TW201103959A - Fine pigment composition and manufacturing method thereof - Google Patents

Abstract

The issue of this invention is to provide a fine pigment composition containing an organic pigment of extremely small primary particle diameter and in which the coagulation of the organic pigment can be significantly inhibited, and a manufacturing method capable of preparing the fine pigment composition easily. The solution means of this invention is a fine pigment composition containing a triazine compound represented by the formula (1).( in the formula (1), A represents an acidic group or basic group; B represents –OH, -Cl, an acidic group, or basic group; D represents –H, -Cl, -OH, or an aromatic amine residue).

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fine pigment composition containing a fine organic pigment and a method for producing the same. [Prior Art] In printing inks or paints, for example, inks for inkjet printers and inks for color filters, by dispersing pigments in a fine state, high coloring power can be maintained and maintained. The suitability of the vivid color, gloss, and the like of the printed matter or the coated product, or the suitability of the color, contrast, and the like of the coating film such as a color filter. In recent years, in view of the demand for high-quality printed matter and the like on the market, an ink or the like obtained by dispersing finer pigment particles is strongly desired. Therefore, in order to make the pigment finer, the pigment obtained at a time can be widely used to make the particle diameter of the primary particles smaller by a method such as salt milling. However, in general, pigment particles which are temporarily dispersed in a mixture of water 'solvent, resin, etc. (developer such as paint or ink) tend to agglomerate in a mixture (pigment dispersion) due to the primary particles of the pigment. The smaller the particle diameter, the stronger the tendency to aggregate and form secondary particles. Even if the pigment is refined by salt milling or the like as described above, it is difficult to stabilize the finely divided pigment particles and disperse them. Further, if the pigment particles are aggregated in the pigment dispersion as described above, there are various undesirable phenomena such as an increase in the viscosity of the pigment dispersion, a decrease in the gloss of the coating surface of the color developing material, and a decrease in the performance of the coating film. -5- 201103959 This improvement strategy proposes surface treatment of pigments such as metallic soaps, or specific pigment derivatives, dispersants containing partial skeletons of organic pigments, etc. Use (for example, refer to Patent Documents 1 to 3). However, in view of the above-mentioned techniques, it is possible to obtain a certain degree of improvement effect by refining and aggregating the pigment particles. However, in view of the current situation, it is desired to disperse inks of finer pigment particles. It may not be met. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] US Patent No. 3 5 8 2 3 8 0 (Patent Document 2) Japanese Patent Publication No. Hei 3-9957 (Patent Document 3) JP-A-2003-26950 [Problem to be Solved by the Invention] In view of the above problems, an object of the present invention is to provide a fine pigment composition containing an organic pigment having a small primary particle diameter and capable of remarkably suppressing aggregation thereof, and can be easily obtained. A method of producing the fine pigment composition is prepared. [Means for Solving the Problems] The present inventors have repeatedly focused on the results of the discussion in order to solve the above problems. That is, the first aspect of the present invention relates to a fine pigment -6 - 201103959 composition containing a triazine compound represented by the formula (1). 【化1】

(In the formula (1), A represents an acidic group or a basic group. B represents -OH ' -C1, an acidic group or a basic group. D represents -H, -Cl, -OH or an aromatic amine residue.) In the present invention, the aromatic amine residue D of the above triazine compound may be a group represented by the formula (2) or (3). [Chemical 2]

(2) (In the formula (2), Y represents -H, -OH or ·ΝΗ2 [Chemical 3]

f S1 201103959 (In the formula (3), Q1, Q2, Q3, and Q4 each independently represent -Η, a halogen atom, a lower alkyl group or a lower alkoxy group. X represents -Η, -OH or -NH2. W represents - CH2-, -〇-, -S〇2- or (4), η represents an integer of 0 to 2.) [Chemical 4] One (4) In the present invention, the aromatic amine residue of the aforementioned triazine compound D may be a group represented by the formula (5). [5] R3

(In the formula (5), R1, R2 and R3 each independently represent -Η, -C1, -Ν02, -ΝΗ2, lower alkyl, lower alkoxy, -CF3'-S03H, -S02N (C2Hs) 2 '-COOH, -COOCHj ' -CONH2, -S〇2-NH2-Ph (Ph represents phenyl), -CONH-Ph (Ph represents a phenyl group which may have a substituent of -H, -Cl, or a alkenyl group) Any of the groups. In the present invention, the aromatic amine residue D of the above triazine compound may be a group represented by the formula (6). 201103959 【化6】 Z4 Z1

(In the formula (6), Z1, Z2, Z3, and Z4 each independently represent any one of -Η, -Cl, -OH, -ΝΗ2, -S03H, -COOH.) In the present invention, the aforementioned triazine The group represented by A of the compound may be any acidic group selected from the groups represented by the formulae (7) and (8). 【化7】

