JP5299151B2 - Fine pigment composition and method for producing the same - Google Patents

Abstract

PURPOSE: A micro pigment composition is provided to effectively prevent the aggregation of pigment even when the composition is dispersed in a pigment dispersion composition and to form a thin film with excellent transparency. CONSTITUTION: A micro pigment composition comprises a triazine compound represented by formula (1) and organic pigments. In chemical formula (1), A represents an acid group or base group; B represents -OH, -Cl, acid group or base group; D represents -H, -Cl, -OH or aromatic amine moiety. A method for preparing the micro pigment composition comprises performing coupling reaction of diazonium salts with couplers in the presence of the triazine compound represented by formula (1).

Description

  The present invention relates to a fine pigment composition containing a fine organic pigment and a method for producing the same.

  In printing inks and paints, such as inks for ink jet printers and color filter inks, the pigments are dispersed in a fine state to exert high coloring power and suitability for vivid colors, gloss, etc. Or having appropriateness such as chromaticity and contrast of a coating film such as a color filter. In recent years, there has been a strong demand for inks obtained by dispersing finer pigment particles because of market demand for high-quality printed materials.

Therefore, in order to make the pigment finer, it is widely practiced to reduce the particle diameter of the primary particles of the pigment once obtained by a method such as salt milling.
However, in general, pigment particles once dispersed in a mixture of water, solvent, resin, etc. (vehicles such as paints and inks) tend to aggregate in the mixture (pigment dispersion). The smaller the particle diameter, the stronger the tendency to agglomerate to form secondary particles. Therefore, even if the pigment is refined by salt milling as described above, the refined pigment particles can be stably dispersed. Is considered difficult. When the pigment particles aggregate in the pigment dispersion in this way, various undesirable phenomena such as an increase in the viscosity of the pigment dispersion, a decrease in the gloss of the painted surface of the developed color, and a decrease in the performance of the coating film may occur. There are many.

  As an improvement measure, use of a surface treatment of a pigment with metal soap or the like, or a dispersant containing a specific pigment derivative or a partial skeleton of an organic dye has been proposed (for example, see Patent Documents 1 to 3).

  However, according to these techniques, although some improvement effect can be obtained with respect to the refinement and agglomeration of the pigment particles, it is always possible to satisfy the demand for inks in which finer pigment particles are dispersed. The current situation is not.

US Pat. No. 3,582,380 Japanese Patent Laid-Open No. 3-9957 JP 2003-26950 A

  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 very small primary particle diameter and capable of remarkably suppressing the aggregation, and the fine pigment composition. It is an object of the present invention to provide a production method capable of easily preparing the above.

  The inventors of the present invention have reached the present invention as a result of intensive studies to solve the above problems. That is, the first of the present invention relates to a fine pigment composition comprising a triazine compound represented by the formula (1) and an organic pigment.

(In the formula (1), A represents any acidic group selected from the group represented by the formula (7), or —NH— (CH ₂ ) ₃ —N (CH ₃ ) ₂ , —NH— (CH _{2 ) 3 -N (C 2 H 5} ) 2, -NH- (CH 2) 3 -N (C 3 H 7) 2 and -NH- (CH ₂₎ is selected from _{3 -N (C 4 H 9)} 2 .B showing the Ruizure of basic groups, .D showing an -OH or -Cl represents any aromatic amine residue of a group of groups represented by the formula (9).)

(In formula (7), R ^Four , R ^Five , R ⁶ Are each independently -H, -NO ₂ , -Cl, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, -CF _Three , -SO _Three H, -SO ₂ N (C ₂ H _Five ) ₂ , -COOH, -COOCH _Three , -CONH ₂ , -SO ₂ -NH ₂ -Ph (Ph represents a phenyl group) or -CONH-Ph (Ph represents a phenyl group which may have a substituent of -H, -Cl, or a methylene group). )

  In the present invention, the organic pigment may be an azo pigment or a condensed polycyclic pigment, and the azo pigment is preferably Color Index Pigment Yellow 74 or Pigment Red 269, and the condensed polycyclic pigment is a color index. Pigment Violet 23 or Pigment Red 254 is preferable.

  The second of the present invention relates to a method for producing a fine pigment composition containing an azo pigment, wherein a diazonium salt is subjected to a coupling reaction with a coupler in the presence of a triazine compound represented by the formula (1). Moreover, in this invention, you may add so that the said triazine compound may be 0.1-20 parts with respect to 100 parts of couplers.

  A third aspect of the present invention relates to a method for producing a fine pigment composition containing a condensed polycyclic pigment, wherein a crude pigment is pigmented in the presence of a triazine compound represented by the formula (1). Moreover, in this invention, you may add so that the said triazine compound may be 0.1-20 parts with respect to 100 parts of crude pigments.

