JP2006284691A - Green pigment composition for color filter, and color filter containing same in green pixel portion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a green pigment composition for a color filter, and the color filter which is superior in contrast of a coating film when the green pigment composition is used for a green pixel portion. <P>SOLUTION: The green pigment composition for the color filter is characterized by containing a metal halide phthalocyanine and a copolymer of methyl methacrylate and another copolymerizable ethylenically unsaturated monomer as an acrylic resin, and having 0.01-0.1 μm average particle size of primary particles and 1-2 aspect ratio of the primary particles. The green pigment composition for the color filter contains the green pigment composition and a yellow pigment. The color filter contains the green pigment composition for the color filter in the green pixel portion. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a green pigment composition for a color filter used in liquid crystal display devices such as a liquid crystal color display, a video camera, and a color electroluminescence display, and a color filter containing the same in a green pixel portion.

  A color filter used in a liquid crystal display device is one in which each colored pixel portion (also referred to as a pattern) of red (R), green (G), and blue (B) is formed on a transparent substrate such as glass. Each of these colored pixel portions has a structure in which a synthetic resin thin film in which an organic pigment is dispersed is provided on a substrate, and red, green, and blue pigments are used as the organic pigment.

  Among these colored pixel portions, as a green pigment for forming a green pixel portion, generally, a halogenated copper phthalocyanine pigment (CI Pigment Green 36) is used. If necessary, a yellow pigment is used in combination.

  A photocurable composition for a color filter for forming a colored pixel portion uses an organic pigment, an organic solvent, and a dispersant as essential components, and these are mixed and stirred and dispersed so as to be uniform. (Also called a colored color paste) is prepared, and then a photocurable compound and, if necessary, a thermoplastic resin or a photopolymerization initiator are added thereto.

  Therefore, organic pigments used for producing a color filter are required to be excellent in the contrast of the coating film of the color filter coloring pixel portion using the pigment dispersion.

  Patent Document 1 describes a green pigment composition for a color filter in which a halogenated copper phthalocyanine pigment is subjected to a solvent salt milling treatment with a low-magnification water-soluble inorganic salt in the presence of a (meth) acrylic resin. However, when a pigment dispersion is prepared using the pigment composition, (1) the fluidity and storage stability of the dispersion are insufficient, (2) the content of the acrylic resin is large, and the dispersion is The excess acrylic resin that does not contribute causes the coating surface of the color filter green pixel portion to become rough and the coloring power and contrast to decrease, and (3) the yellowness of the hue when forming the coating film of the green pixel portion. However, the coloring power and brightness are insufficient, and it is difficult to make the color filter thin. Further, there was no description of contrast or description suggesting it in the suitability of the coating film.

Japanese Patent Laid-Open No. 7-13016 (claimed second column, left column, claims, third page paragraph numbers 0011, 0013, 0014, fifth page paragraph numbers 0029, 0030).

  The problem to be solved by the present invention is to provide a green pigment composition for a color filter and a color filter having excellent coating film contrast when the pigment composition is used in a green pixel portion.

  Therefore, the present inventors have made extensive studies in view of the above-mentioned circumstances, and as a result, a crude pigment of a metal halide phthalocyanine is used as an acrylic resin, a copolymer comprising methyl methacrylate and another copolymerizable ethylenically unsaturated monomer. It was found that the above-mentioned problems can be solved by controlling the average particle diameter of pigment primary particles and the aspect ratio thereof within a certain range by performing solvent salt milling in the presence of It was.

  That is, the present invention contains a halogenated metal phthalocyanine represented by the following general formula (1) and a copolymer composed of methyl methacrylate and another copolymerizable ethylenically unsaturated monomer as an acrylic resin, A green pigment composition for a color filter, wherein the average particle diameter of the primary particles is in the range of 0.01 to 0.1 μm, and the aspect ratio of the primary particles is in the range of 1 to 2, and the pigment composition The present invention provides a color filter containing a product in a green pixel portion.

（式中、中心金属ＭはＡｌ、Ｓｉ、Ｓｃ、Ｔｉ、Ｖ、Ｍｇ、Ｆｅ、Ｃｏ、Ｎｉ、Ｚｎ、Ｇａ、Ｇｅ、Ｙ、Ｚｒ、Ｎｂ、Ｉｎ、ＳｎおよびＰｂを表す。Ｘは水素原子およびフッ素原子、塩素原子、臭素原子、ヨウ素原子のいずれかのハロゲン原子を表し、１つのベンゼン環に結合する４個のＸは全て同一でも異なっていてもよい。また４個のベンゼン環に結合するＸのうち、８〜１５個はフッ素原子、塩素原子、臭素原子、ヨウ素原子のいずれかのハロゲン原子で、残りは水素原子を表し、ハロゲン原子の置換基数ｍは８〜１５の整数を表す。中心金属Ｍに結合するＹはフッ素原子、塩素原子、臭素原子、ヨウ素原子のいずれかのハロゲン原子、酸素原子、水酸基およびスルホン酸基を表し、ｎは０〜２の整数を表す。中心金属Ｍの原子価が２価の場合、ｎ＝０でＹは存在しない。同原子価が３価の場合、ｎ＝１でＹはハロゲン原子、水酸基およびスルホン酸基からなる群から選ばれる基の１つが中心金属Ｍに結合する。同原子価が４価の場合、ｎ＝２でＹは酸素の１つが中心金属Ｍに結合するか、またはハロゲン原子、水酸基およびスルホン酸基からなる群から選ばれる基の２つが中心金属Ｍに結合する。）

(In the formula, the central metal M represents Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn, and Pb. X represents a hydrogen atom. And a halogen atom of fluorine atom, chlorine atom, bromine atom or iodine atom, and all four Xs bonded to one benzene ring may be the same or different, and also bonded to four benzene rings. 8 to 15 of the X to be represented are halogen atoms of fluorine atom, chlorine atom, bromine atom or iodine atom, the remainder represents a hydrogen atom, and the number m of substituents of the halogen atom represents an integer of 8 to 15 Y bonded to the central metal M represents a halogen atom of any one of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an oxygen atom, a hydroxyl group and a sulfonic acid group, and n represents an integer of 0 to 2. The valence of M is 2 In the case of n = 0, there is no Y. When the valence is trivalent, n = 1 and Y is one of the groups selected from the group consisting of a halogen atom, a hydroxyl group and a sulfonic acid group bonded to the central metal M. When the valence is tetravalent, n = 2 and Y is one of oxygens bonded to the central metal M, or two of the groups selected from the group consisting of a halogen atom, a hydroxyl group and a sulfonic acid group are the central metal Binds to M.)