【化8】

(In the formulae (7) and (8), R4, R5 and R6 each independently represent -H, -N〇2, -C1, lower alkyl, lower alkoxy, -CF3, -S03H, -S02N ( C2H5) 2, -COOH ' -COOCHs ' -CONH2 ' -S〇2- 201103959 NH2-Ph (P represents phenyl), -CONH-Ph (P represents a substituent which may have -Η, -Cl, a alkenyl group Any of the phenyl groups.) In the present invention, the base of the above triazine compound represented by A may be -NH-(CH2) 3-N(CH3) 2, -NH- (CH2) Any of the basic groups selected by 3-N(C2H5)2, -NH-(CH2)3-N(C3H7)2 and -NH-(CH2)3-N(C4H9)2. In the present invention, the base of the triazine compound represented by B may be any acidic group selected from the groups represented by the formulas (7) and (8), or may be -NH-(CH2). 3-N ( CH3 ) 2, -NH- ( CH2 ) 3-N ( C2H5 ) 2 , -NH- ( CH 2 ) 3-N ( C3H7 ) 2 and -NH- ( CH 2 ) 3-N ( C4H9) 2 Any of the basic groups. In the present invention, the above-mentioned organic pigment may be an azo-based pigment or a condensed polycyclic-based pigment 'azo-based pigment, and is preferably a color index of pigment yellow 74 or pigment red 269, and a condensed polycyclic pigment. It is preferred to use the color index of the pigment purple 23 or the pigment red 254. A second aspect of the present invention relates to a method for producing a fine pigment composition containing an azo-based pigment, which is characterized in that a diazonium salt and a pro are present in the presence of a compound of the formula (π) Further, in the present invention, for the 100 parts of the coupling, the triazine compound may be added in an amount of from 0.1 to 2 parts. The third aspect of the present invention relates to a condensation-containing polycyclic ring. A method for producing a fine pigment composition of a pigment, which is characterized in that the crude pigment is pigmented in the presence of a three-degenerate η substance represented by the formula (1). Further, in the present invention, 100 parts of the crude pigment is used. Further, g, the triazine compound may be added with 〇1 -10- 201103959 to 20 parts. [Effects of the Invention] The fine pigment composition of the present invention contains a specific triazine compound, so that the primary particle diameter of the organic pigment is extremely small. Further, the aggregation of the pigment composition is remarkably suppressed, and even when the pigment composition is dispersed in the pigment dispersion composition, aggregation thereof can be effectively prevented. Therefore, the film formed by using the pigment dispersion composition is excellent in transparency. also The fine pigment composition can be easily obtained by the production method of the present invention. [Embodiment] The fine pigment composition of the present invention is characterized by containing the following three formulas (1) Azin compound.

(In the formula (1), A represents an acidic group or a basic group. B represents -OH, -C1, an acidic group or a basic group. D represents -H, -Cl, -OH or an aromatic amine residue.) In the present invention, the primary pigment diameter of the organic pigment is kept small by g-11-201103959 because the fine pigment composition contains the triazine compound represented by the formula (1 Γ ς ). Further, the pigment dispersion prepared by using the fine pigment composition of the present invention is effective in suppressing aggregation of primary particles of the organic pigment by multiplying effects with other dispersants and the like. Thus, the mechanism for remarkably suppressing the aggregation of the fine organic pigment by the above triazine compound is still unknown, but the triamethylene ring is the parent skeleton, and the functional group having acidity and/or basicity in the side chain is obtained. The triazine compound can be adsorbed on the surface of the primary particles of the organic pigment, and the π-electron action of the triazine ring contained in the adsorbed triazine compound can inhibit the crystal growth of the pigment particles while the triazine compound is inhibited. It can be greatly improved in affinity with a dispersing agent or the like as needed, thereby achieving an excellent dispersion effect. In the formula (1), D represents -Η, -C1, -ΟΗ or an aromatic amine residue, and in terms of an aromatic amine residue, it is represented by the following formula (2), (3), (5) or (6) The basis of the show is better. A triazine compound having such an aromatic amine residue is a compound rich in π electrons which is close to the surface of the gradually formed pigment crystal particles and which interacts with all the π electrons of the pigment molecule. It is possible to suppress/control the crystal growth of the primary particles of the pigment. Further, when D is -C1, the triazine compound is close to the surface of the gradually formed pigment crystal particle due to the π-electron triazine ring, and acts on the surface of the pigment particle by interacting with all the π electrons of the pigment molecule. It is involved in the action of the bulky chlorine atom, and it is possible to suppress/control the crystal growth of the primary particles of the pigment. -12- 201103959

(In the formula (2), Y represents -H, -OH or -NH2.) [Chemical 1 1]

Q1 Q3

(In the formula (3), Q1, Q2, Q3 and Q4 each independently represent -Η, a halogen atom, a lower alkyl group or a lower alkoxy group. X represents -Η, -OH or -NH2. W represents -CH2- , -Ο-, -S02- or (4), η represents an integer from 0 to 2.) [Chemical 1 2]

(4) ί S ] -13- (5) 201103959 【化1 3】

(In the formula (5), R1, R2 and R3 each independently represent -Η, -Ν02, -ΝΗ2, lower alkyl, lower alkoxy, -CF3, -S03 S02N (C2H5) 2, -COOH, - COOCH3 '-CONH2' - NH2-Ph (P represents phenyl), -CONH-Ph (P represents a phenyl group which may have a substituent of -Cl, a alkenyl group). In the present invention, The lower of the lower alkyl group and the lower alkoxy group means a carbon number of 1 to 4. , -C1 Η ' -S〇2-有-Η » Thoughts [Chemical 1 4]

(In the formula (6), Z1, Z2, Z3, and Z4 each independently represent any of -Cl, -OH, -NH2, _s〇3H, and -COOH.) In the present invention, the aroma of the triazine compound In the case of the amine residue D, the above-described constitution may be satisfied. However, if the crystal of the organic pigment is inhibited, if the growth of the primary particle diameter is small, the primary particle diameter becomes small (9). Any base of the group shown is preferred. [化1 5]

In the formula (1), 'A' represents an acidic group or a basic group. In the case of such a substituent, it is not particularly limited, but in terms of an acidic group, a group having a sulfonic acid group or a carboxylic acid group is preferred, and specifically, it is acidic due to an aromatic group having a π electron. Any one selected from the formulas (7) and (8) of the substituent is preferred. [Si -15- 201103959

