JP2007204655A - Pigment yellow 12 - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fine Yellow 12 preparing printing ink excellent in transparency and heat resistance. <P>SOLUTION: This C. I. Pigment Yellow 12 is characterized by showing ≥0.94 and ≤1.80 half value width of peak intensity within 8.0 to 11.8° (2θ) in an X-ray diffraction measurement after drying the wet cake of the pigment at 90°C. The coupler components of the Pigment Yellow 12 are 70-100 mol acetoacetanilide, 0-30 mol% coupler component expressed by the following formula, and 0-10 mol% coupler component containing a polar group. The formula is: CH<SB>3</SB>COCH<SB>2</SB>CONH-X [wherein, X is phenyl group having a substituent selected from methyl, methoxy and chlorine atom]. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention provides C.I. which is excellent in transparency and heat resistance. I. Pigment Yellow 12 (hereinafter, simply referred to as “Pigment Yellow 12”).

  Printing inks containing disazo pigments require transparency and tinting strength. There is a close relationship between the fineness of the particles, the transparency and the coloring power, and obtaining fine pigments leads to the improvement of these performances.

Among the disazo pigments, Pigment Yellow 12 is most often used as a pigment for printing ink. Pi

Conventionally, Pigment Yellow 12 has caused crystal growth due to heat in a wet cake flushing process, resulting in a decrease in quality such as transparency and density.

As means for solving the deterioration in quality due to crystal growth, for example, Patent Document 1 discloses a technique for obtaining a pigment by mixed coupling of acetoacetanilide and a polar group-containing acetoacetanilide. According to this technique, it is possible to produce a yellow ink excellent in transparency and density, but there is room for improvement in transparency.

On the other hand, a method of using an aluminum compound in the synthesis of Pigment Yellow 12 is known. As a method of using an aluminum compound, after synthesizing Pigment Yellow 12 pigment, an alkali salt solution of rosin acid is added to the pigment slurry on the alkali side, and then a liquid sulfuric acid band (aluminum sulfate solution) is added for treatment. Thus, an aluminum salt of rosin acid is deposited on the pigment surface. In this way, flushing wastewater is clarified thanks to the agglomerating aluminum.

Patent Document 2 discloses a technique for treating pigment surface particles with rosin acid and aluminum hydroxide after the pigment yellow 12 is coupled. According to this technique, the time of the flushing process can be shortened, and a clear flushing waste water can be obtained.

However, these aluminum hydroxide treatments did not contribute to the transparency and heat resistance of Pigment Yellow 12.

Japanese Patent Publication No.55-100630 JP 2003-105222 A

An object of the present invention is to provide a fine yellow 12 capable of adjusting a printing ink having excellent transparency and heat resistance.

The X-ray diffraction measurement after drying the pigment wet cake at 90 ° C. indicates that the half width of the intensity peak at 8.0 to 11.8 degrees (2θ) is 0.94 to 1.80. Characteristic C.I. I. Related to Pigment Yellow 12.

  Furthermore, the present invention relates to C.I. I. Pigment yellow 12 and C.I. I. C.I. comprising 0.1 to 25% by weight of aluminum hydroxide based on CI Pigment Yellow 12. I. Related to Pigment Yellow 12.

Furthermore, the present invention provides the C.I. I. The present invention relates to a coloring composition comprising Pigment Yellow 12 dispersed in a vehicle.

Pigment Yellow 12 obtained by the present invention has excellent heat resistance. For this reason, it is difficult for crystals to grow due to the heat received in the flushing step, and a printing ink having excellent transparency can be obtained because it is blended in the printing ink while maintaining fine pigment particles.

Pigment Yellow 12 in which the half-value width of the intensity peak at 8.0 to 11.8 degrees (2θ) is 0.94 or more and 1.80 or less in X-ray diffraction measurement after drying the pigment wet cake of the present invention at 90 ° C. Can be obtained by carrying out the tetrazotization of 3,3′-dichlorobenzidine and the coupler component in the presence of aluminum hydroxide. Aluminum hydroxide can be added as it is or can be produced during the coupling.