According to the green pigment composition of the present invention, a crude pigment composed of a halogenated metal phthalocyanine represented by the general formula (1) is used as an acrylic resin and methyl methacrylate and another copolymerizable ethylenically unsaturated monomer. The solvent salt milling treatment in the presence of a copolymer comprising a conventionally known copper halide phthalocyanine pigment, an acetate-based compound-treated pigment of the pigment, or a halogenated metal phthalocyanine not containing the acrylic resin Compared with the pigment, the color filter green pixel portion prepared using the pigment composition has a particularly remarkable effect of being superior in the contrast of the coating film.
Therefore, the green pigment composition of the present invention is optimal for forming a color filter green pixel portion.

  Hereinafter, the present invention will be described in detail.

  The green pigment composition for a color filter of the present invention is a copolymer comprising a halogenated metal phthalocyanine represented by the following general formula (1), methyl methacrylate as an acrylic resin and another copolymerizable ethylenically unsaturated monomer. The primary feature is that the average particle diameter of the primary particles containing the polymer is in the range of 0.01 to 0.1 μm, and the aspect ratio of the primary particles is in the range of 1 to 2. .

（式中、中心金属ＭはＡｌ、Ｓｉ、Ｓｃ、Ｔｉ、Ｖ、Ｍｇ、Ｆｅ、Ｃｏ、Ｎｉ、Ｚｎ、Ｇａ、Ｇｅ、Ｙ、Ｚｒ、Ｎｂ、Ｉｎ、ＳｎおよびＰｂを表す。Ｘは水素原子およびフッ素原子、塩素原子、臭素原子、ヨウ素原子のいずれかのハロゲン原子を表し、１つのベンゼン環に結合する４個のＸは全て同一でも異なっていてもよい。また４個のベンゼン環に結合するＸのうち、８〜１５個はフッ素原子、塩素原子、臭素原子、ヨウ素原子のいずれかのハロゲン原子で、残りは水素原子を表し、ハロゲン原子の置換基数ｍは８〜１５の整数を表す。中心金属Ｍに結合するＹはフッ素原子、塩素原子、臭素原子、ヨウ素原子のいずれかのハロゲン原子、酸素原子、水酸基およびスルホン酸基を表し、ｎは０〜２の整数を表す。中心金属Ｍの原子価が２価の場合、ｎ＝０でＹは存在しない。同原子価が３価の場合、ｎ＝１でＹはハロゲン原子、水酸基およびスルホン酸基からなる群から選ばれる基の１つが中心金属Ｍに結合する。同原子価が４価の場合、ｎ＝２でＹは酸素原子の１つが中心金属Ｍに結合するか、またはハロゲン原子、水酸基およびスルホン酸基からなる群から選ばれる基の２つが中心金属Ｍに結合する。）

(In the formula, the central metal M represents Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn, and Pb. X represents a hydrogen atom. And a halogen atom of fluorine atom, chlorine atom, bromine atom or iodine atom, and all four Xs bonded to one benzene ring may be the same or different, and also bonded to four benzene rings. 8 to 15 of the X to be represented are halogen atoms of fluorine atom, chlorine atom, bromine atom or iodine atom, the remainder represents a hydrogen atom, and the number m of substituents of the halogen atom represents an integer of 8 to 15 Y bonded to the central metal M represents a halogen atom of any one of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an oxygen atom, a hydroxyl group and a sulfonic acid group, and n represents an integer of 0 to 2. The valence of M is 2 In the case of n = 0, there is no Y. When the valence is trivalent, n = 1 and Y is one of the groups selected from the group consisting of a halogen atom, a hydroxyl group and a sulfonic acid group bonded to the central metal M. When the valence is tetravalent, n = 2 and Y is one of oxygen atoms bonded to the central metal M, or two groups selected from the group consisting of a halogen atom, a hydroxyl group and a sulfonic acid group. Bonds to metal M.)

  The metal halide phthalocyanine used in the present invention may be either a crude pigment or a pigment.

  The metal halide phthalocyanine used in the present invention contains a phthalocyanine molecule (structure) in the chemical structure, and a total of 8 to 15 fluorine atoms, chlorine on four benzene rings per phthalocyanine molecule (structure). It is made of a substance having a structure in which any one of atoms, bromine atoms and iodine atoms is bonded to the remaining hydrogen atoms. The halogenated metal phthalocyanine is not particularly limited to the degree of halogenation or the type of halogen atom, but the halogen atom for X is preferably a chlorine atom and a bromine atom. The center metal M is preferably Zn.

  More specifically, a metal selected from the group consisting of Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn, and Pb is mainly used. The metal M is a halogenated metal phthalocyanine in which 8 to 15 halogen atoms and hydrogen atoms per phthalocyanine molecule are bonded to the benzene ring of the phthalocyanine molecule. In addition, the halogen atom, oxygen atom, hydroxyl group and sulfonic acid group of any one of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom may be bonded to the central metal M (in the present invention, the central metal M has a binder. Referred to as Y).

  When the central metal M is divalent, there is no connector Y. When the central metal M is trivalent, any one of the halogen atoms, hydroxyl groups or sulfonic acid groups is present. When the central metal M is tetravalent, one of oxygen is present as a bond Y, or any two bond Y of the halogen atom, hydroxyl group or sulfonic acid group, which may be the same or different, are present. Exists.

  In the halogenated metal phthalocyanine of the general formula (1) used in the present invention, all four Xs bonded to one benzene ring may be the same or different. Further, as described above, among Xs bonded to the four benzene rings, 8 to 15 are halogen atoms of any one of fluorine atom, chlorine atom, bromine atom and iodine atom, and the rest are hydrogen atoms. When the number of halogen atoms of X bonded to the benzene ring is constant, the hue becomes more yellowish as it goes to the left in the order of iodine atom> bromine atom> chlorine atom> fluorine atom. Here, 9 to 15, preferably 13 to 15 bromine atoms out of 8 to 15 halogen atoms per phthalocyanine molecule are bonded to the benzene ring of the phthalocyanine molecule. The halogenated metal phthalocyanine has a bright yellowish green color and is optimal for use in the green pixel portion of a color filter.

  The metal halide phthalocyanine of the general formula (1) used in the present invention is insoluble or hardly soluble in water or an organic solvent.

  Examples of such a material include phthalocyanine green such as polyhalogenated metal phthalocyanine having a structure in which a halogen atom such as a chlorine atom or a bromine atom and a hydrogen atom are added to various crystalline metal phthalocyanines of the central metal M described above.

  The above-mentioned halogenated metal phthalocyanine having the specific central metal M can be used alone or in combination of two or more.