[化1 7] R4

(In the formulae (7) and (8), R4, R5 and R6 each independently represent -H, -N02, -C1, lower alkyl, lower alkoxy, -CF3, -S03H, -S02N (C2H5). 2 ' -COOH ' -COOCHa ' -CONH2 ' -S〇2-NH2-Ph (P represents phenyl), -CONH-Ph (P represents a phenyl group which may have a substituent of -H, -Cl, a alkenyl group Any one of the bases.) Further, in terms of a basic group, a group having an amine-based basic group is preferred, specifically, -NH-(CH2) 3-N(CH3) 2 '-NH- (CH2) 3-N (C2H5) 2, -NH-(CH2) 3-N(C3H7) 2 and -NH-(CH2) 3-N(C4H9) 2 are preferably any one selected. When such a basic group having an amine basic group is used, the same effect can be obtained by either. Further, these basic groups are preferably used in the preparation of the fine pigment composition (for the coupling reaction to be described later, etc.) from the viewpoint of solubility in a solvent generally used. The alkyl group at the terminal of the basic group has a carbon number of 1 to 4 and a small carbon number. Therefore, the solubility in a solvent is high, and the preparation of the fine pigment group -16-201103959 can be easily provided. On the other hand, if the carbon number exceeds 4', the solubility in the solvent is lowered, and it is difficult to prepare a fine pigment composition. In the formula (1), 'B' represents -OH, -C1, an acidic group or an alkaline group. base. Further, when B represents an acidic group or a basic group, the above is not particularly limited, and, in selection, it may be independently carried out independently from the acidic group and the basic group a shown in the above A. In the present invention, the object of the present invention can be attained by the triazine compound having the above-described constitution. Preferred examples thereof include the triazine compounds represented by the following formulas (10) to (16). [化1 8] CH3

(10)

[S -17- 201103959 [化1 9] ch3 ch3

Cl

[Chemical 2 1 I

[Chemical 2 2] 〇CH3

-18- (14) (15)201103959 [Chemical 2 3] ch3 CH3

[Chem. 2 4]

(1 6) The triazine compound having the above composition may be produced by a known method or a method, and may be used. The organic pigment used in the present invention is not particularly limited, and an azo pigment or a condensed pigment is preferred. In the case of the azo-based pigment, the color index (hereinafter referred to as CJ.) is yellow, 1, 3, 12, 13' 14, 17, 55 from the viewpoint of the crystallization inhibitory effect of the compound of the present invention. , 73, 74, 75, 81, 83, 97, 120, 151, 154, 156, 165, 175, 180, 194; C·1. Pigment Red 5, 146, 147, 150, 170, 176, 184, 185 3,269 is better, which is better with CI•Pigment Yellow 74, CM•Pigment Red 269.

