JPH06240161A - Dioxazine pigment derivative and its application - Google Patents

Abstract

(57) [Summary] (Modified) [Objective] To provide a pigment derivative which is added to an organic pigment to improve its pigment suitability, especially fluidity and non-aggregation property. [Structure] The following general formula (I) in the form of free acid Specifically, for example A dioxazine pigment derivative represented by.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a pigment derivative and its application.

[0002]

2. Description of the Related Art In non-aqueous dispersions such as paints and printing inks, pigments often agglomerate, sediment, increase viscosity, decrease coloring power, and color when mixed with other pigments. It causes various problems such as division. For the purpose of solving the problems associated with the deterioration of the fluidity and non-aggregation property, many proposals have been made mainly for phthalocyanine pigments and quinacridone pigments. For example, Japanese Patent Publication No. 41-2466 and Japanese Patent Publication No. 50-401.
As disclosed in JP-B-9, a method of mixing a sulfonated product of a pigment or a metal salt thereof, JP-B-38-2713.
US Pat. No. 4,968,639 and a method of incorporating a substituted aminomethyl derivative as disclosed in JP-B-39-16787, USP
2761868 and JP-A-55-10846
A method of mixing a phthalimidomethyl derivative as disclosed in Japanese Patent No. 6 is known.

However, although these methods tend to improve the non-aggregating property, the color separation when mixed with a white pigment is still large and is not satisfactory.

Further, JP-A-1-213366 and JP-B-1-34268 disclose pigment derivatives for the purpose of improving these drawbacks. However, these pigment derivatives have not yet been sufficiently satisfied, and development of a method for industrially advantageously solving various problems associated with deterioration of fluidity and non-aggregation of pigment is strongly desired. .

As a result of intensive studies aimed at solving such a problem, the present inventors have found a specific dioxazine pigment derivative and completed the present invention.

[0006]

The present invention relates to the general formula (I) in the form of the free acid.

[0007]

[Chemical 2]

[In the formula, R ₁ is a saturated or unsaturated fatty acid having 1 to 10 carbon atoms which may be substituted. A linear or branched alkylene group having a prime number of 1 to 10, R ₂ and R ₃ are each independently a saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group having a carbon number of 1 to 20 which may be substituted. It represents a group or forms, together with an adjacent nitrogen atom, a heterocycle which may further contain a nitrogen, oxygen or sulfur atom. Or an alkyl group having 1 to 6 carbon atoms, and the alkyl group is a heterocyclic-substituted alkyl group having a carbon atom of a heterocyclic ring containing at least one of nitrogen, oxygen or sulfur atom. Alternatively, m is a number of 0 to 3 (provided that R ₁ is an unsubstituted aliphatic hydrocarbon group, m is a number of 1 to 3), n is a number of 1 to 4, and m and n Is 1 to 5. ] The dioxazine pigment derivative shown by these, and its application.

Examples of the aliphatic hydrocarbon group represented by R ₁ include optionally substituted alkyl, alkenyl and alkynyl groups, preferably an optionally substituted alkyl group having 1 to 6 carbon atoms. Examples of the aromatic hydrocarbon group include optionally substituted phenyl and naphthyl groups. The substituent of the hydrocarbon group represented by R ₁ is substituted with an amino group which may be substituted with an alkyl or hydroxyalkyl group having 1 to 6 carbon atoms, a hydroxy group or an alkoxy group having 1 to 6 carbon atoms. There may be mentioned an alkoxy group having 1 to 6 carbon atoms.

[0010] Is the following formula,

[0011]

[Chemical 3]

(Wherein R ₂ has the above-mentioned meaning) and is preferably a 5- or 6-membered heterocycle which may further contain a nitrogen atom. As such a heterocyclic residue, for example,

[0013]

[Chemical 4]

(Wherein R ₂ has the above-mentioned meaning) and the like. Examples of the aliphatic hydrocarbon group represented by R ₂ and R ₃ each independently include optionally substituted alkyl, alkenyl and alkynyl groups having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the optionally substituted alkyl group and the aromatic hydrocarbon group include optionally substituted phenyl and naphthyl groups. Examples of the substituent of these hydrocarbon groups include the substituents described above for R ₁ .

