JPS59168070A - Pigment composition - Google Patents

Abstract

PURPOSE:To provide a pigment compsn. having excellent non-cohesiveness, by adding a copper phthalocyanine derivative to a highly halogenated copper phthalocyanine. CONSTITUTION:A pigment compsn. is obtd. by adding 0.5-30pts.wt. copper phthalocyanine derivative (A) of the formula [wherein CuPc is a copper phthalocyanine residue; X is Cl, Br; l is 1-12; A is -SO2-, -CO-; R1, R2 are each (substd.) alkyl or forms an N atom-contg. heterocyclic ring when combined together; n, m are each 1-4] to 100pts.wt. highly halogenated copper phthalocyanine (B) such as highly chlorinated copper phthalocyanine. Thought compd. B is an excellent green pigment, the particle size thereof is small and the pigment tends to aggramerate so that it exhibits a high structural viscosity in flow characteristics and there is a possibility that segregation or sedimention is caused when mixed with other kinds of pigments. By adding compd. A, a pigment compsn. having wholly improved non-cohesiveness can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a pigment composition that is suitable for use, particularly excellent in non-aggregation properties.

Highly halogenated copper phthalocyanine is a green pigment that is widely used in coloring materials due to its beautiful color tone, high coloring power, and excellent color fastness.
Depending on the application, it has properties that 1 is not satisfactory.

Generally, the particle size of highly halogenated copper phthalocyanine is very small, and one of the major drawbacks caused by this is agglomeration. This tendency is markedly observed in non-aqueous low-viscosity dispersions such as paints and gravure inks, but as a result of pigment aggregation,
It exhibits a large structural viscosity in terms of fluidity, and may cause practical problems such as color separation and pigment sedimentation in paints mixed with other types of pigments.

Several methods have been proposed to correct this shortcoming. For example, as seen in USP 3,891,455, a method of mixing copper phthalocyanine derivatives with logogenated copper phthalocyanine, Japanese Patent Publication No. 40-4143.
There is a method of mixing copper phthalocyanine halide with a copper halide phthalocyanine as shown in Japanese Patent Publication No. Additional tests of these methods revealed that gravure inks showed excellent gloss and low viscosity, but the effect on paint systems was small. Also, JP-A-52
When a blue copper phthalocyanine derivative, which is not found in Japanese Patent No. 132031, is mixed with highly halogenated copper phthalocyanine, the paint system exhibits low viscosity, but has the disadvantage that the hue becomes bluish.

The feature of the present invention is to eliminate these drawbacks and to obtain a highly halogenated copper phthalodianine pigment composition that has comprehensively improved non-aggregation properties.

That is, the present invention provides highly halogenated copper phthalocyanine 10
0 parts by weight and the general formula (1) shown by the following general formula (1) (wherein, CuPC is a copper phthalocyanine residue, X is a chlorine atom or a bromine atom, t is a number from 1 to 12, and A is -802-
or -co-1R1 and R2 are each independently an unsubstituted alkyl group, or R1 and R2 are a heterocyclic ring containing at least a nitrogen atom and may further contain an oxygen atom or a sulfur atom, n, , m are each independently from 1 to
Each represents the number 4. ) The copper phthalocyanine derivative represented by the above general formula can be produced by various methods. For example, copper phthalocyanine polysulfonic acid is dissolved in a mixture of aluminum chloride and sodium chloride, bromine or chlorine is introduced, and after halogenation, the product is poured into a large amount of water, and the product is separated and dried. Next, it is dissolved in a solvent such as chlorosulfonic acid, the sulfone group is changed to a chlorosulfone group using a chlorinating agent such as thionyl chloride, and the mixture is separated by placing it in ice water. Next, an amine represented by the following general formula (n) is added in the presence or absence of a solvent, and the product can be produced by dehydrochlorination reaction at a temperature of 0°C to 200°C.