In view of the crystallization-inhibiting effect of the triazine compound of the present invention, CI Pigment Red ία ' 177 ί S -19- 201103959 2 02, 207, 209, 254: CI Pigment Blue Color 15: 3, 15: 6; CI pigment green 36, 58; CI pigment yellow 138, 150, 185; CI pigment purple 23 is better, which is better with CI pigment red 254, CI purple 23. The organic pigment used in the present invention is preferably a primary particle having a long diameter of 50 to 150 nm and a short diameter of 30 to 1 nm. In the present invention, the primary particle size is such that the primary particle diameter is extremely small or the height is made fine. The fine pigment composition of the present invention is obtained by reacting a compound which is a raw material of a desired organic pigment in the presence of the above-mentioned triazine compound, or by pigmenting a crude pigment. For example, when an azo-based pigment is used as the organic pigment, the diazonium salt as a raw material is subjected to a kneading reaction in the presence of the above-mentioned triazine compound, and an azo-based pigment is produced by a pot reaction. When the crystal of the pigment grows, the triazine compound is close to the surface of the gradually formed pigment crystal particle, and the crystal growth of the primary particle of the pigment is suppressed/controlled by interaction with the π electron of the pigment molecule. Further, a fine pigment composition containing an azo-based pigment having a primary particle diameter as described above can be obtained. Further, the above triazine compound may be present in the coupling reaction, regardless of the method of addition. Further, the coupling reaction system can be carried out by a known method. Further, the coupling agent used in the present invention is not particularly limited as long as it is a coupling reaction which can be used for the synthesis of the above azo-based pigment. Further, the diazonium salt used in the present invention is not particularly limited as long as it can be used for the coupling reaction of the above azo-based pigment, and may be a diazo gun for nitriding various amine di--20-201103959. Become a metal salt. Further, as the solvent to be used in the coupling reaction, a known general solvent can be appropriately selected and used. Further, the amount of the triazine compound to be added is not particularly limited, and for the 100 parts of the coupling, the triazine compound is added in an amount of from 0.1 to 20 parts. When the amount of the triazine compound added is less than 0.1 part, the effect of suppressing the crystal growth is small, and if it is 20 parts, the performance of the final product (transparency, contrast, etc. of the final product) is affected. Further, although the ratio of use of the coupling compound to the diazonium salt is based on the reaction of the molar reaction, it can be appropriately adjusted by the types and the like. After the coupling reaction is carried out as described above, it is filtered, washed with a predetermined method, and dried, and then pulverized by a disperser such as a roll mill or a bead mill to obtain an azo-based pigment having a very small primary particle. Fine pigment composition. Further, as described above, after drying, although larger secondary particles are formed by primary particles aggregating, it is not necessary to use a dispersing machine as described above, and it is not necessary to pass a micronization step such as a salt mill which is generally required. The secondary particles can be easily pulverized and returned to the state of the primary particles having a very small particle diameter. When a condensed polycyclic pigment is used as the organic pigment, it is different from the case of the azo pigment. The fine pigment composition can be produced by the step of pigmenting the crude pigment in the presence of the triazine compound. This is caused by the difficulty in adding the aforementioned triazine compound when preparing the crude pigment. Therefore, it has been found that the crystal growth of the finely divided pigment particles can be effectively suppressed by the presence of the triazine compound in the step of pigmentation (fine refinement) after the preparation of the pigment having a very large primary particle diameter. A condensed polycyclic pigment having a very small primary particle can be obtained. The basic principle is the same as in the case of the azo system -21 - 201103959 pigment, due to the interaction between the aforementioned triazine compound and the π-electron of the pigment and the constitution of its side chain. In other words, the crude pigment having a very large particle diameter is temporarily prepared, and after the pigment particles are refined by a method such as salt milling, if the recrystallization continues to grow, at this time, due to the presence of the triazine compound, And its crystal growth can be effectively suppressed. Further, the crude pigment in the present invention is a compound obtained by reacting a raw material compound of a condensed polycyclic-based pigment source and having a large particle diameter (for example, about 10 to several hundreds of μm), and it is not possible to directly obtain dispersibility as a pigment or It is called by bright hair color. The crude pigment of such a condensed polycyclic pigment can be prepared by a known method. In the present invention, the crude pigment as described above is pigmented in the presence of the aforementioned triazine compound. The term "pigmentation" as used in the present invention means a step of integrating the particle diameter of the crude pigment into a suitable particle diameter range as a pigment. Moreover, the range of the suitable particle size varies depending on the use, and is about 0.05 to 0·3 μηι. Further, the method of pigmentation described above can be carried out by a known method such as salt milling. In the case of the pigmentation, the amount of the triazine compound to be added is not particularly limited, and for the 100 parts of the crude pigment, the triazine compound is added in an amount of 0.1 to 20 parts. When the amount of the triazine compound added is less than 〇1 part', the effect of suppressing the crystal growth is small, and if it is more than 20 parts, the performance of the final product (transparency, contrast, etc. of the final product) is affected. After being pigmented as described above, after being washed with water in a predetermined manner and dried, it can be pulverized by a disperser such as a roll mill or a bead mill. -22-201103959 'A highly refined primary particle-containing particle is obtained. A fine pigment composition of a condensed polycyclic pigment having a very small diameter. A fine pigment composition containing the triazine compound of the present invention and a desired organic pigment as described above, wherein the desired organic pigment is highly refined, and may have a primary particle aspect such as an organic pigment. The system has a long diameter of 50 to 150 nm and a short diameter of 30 to 100 nm. Further, the fine pigment composition of the present invention is one in which the primary particles of the organic pigment contained are extremely small, highly refined, and the aggregation property thereof is remarkably suppressed, that is, even if the pigment composition is dispersed in the pigment dispersion composition. In the case of the product, it is possible to effectively prevent the aggregation due to the synergistic effect with the dispersant or the like, and is suitable for printing inks, paints, and the like which are required to have high color development characteristics, etc., particularly ink jet printers. Ink, ink for color filters, etc. [Examples] Hereinafter, the present invention will be described in more detail by way of examples and comparative examples. In addition, the "parts" or "%" in the examples are weight basis. (Production Example 1) A mixture of 7.3 parts of Cyanuric chloride and 1 part of C1 cyanide chloride in 100 parts of water (trade name: ASA amino benzene) 6.8 parts of sulfonic acid, manufactured by SUGAI Chemical Co., Ltd., and allowed to react at 20 ° C for 1 hour. Next, 4 parts of 4,4'-methyl-2-bis-6-xylyleneamine (trade name: KAYABOND C-200S, manufactured by Sakamoto Chemical Co., Ltd.) in an amount of one C1 reaction with the reactant was added. , make it reverse at 70 ° C