  The green pigment composition for a color filter of the present invention comprises a crude pigment composed of a halogenated metal phthalocyanine represented by the general formula (1) as an acrylic resin, and other copolymerizable ethylenic unsaturated compounds with methyl methacrylate. Hot solvent salt milling treatment in the presence of a copolymer of monomers in the range of the water-soluble inorganic salt ratio (compared to the crude pigment) in the range of 10 to 30 times (in the present invention, the crude pigment during the solvent salt milling treatment) And the method of adding and mixing the acrylic resin and kneading and grinding are also referred to as co-grinding.), Thereby having the average particle diameter of the primary particles and the aspect ratio within the range specified in the present invention. A pigment composition is obtained.

  The kneaded mixture obtained here is washed with water or warm water (about 5 to 20 times the amount of the kneaded mixture), filtered, completely removed of the water-soluble inorganic salt, and then washed, dried, and pulverized. Through the process, the green pigment composition for a color filter of the present invention can be prepared. In addition, although it does not specifically limit as conditions for the solvent salt milling process to be described later, it is an object to be refined (in the present invention, a halogenated metal phthalocyanine, preferably a crude pigment of the phthalocyanine). It is preferable to process in the state, ie, heat.

  The crude pigment composed of the metal halide phthalocyanine represented by the general formula (1) used in the present invention is phthalocyanine green containing coarse particles immediately after synthesis. The crude pigment can be produced by a known and commonly used production method such as an aluminum chloride method, a chlorosulfonic acid method, a halogenated phthalonitrile method, or the like.

  In any of the above production methods, when the reaction mixture obtained after completion of the reaction is poured into an acidic aqueous solution such as water or hydrochloric acid, a crude pigment composed of a metal halide phthalocyanine is precipitated. After the crude pigment is filtered, it is washed with water or an aqueous alkali solution such as aqueous sodium hydrogensulfate, aqueous sodium hydrogencarbonate, or aqueous sodium hydroxide, and if necessary, acetone, toluene, methyl alcohol, ethyl alcohol, dimethylformamide, etc. It is preferable to use after washing and drying with an organic solvent.

  Examples of the acrylic resin used in the present invention include copolymers comprising methyl methacrylate and other copolymerizable ethylenically unsaturated monomers. The copolymer may have any structure such as random, block, or graft.

  Other copolymerizable ethylenically unsaturated monomers include aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, unsaturated carboxylic acid glycidyl esters, carboxylic acid vinyl esters, Examples include saturated ethers, vinyl cyanide compounds such as vinylidene cyanide, unsaturated amides or unsaturated imides, aliphatic conjugated dienes, macromonomers having a monoacryloyl group or a monomethacryloyl group at the polymer chain end. be able to. Among them, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, isobornyl methacrylate, dicyclopentadi Enilmethacrylate Unsaturated carboxylic acid esters are preferred and the like, further, benzyl acrylate, benzyl methacrylate is more preferable.

  These other copolymerizable ethylenically unsaturated monomers can be used alone or in combination of two or more. The monomer that can be used in combination here is not particularly limited, but for example, methacrylic acid, acrylic acid, propiolic acid, crotonic acid, pentenoic acid, hexenoic acid, sorbic acid having at least one carboxyl group in the molecule. And unsaturated monocarboxylic acids such as heptenoic acid, undecylenic acid, linolenic acid, linoleic acid, linoelaidic acid, elaidic acid, oleic acid, ricinoleic acid, and arachidonic acid.

  The acrylic resin used in the present invention is preferably a copolymer composed of the above-mentioned ones that are solid and water-insoluble at room temperature. For example, a copolymer composed of methyl methacrylate and benzyl acrylate, or methyl methacrylate and benzyl methacrylate. A polymer is mentioned. These physical property values are not particularly limited, but those having a weight average molecular weight (Mw) in the range of 4,000 to 20,000 and an acid value in the range of 0 to 90 KOHmg / g are preferable. . In the case where the acrylic resin is an amine resin, the hue of the green pigment composition obtained when the central metal M of the metal halide phthalocyanine represented by the general formula (1) is limited to Zn, and This is not preferable in that the chromaticity of the coating film of the color filter shifts to the bluish side and the X-ray diffraction peak changes as a physical property value.

  The acid value of the acrylic resin is determined by dissolving 1 g of resin in 200 ml of an acetone / methyl ethyl ketone mixed solvent (1: 1 by mass ratio), adding 5 ml of water, titrating with KOH aqueous solution, and necessary for neutralization. The amount of KOH is expressed in mg. Moreover, the weight average molecular weight (Mw) of the said acrylic resin was measured by GPC method (polystyrene conversion).

  The green pigment composition for a color filter of the present invention is improved in dispersion stability as well as dispersibility of the halogenated metal phthalocyanine in the resin by co-grinding with the acrylic resin, and the flowability and storage stability of the pigment dispersion. Excellent in properties. As a result, the contrast of the coating film of the color filter green pixel portion is improved. In the conventional co-grinding of a crude pigment made of copper halide phthalocyanine and the acrylic resin, the viscosity of the pigment dispersion prepared using the green pigment composition obtained here is remarkably increased. It is difficult to disperse the pigment, which is not suitable for forming a color filter green pixel portion.

  In the green pigment composition for a color filter of the present invention, the content of the acrylic resin is preferably in the range of 3 to 15 parts in terms of mass with respect to 100 parts of the metal halide phthalocyanine. More preferably in the range of 10 parts. When the content of the acrylic resin is less than 3 parts, the contrast of the coating film of the color filter green pixel part is lowered. Moreover, even if the content exceeds 15 parts, the coloring power of the coating film of the color filter green pixel portion is lowered and the film thickness of the coating film is increased.

  Examples of the water-soluble inorganic salt used in the present invention include inorganic salts such as sodium chloride, potassium chloride and sodium sulfate, and those having an average particle diameter of 0.3 to 50 μm are preferably used. In addition, the water-soluble inorganic salt can be used as a recovered product or a finely pulverized product. For example, taking sodium chloride as an example, the average particle diameter of the recovered product is preferably 20 to 40 μm, and that of the finely pulverized product is preferably in the range of 0.3 to 10 μm. A finely pulverized product can be easily obtained by pulverizing a normal water-soluble inorganic salt.

  Further, the magnification of the water-soluble inorganic salt is preferably 10 to 30 times that of the crude pigment composed of the metal halide phthalocyanine represented by the general formula (1). Especially, the quality of the pigment composition and its production Considering the property, it is more preferably 11 to 20 times. Here, the magnification of the water-soluble inorganic salt refers to the number of parts of the water-soluble inorganic salt per part of the crude pigment composed of the halogenated metal phthalocyanine represented by the general formula (1), and the unit is expressed in double. is there.

  The organic solvent used in the present invention is preferably a water-soluble organic solvent capable of suppressing crystal growth, such as diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol, and the like. These can be used alone or in combination of two or more.

