispersant and/or 0 to 20 parts by mass of the anthraquinone derivative are stirred with respect to 100 parts by mass of the organic pigment composition of the present invention. Disperse to make it uniform, and a dispersion can be obtained. Then, in the dispersion, 3 to 20 parts by mass of the photosensitive resin is added to 1 part by mass of the organic pigment composition of the present invention, and photopolymerization is 0.05 to 3 parts by mass based on 1 part by mass of the photosensitive resin. The initiator and the organic solvent to be further added as needed are stirred and dispersed to make them uniform, and a photosensitive composition for the pixel portion of the color filter can be obtained.

Examples of the photosensitive resin that can be used in this case include an amine ester resin, an acrylic resin, a polyaminic acid resin, a polyimide resin, and a styrene maleic acid system. a thermoplastic resin such as a resin or a styrene maleic anhydride resin; or, for example, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylic acid 2-functional monomer such as ester, bis(acryloxyethoxy) bisphenol A, 3-methylpentanediol diacrylate, such as trimethylolpropane triacrylate, neopentyl alcohol triacrylate A photopolymerizable monomer such as a polyfunctional monomer such as tris(2-hydroxyethyl) isocyanate, dipentaerythritol hexaacrylate or dipentaerythritol pentaacrylate.

As the photopolymerization initiator, for example, acetophenone, diphenyl ketone, benzoin dimethyl ketal, benzammonium peroxide, 2-chloro 9-oxosulfur , 1,3-bis(4'-azidobenzylidene)-2-propane, 1,3-bis(4'-azidobenzylidene)-2-propane-2'-sulfonic acid, 4 , 4'-diaziridine-2,2'-disulfonic acid and the like.

The photosensitive composition for the color filter pixel portion prepared in this manner is subjected to ultraviolet light pattern exposure through a photomask, and then the unexposed portion is washed with an organic solvent or alkaline water or the like, whereby a color filter can be obtained.

Hereinafter, the present invention will be specifically disclosed using a synthesis example, a comparative synthesis example, an example, and a comparative example. In these examples, "%" means the mass percentage.

(Synthesis Example 1)

1540 parts of propylene glycol monomethyl ether acetate was added to a four-necked flask equipped with a stirrer, a thermometer, a cooling tube and a nitrogen inlet tube, and the temperature was raised to 110 ° C under a nitrogen gas stream, and methyl methacrylate was added dropwise over 4 hours. A mixture of 623 parts, 307 parts of n-butyl methacrylate, 70 parts of glycidyl methacrylate, and 18 parts of tert-butyl peroxy-2-ethylhexanoate (hereinafter abbreviated as TBPEH). After completion of the dropwise addition, the mixture was reacted at 110 ° C for 7 hours to obtain a solution of a copolymer (B-1) having a nonvolatile content of 40.5% and a weight average molecular weight of 16,000.

(Synthesis Example 2)

1540 parts of propylene glycol monomethyl ether acetate was added to the four-necked flask similar to the synthesis example 1, and after heating up to 110 degreeC in nitrogen gas flow, 597 parts of methyl methacrylate and methacrylic acid were added dropwise over 4 hours. A mixture of 261 parts of butyl ester, 142 parts of glycidyl methacrylate and 18 parts of TBPEH. After completion of the dropwise addition, the mixture was reacted at 110 ° C for 7 hours to obtain a solution of a copolymer (B-2) having a nonvolatile content of 39.8% and a weight average molecular weight of 15,000.

(Synthesis Example 3)

1540 parts of propylene glycol monomethyl ether acetate was added to the four-necked flask similar to the synthesis example 1, and after heating up to 110 degreeC in nitrogen gas flow, 547 parts of methyl methacrylate and methacrylic acid were added dropwise over 4 hours. A mixture of 173 parts of butyl ester, 280 parts of glycidyl methacrylate and 18 parts of TBPEH. After completion of the dropwise addition, the mixture was reacted at 110 ° C for 7 hours to obtain a solution of a copolymer (B-3) having a nonvolatile content of 40.0% and a weight average molecular weight of 16,000.