{ S I -23- 201103959 Should be 1 hour. The obtained reaction product was filtered, and the residue was washed with water, and then allowed to stand overnight in a constant temperature bath of 8 (TC) to be dried to obtain 17.0 parts of the triazine compound represented by the formula (10). (Production Example 2). The addition of 3.4 parts of aminobenzenesulfonic acid to 6.8 parts of the aminobenzenesulfonic acid was carried out, and the same procedure as in Production Example 1 was carried out to obtain 14.8 parts of the triazine compound represented by the formula (11). In addition to the addition of 4.3 parts of p-phenylenediamine (trade name: p-phenylenediamine, Wako Pure Chemical Industries, Ltd.) to replace 4 parts of 4,4'-methyl 2,6-dimethylaniline, the rest were carried out. In the same manner as in Production Example 1, 12.5 parts of the triazine compound represented by the above formula (丨) was obtained. (Production Example 4) Except that 3-amino-4-methoxybenzoanilide was added (trade name: M_4) 9.5 parts of 〇, Samsung Chemical Industry Co., Ltd. were substituted for 4,4, _methyl 2,6-dimethylamine, except for 10 parts, and the same operation as in Production Example 1 was carried out to obtain the above formula ( I3) 166 parts of the compound of Sanxiao. (Production Example 5) In 100 parts of water, 73 parts of cyanuric chloride and 1 part of CI of cyanuric chloride were added. 6.8 parts of acid, 2 (rc), anti--24-201103959 should be 1 hour. Then, the amount of 3-amino-4-methoxybenzimidamide reacted with one of the reactants of this reactant is added (commodity Name: M-40, manufactured by Samsung Chemical Industry Co., Ltd., 9.5 parts, and allowed to react at 75 ° C for 1 hour. Thereafter, sodium hydroxide was added to adjust to pH 6 and stirred at 90 ° C for 2 hours to hydrolyze residual C1. After the residue was washed with water, the residue was allowed to stand in a thermostat at 80 ° C for 1 night and dried to obtain 5.9 parts of the triazine compound represented by the formula (14). (Production Example 6) In water To 100 parts, 6.8 parts of a mixture of 7/3 parts of cyanuric chloride and 1 part of C1 of cyanuric chloride was added, and the mixture was reacted at 20 ° C for 1 hour. 4 parts of 4,4'-methyl 2,6-dimethylaniline (trade name: KAYABOND C-200S, manufactured by Nippon Kasei Co., Ltd.) in an amount of 1 C1 of the reaction product, at 70 ° C The reaction was allowed to proceed for 1 hour. Thereafter, sodium hydroxide was added to adjust to p Η 6, and the mixture was stirred at 90 ° C for 2 hours to hydrolyze the residual C1. The obtained reactant was filtered, and the residue was washed with water at 80 ° C. Constant The mixture was allowed to stand overnight for 1 night to obtain 16.4 parts of the triazine compound represented by the formula (i 5 ). (Production Example 7) In addition to the addition of dibutylaminopropylamine (trade name: N, N - The same operation as in Production Example 1 was carried out except that 6.8 parts of dibutyl-1,3-propanediamine and Wako Pure Chemicals were used to replace 6.8 parts of aminobenzenesulfonic acid, and the above formula (1 6 ) was obtained. Shown 7.4 parts of triazine compound 1. [S 1 -25-201103959 (Example 1) 50 parts of 2-methoxy-4-nitro-phenylamine (trade name: Kak0 Red B Base cone, manufactured by Showa Chemical Co., Ltd.) was added to 400 parts of water and 35% hydrochloric acid 79. After stirring the mixture, the solution is cooled to 0 to 5 ° C, and after adding 1.5 parts of sodium nitrite, the diazotized 'diazotization solution is prepared by a predetermined method. . Further, the coupling liquid system is prepared as will be described later. First, add 66 parts of the compound 2_methoxy-acetamidine aniline (trade name: Acetoacetic-o-anisidide, manufactured by Samsung Chemical Industry Co., Ltd.) to water for 30,000 parts. This was dissolved in a mixed solution of 48 parts by weight of a 30% by weight aqueous sodium hydroxide solution. Then, this solution was added to an aqueous solution obtained by adding 30 parts of sodium acetate to 900 parts of water, and then a mixture of 150 parts of water and 28 parts of 80% acetic acid was added to precipitate a coupling. Then, 3 parts of the triazine compound obtained in Production Example 1 was added to the precipitate to prepare a suspension (couple liquid). In the coupling liquid, the diazo hydride was stirred at 25 ° C. The addition was carried out slowly for 12 minutes, and the diazonium salt was coupled with the coupling, and then heated at 90 ° C for 30 minutes to form an azo yellow pigment CI pigment yellow 74. After the reaction solution was placed at room temperature, it was filtered, washed with water, dried, and then pulverized by a small pulverizer to obtain a triazine compound represented by formula (1) and an azo yellow pigment C. · 〗 〖Pigment yellow 74 fine pigment composition 1 1 8 parts. -26- 201103959 (Example 2) 50 parts of 3-amino-4-methoxybenzimidaniline (trade name: M-40, manufactured by Samsung Chemical Industry Co., Ltd.) was added to 1 part of water. The mixture was dispersed, the temperature of the solution was adjusted to 0 to 5 ° C, and 7 parts of 35% hydrochloric acid was added and stirred for 20 minutes, and then 15 parts of sodium nitrite was added to be diazotized by a predetermined method. After further adding 80 parts of 80% acetic acid and 15 parts of sodium acetate to form a diazo salt, one part of the triazine compound obtained in Production Example 1 was added to prepare a diazo gun salt solution. Further, 69 parts of N-(5-chloro-2-methoxyphenyl)-3-hydroxy-2-naphthylcarboxamide (trade name: NAPHTHOL AC-CA, manufactured by Samsung Chemical Industry Co., Ltd.) was dissolved in 1700 parts of water. The mixture liquid was prepared by mixing with 48 parts of a 30% by weight aqueous sodium hydroxide solution. The conjugate liquid is adjusted so that the liquid temperature is 1 〇 ° C or less, and the mixture is added to the diazo salt solution while stirring to carry out a coupling reaction, and then heated at 90 ° C for 30 minutes to form an azo red pigment CI pigment. Red 269. After the reaction solution was placed at room temperature, it was filtered, washed with water, dried, and then pulverized by a small pulverizer to obtain a triazine compound represented by formula (10) and an azo red pigment CI. Pigment red 269 fine pigment composition 1 2 1 part. (Example 3) S3 was carried out in the same manner as in Example 2 except that 3 parts of the triazine compound represented by the formula (1) obtained in Production Example 1 was added, and the formula (1) was obtained. Triazine compound and azo red pigment CI pigment#