  The amount of the organic solvent used is not particularly limited, but is 0.01 to 5 parts per 1 part of the crude pigment composed of the halogenated metal phthalocyanine represented by the general formula (1) in terms of mass. It is preferable that it is the range of these.

  The solvent salt milling treatment of the present invention includes a crude pigment composed of a halogenated metal phthalocyanine represented by the general formula (1), methyl methacrylate as the acrylic resin, and other copolymerizable ethylenically unsaturated monomers. This means that the copolymer, a water-soluble inorganic salt, and an organic solvent that does not dissolve the copolymer are mechanically kneaded and ground. Examples of means for kneading and grinding at this time include kneaders such as a kneader, a mix muller, an extruder, a ball mill, and a roll mill. This solvent salt milling treatment can easily suppress the crystal growth of the pigment, and can easily obtain a green pigment composition for a color filter having an average primary particle diameter and an aspect ratio as specified in the present invention. preferable.

  The conditions for the solvent salt milling treatment of the present invention are not particularly limited, but it is an object to be refined (a metal halide phthalocyanine represented by the general formula (1), preferably a crude product comprising the phthalocyanine. It is preferable to carry out the treatment in a state in which the (pigment) is heated, that is, when heated. The temperature of the solvent salt milling treatment is preferably in the range of 30 to 150 ° C, and more preferably in the range of 80 to 110 ° C. The time for the solvent salt milling treatment is preferably in the range of 3 to 20 hours, and more preferably in the range of 4 to 10 hours.

  Thus, a green pigment composition comprising a metal halide phthalocyanine represented by the general formula (1) and a copolymer comprising methyl methacrylate and another copolymerizable ethylenically unsaturated monomer as an acrylic resin, A kneaded mixture containing a basic inorganic salt and an organic solvent as main components can be obtained.

  The kneaded mixture taken out from the kneader must completely remove the water-soluble inorganic salt and the organic solvent contained in the kneaded mixture in order to obtain the green pigment composition for color filter (powder) of the present invention. I must. The removal is not particularly limited. For example, the kneaded mixture is poured into about 5 to 20 times the amount of water or warm water (compared to the kneaded mixture), and the mixture is dissolved for a predetermined time, and the aqueous slurry is filtered. . Next, the filtrate is washed several times until the specific conductivity of the filtrate is comparable to that of purified water (in order to make the concentration of the pigment composition as close to zero as possible) Completely remove organic solvent. In addition, as these removal methods, it can also wash | clean using an acid and alkaline aqueous solution together if necessary. Further, the water-soluble inorganic salt and organic solvent removed here can be recovered and reused.

  Examples of drying after filtration and washing include batch or continuous drying in which the pigment composition is dehydrated and / or desolved by heating at 80 to 120 ° C. with a heating source installed in a dryer, freeze drying, or the like. Use. Examples of the dryer include a box dryer, a band dryer, and a spray dryer.

  As the pulverization after drying, it is not an operation to increase the specific surface area of the pigment composition or to reduce the average particle diameter or aspect ratio of the primary particles, but using a box dryer or a band dryer. When the pigment composition becomes a lamp shape or the like, this is an operation for solving this and making it into powder. Examples of the pulverizer include a mortar, a hammer mill, a disk mill, a pin mill, a jet mill, and a juicer mixer.

  Thus, the metal halide phthalocyanine represented by the general formula (1), methyl methacrylate as the acrylic resin, and other copolymerizable ethylene are obtained through the filtration, washing, drying, and pulverization steps. Of the present invention, wherein the average particle diameter of the primary particles is in the range of 0.01 to 0.1 μm, and the aspect ratio of the primary particles is in the range of 1 to 2. A powder of a green pigment composition for a color filter can be prepared. The pigment composition can be used for forming a color filter green pixel portion.

  Since the green pigment composition of the present invention has the average particle diameter and aspect ratio of primary particles as described above, the pigment is finely dispersed in the liquid medium, and the dispersibility and dispersion stability of the pigment are improved. A pigment dispersion using this pigment composition is excellent in fluidity because of its low viscosity immediately after production and after aging. In addition, this pigment dispersion is excellent in storage stability because of a small change in viscosity immediately after production and after aging.

  When a color filter green pixel portion is produced using this pigment composition, the coating properties of the green pixel portion are excellent, and a coating film having a uniform film thickness can be formed to obtain a color filter with high contrast. . Here, the contrast is the transmitted light intensity when the object to be measured is sandwiched with the polarization directions of the two polarizing plates parallel to each other and the object to be measured is sandwiched with the polarization direction of the two polarizers perpendicular to each other. This is divided by the transmitted light intensity and is also called depolarization.

  If the average particle diameter of the primary particles of the green pigment composition for a color filter of the present invention is less than 0.01 μm, the cohesiveness of the pigment becomes strong and difficult to disperse, and the viscosity of the pigment dispersion increases with time. In addition, since the pigment is likely to aggregate, secondary particles having a larger particle diameter may be formed in the dispersed state, which causes a decrease in the contrast of the color filter coating film. Even if the average particle diameter of the primary particles of the pigment composition exceeds 0.1 μm, it is the same as described above. Further, even when the aspect ratio of the primary particles is larger than 2, the same as described above.

  That is, if the average particle diameter and aspect ratio of the primary particles deviate from the preferred range, the fluidity and storage stability of the pigment dispersion prepared by using the green pigment composition of the present invention will be reduced. . Due to this, the color filter green pixel portion using this pigment dispersion is not preferable because the contrast of the coating film is lowered.

  The average particle diameter of the primary particles in the present invention refers to that of the primary particles of the pigment constituting the aggregate on the two-dimensional image by photographing the particles in the field of view with a transmission electron microscope JEM-2010 (manufactured by JEOL Ltd.) This is a value obtained by obtaining the longer diameter (major diameter) of 50 pieces and averaging them. At this time, the green pigment composition of the present invention as a sample is ultrasonically dispersed in a solvent and then the particles are photographed with the microscope. A scanning electron microscope may be used instead of the transmission electron microscope.

  In the green pigment composition of the present invention, the pigment is compared with a conventionally known halogenated copper phthalocyanine pigment, an acetate-based compound-treated pigment of the pigment, or an untreated pigment of a halogenated metal phthalocyanine that does not contain the acrylic resin. The primary particles have a weak cohesive force and are more easily solved. From the electron micrograph, it is possible to observe primary pigment particles that cannot be observed with the above-described conventionally known pigment, the treated pigment, or the untreated pigment of the metal halide phthalocyanine.

  Moreover, when the primary particles of the green pigment composition of the present invention have an aspect ratio of 1 to 2, the flow characteristics in the photocurable composition described later are improved, and the viscosity of the photocurable composition is lowered. There is a tendency. As a result, the applicability of the color filter to the transparent substrate is improved.