As the aluminum hydroxide, it is preferable to use a water-soluble aluminum salt such as liquid sulfuric acid band (8% aluminum sulfate solution in terms of aluminum oxide) or aluminum chloride hexahydrate. The pH during the coupling reaction is 4-5, and the liquid sulfuric acid band is present as aluminum hydroxide in the pH 4-11 region. In coupler solutions with a pH of 13 or higher, they are dissolved as aluminate. Also, tetrazo solution, which is a strong acid, is dissolved as aluminum chloride.

In the case of a liquid sulfuric acid band (8% aluminum sulfate solution in terms of aluminum oxide), the amount of aluminum hydroxide added is 0.1 to 25% by weight, preferably 3 to 15% by weight, based on the pigment produced. If the addition amount is larger than the above upper limit, the pigment surface becomes hydrophilic, resulting in poor flushing properties and poor dispersion. If the amount added is less than the above amount, the transparency and heat resistance are not improved.

As a method of dissolving the aluminum compound in the coupler component, a method of adding 0.1 to 25% by weight of a water-soluble aluminum salt to the pigment component after adding and dissolving the coupler component and caustic soda in water is preferable. Since the coupler solution is alkaline with a pH of 13 or higher, the added water-soluble aluminum salt exists as sodium aluminate.

As a method for dissolving the aluminum compound in the tetrazo solution, a method in which a water-soluble aluminum salt is added and dissolved immediately before the coupling reaction is preferable.

The coupler component of Pigment Yellow 12 in the present invention is 70 to 100 mol of acetoacetanilide, 0 to 30 mol% of the coupler component represented by the general formula (1), and the general formula (2) and / or the general formula ( The coupler component represented by 3) is composed of 0 to 10 mol%.

Formula _{(1) CH 3 COCH 2 CONH} -X
(Wherein X represents a phenyl group having the same or different substituents selected from the group consisting of a methyl group, a methoxy group and a chlorine atom.)

Formula _{(2) CH 3 COCH 2 CONH} -Y
Wherein Y represents a phenyl group having a substituent selected from the group consisting of a chlorine atom, a —CONH ₂ group, a —SO ₂ NH ₂ group and a —NHCOR group, provided that R is a hydrogen atom, C ₁ -C ₄ alkyl group (the alkyl groups may be bonded to each other to form a ring) or C ₁ -C ₄ alkylene NR ′ ₂ group, R ′ is a hydrogen atom or C ₁ -C which may be different from each other _{4 represents} an alkyl group (the alkyl groups may be bonded to each other to form a ring).)

Formula _{(3) CH 3 COCH 2 CONH} -Z
(In the formula, Z represents a phenyl group having a substituent selected from the group consisting of a carboxylic acid group or an alkali metal salt thereof, a hydroxyl group and a sulfonic acid group or an alkali metal salt thereof.)

  In the present invention, the coupling reaction between the tetrazo solution of 3,3′-dichlorobenzidine and the coupler component is not particularly limited, but an acidic buffer solution having a pH adjusted to about 4.7 is prepared, and the coupler solution and the tetrazo solution are added simultaneously. Is used. In order to improve the pigment properties of the obtained pigment composition, rosin treatment may be performed, or a water-soluble inorganic salt such as a liquid sulfuric acid band, aluminum chloride or calcium chloride may be added after completion of the coupling reaction. Moreover, you may heat. Thereafter, a wet cake of Pigment Yellow 12 for use in the flushing process is obtained by filtering, washing with water and pressing to a pigment content of about 30%.

  The coloring composition of the present invention comprises Pigment Yellow 12 of the present invention and a vehicle. Vehicles include printing ink vehicles, paint vehicles, molded plastic colorant vehicles, and the like. Examples of the vehicle for printing ink include vehicles for offset ink, gravure ink, and inkjet ink.

  As offset printing vehicles, rosin-modified phenolic resins, petroleum resins, alkyd resins, or resins such as these drying oil-modified resins 20 to 50% by weight, vegetable oils such as linseed oil, tung oil, soybean oil, 0 to 30% by weight, It consists of 0 to 60% by weight of a solvent such as n-paraffin, isoparaffin and α-olefin.