  Since the fine pigment composition according to the present invention contains a specific triazine compound, the primary particle diameter of the organic pigment is extremely small and the aggregation thereof can be remarkably suppressed. Therefore, the pigment composition is contained in the pigment dispersion composition. Even when dispersed, the aggregation can be effectively prevented. Therefore, the thin film formed using the pigment dispersion composition has very good transparency. The fine pigment composition can be easily obtained by the production method according to the present invention.

  The fine pigment composition of the present invention comprises a triazine compound represented by the following formula (1) and an organic pigment.

(In the formula (1), A represents an acidic group or a basic group, B represents —OH, —Cl, an acidic group or a basic group. D represents —H, —Cl, —OH or aromatic. Group amine residue.)

In the present invention, when the triazine compound represented by the formula (1) is contained in the fine pigment composition, the primary particle diameter of the organic pigment is kept extremely small. In addition, the pigment dispersion prepared using the fine pigment composition of the present invention can be one in which agglomeration of the primary particles of the organic pigment is effectively suppressed by a synergistic effect with other dispersants and the like.
Thus, although the mechanism by which the aggregation of fine organic pigments is remarkably suppressed by the triazine compound is not necessarily clear, it has an acidic and / or basic functional group in its side chain with the triazine ring as a base skeleton. As a result, the triazine compound is adsorbed on the primary particle surface of the organic pigment and the pi electrons of the triazine ring suppress the crystal growth of the pigment particles, and the affinity with the dispersant is greatly improved. It is considered that a good dispersion effect is achieved.

  In the formula (1), D represents —H, —Cl, —OH or an aromatic amine residue, and examples of the aromatic amine residue include the following formula (2), (3), (5) or (6). It is preferable that it is group shown by these. The triazine compound having such an aromatic amine residue is a π-electron rich compound, approaches the pigment crystal particle surface on which the compound is being formed, and interacts with the π electron that the pigment molecule has, It is considered that the crystal growth of the primary particles of the pigment can be suppressed / controlled. Further, when D is —Cl, the triazine compound is brought close to the surface of the pigment crystal particle being formed by the triazine ring having π electrons, and the pigment particles are caused to interact with the π electrons of the pigment molecules. It is considered that the crystal growth of the primary particles of the pigment can be suppressed / controlled in combination with the movement of the bulky chlorine atom acting on the surface.

(In formula (2), Y represents —H, —OH or —NH _2. )

(In formula (3), Q ¹ , Q ² , Q ³ and Q ⁴ each independently represent —H, a halogen atom, a lower alkyl group or a lower alkoxy group. X represents —H, —OH or -NH ₂ , W represents —CH ₂ —, —O—, —SO ₂ — or formula (4), and n represents an integer of 0 to 2.

(In the formula (5), R ¹ , R ² and R ³ are each independently —H, —Cl, —NO ₂ , —NH ₂ , a lower alkyl group, a lower alkoxyl group, —CF ₃ , —SO. _{3 H, -SO 2 N (C} 2 H 5) 2, -COOH, -COOCH 3, -CONH 2, -SO 2 -NH 2 -Ph (Ph represents a phenyl group), - CONH-Ph (Ph is , -H, -Cl, and a phenyl group which may have a substituent of a methylene group).

  In the present invention, “lower” in the lower alkyl group and lower alkoxy group means one having 1 to 4 carbon atoms.

(In the formula ^{(6), Z 1, Z} 2, Z 3, Z 4 are respectively independently, -H, -Cl, -OH, -NH 2, -SO 3 H, any of the -COOH .)

  In the present invention, D, which is an aromatic amine residue of the triazine compound, may satisfy the above-described configuration, but from the viewpoint of suppressing the crystal growth of the organic pigment and reducing the primary particle size, Any of the group of groups represented by (9) is preferred.

  In formula (1), A represents an acidic group or a basic group. The substituent is not particularly limited as long as it is such a substituent, but as the acidic group, a group having a sulfonic acid group or a carboxylic acid group is preferable. Specifically, an acidic substitution is performed on an aromatic group having π electrons. It is preferably any group selected from formulas (7) and (8) having a group.

(In formulas (7) and (8), R ⁴ , R ⁵ and R ⁶ are each independently —H, —NO ₂ , —Cl, a lower alkyl group, a lower alkoxyl group, —CF ₃ , —SO. _{3 H, -SO 2 N (C} 2 H 5) 2, -COOH, -COOCH 3, -CONH 2, -SO 2 -NH 2 -Ph (Ph represents a phenyl group), - CONH-Ph (Ph is , -H, -Cl, and a phenyl group which may have a substituent of a methylene group).