  In order to obtain the aspect ratio, first, as in the case of obtaining the average particle diameter of the primary particles, the particles in the field of view are photographed with a transmission electron microscope or a scanning electron microscope. Then, for 50 primary particles constituting the aggregate on the two-dimensional image, an average value of the longer diameter (major axis) and the shorter diameter (minor axis) is obtained and calculated using these values. To do. The aspect ratio indicates a numerical value of 1 or more, but the smaller the aspect ratio (closer to 1), the closer to a square as a two-dimensional shape and the closer to a cube as a three-dimensional shape.

  The green pigment composition of the present invention has primary particles as compared with a conventionally known copper halide phthalocyanine pigment, an acetate ester compound treated pigment of the pigment, or a halogenated metal phthalocyanine untreated pigment not containing the acrylic resin. The average particle diameter is in the above-described range, and the particle size distribution of the pigment is narrower and sharper (light scattering by coarse particles is less). In addition, since there are few fine irregularities on the pigment surface and it is rich in smoothness, the dispersibility and dispersion stability of the pigment are improved, and the color filter green color with high contrast as well as improved heat resistance when manufacturing the color filter green pixel part. A pixel portion can be obtained.

  The color filter green pixel portion obtained by using the green pigment composition of the present invention is based on the results of visual evaluation. From the results of visual evaluation, a conventionally known copper halide phthalocyanine pigment, an acetate-based compound-treated pigment of the pigment, or the acrylic resin The hue becomes more yellow than the green pixel portion obtained from the untreated pigment of metal halide phthalocyanine that does not contain, and exhibits a green color with excellent transparency.

  For the purpose of improving the dispersibility of the pigment, a conventionally known pigment dispersant, surfactant, pigment derivative or the like may be used in combination with the green pigment composition for a color filter of the present invention in an amount of about 1%. Specifically, examples of the pigment derivative include a low halogenated copper phthalocyanine sulfonic acid derivative.

  Since the green pigment composition of the present invention is toned (yellowed) to a desired chromaticity for forming a color filter green pixel portion, a yellow pigment can be used in combination as necessary. These yellow pigments are preferably added in a range that does not impair the color characteristics. These yellow pigments may be surface-treated yellow pigments whose surface is covered with a known and commonly used pigment derivative, dispersant, surfactant, resin, or other surface treatment agent. Good. Furthermore, you may use the said yellow pigment adjusted to the same particle diameter as the green pigment composition of this invention, or its yellow process pigment.

  The yellow pigment used in combination with the present invention can be used as a color filter green pixel portion in order to pick up a desired emission line of a backlight light source having a wavelength (Tmax) at which the transmittance of the spectral transmission spectrum is maximized.

  Examples of the yellow pigment for toning used in the present invention include C.I. I. Pigment Yellow 83, 128, 138, 139, 150, 154, 180, 185, and the like.

  These yellow pigments can be used singly or in combination of two or more. Among the yellow pigments, C.I. I. Pigment Yellow 138, 139, and 150 are preferable in terms of excellent chromaticity and transparency.

  The content ratio of the yellow pigment can be appropriately selected depending on the application. In general, when used for color filter applications, it is preferably in the range of 10 to 60%, in terms of mass, with respect to the total amount of the green pigment composition of the present invention and the yellow pigment, and in particular, 30 to 50% It is more preferable that it is in the range.

  According to the green pigment composition of the present invention, a small amount is sufficient even when the yellow pigment is used in combination with the green pigment composition. Therefore, compared with the conventional case where two or more different color pigments are mixed for toning, Reaggregation hardly occurs and turbidity is low. In addition, a color filter green pixel portion having excellent chromaticity and transparency can be obtained. Further, when the green pigment composition of the present invention and the yellow pigment are used in combination, the disadvantage that the portion having the intended chromaticity and hue and the portion that does not occur in the color filter green pixel portion are hardly formed. This is preferable.

  The color filter green pixel portion prepared by using the green pigment composition of the present invention in combination with a yellow pigment contains a conventionally known copper halide phthalocyanine pigment, an acetate-based compound-treated pigment of the pigment, or the acrylic resin. Compared to the untreated pigments of non-halogenated metal phthalocyanines combined with yellow pigments, the decrease in brightness when using a liquid crystal display is small, and the amount of light transmitted in the green region is large. preferable.

  The green pigment composition of the present invention can be used for preparing a green pixel portion of a color filter and a green pigment for forming the green pixel portion by a conventionally known method. In producing a color filter green pixel portion using the green pigment composition of the present invention, a pigment dispersion method can be suitably employed.

  A typical method in this method is a photolithography method, in which a photocurable composition to be described later is applied to a surface of a transparent substrate for a color filter on which a black matrix is provided, followed by heat drying (prebaking). After that, pattern exposure is performed by irradiating ultraviolet rays through a photomask to cure the photo-curable compound at a location corresponding to the pixel portion, and then developing the unexposed portion with a developer to remove non-pixels. This is a method of removing the portion and fixing the pixel portion to the transparent substrate. In this method, a pixel portion made of a cured colored film of a photocurable composition is formed on a transparent substrate.

  A photocurable composition to be described later is prepared for each color of red, green, and blue, and a color filter having colored pixel portions of red, green, and blue at predetermined positions is manufactured by repeating the above-described operation. I can do it. As described above, a green pixel portion and a green pigment for forming the green pixel portion are prepared from the green pigment composition of the present invention. In addition, in order to prepare the photocurable composition for forming the red pixel portion and the blue pixel portion, known and commonly used red pigments and blue pigments can be used, respectively.

  Examples of the pigment for forming the red pixel portion include C.I. I. Pigment Red 122, 123, 149, 177, 179, 209, 254, and the like as pigments for forming the blue pixel portion include, for example, C.I. I. Pigment Blue 15: 1, 15: 2, 15: 6, and the like. For the formation of the red pixel portion, a yellow pigment can be used together with the green pixel portion, and for the formation of the blue pixel portion, a purple pigment or a blue pigment having a more red hue can be used in combination. Thereafter, if necessary, the entire color filter can be heat-treated (post-baked) in order to thermally cure the unreacted photocurable compound.

  Examples of a method for applying a photocurable composition described later on a transparent substrate such as glass include a spin coat method, a roll coat method, and an ink jet method.

  Although the drying conditions of the coating film of the photocurable composition apply | coated to the transparent substrate differ also with the kind of each component, a compounding ratio, etc., they are 50-150 degreeC and are about 1 to 15 minutes normally. This heat treatment is generally referred to as “pre-baking”. Moreover, as light used for photocuring of a photocurable composition, it is preferable to use the ultraviolet-ray of a wavelength range of 200-500 nm, or visible light. Various light sources that emit light in this wavelength range can be used.