(Synthesis Example 4)

1540 parts of propylene glycol monomethyl ether acetate was added to the four-necked flask similar to the synthesis example 1, and after heating up to 110 degreeC in nitrogen gas flow, 856 parts of benzyl methacrylate and meth A mixture of 142 parts of glyceride and 18 parts of TBPEH. After completion of the dropwise addition, the mixture was reacted at 110 ° C for 7 hours to obtain a solution of a copolymer (B-4) having a nonvolatile content of 38.1% and a weight average molecular weight of 14,000.

(Synthesis Example 5)

The solid of the copolymer (B-2) obtained by subjecting the solution of the copolymer (B-2) of Synthesis Example 2 to drying under reduced pressure (60 ° C, 10 hours) was reacted with hydrochloric acid to obtain a copolymer (B). The epoxy group in -2) is ring-opened to form an α-chlorohydrin copolymer (B-5).

(Synthesis Example 6)

1540 parts of propylene glycol monomethyl ether acetate was added to the four-necked flask similar to the synthesis example 1, and after heating up to 110 degreeC in nitrogen gas flow, 597 parts of methyl methacrylate and methacrylic acid were added dropwise over 4 hours. A mixture of 261 parts of butyl ester and 18 parts of TBPEH. After completion of the dropwise addition, the mixture was reacted at 110 ° C for 7 hours to obtain a solution of a copolymer (B-6) having a nonvolatile content of 39.8% and a weight average molecular weight of 15,000.

[Example 1]

10 g of FASTOGEN GREEN A110 (polybrominated zinc bromide pigment manufactured by DIC Corporation), 1.25 g of the copolymer (B-1) solution (solid content: 40.5%) of the above Synthesis Example 1 and 589 g of water were added together. In a 1 liter autoclave, the temperature was raised to 130 ° C in one hour while stirring, and stirring was continued at this temperature for 1 hour, whereby the surface of the pigment was subjected to resin treatment. After standing to cool to room temperature, it was suction-filtered and washed with 2 liters of warm water. The obtained wet cake was dried at 90 ° C for 12 hours, and pulverized by a bench mill to obtain an organic pigment composition (X-1) having an average particle diameter of 100 nm or less of primary particles.

[Embodiment 2]

The copolymer (B-2) solution of Synthesis Example 2 was used in such a manner that 1.25 g of the copolymer (B-1) solution of Synthesis Example 1 (solid content: 40.5%) was equal to the nonvolatile content (solid content) An organic pigment composition (X-2) having an average particle diameter of primary particles of 100 nm or less was obtained in the same manner as in Example 1 except for the above.

[Example 3]

The copolymer (B-3) solution of Synthesis Example 3 was used in an amount equal to 1.25 g of the copolymer (B-1) solution of Synthesis Example 1 (solid content: 40.5%) in terms of nonvolatile content (solid content component) An organic pigment composition (X-3) having an average particle diameter of 100 nm or less of primary particles was obtained in the same manner as in Example 1 except for the above.

(Comparative Example 1)

Hydran AP-40F (aqueous dispersion of polyurethane resin manufactured by DIC Co., Ltd.) was used in an amount equivalent to 1.25 g of the copolymer (B-1) solution of Synthesis Example 1 (solid content: 40.5%) in terms of nonvolatile content. Except that, an organic pigment composition (X-4) was obtained in the same manner as in Example 1.

[Example 4]

2.48 parts of the organic pigment composition (X-1) obtained in the above Example 1 and 1.24 parts of BYK-LPN6919 (dispersant manufactured by BYK-Chemie Co., Ltd.) manufactured by BYK-Chemie Co., Ltd., UNIDIC ZL295 (DIC Co., Ltd.) 1.86 parts of the produced acrylic resin and 10.92 parts of propylene glycol monomethyl ether acetate were used together with a zircon ball of 0.3 to 0.4 mm to be dispersed by a paint conditioner manufactured by Toyo Seiki Co., Ltd. for 2 hours.

4.0 parts of the coloring composition (I), 2.10 parts of UNIDIC ZL295, and 2.00 parts of propylene glycol monomethyl ether acetate were added, and mixed by a paint adjuster, thereby obtaining an evaluation composition for forming a green pixel portion for a color filter. .