Further, as the basic group, a group having an amine-based basic group is preferable, and specifically, —NH— (CH ₂ ) ₃ —N (CH ₃ ) ₂ , —NH— (CH ₂ ) ₃ Any selected from —N (C ₂ H ₅ ) ₂ , —NH— (CH ₂ ) ₃ —N (C ₃ H ₇ ) ₂ and —NH— (CH ₂ ) ₃ —N (C ₄ H ₉ ) ₂ These basic groups are preferred.

  In formula (1), B represents —OH, —Cl, an acidic group or a basic group. Moreover, when B shows an acidic group or a basic group, there is no limitation in particular about them, The acidic group and basic group which were shown in above-mentioned A can be selected independently of A. .

  In the present invention, the triazine compound having the above-described configuration can achieve the object of the present invention. As a preferable example, a triazine compound represented by the following formulas (10) to (16) is used. Can be mentioned.

  The triazine compound having the above-described configuration can be produced by a known method, or a commercially available product may be used.

  The organic pigment used in the present invention is not particularly limited, but an azo pigment or a condensation pigment is preferable.

  As the azo pigment, a color index (hereinafter referred to as CI) Pigment Yellow 1, 3, 12, 13, 14, 17, 55, 73, 74 is used from the viewpoint of the crystal suppression effect by the triazine compound of the present invention. 75, 81, 83, 97, 120, 151, 154, 156, 165, 175, 180, 194, C.I. I. Pigment Red 5, 146, 147, 150, 170, 176, 184, 185, 213, 269 are preferable. I. Pigment yellow 74, C.I. I. Pigment Red 269 is more preferable.

  Examples of the condensed polycyclic pigment include C.I. from the viewpoint of the crystal suppression effect by the triazine compound of the present invention. I. Pigment red 122, 177, 202, 207, 209, 254, C.I. I. Pigment blue 15: 3, 15: 6, C.I. I. Pigment green 36, 58, C.I. I. Pigment yellow 138, 150, 185, C.I. I. Pigment Violet 23 is preferable. I. Pigment red 254, C.I. I. Violet 23 is more preferable.

  The organic pigment used in the present invention preferably has, as primary particles, a major axis of 50 to 150 nm and a minor axis of 30 to 100 nm. In the present invention, a particle having such a primary particle size is said to have a very small primary particle size or highly refined.

  The fine pigment composition of the present invention can be obtained by reacting a compound as 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 pigment is used as the organic pigment, an azo pigment is produced by a coupling reaction by performing a coupling reaction between a diazonium salt as a raw material and a coupler in the presence of the triazine compound. When the crystal grows, the triazine compound approaches the surface of the pigment crystal particle being formed, and the crystal growth of the primary particle of the pigment is suppressed / controlled by the interaction with the π electrons of the pigment molecule. As described above, it is considered that a fine pigment composition containing an azo pigment having an extremely small primary particle diameter can be obtained. The triazine compound may be present at the time of the coupling reaction, and the addition method is not limited. The coupling reaction can be performed by a known method. The coupler used in the present invention is not particularly limited as long as it can be used in the coupling reaction when synthesizing the azo pigment. Further, the diazonium salt used in the present invention is not particularly limited as long as it can be used in the coupling reaction of the azo pigment, and a diazonium obtained by diazotizing various amines is used as a metal salt.

  The amount of the triazine compound added is not particularly limited, but is added so that the triazine compound is 0.1 to 20 parts with respect to 100 parts of the coupler. When the added amount of the triazine compound is less than 0.1 part, the crystal growth suppressing effect is small, and when it is more than 20 parts, the performance of the final product is affected (transparency, contrast, etc. of the final product). . Moreover, although the use ratio of a coupler and a diazonium salt is based on equimolar reaction, you may adjust suitably according to those types.

  After the coupling reaction as described above, it is filtered, washed with water by a conventional method, dried, and then pulverized with a disperser such as a roll mill, a bead mill, etc., so that a fine pigment composition containing an azo pigment having extremely small primary particles You can get things. In addition, after drying as described above, primary particles agglomerate and larger secondary particles are formed. Salt milling ordinarily required only by using a disperser as described above. The secondary particles can be easily pulverized and returned to the state of primary particles having a very small particle size without going through the above-mentioned refinement process.