  Examples of the developing method include a liquid piling method, a dipping method, and a spray method. After exposure and development of the photocurable composition, the transparent substrate on which the necessary color pixel portion is formed is washed with water and dried. The color filter thus obtained is subjected to heat treatment (post-baking) at 100 to 280 ° C. for a predetermined time by a heating device such as a hot plate or an oven to remove volatile components in the coating film and at the same time photocuring. The unreacted photocurable compound remaining in the cured colored film of the curable composition is thermally cured to complete the color filter.

  The above-described photocurable composition (also referred to as a pigment-dispersed photoresist) for forming the color filter green pixel portion includes the green pigment composition of the present invention, a dispersant, a photocurable compound, and an organic solvent. Can be prepared by mixing them using a thermoplastic resin as necessary. When the colored resin film that forms the green pixel portion requires toughness that can withstand baking performed in the actual production of a color filter, a photocurable compound is used in preparing the photocurable composition. In addition, it is essential to use this thermoplastic resin in combination. When a thermoplastic resin is used in combination, it is preferable to use an organic solvent that dissolves it.

  As a method for producing the photocurable composition, the green pigment composition of the present invention, an organic solvent and a dispersant are used as essential components, and these are mixed and stirred and dispersed so as to be uniform. After preparing a pigment dispersion (also called a colored paste) for forming the green pixel portion of the color filter, a photocurable compound and, if necessary, a thermoplastic resin and a photopolymerization initiator are added thereto. In addition, the method of using the photocurable composition is common.

  As described above, the green pigment composition of the present invention used here includes, as an acrylic resin, a general formula (1) containing a copolymer composed of methyl methacrylate and another copolymerizable ethylenically unsaturated monomer as an acrylic resin. A metal halide phthalocyanine represented by the formula (1) and a yellow pigment can be used in combination, if necessary.

  Examples of the dispersant used here include Dispersic 130, Dispersic 161, Dispersic 162, Dispersic 163, Dispersic 170, Dispersic 170, Dispersic 170, Dispersic 170, Dispersic 170, Dispersic 170, Dispersic 170, Dispersic 170, Dispersic 170 Further, a leveling agent, a coupling agent, a cationic surfactant, and the like can be used together.

  Examples of the organic solvent used here include aromatic solvents such as toluene, xylene and methoxybenzene, acetate solvents such as ethyl acetate and butyl acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, ethoxy Propionate solvents such as ethyl propionate, alcohol solvents such as methanol and ethanol, ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether and diethylene glycol dimethyl ether, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone , Aliphatic hydrocarbon solvents such as hexane, N, N-dimethylformamide, γ-butyrolactam, N-methyl-2- Pyrrolidone, aniline, nitrogen compound-based solvent such as pyridine, .gamma.-lactone solvents butyrolactone, carbamic acid esters such as a mixture of 48:52 of methyl carbamate and ethyl carbamate acid. As the organic solvent, polar solvents such as propionate-based, alcohol-based, ether-based, ketone-based, nitrogen compound-based, and lactone-based solvents that are water-soluble are particularly preferable. When a water-soluble organic solvent is used, water can be used in combination.

  Examples of the thermoplastic resin used for preparing the photocurable composition include urethane resins, acrylic resins, polyamic acid resins, polyimide resins, styrene maleic acid resins, styrene maleic anhydride resins, and the like. It is done.

  Examples of the photocurable compound include 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, 3-methylpentanediol di Multifunctional with relatively low molecular weight such as bifunctional monomer such as acrylate, trimethylol propaton triacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate Monofunctional, polyester acrylate, polyurethane acrylate, polyether acrylate, etc. It is.

  Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyldimethylketanol, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis (4′-azidobenzal) -2-propane, 1,3-bis (4 '-Azidobenzal) -2-propane-2'-sulfonic acid, 4,4'-diazidostilbene-2,2'-disulfonic acid and the like.

  The green pigment composition of the present invention comprises 300 to 1000 parts of an organic solvent and 0 to 100 parts of a dispersant per 100 parts of the pigment composition in terms of mass using each of the materials as described above. A pigment dispersion can be obtained by stirring and dispersing so as to be uniform. The pigment dispersion is then combined with 3-20 parts of thermoplastic resin and photocurable compound per part of the green pigment composition of the present invention and 0.05-3 parts of light per part of the photocurable compound. A photo-curable composition for forming a color filter green pixel portion can be obtained by adding a polymerization initiator and, if necessary, further an organic solvent and stirring and dispersing so as to be uniform.

  As the developer, a publicly known and commonly used organic solvent or alkaline aqueous solution can be used. In particular, when the photocurable composition contains a thermoplastic resin or a photocurable compound, and at least one of them has an acid value and exhibits alkali solubility, the color filter can be washed with an alkaline aqueous solution. This is effective for forming the green pixel portion.

  The color filter green pixel portion prepared using the green pigment composition of the present invention has been described in detail regarding the manufacturing method using the photolithography method among the pigment dispersion methods, but other electrodeposition methods, transfer methods, A color filter may be manufactured by forming a green pixel portion by a manufacturing method such as a micelle electrolysis method or a PVED (Photovoltaic Electrodeposition) method.

  The color filter uses a red pigment, a blue pigment, and a photocurable composition of each color obtained by using the green pigment composition of the present invention, and encloses a liquid crystal material between a pair of parallel transparent electrodes, and is transparent. The electrode is divided into discontinuous fine sections, and any one of red (R), green (G), and blue (B) is assigned to each of the fine sections divided into a lattice by the black matrix on the transparent electrode. It can be obtained by a method of providing color filter colored pixel portions selected from colors alternately in a pattern, or a method of providing a transparent electrode after forming a color filter colored pixel portion on a substrate.

  The green pigment composition of the present invention is optimal for forming the color filter green pixel portion as described above.

  The green pigment composition of the present invention is excellent in the storage stability of the pigment dispersion for color filter due to the dispersibility and dispersion stability of the pigment, and further in the yellow of the coating film contrast of the color filter green pixel portion. It is a pigment composition exhibiting a hue of taste, and in addition to the color filter applications described above, paint, plastic (resin molded product), printing ink, rubber, leather, textile printing, electrostatic charge image developing toner, inkjet recording ink, It can also be used for coloring applications such as thermal transfer inks.

  Hereinafter, the present invention will be described in detail with reference to production examples, examples, and comparative examples. The present invention is not limited to these examples. Unless otherwise specified, both “part” and “%” are based on mass.