The heterocycle formed by R ₂ and R ₃ together with the adjacent nitrogen atom is represented by the following formula:

[0016]

[Chemical 5]

Examples include those described above. The heterocycle of the heterocycle-substituted alkyl represented by X is represented by the following formula:

[0018]

[Chemical 6]

Examples thereof include those described above.

The above heterocycles may be optionally substituted with a lower alkyl group or the like. The dioxazine pigment derivative represented by the general formula (I) can be prepared by a method known per se, for example, by reacting the dioxazine pigment with chlorosulfonic acid,

[0021]

[Chemical 7]

It can be produced by reacting an amine represented by the formula (wherein R ₁ , R ₂ and X have the above meanings).

For the reaction with chlorosulfonic acid, for example, an organic solvent is used, if necessary, and the dioxazine pigment and chlorosulfonic acid in a molar ratio of 1 to 10 are added to -10.
It can be carried out at a temperature of ~ 150 ° C. If necessary, a halogenating agent such as thionyl chloride, phosphorus oxychloride or phosphorus pentachloride may be added. The m and n in the general formula (I) and the total thereof can be appropriately selected depending on the amount of chlorosulfonic acid used and the reaction temperature. The reaction of the reaction product obtained here with an amine can be carried out, for example, by reacting the reaction product with an amine or a salt thereof in water or an organic solvent at a temperature of 0 to 150 ° C.

[0024] Dimethyl-N'-ethylethylenediamine, N, N-diethyl-N'-methylethylenediamine, N, N, N '
-Triethylethylenediamine, N, N'-diethyl-
N-stearylethylenediamine, N'-benzyl-
N, N-dimethylethylenediamine, N, N-diethyl-N'-methyl-1,3-propanediamine, N, N-
Diethyl-N′-ethoxyethyl-1,3-propanediamine, bis (N, N-diethylaminoethyl) amine, bis (N, N-dimethylaminopropyl) amine,
N, N-diethyl-N'-diethylaminoethyl-1,
3-propanediamine, N, N-dibutyl-N'-diethylaminoethyl-1,3-propanediamine, N,
N'-diethyl-2-aminomethylpyrrolidine, N,
N'-diethyl-2-aminomethylpiperidine and the like.

Also, the formula

[0026]

[Chemical 8]

Examples of the heterocyclic amine represented by: N-methylpiperazine, N-ethylpiperazine, N-butylpiperazine, N-hydroxyethylpiperazine, N, N-
Examples include diethylpiperazineethanamine, N, N-dibutylpiperazineethanamine, and N-benzylpiperazine.

The above amines can be prepared by known methods, for example H ₂
N-X represented by amine or piperazine with p-
Use of alkylating agents such as butyl toluene sulfonate, monochlorotriethylamine, benzyl chloride, and other halogenated alkyl groups that may be substituted, sulfates, benzene sulfonates, p-toluene sulfonates, phosphates, etc. It may be manufactured by things.

The sulfonic acid group in the general formula (I) may be a free acid as it is or a salt with a monovalent to trivalent metal or an organic amine. Here, examples of the monovalent metal include sodium, potassium, magnesium, calcium, strontium, barium, and aluminum.

As the organic amine, the above-mentioned amines used for the production of dioxazine pigment derivatives, or aliphatic amines such as ethylamine, propylamine, amylamine, hexylamine, octylamine, dodecylamine, stearylamine, diethylamine, dibutylamine and triethylamine are used. Examples thereof include heterocyclic amines such as amine, pyrrolidine, pipecoline, piperidine, piperazine and morpholine, and aromatic amines such as aniline and toluidine.

The metal or organic amine salt of the pigment derivative can be easily obtained by a known method, for example, by mixing an aqueous suspension of the derivative with an aqueous chloride solution or suspension of the metal or organic amine.

The pigment composition of the present invention can be produced by blending the above-mentioned dioxazine pigment derivative with an organic pigment by a method known per se. Examples of organic pigments include dianthraquinonyl-based, anthrapyrimidine-based, flavantron-based, anthanthrone-based, indanthrone-based, pyrantrone-based, violanthrone-based, isoviolantrone-based, phthalocyanine-based, quinacridone-based, quinophthalone-based, diketopyrrolol Pyrrole-based, dioxazine-based,
Examples include isoindolinone-based, perinone-based, perylene-based, thioindigo-based pigments, and the like. Of these, the dioxazine-based pigment is most advantageously used.