When a condensed polycyclic pigment is used as the organic pigment, unlike the case of an azo pigment, a fine pigment composition is produced through a step of pigmenting a crude pigment in the presence of the triazine compound. This is because it is difficult to add the triazine compound when preparing a crude pigment. Therefore, in the step of pigmentation (miniaturization) after the preparation of a crude pigment having a very large primary particle diameter, the crystal growth of the miniaturized pigment particles is effectively suppressed when the triazine compound is present. It was found that a condensed polycyclic pigment having extremely small primary particles can be obtained. As in the case of the azo pigment, the basic principle is considered to be due to the interaction of the triazine compound and the pigment by π electrons and the structure of the side chain. That is, once a crude pigment having a very large particle diameter is prepared, a crystal is grown again after the pigment particles are refined by a method such as salt milling. The presence of the triazine compound is considered to suppress the crystal growth effectively.
In the present invention, the crude pigment is a compound having a large particle size (for example, about 10 to several hundred μm) obtained by reacting a raw material compound that is a basis for the condensed polycyclic pigment, This means that dispersibility as a pigment and clear color development cannot be obtained. Such a crude 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 triazine compound. Pigmentation in the present invention means a step of aligning the particle diameter of the crude pigment within an appropriate particle diameter range as a pigment. Moreover, although it changes with uses etc. with an appropriate particle range, it is set as about 0.05-0.3 micrometer.

  The pigmentation method can be performed using a known method such as salt milling. The amount of the triazine compound added during pigmentation is not particularly limited, but the triazine compound is added in an amount of 0.1 to 20 parts per 100 parts of the crude pigment. When the added amount of the triazine compound is less than 0.1 part, the crystal growth suppressing effect is small, and when it is more than 20 parts, the performance of the final product is affected (transparency, contrast, etc. of the final product). .

  After being pigmented as described above, it is washed with water by a conventional method, dried, and then pulverized with a disperser such as a roll mill or a bead mill, so that it is highly refined, and a condensed polycycle having a very small primary particle size. A fine pigment composition containing a pigment can be obtained.

  The fine pigment composition containing the predetermined triazine compound and the desired organic pigment according to the present invention obtained as described above has the desired organic pigment highly refined, for example, primary particles of the organic pigment. As described above, a material having a major axis of 50 to 150 nm and a minor axis of 30 to 100 nm can be obtained. Further, in this way, the fine pigment composition according to the present invention is such that the primary particles of the organic pigment contained are extremely small, highly refined, and can remarkably suppress the agglomeration, that is, Even when the pigment composition is dispersed in the pigment dispersion composition, it is possible to effectively prevent aggregation due to a synergistic effect with the dispersant and the like, so a printing ink that requires advanced color characteristics, It can be suitably used for paints, in particular, ink for ink jet printers, color filter inks, and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the examples, “parts” and “%” are based on weight.
(Production Example 1)
Add 6.8 parts of sulfanilic acid (trade name: ASA sulfanilic acid, manufactured by Sugai Chemical Industry) in an amount to react with 7.3 parts of cyanuric chloride and one Cl of cyanuric chloride in 100 parts of water, and at 20 ° C. for 1 hour. Reacted. Next, 10 parts of 4,4′-methylenedi-2,6-xylidine (trade name: KAYABOND C-200S, manufactured by Nippon Kayaku Co., Ltd.) in an amount capable of reacting with one Cl of the reaction product is added and the mixture is added at 70 ° C. The reaction was carried out for 1 hour. The obtained reaction product was filtered and the residue was washed with water, and then allowed to stand overnight in a thermostatic bath at 80 ° C. and dried to obtain 17.0 parts of a triazine compound represented by the formula (10).

(Production Example 2)
The same operation as in Production Example 1 was conducted except that 3.4 parts of sulfanilic acid was added instead of 6.8 parts of sulfanilic acid, to obtain 14.8 parts of a triazine compound represented by the formula (11).

(Production Example 3)
The same as Production Example 1 except that 4.3 parts of paraphenylenediamine (trade name: p-phenylenediamine, manufactured by Wako Pure Chemical Industries) was added in place of 10 parts of 4,4′-methylenedi-2,6-xylidine. Thus, 12.5 parts of a triazine compound represented by the formula (12) was obtained.

(Production Example 4)
In place of 10 parts of 4,4′-methylenedi-2,6-xylidine, 9.5 parts of 3-amino-4-methoxybenzanilide (trade name: M-40, manufactured by Samsung Chemical Industries) was added. The same operation as in Production Example 1 was performed to obtain 16.6 parts of a triazine compound represented by the formula (13).

(Production Example 5)
To 100 parts of water, 7.3 parts of cyanuric chloride and 6.8 parts of sulfanilic acid in an amount capable of reacting with one Cl of cyanuric chloride were added and reacted at 20 ° C. for 1 hour. Next, 9.5 parts of 3-amino-4-methoxybenzanilide (trade name: M-40, manufactured by Samsung Chemical Industry Co., Ltd.) in an amount to react with one Cl of the reaction product was added, and 1 at 75 ° C. Reacted for hours. Thereafter, sodium hydroxide was added to adjust to pH 6, and the mixture was further stirred at 90 ° C. for 2 hours to hydrolyze the remaining Cl. The obtained reaction product was filtered, and the residue was washed with water, and then left to stand overnight in a constant temperature bath at 80 ° C. and dried to obtain 15.9 parts of a triazine compound represented by the formula (14).