L -27- 201103959 Color 2 69 fine pigment composition 121 parts. (Example 4) The same procedure as in Example 3 was carried out except that 3 parts of the triazine compound represented by the formula (1 1 ) obtained in Production Example 2 was added. A fine pigment composition of the azine compound and the azo red pigment CI Pigment Red 2 69. (Example 5) The same procedure as in Example 3 was carried out except that 3 parts of the triazine compound represented by the formula (1 2) obtained in Production Example 3 was added, and the obtained formula (12) was obtained. The fine pigment composition of the azine compound and the azo red pigment CI Pigment Red 269 was 121 parts. (Example 6) The same procedure as in Example 3 was carried out except that 3 parts of the triazine compound represented by the formula (13) obtained in Production Example 4 was added, and the obtained formula (13) was obtained. 121 parts of a fine pigment composition of a azine compound and an azo red pigment CI Pigment Red 2 69. (Example 7) The same procedure as in Example 6 was carried out except that 0.8 parts of the triazine compound represented by the formula (13) obtained in Production Example 4 was added, and the obtained formula (13) was obtained. Iridazine compound and azo red pigment CI Pigment -28 - 201103959 Red 269 fine pigment composition 121 parts. (Example 8) The same procedure as in Example 6 was carried out except that the Izine compound of the formula (13) obtained in the production example 4 was added in an amount of 1.5 parts, and the obtained formula (13) was obtained. The triazine compound and the azo red pigment CI Pigment Red 269 were fine pigment compositions of 121 parts. (Example 9) The same procedure as in Example 6 was carried out except that 5 parts of the triazine compound represented by the formula (13) obtained in Production Example 4 was added, and the obtained formula (13) was obtained. 1 2 parts of a fine pigment composition of a azine compound and an azo red pigment CI Pigment Red 2 69. (Example 1) The same procedure as in Example 6 was carried out except that 10 parts of the triazine compound represented by the formula (13) obtained in Production Example 4 was added, and the obtained formula (13) was obtained. 1 2 parts of the fine pigment composition of the triazine compound and the azo red pigment c · I · Pigment Red 269. (Example 1 1) The same procedure as in Example 6 was carried out except that 20 parts of the triazine compound represented by the formula (13) obtained in Production Example 4 was added, and the obtained content represented by the formula (13) was obtained. Triazine compound and azo red pigment cj. Yan Ke, t S 1 -29- 201103959 Red 269 fine pigment composition 121 parts. (Example 1 2) The same procedure as in Example 3 was carried out except that 3 parts of the triazine compound represented by the formula (14) obtained in Production Example 5 was added, and the obtained content represented by the formula (1 4) was obtained. Triazine compound and azo red pigment C. I. Pigment red 269 fine pigment composition 1 2 1 part. (Example 1 3) The procedure of (1) was carried out in the same manner as in Example 12 except that 1.5 parts of the triazine compound represented by the formula (14) obtained in Production Example 5 was added. The triazine compound shown and the azo red pigment CI Pigment Red 269 fine pigment composition 121 parts β (Comparative Example 1) Except that the triazine compound represented by the formula (10) is not added, In the same manner as in Example 1, 1 5 parts of a pigment composition containing an azo yellow pigment CI pigment yellow 74 was obtained. (Comparative Example 2) The same procedure as in Example 2 was carried out except that the triazine compound represented by the formula (10) was not added, and 120 parts of the pigment composition containing the azo red pigment C.I. Pigment Red 269 was obtained. -30-201103959 (Measurement of Pigment Particle Diameter) The pigment composition prepared in Examples 1 to 13 and Comparative Examples 1 and 2 was measured using an image taken by a CCD camera attached to an electron microscope. The particle diameter of the primary particles of the organic pigment in the pigment composition. The electron microscope is a JEM-101 type 1 manufactured by JEOL DATUM Co., Ltd., and has a pressurization voltage of 8 〇 kV and a measurement magnification of 50,000 times. The CCD camera uses MegaVeiw III manufactured by 0LYMPUS. The results are not shown in the table (modulation of ink). 7.5 parts of the pigment compositions of the above Examples 1 to 13 and Comparative Examples 1 and 2, 4 parts of a dispersing agent (JONCRYL 61J, manufactured by BASF Corporation), and 5 parts of isopropyl alcohol. 13.5 parts of deionized water and glass beads (2.5 to 3.5 mm in diameter) were placed in a 140 mL glass container to disperse the paint conditioner for 60 minutes. Then, 20 parts of a dispersing agent (j〇ncRYL7001, manufactured by BASF Corporation) was further added and dispersed for 5 minutes in the same manner, and then the glass beads were removed to prepare a pigment as a pigment dispersion. This ink was applied to a polypropylene film by a coating bar to have a wet film thickness of 0.15 μm, and dried (evaluated). The film prepared on the polypropylene film as described above was visually confirmed.

X clarity. In addition, the evaluation criteria are different from "χ" (opaque). "◎" is excellent, and "〇" is excellent. The evaluation results are shown in Table 1. -31 - 201103959 [Table 1] Pigment Composition Transparency Particle Diameter [nm] Long Diameter Short Diameter Example 1 ◎ 90 40 Example 2 〇 100 80 Example 3 〇 100 50 Example 4 〇 110 80 Example 5 〇 80 60 Embodiment ό 〇 130 80 Example 7 〇 120 80 Example 8 〇 80 60 Example 9 〇 80 Γ 50 Example 10 〇 80 50 Example 11 〇 60 40 Example 12 〇 80 60 Example 13 〇 too 80 Comparative Example 1 X 200 100 Comparative Example 2 X 180 100 As shown in Table 1, the organic pigment contained in the fine pigment composition of Examples 1 to 13 was shown, and the primary particles were extremely small, and the fine pigment composition was used. The pigment dispersion (ink) is excellent in transparency, and in the pigment dispersion, aggregation of primary particles is remarkably suppressed. (Example 1 4) Red crude pigment of a condensed polycyclic pigment (C.I. Pigment Red 2 5 4, trade name: Cromophtal Red 2030, Chiba Specialty

