JPH08253696A - Pigment dispersing agent and pigment composition using the same - Google Patents

Abstract

PURPOSE: To obtain a pigment dispersing agent comprising a specific phthalocyanine-based compound, readily producible and suitable for obtaining a coating material, printed material having good glass, coloring power, freshness, transparency, etc., because of its excellent dispersibility in coating materials, ink, etc. CONSTITUTION: This pigment-dispersing agent comprises a compound of the formula [P is a metallophthalocyanine residue; A is O, S or SO3 or a group of the formula NR3 (R3 is H or a 1-8C alkyl); R1 and R2 are each a 1-8C alkyl or an N-containing heterocycle; (k) and (h) are each 0-15 and (k+h) is 1-15; (m) and (n) are each 14], e.g. decabromotrichlorobis [2-(N,N-diethylamino) ethyl]thio}-copper phthalocyanine. The compound of the formula is obtained by carrying out condensation reaction of a metallophthalocyanine halide with an amine compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pigment dispersant exhibiting an excellent effect on suitability for paints, inks, etc., particularly non-aggregating property, and a pigment composition using the same.

[0002]

2. Description of the Related Art Generally, pigments contained in paints and inks are
In order to obtain a clear color tone and high coloring power, it is necessary to disperse the fine particles. However, it is difficult to stably disperse fine pigment particles, and particularly in a low viscosity dispersion system, the pigment particles have a strong tendency to aggregate. Aggregation of pigments often shows fluidity, particularly structural viscosity, and causes deterioration of coloring power, vividness, and gloss, thereby impairing the commercial value of paints and inks. Several methods have been proposed to reduce pigment agglomeration. For example, USP3370971 and USP296551
1, a method of coating pigment particles with a colorless compound such as silicon oxide, aluminum oxide or tertiary butylbenzoic acid, JP-B-41-2466, JP-B-1.
─34268 and USP2855553, an organic pigment as a base skeleton having a sulfonic acid group in a side chain,
There is a method in which a compound obtained by introducing a substituent such as a sulfonamide group, an aminomethyl group or a phthalimide group is mixed with a pigment.

When these methods are supplemented, the effect on the non-cohesiveness of each is often influenced by the composition of the dispersion varnish, and there is no effective method for all dispersion systems, but Japanese Examined Patent Publication No. 1-34268. Compounds in which a tertiary amino group is introduced into a dye as shown in 1) are effective as a whole and have been put into practical use in many cases. However, this type of compound is not always sufficiently effective against non-aggregation
There are some manufacturing issues. For example, there are dyes that cannot be produced or are difficult to produce due to their chemical structure, or acid compounds of intermediates are decomposed and acidic compounds are mixed as impurities. In particular, for phthalocyanine dyes used in large amounts as blue and green pigments, sulfonic acid compounds are mixed as impurities, and in the case of highly halogenated phthalocyanine dyes, manufacturing conditions are found as shown in Japanese Patent Publication No. 4-5702. There was a drawback that it became harsh.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks and exhibits an excellent effect on suitability for paints and inks, especially non-aggregating property, as compared with conventional pigment dispersants, and is easy to use. The present invention provides a phthalocyanine-based pigment dispersant that can be produced according to the above, and a pigment composition using the same.

[0005]

The present invention has the following general formula:
The present invention relates to the pigment dispersant represented by (1).(In the formula, P represents a metal phthalocyanine residue, A is O,
NR₃, S or SO ₂Represents R₁And R₂Are each
Independently an alkyl group having 1 to 8 carbon atoms, or R₁And R₂When
Represents a heterocycle containing at least a nitrogen atom, and R₃Is hydrogen
Represents an atom or an alkyl group having 1 to 8 carbon atoms. k and h are
Each is independently a number from 0 to 15, but k + h is 1 to 1
5 and m and n each independently represent a number from 1 to 4.
You ) Further, the present invention provides the pigment as 100 parts by weight and the above-mentioned one.
0.5 to 30 parts by weight of the pigment dispersant represented by the general formula (1)
To a pigment composition comprising