(Production Example 6)
To 100 parts of water, 7.3 parts of cyanuric chloride and 6.8 parts of sulfanilic acid in an amount capable of reacting with one Cl of cyanuric chloride were added and reacted at 20 ° C. for 1 hour. Next, 10 parts of 4,4′-methylenedi-2,6-xylidine (trade name: KAYABOND C-200S, manufactured by Nippon Kayaku Co., Ltd.) in an amount capable of reacting with one Cl of the reaction product is added and the mixture is added at 70 ° C. The reaction was carried out for 1 hour. Thereafter, sodium hydroxide was added to adjust to pH 6, and the mixture was further stirred at 90 ° C. for 2 hours to hydrolyze the remaining Cl. The obtained reaction product was filtered, and the residue was washed with water, and then allowed to stand overnight in a constant temperature bath at 80 ° C. and dried to obtain 16.4 parts of a triazine compound represented by the formula (15).

(Production Example 7)
Except that 6.8 parts of sulfanilic acid was replaced with 7.3 parts of dibutylaminopropylamine (trade name: N, N-dibutyl-1,3-propanediamine, manufactured by Wako Pure Chemical Industries), Production Example 1 and The same operation was performed to obtain 17.4 parts of a triazine compound represented by the formula (16).

Example 1
50 parts of 2-methoxy-4-nitro-aniline (trade name: Kako Red B Base conc, manufactured by Showa Kako) was added to a mixed liquid of 400 parts of water and 79 parts of 35% hydrochloric acid, and this liquid was stirred. Was cooled to 0 to 5 ° C., 21.5 parts of sodium nitrite was further added, and diazotized by a conventional method to prepare a diazotized liquid.
The coupler liquid was prepared as follows. First, 66 parts of 2-methoxy-acetoacetanilide (trade name: acetoacetic acid O-anisidite, manufactured by Samsung Chemical Industry), which is a coupler, is added to a mixed solution of 300 parts of water and 48 parts of a 30% by weight aqueous caustic soda solution. And dissolved. 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 mixed solution of 150 parts of water and 28 parts of 80% acetic acid was further added to precipitate the coupler. . Next, 3 parts of the triazine compound obtained in Production Example 1 was added to this precipitation solution to prepare a suspension (coupler solution).
The diazotized liquid is gradually added to the coupler liquid over a period of 120 minutes while stirring at 25 ° C., and the diazonium salt is allowed to undergo a coupling reaction with the coupler, followed by heating at 90 ° C. for 30 minutes to obtain an azo yellow pigment. C. I. Pigment Yellow 74 was produced.
The reaction solution was allowed to stand at room temperature, then filtered by a conventional method, washed with water, dried, and then pulverized by a sample mill to obtain a triazine compound represented by the formula (10) and an azo yellow pigment C.I. I. 118 parts of a fine pigment composition containing CI Pigment Yellow 74 were obtained.

(Example 2)
50 parts of 3-amino-4-methoxybenzanilide (trade name: M-40, manufactured by Samsung Chemical Industry Co., Ltd.) is added to 1000 parts of water and dispersed, and the liquid temperature is adjusted to 0 to 5 ° C. After adding 78 parts of hydrochloric acid and stirring for 20 minutes, 15 parts of sodium nitrite was added and diazotized by a conventional method. Further, 25 parts of 80% acetic acid and 15 parts of sodium acetate were added to form a diazonium salt, and then 1 part of the triazine compound obtained in Production Example 1 was added to prepare a diazonium salt solution.
Further, 69 parts of N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthalenecarboxamide (trade name: Naphthol AC-CA, manufactured by Samsung Chemical Industry), 1700 parts of water and 30% by weight of caustic soda A coupler solution was prepared by dissolving in 48 parts of an aqueous solution.
The coupler solution was adjusted so that the solution temperature was 10 ° C. or lower, added to the diazonium salt solution with stirring to cause a coupling reaction, and then heated at 90 ° C. for 30 minutes to obtain an azo red pigment C . I. Pigment Red 269 was produced.
The reaction solution was allowed to stand at room temperature, then filtered by a conventional method, washed with water, dried, and then pulverized by a sample mill to obtain a triazine compound represented by formula (10) and an azo red pigment C.I. I. 121 parts of a fine pigment composition containing CI Pigment Red 269 were obtained.