The composition for evaluation was spin-coated on the soda glass so as to change the film thickness, and dried at 90 ° C for 3 minutes to obtain a glass substrate for evaluation. Using this glass substrate, the chromaticity (x, y) under the C light source was measured using MCPD-3000 manufactured by Otsuka Electronics Co., Ltd. Further, the chromaticity of the glass substrate for evaluation after heating at 230 ° C for 1 hour was also measured.

[Example 5]

An equivalent amount of the organic pigment composition (X-2) obtained in Example 2 was used instead of 2.48 parts of the organic pigment composition (X-1) obtained in the above Example 1, except that, in addition to Example 4, A series of operations were carried out in the same manner to obtain a glass substrate for evaluation, and the measurement was carried out in the same manner.

[Embodiment 6]

The same amount of the organic pigment composition (X-3) obtained in Example 3 was used instead of 2.48 parts of the organic pigment composition (X-1) obtained in the above Example 1, except A series of operations were carried out in the same manner as in Example 4 to obtain a glass substrate for evaluation, and the measurement was carried out in the same manner.

(Comparative Example 2)

The same amount of the organic pigment composition (X-4) obtained in Comparative Example 1 was used instead of 2.48 parts of the organic pigment composition (X-1) obtained in the above Example 1, except that, in addition to Example 4, A series of operations were carried out in the same manner to obtain a glass substrate for evaluation, and the measurement was carried out in the same manner.

The evaluation results of the above Examples 4 to 6 and Comparative Example 2 are shown in Table 1. Further, the term "PB" in the table means after heating at 230 ° C for 1 hour.

As can be seen from the comparison between Example 4 and Comparative Example 2 of Table 1 above, it is understood that the specific copolymer (B) used in the present invention has a luminance value after initial and PB as compared with the previously used polyurethane resin. The difference in chromaticity values is small, and even if subjected to a thermal history, variations in luminance and chromaticity are small, and heat resistance is excellent.

In Examples 4 to 6, both the brightness and the chromaticity absolute value of the PB were improved as compared with the initial one, and the following tendency was observed: the side chain epoxy was added based on the specific content of the specific copolymer (B). The higher the absolute value of the initial brightness.

[Embodiment 7]

85 parts of FASTOGEN BLUE AE-8 (ε-type copper phthalocyanine pigment manufactured by DIC Corporation) and 5 parts of copper phthalocyanine phthalimide methyl derivative having an average substituent number of 1.4, and the synthesis example 2 The solution of the copolymer (B-2) was dried under reduced pressure (60 ° C, 10 hours) to obtain 10 parts of a solid of the copolymer (B-2), 1000 parts of pulverized sodium chloride, and diethylene glycol 160. The mixture was added to a double-arm type kneader and kneaded at 80 to 90 ° C for 10 hours.

The obtained content was washed with a large amount of excess water and filtered, and washed with water until the specific conductivity of the filtrate became a ratio of the original water to a conductivity of +20 μS/cm or less, whereby a wet cake of the ε-type copper phthalocyanine pigment composition was obtained. The wet cake obtained was transferred to a beaker, and 3000 parts of a 2% hydrochloric acid aqueous solution was added thereto, and the mixture was stirred and dispersed to prepare a slurry. After stirring at 70 ° C for 1 hour, the mixture was filtered and washed with water to obtain a wet cake.

The obtained wet cake was transferred to a beaker, and 3000 parts of water at room temperature was added, and the mixture was stirred and dispersed to prepare a slurry. Then, an aqueous solution of 5 parts of sodium oxalic acid sulfonic acid derivative having an average number of substituents of 0.8 was added to the above pigment slurry, and after stirring for 1 hour, hydrochloric acid was added to restore the pH of the slurry to 7 and precipitated to the pigment. The surface. After maintaining for 1 hour in this state, it was filtered, washed with warm water, dried, and pulverized to obtain a blue pigment composition having an average particle diameter of primary particles of 100 nm or less.