The amount of the dioxazine pigment derivative used is preferably 0.5 to 30% by weight, more preferably 1 to 20% by weight, based on the organic pigment.

The blending method includes, for example, a method of simply mixing the respective dry powders, press cakes, etc., mechanical mixing with various crushers such as a kneader, bees mill, attritor, etc., or a pigment in water or an organic solvent. The dioxazine pigment derivative on the surface of the pigment by adding the dioxazine pigment derivative as a dry powder or in a state of being suspended in water or an organic solvent, or by adding the pigment to a solvent having a strong dissolving power such as sulfuric acid. Examples thereof include a method of dissolving the dioxazine pigment derivative and coprecipitating it with a poor solvent such as water.

The pigment composition of the present invention can be used with excellent pigment suitability for various uses such as paints, printing inks, plastic coloring, printing, and especially when used for paints and printing inks, Compared to the case where an organic pigment is used alone in a non-aqueous dispersion system, the dispersion viscosity is lowered, good fluidity is exhibited, at the same time there is no color separation, the coloring power is high, and the gloss of the printed matter or coating film is good. Moreover, a good product having high transparency can be obtained.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, parts and% represent parts by weight and% by weight. The dioxazine pigment derivative in the examples is represented as a free acid.

[0037]

【Example】

Example-1 Crude C.I. I. Pigment Violet23 40
This was added to 320 parts of chlorosulfonic acid, heated at 60 ° C. for 3 hours, and poured into 3000 parts of ice water. The resulting suspension was filtered and washed with water to obtain 240 parts of filter cake. The filter cake of this reaction product was added to 1000 parts of ice water to form a slurry, and 35 parts of N, N-diethyl-N'-methylethylenediamine was added, and the mixture was stirred at room temperature for 3 hours, filtered, washed with water, and dried to obtain a pigment of the following formula. The derivative was obtained.

[0038]

[Chemical 9]

[0039]

10 parts of the obtained pigment derivative were mixed with C.I. I. P
100 parts of a pigment composition was obtained by mixing with 90 parts of Pigment Violet 23 pigment.

Examples-2 and 3 The pigment derivative obtained in Example-1 and C.I. I. Pigme
nt Violet 23 pigment was mixed in the ratio shown in Table 1 to obtain a pigment composition.

[0042]

[Table 1]

Example-4 Filter cake 2 of the reaction product of Violet23 and chlorosulfonic acid obtained in the same manner as in Example-1.
40 parts was added to 1000 parts of ice water to make a slurry, and N, N-
55 parts of diethyl-N'-ethoxyethyl-1,3-propanediamine was added, and the mixture was stirred at room temperature for 3 hours, filtered, washed with water, and dried to obtain a pigment derivative of the following formula.

[0044]

[Chemical 10]

10 parts of the obtained pigment derivative were mixed with C.I. I. P
100 parts of a pigment composition was obtained by mixing with 90 parts of Pigment Violet 23 pigment.

Example-5 Filter cake 2 of the reaction product of Violet23 and chlorosulfonic acid, obtained in the same manner as in Example-1.
40 parts was added to 1000 parts of ice water to make a slurry, and N, N-
77 parts of dibutyl-N'-diethylaminoethyl-1,3-propanediamine was added, stirred at room temperature for 3 hours, filtered,
After washing with water and drying, a pigment derivative of the following formula was obtained.

[0047]

[Chemical 11]

10 parts of the obtained pigment derivative were mixed with C.I. I. P
100 parts of a pigment composition was obtained by mixing with 90 parts of Pigment Violet 23 pigment.

Example-6 Filter cake 2 of the reaction product of Violet23 and chlorosulfonic acid obtained in the same manner as in Example-1.
40 parts was added to 1000 parts of ice water to make a slurry, and N, N-
Add 66 parts of dibutylpiperazineethanamine at room temperature for 3
The mixture was stirred for a time, filtered, washed with water, and dried to obtain a pigment derivative of the formula below.

[0050]

[Chemical 12]

10 parts of the obtained pigment derivative were mixed with C.I. I. P
100 parts of a pigment composition was obtained by mixing with 90 parts of Pigment Violet 23 pigment.