(Example 3)
The triazine compound represented by the formula (10) and the azo red pigment C.I. were added in the same manner as in Example 2 except that 3 parts of the triazine compound represented by the formula (10) obtained in Production Example 1 was added. I. 121 parts of a fine pigment composition containing CI Pigment Red 269 were obtained.

Example 4
The triazine compound represented by the formula (11) and the azo red pigment C.I. were added in the same manner as in Example 3 except that 3 parts of the triazine compound represented by the formula (11) obtained in Production Example 2 was added. I. 121 parts of a fine pigment composition containing CI Pigment Red 269 were obtained.

(Example 5)
A triazine compound represented by the formula (12) and an azo red pigment C.I. were added in the same manner as in Example 3 except that 3 parts of the triazine compound represented by the formula (12) obtained in Production Example 3 was added. I. 121 parts of a fine pigment composition containing CI Pigment Red 269 were obtained.

(Example 6)
A triazine compound represented by the formula (13) and an azo red pigment C.I. were added in the same manner as in Example 3 except that 3 parts of the triazine compound represented by the formula (13) obtained in Production Example 4 was added. I. 121 parts of a fine pigment composition containing CI Pigment Red 269 were obtained.

(Example 7)
The triazine compound represented by the formula (13) and the azo red pigment C were obtained in the same manner as in Example 6 except that 0.8 part of the triazine compound represented by the formula (13) obtained in Production Example 4 was added. . I. 121 parts of a fine pigment composition containing CI Pigment Red 269 were obtained.

(Example 8)
The triazine compound represented by the formula (13) and the azo red pigment C were obtained in the same manner as in Example 6 except that 1.5 parts of the triazine compound represented by the formula (13) obtained in Production Example 4 was added. . I. 121 parts of a fine pigment composition containing CI Pigment Red 269 were obtained.

Example 9
A triazine compound represented by the formula (13) and an azo red pigment C.I. were added in the same manner as in Example 6 except that 5 parts of the triazine compound represented by the formula (13) obtained in Production Example 4 was added. I. 121 parts of a fine pigment composition containing CI Pigment Red 269 were obtained.

(Example 10)
A triazine compound represented by the formula (13) and an azo red pigment C.I. were added in the same manner as in Example 6 except that 10 parts of the triazine compound represented by the formula (13) obtained in Production Example 4 was added. I. 121 parts of a fine pigment composition containing CI Pigment Red 269 were obtained.

(Example 11)
A triazine compound represented by the formula (13) and an azo red pigment C.I. were added in the same manner as in Example 6 except that 20 parts of the triazine compound represented by the formula (13) obtained in Production Example 4 was added. I. 121 parts of a fine pigment composition containing CI Pigment Red 269 were obtained.

(Example 12)
A triazine compound represented by the formula (14) and an azo red pigment C.I. were added in the same manner as in Example 3 except that 3 parts of the triazine compound represented by the formula (14) obtained in Production Example 5 was added. I. 121 parts of a fine pigment composition containing CI Pigment Red 269 were obtained.

(Example 13)
The triazine compound represented by the formula (14) and the azo red pigment C were obtained 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. . I. 121 parts of a fine pigment composition containing CI Pigment Red 269 were obtained.

(Comparative Example 1)
In the same manner as in Example 1, except that the triazine compound represented by the formula (10) was not added, the azo yellow pigment C.I. I. 115 parts of a pigment composition containing CI Pigment Yellow 74 were obtained.

(Comparative Example 2)
In the same manner as in Example 2, except that the triazine compound represented by the formula (10) was not added, the azo red pigment C.I. I. 120 parts of a pigment composition containing Pigment Red 269 were obtained.

(Measurement of pigment particle diameter)
For the pigment compositions prepared in Examples 1 to 13 and Comparative Examples 1 and 2, using the images taken with a CCD camera connected to an electron microscope, the particle size of the primary particles of the organic pigment contained in the pigment composition was determined. It was measured. The electron microscope used was JEM-1011 manufactured by JEOL Datum Co., Ltd., the applied voltage was 80 kV, the measurement magnification was 50,000 times, and the CCD camera used was MegaView III manufactured by Olympus. The results are shown in Table 1.

(Preparation of ink)
7.5 parts of the pigment compositions of Examples 1 to 13 and Comparative Examples 1 and 2, 4 parts of a dispersant (Johncrill 61J, manufactured by BASF), 5 parts of isopropyl alcohol, 13.5 parts of deionized water, glass beads (Diameter 2.5-3.5 mm) was put in a 140 mL glass container and dispersed for 60 minutes with a paint conditioner. Next, 20 parts of a dispersant (Johncrill 7001, manufactured by BASF) was further added and dispersed in the same manner for 5 minutes, and then the glass beads were removed to prepare an ink as a pigment dispersion. This ink was spread on a polypropylene film using a bar coater so that the wet film thickness was 0.15 μm and dried.