(Production Example 1)
The brominated chlorinated zinc phthalocyanine crude pigment is first produced from phthalodinitrile and zinc chloride as raw materials. This 1-chloronaphthalene solution has light absorption at 750-850 nm. For halogenation, 3.1 parts of thionyl chloride, 3.7 parts of anhydrous aluminum chloride and 0.5 part of sodium chloride are mixed at 40 ° C., and 2.6 parts of bromine are added dropwise. 1 part of the prepared zinc phthalocyanine is added thereto, and the mixture is reacted at 90 ° C. for 15 hours. Thereafter, the reaction mixture is poured into water to precipitate a crude zinc halide phthalocyanine pigment. This aqueous slurry was filtered, washed with hot water at 60 ° C., washed with 1% aqueous sodium hydrogen sulfate, washed with acetone containing 7% toluene, washed with hot water at 60 ° C., dried at 90 ° C., and 2.6 parts. A purified zinc halide phthalocyanine crude pigment was obtained. The analysis result of the halogen content by mass spectrometry of the crude pigment is that the average composition ZnPcBr ₁₄ Cl ₁ H (central metal M = Zn, n = 0, X = 14 bromine atoms and 1 chlorine atom, m = 15 and 1 hydrogen atom).

(Production Example 2)
350 parts of brominated chlorinated zinc phthalocyanine crude pigment of Production Example 1, 3850 parts of crushed sodium chloride, Unidic ZL-295 which is an acrylic resin [methyl methacrylate and benzyl acrylate copolymer (acid value 80 KOH mg / g, weight) 17.5 parts of a solid having an average molecular weight of 12,000)] and 550 parts of diethylene glycol were charged into a double-arm kneader having a capacity of 8 L and kneaded and ground at 90 ° C. for 4 hours. After the kneading and grinding, the kneader cake (kneaded mixture) is put into 60 L of water and stirred at 60 ° C. for 1 hour, and the aqueous slurry is filtered. Subsequently, the filtrate was washed with water to such an extent that the specific conductivity of the filtrate was not inferior to that of purified water, thereby completely removing the water-soluble inorganic salt and the organic solvent. The pigment cake obtained in this way is dried at 80-120 ° C. for 24 hours in a box dryer, pulverized with a juicer mixer, and a green pigment for a color filter having an average primary particle size of 0.03 μm and an aspect ratio of 2. A composition (a) was obtained.

(Production Example 3)
350 parts of crude brominated chlorinated zinc phthalocyanine pigment of Production Example 1, 3850 parts of crushed sodium chloride, a copolymer consisting of methyl methacrylate and benzyl methacrylate as an acrylic resin (acid value 0 KOH mg / g, weight average molecular weight 14,000) )] Solid matter and 550 parts of diethylene glycol were charged into a double arm kneader having a capacity of 8 L and kneaded and ground at 90 ° C. for 4 hours. After the kneading and grinding, the kneader cake (kneaded mixture) is put into 60 L of water and stirred at 60 ° C. for 1 hour, and the aqueous slurry is filtered. Subsequently, the filtrate was washed with water to such an extent that the specific conductivity of the filtrate was not inferior to that of purified water, thereby completely removing the water-soluble inorganic salt and the organic solvent. The pigment cake obtained in this way is dried at 80-120 ° C. for 24 hours in a box dryer, pulverized with a juicer mixer, and a green pigment for a color filter having an average primary particle size of 0.03 μm and an aspect ratio of 2. A composition (b) was obtained.

(Production Example 4)
A color filter having an average primary particle size of 0.03 μm and an aspect ratio of 2 was prepared in the same manner as in Production Example 2 except that the amount of acrylic resin (solid) added was 35 parts in Production Example 2. A green pigment composition (c) was obtained.

(Production Example 5)
In Production Example 2, the same operation as in Production Example 2 was carried out except that no acrylic resin was added (no treatment), and a green pigment for color filters having an average primary particle diameter of 0.06 μm and an aspect ratio of 2 ( d) was obtained.

(Production Example 6)
C. I. Pigment Green 36 (chlorinated brominated copper phthalocyanine, average number of substituents (chlorine: bromine = 3: 13) 350 parts, pulverized sodium chloride 2450 parts, acetic acid stearyl ester compound 17.5 parts, diethylene glycol 550 parts A double-arm kneader with a capacity of 8 L was charged and kneaded and ground at 90 ° C. for 6 hours. After the kneading and grinding, the kneader cake (kneaded mixture) is put into 60 L of water and stirred at 60 ° C. for 1 hour, and the aqueous slurry is filtered. Subsequently, the filtrate was washed with water to such an extent that the specific conductivity of the filtrate was not inferior to that of purified water, thereby completely removing the water-soluble inorganic salt and the organic solvent. The pigment cake obtained in this manner was dried overnight at 80-120 ° C. in a box-type dryer, pulverized in a juicer mixer, and the green particles for color filters having an average primary particle size of 0.06 μm and an aspect ratio of 2 were obtained. A composition (e) was obtained.

(Production Example 7)
In Production Example 6, the same operation as in Production Example 5 was carried out except that no stearyl acetate compound was added (no treatment). For color filters having an average primary particle size of 0.04 μm and an aspect ratio of 2 Green pigment (f) Q was obtained.

  Using the green pigment composition (a) obtained in Production Example 2 as a green pigment, a color filter green pixel portion was produced by photolithography.

  As a method for producing a color filter green pixel portion, 10 parts of a green pigment composition (a), 2.5 parts of N, N′-dimethylformamide (organic solvent), Dispersic 161 (dispersant manufactured by BYK Chemie) 6.78 Part, 80.80 parts of Euker Ester EEP (Union Carbide organic solvent) is added with 0.5 mmφ Sepul beads, and dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 1 hour to obtain a pigment dispersion (colored paste). Obtained. 75.00 parts of this pigment dispersion and Aronix M7100 (polyester acrylate resin, manufactured by Toa Gosei Chemical Co., Ltd., corresponding to a photocurable compound) 5.50 parts, KAYARAD DPHA (dipentaerylate hexaacrylate, 5.00 parts by Nippon Kayaku Co., Ltd., corresponding to a photocurable compound.) 5.00 parts, KAYACURE BP-100 (benzophenone, Nippon Kayaku Co., Ltd., corresponding to a photopolymerization initiator) 1.00 parts. 13.5 parts of Euker ester EFP was stirred with a dispersion stirrer to obtain a photocurable composition for forming a color filter green pixel part. The photocurable composition was applied to 1 mm thick glass so as to have a dry film thickness of 1 μm.

  Next, after performing pattern exposure with ultraviolet rays through a photomask, the unexposed portion was washed with an organic solvent to produce a color filter green pixel portion.

  A color filter green pixel portion was produced in the same manner as in Example 1 except that the green pigment composition (b) obtained in Production Example 3 was used as a green pigment.