Vehicles for gravure ink include, for example, gum rosin, wood rosin, tall oil rosin, calcified rosin, lime rosin, rosin ester, maleic acid resin, vinyl resin, gilsonairo, dammar, shellac, polyamide resin, vinyl resin, nitrocellulose, cyclization Rubber, chlorinated rubber, ethyl cellulose, cellulose acetate, ethylene-vinyl acetate copolymer resin, urethane resin, polyester resin, alkyd resin and other resin mixtures, n-hexane, toluene, methanol, acetone, ethyl acetate, ethyl lactate, ethylene Consists of solvents such as glycol monoethyl ether, ethylene glycol monobutyl ether, isopropyl alcohol, chlorobenzole, ethyl ether, methyl ethyl methone, ethyl acetoacetate, etc. If, by weight ratio, resin mixture: solvent = 10-50 parts: the preferred range of 30 to 80 parts.
[Examples] The present invention will be specifically described with reference to the following examples. In the examples, “parts” represents parts by weight, and “%” represents% by weight.

To 400 parts of water, 25.3 parts of 3,3'-dichlorobenzidine and 16.5 parts of 35% hydrochloric acid were added. After cooling this solution to 0 ° C., 70 parts of 20% sodium nitrite solution was added and stirred for 1 hour. A small amount of sulfamic acid was added to eliminate excess sodium nitrite to obtain a tetrazo solution of 3,3'-dichlorobenzidine.
Next, 247.0 parts of acetoacetanilide, 7.0 parts of 2-hydroxy-5-acetoacetylaminobenzoic acid, 6.5 parts of 2-acetoacetylaminobenzoic acid, and 5.5 parts of acetoaceto-p-carbamoylanilide are dissolved in an aqueous solution containing 106 parts of caustic soda. Further, 40 parts of a liquid sulfuric acid band was added to prepare a coupler aqueous solution at 10 ° C. and 1.2 mol / l. Further, 2500 parts of a buffer solution having a pH of 4.7 at 15 ° C. consisting of 114 parts of 80% acetic acid, 32 parts of caustic soda and water was prepared as an acidic aqueous solution and charged into a reactor having a stirrer. To this pH buffer solution, the tetrazo solution and the coupler solution were added simultaneously, taking about 40 minutes while adjusting the flow rate of both solutions so that tetrazo was not released during the reaction. The coupling reaction temperature was kept below 20 ° C. A caustic soda solution was added to adjust the pH to 10.5, 240 parts of disproportionated rosin was added, and the pH was adjusted to 5 with an aqueous hydrochloric acid solution. The resulting disazo pigment slurry was heated to 90 ° C. and held for 20 minutes, then filtered, washed with water, and pressed to obtain a wet cake with a pigment content of 30%.

  Coupling was performed with the amount of liquid sulfuric acid band added to the coupler solution in Example 1 being 30 parts. Thereafter, post-treatment, heating, filtration, washing with water and pressing were carried out in the same manner as in Example 1 to obtain a wet cake having a pigment content of 30.0%.

  Coupling was carried out by dissolving 40 parts of a liquid sulfuric acid band in a tetrazo solution instead of the coupler solution of Example 1. Thereafter, post-treatment, heating, filtration, washing with water and pressing were carried out in the same manner as in Example 1 to obtain a wet cake having a pigment content of 30.0%.

  The liquid sulfuric acid band added to the coupler solution in Example 1 was injected over 40 minutes through a separate dedicated injection tube into the buffer solution in which the coupling reaction was in progress. Thereafter, post-treatment, heating, filtration, washing with water and pressing were carried out in the same manner as in Example 1 to obtain a wet cake having a pigment content of 30.0%.

  A tetrazo solution and a coupler solution were prepared in the same manner as in Example 1. In addition, 250 parts of 80% acetic acid and 4000 parts of acetic acid solution consisting of water were prepared as an acidic aqueous solution, and charged into the reactor. The coupler solution was poured into this acetic acid solution over 40 minutes to precipitate the coupler. The tetrazo solution was poured into this coupler slurry in about 40 minutes until tetrazo was slightly detected on the reaction liquid surface. Thereafter, post-treatment, heating, filtration, washing with water and pressing were carried out in the same manner as in Example 1 to obtain a wet cake having a pigment content of 30.0%.