(Evaluation)
The transparency of the thin film prepared on the polypropylene film as described above was confirmed visually. The evaluation criteria are “◎” is very good, “◯” is excellent, and “x” is inferior (opaque). The evaluation results are shown in Table 1.

  As shown in Table 1, the organic pigment contained in the fine pigment compositions of Examples 1 to 13 has very small primary particles, and the pigment dispersion (ink) using the fine pigment composition has transparency. It was shown that the aggregation of primary particles was remarkably suppressed in the pigment dispersion.

(Example 14)
300 parts of condensed red polycyclic pigment (CI Pigment Red 254, trade name: Chromophthal Red 2030, manufactured by Ciba Spatial Chemicals), a triazine represented by formula (10) obtained in Production Example 1 30 parts of compound, neutral anhydrous sodium sulfate (average particle size of about 20 μm, manufactured by Mitajiri Chemical Co., Ltd.), 750 parts of diethylene glycol (manufactured by Nippon Shokubai Co., Ltd.) as a solvent, 5 L kneader (manufactured by Moriyama Co., Ltd.) S5-2GH-S type) and kneaded and ground for 9 hours while controlling the temperature of the kneaded product to 50 ° C. The kneaded and ground product was stirred and dispersed in 30 L of warm water at 40 ° C., then transferred to Nutsche, filtered, and washed with water until the salt cake 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 with a pulverizer (manufactured by Kyoritsu Riko Co., Ltd., small pulverizer, sample mill SK-M2), and the triazine compound represented by the formula (10) and the condensed polycyclic red pigment C.I. I. 330 parts of a fine pigment composition containing CI Pigment Red 254 were obtained.

(Example 15)
A triazine compound represented by the formula (15) and a condensed polycyclic red pigment C.I. were obtained in the same manner as in Example 14 except that the triazine compound represented by the formula (15) obtained in Production Example 6 was used. I. 330 parts of a fine pigment composition containing CI Pigment Red 254 were obtained.

(Example 16)
A triazine compound represented by the formula (11) and a condensed polycyclic red pigment C.I. were obtained in the same manner as in Example 14 except that the triazine compound represented by the formula (11) obtained in Production Example 2 was used. I. 330 parts of a fine pigment composition containing CI Pigment Red 254 were obtained.

(Comparative Example 3)
A condensed polycyclic red pigment C.I. was prepared in the same manner as in Example 14 except that no triazine compound was added. I. 330 parts of a fine pigment composition containing CI Pigment Red 254 were obtained.

(Example 17)
Violet crude pigment of condensed polycyclic pigment (CI Pigment Violet 23, trade name: Hostaperm Violet RL-02, manufactured by Clariant) 500 parts, triazine compound 50 represented by formula (10) obtained in Production Example 1 Parts, neutral anhydrous sodium sulfate (average particle diameter of about 20 μm, manufactured by Mitajiri Chemical Co., Ltd.), 2500 parts of diethylene glycol (manufactured by Nippon Shokubai Co., Ltd.) as a solvent, 5 L kneader (manufactured by Moriyama Co., Ltd., S5- 2GH-S type) and kneaded and ground for 8 hours while controlling the temperature of the kneaded product to 50 ° C. The kneaded and ground product was stirred and dispersed in 30 L of warm water at 40 ° C., then transferred to Nutsche, filtered, and washed with water until the salt cake 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 with a pulverizer (manufactured by Kyoritsu Riko Co., Ltd., small pulverizer, sample mill SK-M2), and the triazine compound represented by the formula (10) and the condensed polycyclic red pigment C.I. I. 550 parts of a fine pigment composition containing Pigment Violet 23 were obtained.

(Example 18)
A triazine compound represented by the formula (12) and a condensed polycyclic red pigment C.I. were obtained in the same manner as in Example 17 except that the triazine compound represented by the formula (12) obtained in Production Example 3 was used. I. 550 parts of a fine pigment composition containing Pigment Violet 23 were obtained.

(Example 19)
The triazine compound represented by the formula (16) and the condensed polycyclic red pigment C.I. were obtained in the same manner as in Example 17 except that the triazine compound represented by the formula (16) obtained in Production Example 7 was used. I. 550 parts of a fine pigment composition containing Pigment Violet 23 were obtained.

(Comparative Example 4)
A condensed polycyclic red pigment C.I. was prepared in the same manner as in Example 17 except that no triazine compound was added. I. 550 parts of a fine pigment composition containing Pigment Violet 23 were obtained.