Example 7 Crude C.I. I. Pigment Violet23 40
This was added to 320 parts of chlorosulfonic acid, stirred at 0 ° C. for 3 hours, and poured into 3000 parts of ice water. The resulting suspension was filtered and washed with water to obtain 220 parts of filter cake. The filter cake of this reaction product was added to 1000 parts of ice water to form a slurry, 62 parts of N, N-ethylpiperazine was added, and the mixture was stirred at room temperature for 3 hours, filtered, washed with water, and dried to obtain a pigment derivative of the following formula.

[0053]

[Chemical 13]

10 parts of the obtained pigment derivative were mixed with C.I. I. P
100 parts of a pigment composition was obtained by mixing with 90 parts of Pigment Violet 23 pigment.

Examples-8 and 9 The pigment derivatives obtained in Example-7 were mixed with the organic pigments shown in Table 2 to obtain pigment compositions.

[0056]

[Table 2]

Example-10 Filter cake 2 of the reaction product of Violet23 and chlorosulfonic acid, obtained in the same manner as in Example-7.
Add 20 parts to 1000 parts of ice water to make a slurry, N, N '
-Diethyl-2-aminomethylpyrrolidine (32 parts) was added, the mixture was stirred at room temperature for 3 hours, filtered, washed with water, and dried to obtain a pigment derivative of the following formula.

[0058]

[Chemical 14]

10 parts of the obtained pigment derivative were mixed with C.I. I. P
100 parts of a pigment composition was obtained by mixing with 90 parts of Pigment Violet 23 pigment.

Example-11 A primary color paint was prepared by using the pigment alone in the amino alkyd resin varnish for baking paint or the pigment composition obtained in Examples-1 to 10, and its viscosity and gloss were measured. In addition, the primary color paint and the titanium oxide paint are 1:10.
The respective performances were investigated by mixing them in a ratio of 1 to prepare a single color paint.

The evaluation method of each performance is as follows,
The results were as shown in Tables 3-5. Viscosity: 25 for each primary color paint using a B-type viscometer
The measurement was performed at 30 ° C. at 30 ° C. Non-Aggregating Property: Each light color paint is applied on art paper, dried for a short time, and a part of the applied surface is rubbed with a finger. Next, the paint is baked, and the color density of the part rubbed with a finger and the part not rubbed are compared. ⊚: No difference ∘: Slight difference ∘: Difference is clearly visible ×: Difference is obvious Coloring power: Each light-color paint is applied on art paper, and the density after baking is based on the pigment alone (100) It was visually judged. Mitsuzawa: Each primary color paint is applied to the glass plate, and after baking 6
The 0 ° -60 ° gloss was measured.

[0062]

[Table 3]

[0063]

[Table 4]

[0064]

[Table 5]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Keisuke Ito 3-1,98 Kasugade, Konohana-ku, Osaka-shi, Osaka Sumitomo Chemical Co., Ltd. (72) Inventor Makoto Akita Kasuga, Konohana-ku, Osaka-shi, Osaka Naka 3-chome 1-98 Sumitomo Chemical Co., Ltd.

Claims (5)

[Claims] 1. A compound of the general formula (I) in the form of the free acid: [In the formula, R ₁ is a saturated or unsaturated fatty acid having 1 to 10 carbon atoms which may be substituted. A linear or branched alkylene group having a prime number of 1 to 10, R ₂ and R ₃ are each independently a saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group having a carbon number of 1 to 20 which may be substituted. It represents a group or forms, together with an adjacent nitrogen atom, a heterocycle which may further contain a nitrogen, oxygen or sulfur atom. Or an alkyl group having 1 to 6 carbon atoms, and the alkyl group is a heterocyclic-substituted alkyl group having a carbon atom of a heterocyclic ring containing at least one of nitrogen, oxygen or sulfur atom. Alternatively, m is a number from 0 to 3 (provided that R ₁ is an unsubstituted aliphatic hydrocarbon group, m is a number from 1 to 3), n is a number from 1 to 4, and m and n Is 1 to 5. ] The dioxazine pigment derivative shown by these. 2. A pigment composition comprising an organic pigment and the dioxazine pigment derivative represented by the general formula (I) according to claim 1. 3. The pigment composition according to claim 2, wherein the amount of the dioxazine pigment derivative is 0.5 to 30% by weight based on the organic pigment. 4. The pigment composition according to claim 2, wherein the organic pigment is a dioxazine-based pigment. 5. A method for improving the pigment suitability of an organic pigment, which comprises using the dioxazine pigment derivative according to claim 1.