General formula (II) (However, mXR1 and R2 in the formula represent the same numbers and groups as in formula (1).) After sulfonation, a halogenation catalyst such as iodine is added, and bromine'1. Introduce bamboo chlorine and separate the product by placing it in ice water. It can then be produced by reacting with an amine represented by general formula (n) in the same manner as above.

The total number of chlorine and/or bromine substituents in the copper phthalocyanine derivative represented by general formula (1) is 1 to 12, but when the total number is in the range of 1 to 4, the color becomes blue and the highly halogenated copper The ratio of mixing with phthalocyanine is limited, and if the total number is in the range of 11 to 12, the manufacturing conditions are generally harsh and by-products are likely to be produced, so the total number is in the range of 5 to 1.
A range of 0 is practically advantageous. When the number of substituents is the same, the bromine-substituted derivative has a yellowish green color compared to the chlorine-substituted derivative. Note that when the number of substituents in a synthesized copper phthalocyanine derivative is actually measured, it generally contains a mixture of several numbers of substituents, so it is the average number thereof.

The amine represented by the general formula (II) includes N,,N-
Dimethylaminopropylamine, NXN-diethylaminepropylamine, N,N-Schiff" ti/L=amine,
NXN-dimethylaminoethylamine, N,N-diethylaminoethylamine, N-aminopropylmorpholine, N-aminopropylbiveridine, N-aminoethylpyrrolidine N1N-diisobutylaminopentylamine, N%N-1ethylaminopentylamine, N , N-dimethylaminopentylamine, N-aminopropyl-2
- Pipecoline, etc. may be mentioned.

The thus produced copper phthalocyanine derivative represented by the general formula (+) and the highly halogenated copper phthalocyanine pigment can be mixed in the form of dry powder, press cake or slurry, or both can be mixed. Dissolve or suspend them separately or together in concentrated sulfuric acid,
Pigmentation can also be carried out simultaneously by precipitation of the pigment by injection into water or by mechanical grinding with crude highly halogenated copper phthalocyanine. Alternatively, the highly halogenated copper phthalocyanine and the copper phthalocyanine derivative can be prepared separately and added at the time of manufacturing paints, printing inks, and the like.

Regarding the highly halogenated copper phthalocyanine pigment composition of the present invention, when less than 0.5 parts by weight of the copper phthalocyanine derivative represented by the general formula (1) is mixed with 100 parts by weight of the highly halogenated copper phthalocyanine pigment, the pigment particles It does not show any practical effect in suppressing agglomeration, and on the other hand, if it is mixed in an amount exceeding 30 parts by weight, problems may occur in solvent resistance and color. It is necessary to mix 5 to 15 parts by weight.

The high 7 chlorinated copper phthalocyanine pigments used in the mixture include highly chlorinated copper phthalocyanine, highly brominated copper phthalocyanine, highly chlorinated brominated copper phthalocyanine, and mixtures thereof.

Although the reason why the pigment composition according to the present invention is non-aggregating is not clear, the copper phthalocyanine derivative used in the present invention has a sea urchin, a sulfonamide group, or a carbonamide group, as is clear from the chemical structural formula. Furthermore, due to the presence of a tertiary amine group, it can be inferred that interaction with the resin contained in the dispersion system occurs.

Since the crushed pigment composition of the present invention is non-aggregating, it can be used in nitrocellulose lacquers, amino alkyd resin baking paints,
When used in various paints such as alkyl, resin air-dry paints, and acrylic resin paints, the viscosity of the paint is usually lower than that of high-density copper phthalonanine pigments, and the elongation that indicates structural viscosity is small. It exhibits good fluidity, with little change over time, and does not cause color separation or sedimentation in paints mixed with other pigments such as titanium white, carbon black, red, and Bengara.

Furthermore, when used in gravure inks for publishing gravure and packaging gravure Kotobuki, it has good fluidity and exhibits excellent printing effects.

Next, an example will be explained. The middle part of the example refers to parts by weight.