(Preparation of color filter)
Using the fine pigment compositions of Examples 14 to 19 and Comparative Examples 3 and 4, mixtures having the compositions shown in Table 2 were prepared. In the table, PR254 is C.I. I. This is an abbreviation for CI Pigment Red 254, and its columns are the compositions of Examples 14 to 16 and Comparative Example 3. I. This is an abbreviation for Pigment Violet 23, and the columns are the compositions for Examples 17 to 19 and Comparative Example 4. As acrylic resin, SPCN-2000 made by Showa Polymer, as dispersant, BYK-LPN6919 made by Big Chemie Japan, Disperbyk-2001 made by Big Chemie Japan, and PV23 as propylene glycol monomethyl ether as solvent Acetate (PMA) was used. Zirconia beads having a diameter of 0.5 mm were used. In addition, the value of the acrylic resin in a table | surface is a value when it adds as a 40% PMA solution. In the evaluation of the fine pigment composition containing PV23, in order to appropriately evaluate as a color filter, C.I. I. A mixture with Pigment Blue 15: 6 (trade name: Phthalocyanine Blue 6005, manufactured by Sanyo Dye) (hereinafter referred to as PB15: 6) was used. The value of the pigment is a value as a mixture, and the mixing ratio (weight basis) was (PB15: 6) / (PV23) = 4/1.

  The mixture prepared with the above composition was put in a 140 mL glass container and dispersed with a paint conditioner for 60 minutes, and then zirconia beads were removed to prepare a pigment dispersion. A thin coating plate (color filter) was prepared from this pigment dispersion using spin coating (MIKASA SPINCENTER IH-DX2).

(Evaluation)
Using the color filter prepared as described above, the Y value and contrast (CR) were measured with a spectrophotometer (SPECTROTOPOMETER CM-3700d).
The method for measuring the contrast is as follows. That is, the color filter was sandwiched between two polarizing plates, and the transmitted light illuminance when the polarizing planes of the respective polarizing plates were made parallel to the transmitted light illuminance when perpendicularized were measured to obtain the ratio. For the measurement of transmitted light illuminance, a luminance meter “LS-100” (manufactured by Minolta) was used. Table 3 shows the measurement results.

  As shown in Table 3, since the color filter using the fine pigment composition obtained in Examples 14 to 19 has high contrast without lowering the Y value, the primary particles of the pigment are extremely small, And it is suggested that the aggregation is effectively suppressed.

Claims (9)

A fine pigment composition comprising a triazine compound represented by the formula (1) and an organic pigment.

(In the formula (1), A represents any acidic group selected from the group represented by the formula (7), or —NH— (CH ₂ ) ₃ —N (CH ₃ ) ₂ , —NH— (CH _{2 ) 3 -N (C 2 H 5} ) 2, -NH- (CH 2) 3 -N (C 3 H 7) 2 and -NH- (CH ₂₎ is selected from _{3 -N (C 4 H 9)} 2 .B showing the Ruizure of basic groups, .D showing an -OH or -Cl represents any aromatic amine residue of a group of groups represented by the formula (9).)

(In the formula (7), R ⁴ , R ⁵ and R ⁶ are each independently —H, —NO ₂ , —Cl, a lower alkyl group having 1 to 4 carbon atoms, or a lower alkoxyl having 1 to 4 carbon atoms. _{group, -CF 3, -SO 3 H,} -SO 2 N (C 2 H 5) 2, -COOH, -COOCH 3, -CONH 2, -SO 2 -NH 2 -Ph (Ph represents a phenyl group) , -CONH-Ph (Ph represents -H, -Cl, a phenyl group which may have a substituent of a methylene group).

The fine pigment composition according to claim 1 , wherein the organic pigment is an azo pigment. The atomized pigment composition according to claim 2 , wherein the azo pigment is Color Index Pigment Yellow 74 or Pigment Red 269. The fine pigment composition according to claim 1 , wherein the organic pigment is a condensed polycyclic pigment. The atomized pigment composition according to claim 4 , wherein the condensed polycyclic pigment is Color Index Pigment Violet 23 or Pigment Red 254. A method for producing a fine pigment composition containing an azo pigment, wherein a diazonium salt is subjected to a coupling reaction with a coupler in the presence of a triazine compound represented by the formula (1) according to claim 1 . The manufacturing method of the fine pigment composition containing the azo pigment of Claim 6 added so that the said triazine compound may be 0.1-20 parts with respect to 100 parts of couplers. A method for producing a fine pigment composition containing a condensed polycyclic pigment, wherein the crude pigment is pigmented in the presence of the triazine compound represented by the formula (1) according to claim 1 . The method for producing a fine pigment composition containing a condensed polycyclic pigment according to claim 8 , wherein the triazine compound is added in an amount of 0.1 to 20 parts per 100 parts of the crude pigment.