  A yellow pigment having the same particle size as that of the green pigment composition of Example 1, C.I. I. Pigment Yellow 138 (quinophthalone yellow pigment) and C.I. having the same particle size as the green pigment composition. I. Pigment Red 254 (diketopyrrolopyrrole red pigment) with the same particle size as the yellow pigment and the green pigment composition. I. Pigment Blue 15: 6 (ε-type copper phthalocyanine-based blue pigment) having the same particle diameter as described above. I. Pigment Violet 23 (dioxazine-based purple pigment) was added to prepare a green pigment composition, a red pigment composition, and a blue pigment composition, the total of which was 100%. Subsequently, according to Example 1, the photocurable composition of green, red, and blue was produced, and the green pixel part (G), the red pixel part (R), and the blue pixel part (B) were formed. As described above, a color filter was manufactured from the obtained RGB color pixel portions.

  A yellow pigment having the same particle diameter as that of the green pigment composition of Example 2, C.I. I. Pigment Yellow 138 (quinophthalone yellow pigment) and C.I. having the same particle size as the green pigment composition. I. Pigment Red 254 (diketopyrrolopyrrole red pigment) with the same particle size as the yellow pigment and the green pigment composition. I. Pigment Blue 15: 6 (ε-type copper phthalocyanine-based blue pigment) having the same particle diameter as described above. I. Pigment Violet 23 (dioxazine-based purple pigment) was added to prepare a green pigment composition, a red pigment composition, and a blue pigment composition, the total of which was 100%. Subsequently, according to Example 1, the photocurable composition of green, red, and blue was produced, and the green pixel part (G), the red pixel part (R), and the blue pixel part (B) were formed. As described above, a color filter was manufactured from the obtained RGB color pixel portions.

(Comparative Example 1)
A color filter green pixel portion was produced in the same manner as in Example 1 except that the green pigment (d) obtained in Production Example 5 was used as a green pigment.

(Comparative Example 2)
A color filter green pixel portion was produced in the same manner as in Example 1 except that the green pigment composition (e) obtained in Production Example 6 was used as a green pigment.

(Comparative Example 3)
A color filter green pixel portion was produced in the same manner as in Example 1 except that the green pigment (f) obtained in Production Example 7 was used as a green pigment composition.

(Measurement of the contrast of the color filter green pixel coating)
For the contrast of the coating film, the color filter green pixel part was installed between two polarizing plates, a light source was installed on one side, and a CCD camera was installed on the opposite side, and the transparency was measured. The ratio of transparency (transmitted light intensity) between when the polarization axis was parallel and when it was perpendicular was calculated and evaluated as contrast. The results are shown in Table 1.

                            Table 1

  As is clear from the results in Table 1, the color filter green pixel portions of Examples 1 and 2 were excellent in the contrast of the coating film. On the other hand, a color filter green pixel of Comparative Examples 1 to 3 using a conventionally known copper halide phthalocyanine pigment, a pigment treated with an acetate ester compound of the pigment, or an untreated pigment of a halogenated metal phthalocyanine not containing the acrylic resin. In the part, the contrast of the coating film was inferior. As described in Table 1, the contrast was improved by about 30 to 80% compared to the conventional case, and the effect was very remarkable.

Further, C.I. is used for the red pixel portion (R). I. Pigment Red 254 is used for the blue pixel portion (B). I. Pigment Blue 15: 6, and further using the green pigment composition of the present invention for the green pixel portion (G), a color filter having green, red and blue color pixel portions formed in accordance with Example 1 Prepared (Examples 3 and 4).
As a result, this color filter has a coating film as compared with the above-mentioned known halogenated copper phthalocyanine pigment, pigment-treated pigment compound-treated pigment, or untreated pigment of halogenated metal phthalocyanine that does not contain the acrylic resin. The contrast was extremely excellent.

As described above, the primary particles comprising the metal halide phthalocyanine represented by the general formula (1) and a copolymer composed of methyl methacrylate and another copolymerizable ethylenically unsaturated monomer as an acrylic resin. The green pigment composition of the present invention having an average particle diameter of 0.01 to 0.1 μm and an aspect ratio of primary particles of 1 to 2 is a conventionally known copper halide phthalocyanine pigment, The color filter green pixel portion prepared using the pigment composition compared to the pigment-treated acetate ester compound-treated pigment or the non-treated halogenated metal phthalocyanine pigment not containing the acrylic resin, It has a particularly remarkable effect of being superior in contrast.
Therefore, the green pigment composition of the present invention is optimal for forming a color filter green pixel portion.

Claims (6)

It contains a halogenated metal phthalocyanine represented by the following general formula (1) and a copolymer of methyl methacrylate and another copolymerizable ethylenically unsaturated monomer as an acrylic resin, and the average of the primary particles A green pigment composition for a color filter, wherein the particle diameter is in the range of 0.01 to 0.1 μm and the aspect ratio of the primary particles is in the range of 1 to 2.

(In the formula, the central metal M represents Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn, and Pb. X represents a hydrogen atom. And a halogen atom of fluorine atom, chlorine atom, bromine atom or iodine atom, and all four Xs bonded to one benzene ring may be the same or different, and also bonded to four benzene rings. 8 to 15 of the X to be represented are halogen atoms of fluorine atom, chlorine atom, bromine atom or iodine atom, the remainder represents a hydrogen atom, and the number m of substituents of the halogen atom represents an integer of 8 to 15 Y bonded to the central metal M represents a halogen atom of any one of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an oxygen atom, a hydroxyl group and a sulfonic acid group, and n represents an integer of 0 to 2. The valence of M is 2 In the case of n = 0, there is no Y. When the valence is trivalent, n = 1 and Y is one of the groups selected from the group consisting of a halogen atom, a hydroxyl group and a sulfonic acid group bonded to the central metal M. When the valence is tetravalent, n = 2 and Y is one of oxygens bonded to the central metal M or two of the groups selected from the group consisting of a halogen atom, a hydroxyl group and a sulfonic acid group are the central metal. Binds to M.)   By subjecting the crude pigment composed of the halogenated metal phthalocyanine represented by the general formula (1) to a hot solvent salt milling process in the presence of an acrylic resin and a water-soluble inorganic salt ratio of 10 to 30 times. The green pigment composition for a color filter according to claim 1, which is obtained.   The green pigment composition for a color filter according to claim 1 or 2, wherein the other copolymerizable ethylenically unsaturated monomer is an unsaturated carboxylic acid ester.   The green pigment composition for a color filter according to any one of claims 1 to 3, wherein the content of the acrylic resin is in the range of 3 to 15 parts with respect to 100 parts of the metal halide phthalocyanine in terms of mass.   A green pigment composition for a color filter comprising the green pigment composition for a color filter according to any one of claims 1 to 4 and a yellow pigment.   A color filter comprising a green pixel portion containing the green pigment composition for a color filter according to any one of claims 1 to 5.