[Comparative Example 1] The same conditions as in Example 1 were used until the coupling reaction without adding a liquid sulfuric acid band to the coupler solution / tetrazo solution. The resulting slurry of disazo pigment was adjusted to pH 10.5 by adding an aqueous sodium hydroxide solution, 240 parts of disproportionated rosin was added, and adjusted to pH 5 with an aqueous hydrochloric acid solution. The obtained disazo pigment slurry was heated to 90 ° C. and held for 20 minutes, and then 20 parts of a liquid sulfuric acid band was added, stirred for 10 minutes, filtered, washed with water, and pressed to obtain a wet cake with a pigment content of 30%. It was.

Evaluation of the performance of the obtained wet cake was performed by the following two methods.
[Evaluation Method 1] The obtained wet cake was converted into ink and the transparency was evaluated.
Ink formation by flushing was performed using a 1 L flasher. 80 parts of the wet cake was put into 190 parts of an offset ink vehicle that had been preheated to 100 degrees, and flushing was performed for 15 minutes. Next, after removing the water that came out by flushing, 100 parts of an offset ink vehicle was added, and the pressure inside the ink was reduced to 100 degrees for 30 minutes to completely remove the water. To this ink, an offset ink vehicle part and 44 parts of solvent were added at a slow point and removed from the flasher. Thereafter, a base ink was obtained by applying a roll temperature of 60 degrees and a pressure of 10 Barr using three rolls. The final ink was obtained by adding 37 parts of the offset ink vehicle, 7 parts of the solvent, and 6 parts of the auxiliary agent to 92 parts of the base ink to adjust the tack to 5.8 to 6.0.
As a method for evaluating the transparency, the test ink was developed with a thickness of about 0.5 mm using a metal spatula on white colored paper printed with black ink using black ink, and the color developed state was visually observed. The transparency of the ink obtained in Example 1 was 10. When the test ink is developed on the black belt, it is judged as opaque when the black belt is not visible at all.

[Evaluation Method 2] The wet cake was dried with a dryer at 90 ° C. for 15 hours, pulverized with an 80 mesh wire mesh, and then subjected to X-ray measurement.
The X-ray diffraction spectrum was measured under the following conditions.
Equipment: Rigaku Ultima2001
X-ray source: CuKα
Voltage: 40kV
Current: 40mA
Measurement range: 5.0 ° to 35.0 °
Step angle: 0.02 °

From this measurement result, data processing was performed under the following conditions to obtain a half width (Δ2θ) at 2θ8.0 to 11.8 °. Here, the half-value width is a black angle value defined by a peak width at an intensity position that is a half intensity of the X-ray diffraction intensity at a certain 2θ peak.
The half width was obtained as follows. First, at 2θ8.0 to 11.8 °, the X-ray diffraction intensity at 2θ = x was a moving average of x ± 0.2, and the data was smoothed. Next, the background was removed using the straight line connecting 2θ = 8.0 and 2θ = 11.8 as the base line. After the above data processing, the maximum intensity was selected and the half width (Δ2θ) was determined. The half width (Δ2θ) obtained here is considered to correspond to the size of the crystal.
The results of transparency and half-value width are summarized in Table 1.

The X-ray diffraction spectrum after smoothing of Example 1 and Comparative Example 1 is shown in FIG. In Comparative Example 1, it can be seen that the particles grow crystals by drying, whereas in Example 1, the crystals hardly grow and have heat resistance. The pigments obtained in the examples are
The X-ray half-value width is larger than that of a pigment obtained by a conventional production method, and the pigment has excellent heat resistance.

X-ray diffraction spectrum

Claims (3)

The X-ray diffraction measurement after drying the wet cake of the pigment at 90 ° C. has a half width of an intensity peak at 8.0 to 11.8 degrees (2θ) of 0.94 to 1.80. . I. Pigment Yellow 12. C. I. Pigment yellow 12 and C.I. I. The C.I. of Claim 1 comprising 0.1 to 25 wt% aluminum hydroxide based on CI Pigment Yellow 12. I. Pigment Yellow 12. The C.I. of claim 1 or 2. I. A coloring composition comprising Pigment Yellow 12 dispersed in a vehicle.

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