Example 1 10 parts of copper phthalocyanine was placed in a four-ton flask equipped with a stirrer, a reflux condenser, a chlorine inlet tube, and a thermometer.
After 100 parts of chlorosulfonic acid was added and completely dissolved, 21 parts of thionyl chloride was added and kept at 115°C for 4 hours. After cooling, 2 parts of iodine was added and the temperature was raised to 90°C. After introducing chlorine gas for 2 hours at a flow rate of 6 parts/hour, let it cool and add 5 parts of ice.
00 parts. Filter, wash with cold water, transfer to a 4-tube flask equipped with a reflux condenser, add 100 parts of water and 21 parts of NXN-diethylamine, and heat at 60°C for 1 hour.
I kept it. After the reaction was completed, it was filtered, washed with water, and dried to obtain 21 parts of the copper phthalocyanine derivative shown below.

The viscosity of a paint prepared by kneading 1.8 parts of the above copper phthalocyanine derivative, 16.2 parts of highly chlorinated copper phthalocyanine pigment, and 382 parts of alkyd melamine resin varnish in a 1-ton ball mill at 25°C during kneading was measured using a BM type viscometer. The results were as follows: The paint containing the copper phthalocyanine derivative did not exhibit structural viscosity.

The results of measurement using the same BM type viscometer after leaving these paints for one week are shown below, and the paints containing the copper phthalocyanine derivative showed less increase in viscosity.

Make a light color paint of 1/10 force and yt using white paint adjusted with the crushed titanium white, and set the viscosity to Ford force and the thickness of the tube to 4.20 to 2.
The time was adjusted to 0 seconds, and the aggregation was observed in a test tube, but no color separation or sedimentation was observed even after one month. Furthermore, the mixed pigment containing the copper phthalocyanine derivative did not aggregate even in nitrocellulose lacquer, acrylic resin paint, and gravure ink, and exhibited good fluidity.

Example 2 10 parts of copper phthalone disulfonic acid, 8 parts of sodium chloride and 0.1 part of iodine were added to a 470 flask equipped with a stirrer and a thermometer, and the temperature was raised to 150°C. Part 2/
After adding bromine for 10 hours, let it cool, and add water for 30 hours.
Injected into 0 parts. It was filtered, washed with dilute hydrochloric acid, and dried. The dried material was placed in a 4-tube flask equipped with a stirrer, a reflux condenser and a thermometer, and 100 parts of chlorosulfonic acid was added to dissolve it, followed by 16 parts of thionyl chloride and kept at 90°C for 1 hour. After cooling, pour into 500 parts of ice, filter, wash with cold water, transfer to a 470 flask equipped with a reflux condenser, and add 1 part of water.
00 parts and 14 parts of NXN-dimethylaminepropylamine were added, and the mixture was kept at 60°C for 1 hour. After the reaction was completed, it was filtered, washed with water, and dried to obtain 20 parts of the copper phthalocyanine derivative shown below.

The viscosities of the alkyl-tomelamine paint prepared from a mixture of 2 parts of the above copper phthalocyanine derivative and 16 parts of the highly chlorinated m7 thalocyanine pigment in the same manner as in Example 1 and the paint of highly chlorinated copper phthalocyanine alone are as follows. Paints containing copper phthalocyanine derivatives did not exhibit structural viscosity.

The viscosity after standing for one week is shown below, and the paint containing the copper phthalocyanine derivative showed little increase in viscosity.

Furthermore, the light-colored paint prepared in the same manner as in Example 1 did not cause color separation or sedimentation. Furthermore, the copper phthalocyanine derivative mixed pigment did not aggregate even in nitrocellulose lacquer, acrylic resin paint, and gravure ink, and exhibited good fluidity.