10 parts of the blue pigment composition thus obtained was added to a polyethylene bottle, and 55 parts of propylene glycol monomethyl ether acetate, BYK (trade name) LPN21116 (manufactured by BYK-Chemie Co., Ltd.) 7.0 parts, 0.3~ were added. 0.4mm cepulbeads( The paint regulator (manufactured by Toyo Seiki Co., Ltd.) was dispersed for 4 hours to obtain a pigment dispersion liquid. 75.00 parts of the pigment dispersion liquid, a polyester acrylate resin (ARONIX (trade name) M7100, manufactured by Toagosei Chemical Co., Ltd.), 5.50 parts, dipentaerythritol hexaacrylate (KAYARAD (trade name)) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 5.00 parts, 1.00 parts of diphenyl ketone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.), and 13.5 parts of UCAR Ester EFP were stirred, using aperture 1.0. The filter of μm is filtered to obtain a color photoresist. This color resist was applied onto a glass of 50 mm × 50 mm and a thickness of 1 mm by a spin coater so as to have a dry film thickness of 2 μm, and then pre-dried at 90 ° C for 20 minutes to form a coating film. Then, after the pattern irradiation of the ultraviolet rays was performed through the photomask, the unexposed portions were washed in a 0.5% aqueous sodium carbonate solution, thereby preparing a color filter.

Using the thus obtained color filter, the luminance Y under the C light source was measured using MCPD-3000 manufactured by Otsuka Electronics Co., Ltd., and the result was 13.49. Further, the brightness of the color filter after heating at 230 ° C for 1 hour was measured and found to be 13.42.

[Embodiment 8]

A blue pigment composition was obtained in the same manner as in Example 7 except that the copolymer (B-5) was used instead of the copolymer (B-2) of Example 7, and a color filter was used and the C light source was measured. The brightness Y was as follows. As a result, the brightness before heating at 230 ° C for 1 hour was 13.50, and the brightness after heating at 230 ° C for 1 hour was 13.43.

(Comparative Example 3)

A blue pigment composition was obtained in the same manner as in Example 7 except that the copolymer (B-6) was used instead of the copolymer (B-2) of Example 7, and a color filter was used and the C light source was measured. The brightness Y was as follows. As a result, the brightness before heating at 230 ° C for 1 hour was 13.45, and the brightness after heating at 230 ° C for 1 hour was 13.26.

The evaluation results of the above Examples 7 to 8 and Comparative Example 3 are shown in Table 2.

[Industrial availability]

According to the present invention, it is possible to provide a coloring matter which is excellent in heat resistance by the interaction of the organic pigment (A) and the specific copolymer (B), and which is small even when subjected to a heat history hue change, in particular, When the pixel portion of the color filter is prepared, it is possible to provide a liquid crystal display device which is high in brightness and can realize liquid crystal display having excellent brightness even if it is subjected to a thermal history for a long period of time.

Claims (5)

An organic pigment composition for a color filter containing 0.1 to 15 parts by weight of the copolymer (B) based on 100 parts by mass of the organic pigment (A), the copolymer (B) containing an epoxy group and/or an α-chlorohydrin Further, a (meth) acrylate having a different number of carbon atoms in a side chain of the single system obtained by polymerizing a monomer mixture containing two or more kinds of the following monomers. An organic pigment composition for a color filter according to the first aspect of the invention, wherein the organic pigment (A) is an anthraquinone pigment. A method for producing an organic pigment composition for a color filter according to any one of claims 1 to 2, which is in a liquid medium, in the presence of a non-volatile component of the copolymer (B) described below, The material (A) is subjected to pressure heating, and the copolymer (B) contains an epoxy group and/or an α-chlorohydrin group, and is obtained by polymerizing a monomer mixture containing two or more of the following monomers. a (meth) acrylate having a different number of carbon atoms in a side chain; or a Solvent salt milling of the organic pigment (A) in the presence of a nonvolatile component of the following copolymer (B), the copolymer The substance (B) contains an epoxy group and/or an α-chlorohydrin group, and is obtained by polymerizing a monomer mixture containing two or more kinds of the following monomers, and the number of carbon atoms of the side chain of the single system is different (A) Base) acrylate. A color filter comprising the organic pigment composition for a color filter according to any one of claims 1 to 2 in the pixel portion. A color filter comprising, in a pixel portion, an organic pigment composition for a color filter obtained by the production method of the third application of the patent application.