30 parts of triazine compound represented by formula (1 〇) obtained in Production Example 1 and neutral anhydrous sodium sulfate (average particle size of about 20 μπι, manufactured by Mitsui Chemical Industry Co., Ltd.) 750 parts of diethylene glycol (manufactured by Nippon Shokubai Co., Ltd.) as a solvent was added to a 5L kneader (Kneader) (manufactured by MORIYAMA, S5-2GH-S type). Temperature control -32- 201103959 The kneaded material was kneaded at a temperature of 50 ° C for 9 hours, stirred and dispersed in 30 L of warm water at 4 ° C, and then filtered (Nutsche), and washed repeatedly to obtain a pigment water paste. . When the pigment is immersed in water, the dried product is pulverized by a pulverizer (manufactured by a joint machine, a small pulverizer SK-M2) to obtain a triazine compound and a condensed polycyclic red pigment CI fine pigment composition 3 30 parts. (Example 1 5) The triazine compound and the condensed polycyclic pigment represented by the formula (15) were used in the same manner as in Example 14 except for the compound (the compound obtained in Production Example 6). The fine pigment composition of red 254 was 3,300 parts. (Example 1 6) The formula (11) was used in the same manner as in Example 14 except that the compound obtained in Production Example 2 was used. a triazine compound and a condensed polycyclic pigment red 2 5 4 fine pigment composition of 3 30 parts. (Comparative Example 3) Except that the triazine compound was not added, the other method was carried out to obtain a red color containing a condensed polycyclic ring; The mixture is ground to a vacuum filter until the Glauber's salt is completely dried at 1 °C for 2 hours), and the triazine is shown as a small pigment (2) shown in formula (10). Performing to obtain a triazine containing a red pigment (C11) Obtained based red pigment containing C. I. Example 14 with the bucket c · I · ί red pigment a fine pigment S3 -33- 201103959 2 54 330 parts of the composition. (Example 1 7) 500 parts of a purple crude material (Ci·Pigment #色23, trade name: Hostaperm Violet RL-02, curiant) to which a condensed polycyclic-type pigment was added was obtained by the production example 1 (10) 5 parts of Sanxiao compound, neutral anhydrous sodium sulfate (average particle size of about 20μπι, manufactured by Mita Chemical Industry Co., Ltd.), 250,000 parts, diethylene glycol (meth)

In a kneader (manufactured by MORIYAMA, S5-2GH-S type) of 800 parts to 5 L, the temperature was kneaded and ground for 8 hours while the temperature of the kneaded material was 50 °C. The kneaded ground material was stirred and dispersed in 30 L of warm water of 4 ° C, and then transferred to a vacuum filter (Nutsche) for filtration' and washed repeatedly until the Glauber's salt was completely removed to obtain a pigment water paste. The pigment water paste was dried at 105 ° C for 2 hours. The dried product was pulverized by a pulverizer (manufactured by Kyoritsu Kogyo Co., Ltd., a small pulverizer, a small pulverizer SK-M2) to obtain a triazine compound represented by the formula (1) and a condensed polycyclic red pigment CI. 550 parts of the fine pigment composition of Pigment Violet 23. (Example 1 8) The same procedure as in Example 17 was carried out except that the triazine compound represented by the formula (1 2) obtained in Production Example 3 was used, and the obtained formula (12) was obtained. 550 parts of a fine pigment composition of a azine compound and a condensed polycyclic red pigment CI pigment violet 23. -34-201103959 (Example 1 9) The same procedure as in Example 17 was carried out except that the triazine compound represented by the formula (16) obtained in Production Example 7 was used, and the obtained formula (16) was obtained. 550 parts of the fine pigment composition of the tri-compound and the condensed polycyclic red pigment cI pigment violet 23 are shown. (Comparative Example 4) The same procedure as in Example 17 was carried out except that the triazine compound was not added, and 550 parts of a fine pigment composition of a condensed polycyclic red pigment CI pigment violet 23 was obtained (modulation of a color filter). Using the fine pigment compositions of Comparative Examples 3 and 4 of Examples 1 4 to 1 9 , a mixture of the compositions shown in Table 2 was prepared. In the table, PR254 is an abbreviation for CI Pigment Red 2 54, which is the abbreviation of Examples 14 to 16 and Comparative Example 3, and the abbreviation of PV23-based CI Pigment Violet 23, which is related to Examples 17 to 19. The composition of Example 4. Further, in the case of acrylic resin, SPCN-2000 and dispersant manufactured by Showa Polymer were used, BYK-LPN6919 manufactured by BYK was used for PR254, Disperbyk-2001 manufactured by BYK was used for PV23, and propylene glycol monomethyl was used as solvent. Ether acetate (PMA). The zirconia beads are those having a diameter of 0.5 mm. In addition, the oxime of the acrylic resin in the table was added as a 40% PMA solution. In addition, in the evaluation of the fine pigment composition containing PV23 ί -35- 201103959 'In order to properly evaluate the color filter, it is used with CI Pigment Blue 15 : 6 (trade name: cordier blue 6005, Shanyang pigment) A mixture of (hereinafter referred to as PB 1 5 : 6). The pigment is the mixture of the mixture, and the mixing ratio (weight basis) is (PB15: 6) / (PV23) = 4/1. [Table 21 PR254 PV23 pigment composition [£ 6.8 7.6 Acrylic resin Cg] 3.1 5.9 Dispersant [g] 3.9 6.8 Solvent Cg] 36.2 39.6 Zirconium oxide particles [d 200 240 The mixture prepared by the above composition was placed in 14 mL In the glass container, after dispersing for 60 minutes in a paint conditioner, zirconia beads were removed to prepare a pigment dispersion. This pigment dispersion was prepared by using a spin coater (MIKASA SPINCORTER IH-DX2) to prepare a film-coated plate (color filter). (Evaluation)