The metal of the metal phthalocyanine of the present invention is
Copper, iron, nickel, cobalt, aluminum, silicon, etc. can be mentioned. The pigment dispersant represented by the above general formula (1) of the present invention can be produced by various methods, but it is a condensation reaction of a halogenated phthalocyanine in which a benzene ring of a metal phthalocyanine is substituted with a halogen and various amine compounds. The method of manufacturing by (Ullmann reaction) is advantageous. As the halogen of the halogenated phthalocyanine used in the reaction, chlorine or bromine is industrially advantageous. The number of substituents of halogen to phthalocyanine is 2 to 16, but in order to make the reaction conditions mild, it is advantageous that the number of substituents is large, and 4 to 16 is preferable. Moreover, the hue of the resulting pigment dispersant can be adjusted by increasing or decreasing the number of substituents. Especially the general formula (1)
It is preferable that k + h is 7 to 15 because the hue of the pigment dispersant becomes green.

As the amine compound, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, diethylaminoethylamine, dimethylaminopentylamine, N-aminopropylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline. , N, N, N′-trimethylethylenediamine, dimethylaminoethanol, dimethylaminopropanol, dimethylaminobutanol, dimethylaminohexanol, diethylaminoethanol, dibutylaminopropanol, dimethylaminoethanethiol, dimethylaminopropanethiol, diethylaminoethanethiol and the like. be able to.

The condensation reaction between the halogenated phthalocyanine and various amine compounds is carried out at 50 to 230 ° C., preferably 1
It is carried out at 00 to 200 ° C., and at this time, an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, pyridine or quinoline, an inorganic compound such as copper powder, copper chloride, copper sulfate or iron chloride is added. Then, the reaction is accelerated. Although the reaction can be carried out without a solvent, an organic solvent such as DMF, DMSO, toluene, xylene, dichlorobenzene, chloronaphthalene or sulfolane can also be used. The compound in which A in the general formula (1) is SO ₂ is obtained by oxidizing the compound in which A in the general formula (1) is S obtained by the above method with hydrogen peroxide or the like.

The pigment composition of the present invention can be produced by mixing the above pigment dispersant and the pigment. The pigment used in the pigment composition of the present invention is a phthalocyanine blue pigment, a phthalocyanine pigment such as a phthalocyanine green pigment, an azo pigment, a quinacridone pigment, an isoindolinone pigment, a perinone pigment, a perylene pigment, a dioxazine pigment. , Anthraquinone pigments, organic pigments such as diketopyrrolopyrrole pigments, and inorganic pigments such as carbon black, titanium oxide, yellow lead, cadmium yellow, cadmium red, rouge, iron black, zinc white, navy blue, ultramarine be able to.

In the pigment composition of the present invention, the ratio of the pigment dispersant to the pigment is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the pigment. If it is less than 0.1 parts by weight, the practical effect of non-aggregating property of the pigment of the dispersion cannot be obtained, and if it is used in excess of 30 parts by weight, the effect of the amount used cannot be obtained. The pigment dispersant and the pigment may be mixed in the form of dry powder, press cake or slurry, respectively, or both may be dissolved or suspended together in sulfuric acid and poured into water for precipitation. You can also Furthermore, a pigment dispersant is added in a process called pigmentation, for example, in the process of applying mechanical energy to a crude pigment by a kneader or a ball mill, or a solvent treatment of fine particles or agglomerated particles of the pigment to prepare appropriate pigment particles. It can also be mixed. At this time, as a secondary effect, the pigment dispersant suppresses excessive pigment particle growth and facilitates preparation of appropriate pigment particles.

The pigment composition of the present invention exhibits extremely excellent dispersion stability in various dispersions. For example, paints such as nitrocellulose lacquer, alkyd paint, acrylic paint, urethane paint, offset inks of various rosin-modified resins, gravure inks of lime rosin, polyamide resin, vinyl chloride resin, nitrocellulose resin, and color filters of various acrylic resins. When used in a coloring composition or the like, the dispersion has a low viscosity, has a small tendency to exhibit structural viscosity, and has a small viscosity change with time. Further, in a color mixture system using two or more kinds of pigments, color separation or sedimentation does not occur. Furthermore, the coating film or printed matter obtained from these dispersions has excellent gloss, vividness, and tinting strength, and a beautiful product having high commercial value can be obtained.