Example 3 44 parts of phthalic anhydride, 21 parts of trimellitic acid, 72 parts of urea, 10 parts of cuprous chloride, 02 parts of ammonium molybdate, and 230 parts of trichlorobenzene were added to a pressure-resistant reactor, and the mixture was heated at 180-200 parts for 6 hours. 50 parts of copper phthalocyanine carboxylic acid was obtained. 10 parts of copper phthalocyanine carboxylic acid, 38 parts of aluminum chloride, 8 parts of sodium chloride, and 0.1 part of iodine were added to a 4-tube flask equipped with a stirrer, a chlorine introduction tube, and a thermometer, and the temperature was raised to 170°C. After introducing chlorine gas at a flow rate of 6 parts/hour for 2 hours, the mixture was allowed to cool and then poured into 300 parts of water. The product obtained by filtration, water washing, and drying was dissolved in 100 parts of chlorosulfonic acid in a 470 flask, and then 10 parts of thionyl chloride was added and the mixture was kept at 90°C for 1 hour. After cooling, the mixture was poured into 500 parts of ice, filtered, washed with cold water, placed in a 4/L flask, added with 100 parts of dioxane and 9 parts of N-aminopropylmorpholine, stirred at room temperature for 1 hour, and then added with 5 parts of sodium carbonate for 1 hour. It was kept at 60°C. After the reaction was completed, it was filtered, washed with water, and dried to obtain 7 parts of copper phthalocyanine derivative j shown below.

2 parts of the above copper phthalocyanine derivative, 28 parts of highly chlorinated copper phthalocyanine pigment, and 27 parts of cyclized rubber varnish for gravure
The viscosity at 25°C at 9 o'clock after kneading of the gravure ink prepared by kneading 0 parts with a 1 ton ball mill and the gravure ink kneaded with the highly chlorinated steel phthalocyanine pigment alone is as follows, and the gravure ink containing the above copper phthalocyanine derivative is low. It showed the viscosity.

Furthermore, the mixed pigment containing the above-mentioned copper phthalocyanine derivative is
It showed good fluidity without causing aggregation even in nitrocellulose lacquer, alkylated melamine resin paint, acrylic resin paint and other gravure inks.

Examples 4 to 10 Pigment mixtures containing copper phthalocyanine derivatives obtained in the same manner as in Example 1 using the following amines instead of N,N-diethylaminopetylamine were also non-aggregating.

Procedural amendment (spontaneous) 15th month of ψ, 1980 Dear Commissioner of the Patent Office 1, Indication of the case 1981 patent application number = J-235?
B No. 2, Title of the invention Pigment composition 3, Relationship to the case of the person making the amendment Patent applicant address Toyo tiih, 2-3-13 Kyobashi, Chuo-ku, Tokyo Name Toyo Ink Mfg. Co., Ltd. Specification Column 5 of "Detailed Description of the Invention", Contents of Amendment (1) "Phthalocyanine" in lines 3-4 of page 6 of the specification was corrected to "phthalocyanine."

(2) "rN,N-dibutylamine" on page 6, lines 15-16 of the specification is corrected to "rN,N-dibutylaminoprobylamine."

(3) "Piperidine" on page 6, line 19 of the specification is corrected to "piperidine."

(4) Number of revolutions 1 in Table 3 on page 16, line 3 of the specification
Correct the viscosity r827J at 2 rpm to r327J.

(5) "N,N-diethylaminopentylamine" related to Example 9 in Table 2 in the third line from the bottom of page 16 of the specification is corrected to "N,N-diethylaminopentylamine."

Claims (1)

[Scope of Claims] l 100 parts by weight of highly halogenated copper phthalocyanine and copper phthalocyanine derivatives 05 to 05 represented by the following general formula (1)
30 parts by weight of a pigment composition. General formula (1) (wherein, CuPc is a copper phthalocyanine residue, X is a chlorine atom or a bromine atom, t is a number from 1 to 12, and A is -8O2-
or -CO-1R], R2 each independently represents a substituted or unsubstituted alkyl group, or R1 and R2 together represent a heterocycle containing at least a nitrogen atom, and nXm each independently represents a number from 1 to 4. ) 2 In the above general formula (1), claim 1 uses a copper phthalocyanine derivative in which t is 5 to 100 numbers.
Pigment composition as described in section.