Y 値 and contrast (CR ) were measured by a spectrophotometer (SPECTROPHOTOMETER CM-3700d) using a color filter prepared as described above. Further, the measurement method of the comparison was as follows. That is, the color filter is sandwiched between two polarizing plates, and the transmittance of the light when the polarizing surfaces of the polarizing plates are parallel and the transmittance of the vertical light are measured, and the ratio is obtained. The measurement of the light transmittance is determined by using a photometer "LS-100" (manufactured by MINOLTA Co., Ltd.). The results of each -36-201103959 are shown in Table 3. [Table 3] Y値CR Example 14 20.8 867 Example 15 20.7 893 Example 16 21.5 979 Comparative Example 3 20.3 439 Example 17 9.9 1585 Example 18 9.9 2074 Example 19 9.8 2307 Comparative Example 4 9.8 1080 As shown in the above, the color filter using the fine pigment composition obtained in Examples 14 to 19 is a result of high contrast without lowering Y値, and it is taught that the primary particles of the pigment are extremely small, and Agglutination can be effectively suppressed. -37-

Claims (1)

201103959 VII. Patent application scope: 1. A fine pigment composition containing a triazine compound represented by formula (1) and an organic pigment; (In the formula (1), A represents an acidic group or a basic group; B represents -OH, -C1, an acidic group or a basic group; and D represents -H, -Cl, -OH or an aromatic amine residue). 2. The fine pigment composition of claim 1, wherein the aromatic amine residue D of the triazine compound is a group represented by the formula (2) or (3); (2) (in the formula (2), Y represents -H' -OH or -NH2); -38- 201103959 [Chemical 3] Q1 Q3 (3) (In the formula (3), Q1, Q2, Q3, and Q4 each independently represent -Η, a halogen atom, a lower alkyl group or a lower alkoxy group; X represents -Η, -OH or -NH2; - CH2-, -Ο-' -S02- or formula (4), and η represents an integer from 0 to 2); [Chemical 4 I - Ο (4) The fine pigment composition of claim 1, wherein the aromatic amine residue D of the triazine compound is a group represented by the formula (5); -39- 201103959 , -N02, -NH2, lower alkyl 'lower alkoxy, -CF3, -so3h, -S02N ( C2H5 ) 2 ' -COOH ' -COOCHj ' -CONH2 ' -S〇2- NH2-Ph (P represents a phenyl group), -CONH-Ph (Ph represents a group of a phenyl group which may have a substituent of -Η, -Cl, a alkenyl group). 4. The fine pigment composition of claim 1, wherein the aromatic amine residue D of the triazine compound is a group represented by the formula (6); (6) In the formula (6), Z1, Z2, Z3, and Z4 each independently represent any of -H, -Cl, -OH, -NH2, -SO3H, and -COOH). 5. The fine pigment composition according to any one of claims 1 to 4, wherein the base of the triazine compound represented by A is selected from any one of the groups represented by formulas (7) and (8). Acid base; 201103959 【化7】 【化8】 (7) (8) In the formulae (7) and (8), R4, R5 and R6 each independently represent -H, -N02, -C1, lower alkyl, lower alkoxy, -CF3, -S03H, -S02N (C2H5) 2, -COOH ' -COOCH3 ' -CONH2 ' -S〇2-NH2-Ph (P represents phenyl), -CONH-Ph (Ph represents benzene which may have a substituent of -H, -Cl, noryl) Any of the bases). The fine pigment composition according to any one of claims 1 to 4, wherein the base of the triazine compound represented by A is -NH-(CH2)3-N(CH3)2, -NH- (CH2) 3-N (C2H5) 2, -NH-(CH2) 3-N (C3H7) 2 and -NH-(CH2) 3-N (C4H9) 2 Any alkaline selected 201103959 7. The fine pigment composition according to any one of 1 to 6, wherein the base of the triazine compound represented by B is any acidic group selected from the groups represented by the formulae (7) and (8). The fine pigment composition according to any one of claims 1 to 6, wherein the base of the triazine compound represented by B is -NH-(CH2)3-N(CH3)2, -NH- (CH2 3-N ( C2H5 ) 2 ' -NH- ( CH2 ) 3-N ( C3H7) 2 and -NH- ( CH2) 3-N ( C4H9) 2 Any basic group selected ο 9. Clause 1 The fine pigment composition according to any one of the above-mentioned, wherein the organic pigment is an azo pigment / 1 〇 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Or pigment red 269. The fine pigment composition according to any one of claims 1 to 8, wherein the organic pigment is a condensed polycyclic pigment. The fine pigment composition of claim 11, wherein the condensed polycyclic system Pigment color index pigment purple 23 or pigment red 254 ^ 13. A method for producing a fine pigment composition containing an azo pigment, characterized by being in the presence of a triazine compound represented by formula (1) The diazonium salt is coupled to the coupling. 14. The method for producing a fine pigment composition containing an azo-based pigment according to claim 13, wherein the triazine compound is added in an amount of 0.1 to 20 parts per part of the coupling. A method for producing a fine pigment composition containing a condensed polycyclic pigment, wherein the crude pigment is pigmented in the presence of a triazine compound represented by the formula (1) at -42 to 201103959. 16. The method for producing a fine pigment composition containing a condensed polycyclic pigment according to claim 15, wherein the triazine compound is added in an amount of 0.1 to 20 parts based on 100 parts of the crude pigment. -43- 201103959 Four designated representatives: (1) The representative representative of the case is: None (2) The symbol of the representative figure is simple: No 201103959 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention: no