[0012]

EXAMPLES Next, examples will be described. In Examples, "parts" means "parts by weight". Example 1 Dodecabromo-trichloro-copper phthalocyanine 10 was placed in a 4-necked flask equipped with a stirrer, a reflux condenser and a thermometer.
Parts, 30 parts of diethylaminoethanethiol, 15 parts of potassium hydroxide and 200 parts of DMF were charged and refluxed for 1 hour. After cooling, 200 parts of water was added, followed by filtration, washing with water and drying to obtain 8 parts of the pigment dispersant (A) shown below.

[0013] (In the formula, P represents a copper phthalocyanine residue.) 1.8 parts of the above pigment dispersant (A), C.I. I. Pigment Green 36 pigment 16.2 parts and alkyd melamine resin varnish 382 parts were kneaded in a ball mill, and as a comparative example, Japanese Patent Examined Publication No. 4 instead of pigment dispersant (A).
-5702, the coating material kneaded using the conventional pigment dispersant obtained in Example 1 and C.I. I. Table 1 shows the results of measuring the viscosity at 25 ° C. with a BM type viscometer at the time of kneading the coating material kneaded with Pigment Green 36 pigment alone. The paint containing the pigment dispersant (A) had a lower viscosity and did not exhibit structural viscosity as compared with the paint containing the pigment dispersant according to the prior art and the paint containing no pigment dispersant.

[0014]

[Table 1]

Table 2 shows the results of measuring these paints with the same BM type viscometer after being left for one week. The paint containing the pigment dispersant (A) showed little increase in viscosity.

[0016]

[Table 2]

In addition, it is 1/1 with white paint prepared with titanium white
Create 0 cut light color paint and adjust viscosity to Ford Cup N
o. No. 4 was adjusted to 20 to 22 seconds, and the mixture was poured into a test tube to observe the agglomerated state. However, the paint containing the pigment dispersant (A) was color-separated even after one month, and neither sedimentation nor hue change was observed. Furthermore, since the pigment dispersant obtained in Example 1 of JP-B-4-5702 is blue-green, C.I. I. The mixture with Pigment Green 36 pigment turned bluish green, but the hue of the mixture hardly changed because the pigment dispersant (A) was green. Example 2 A four-necked flask equipped with an agitator, a reflux condenser and a thermometer was charged with 10 parts of tetrachloro-copper phthalocyanine, 30 parts of diethylaminoethylamine, 15 parts of potassium hydroxide and 200 parts of DMF and refluxed for 3 hours. After cooling, 200 parts of water was added, filtered, washed with water and dried to obtain 9 parts of the pigment dispersant (B) shown below.

[0018] (In the formula, P represents a copper phthalocyanine residue.) 0.5 part of the above pigment dispersant (B), C.I. I. Pigment Blue 15: 3 pigment 9.5 parts and NC gravure ink varnish 90 parts were kneaded in a ball mill, and as a comparative example, obtained in Example 1 of JP-B-57-15620 instead of the pigment dispersant (B). Gravure ink kneaded using a conventional pigment dispersant, and C.I. I. Table 3 shows the results of measuring the viscosity at 25 ° C. with a BM type viscometer when the gravure ink kneaded with Pigment Blue 15: 3 pigment alone was kneaded. The gravure ink containing the pigment dispersant (B) had a lower viscosity than the gravure ink containing the pigment dispersant according to the prior art and the gravure ink containing no pigment dispersant, and did not exhibit structural viscosity. The printed matter obtained by developing these gravure inks with a bar coater had the best gloss and sharpness in the case of the gravure ink containing the pigment dispersant (B).

[0019]

[Table 3]

After leaving these gravure inks for one week,
The results of measurement using the same BM type viscometer are shown in Table 4, but the gravure ink containing the pigment dispersant (B) showed a small increase in viscosity.

[0021]

[Table 4]

Example 3 10 parts of the pigment dispersant (A) prepared in Example 1 was diluted with 5 parts of diluted acetic acid.
Dissolve in 00 parts and add 5 parts of 30% hydrogen peroxide water to add 1
It was cold for hours. After cooling, sodium hydroxide was added to make it weakly alkaline, filtered, washed with water, and dried to obtain 10 parts of a pigment dispersant (C) shown below. (In the formula, P represents a copper phthalocyanine residue.) 0.5 part of the above pigment dispersant (C), C.I. I. Pigment Green 36 pigment 9.5 parts, cyclohexanone 50 parts and acrylic resin (copolymer consisting of 50% butyl methacrylate, 30% butyl acrylate and 20% methacrylic acid) in a mayonnaise bottle together with 250 parts of a steel ball having a diameter of 2 mm. It was charged and dispersed with a paint conditioner to obtain a coloring composition for a color filter. As a comparative example, C.I. was used without using the pigment dispersant (C).
I. Pigment Green 36 pigment alone was also dispersed to prepare a coloring composition for a color filter. The viscosity at 25 ° C. immediately after dispersion of these color filter coloring compositions is B
The results of measurement with an M-type viscometer are shown in Table 5, which shows that the coloring composition for a color filter containing the above pigment dispersant has a low viscosity,
It showed no structural viscosity.

[0023]

[Table 5]

Further, these coloring compositions for color filters were prepared according to No. Use a 10 bar coater to develop the color on PET film,
Gloss and 510 nm of printed matter dried at 110 ° C for 10 minutes
Table 6 shows the transmittance of the color filter. The color filter coloring composition containing the pigment dispersant (C) was superior.

[0025]

[Table 6]

Examples 4 to 8 The following pigment dispersants (D) to (H) were prepared in the same manner as in Example 1 except that various amines shown in Table 7 were used instead of the diethylaminoethanethiol of Example 1. Was manufactured.

[0027]

[Table 7]

Pigment dispersant (D) Pigment dispersant (E) Pigment dispersant (F) Pigment dispersant (G) Pigment dispersant (H) (In the formula, P represents a copper phthalocyanine residue.) 1.8 parts of these pigment dispersants and various pigments 1 shown in Table 8
A coating obtained by kneading 6.2 parts and 382 parts of an alkyd melamine resin varnish with a ball mill, and as a comparative example,
Table 8 shows the results of measuring the viscosity at 25 ° C. when the coating material prepared by kneading the pigment alone without using the pigment dispersant was measured with a BM type viscometer. In each case, the paint containing the pigment dispersant had a low viscosity and did not show structural viscosity.

[0029]

[Table 8]

[0030]

EFFECT OF THE INVENTION The pigment dispersant of the present invention and the pigment composition using the same exhibit excellent non-aggregating property in various dispersion systems such as paints and inks, and therefore have good fluidity and gloss,
It is possible to obtain a coated product or a printed product having good tinting strength, vividness and transparency.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tetsuro Oizumi 2-3-13 Kyobashi, Chuo-ku, Tokyo Toyo Inki Manufacturing Co., Ltd.

Claims (3)

[Claims] 1. A pigment dispersant represented by the following general formula (1).(In the formula, P represents a metal phthalocyanine residue, A is O,
NR₃, S or SO ₂Represents R₁And R₂Are each
Independently an alkyl group having 1 to 8 carbon atoms, or R₁And R₂When
Represents a heterocycle containing at least a nitrogen atom, and R₃Is hydrogen
Represents an atom or an alkyl group having 1 to 8 carbon atoms. k and h are
Each is independently a number from 0 to 15, but k + h is 1 to 1
5 and m and n each independently represent a number from 1 to 4.
You ) 2. A pigment composition comprising 100 parts by weight of the pigment and 0.1 to 30 parts by weight of the pigment dispersant according to claim 1. 3. The pigment composition according to claim 2, wherein the pigment is a phthalocyanine green pigment.