JPH06228454A - Production of beta-type dioxazine pigment - Google Patents

Abstract

PURPOSE:To efficiently obtain a pigment excellent in coloring power, gloss and producibility, useful for printing inks, coatings etc., by incorporating crude dioxazine with a specified amount of a specific dioxazine derivative in the presence of a grinding auxiliary such as an inorganic salt followed by conducting wet grinding. CONSTITUTION:The pigment can be obtained by incorporating (A) 100 pts.wt. of crude dioxazine with (B) 0.2-20 pts.wt. of a dioxazine derivative of the formula [Q is dioxazine residue; R1 and R2 are each (substituted) alkyl, etc.; m and n are each 1-4] in the presence of, as grinding auxiliary, an inorganic salt such as sodium chloride, and at least one kind of organic liquid selected from alcohols such as n-propyl alcohol and polyols such as ethylene glycol, followed by conducting grinding.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a β-type dioxazine pigment by wet-milling crude dioxazine.

[0002]

2. Description of the Related Art Crude dioxazine obtained by a general synthetic reaction in a high-boiling organic solvent does not satisfy the quality of a pigment in terms of color tone, tinting strength, luster and the like. for that reason,
Conventionally, the following pigmentation methods have been industrially adopted.
Wet milling of crude dioxazine in the presence of an inorganic salt and an organic solvent, a so-called solvent salt milling method (BP8
No. 31243, USP2718465, JP-A-58-17167, etc.), a reprecipitation method in which crude dioxazine is dissolved in an organic acid, and then fine crystals are precipitated by pouring it into a solvent having a low solubility (DP946560). ), After dissolving the crude dioxazine in an inorganic acid, it is poured into water to form an α-type metastable dioxazine, and subsequently treated with an organic solvent to transfer to a β-type stable dioxazine (Japanese Patent Publication No. 62-15103). ), Dry milling the crude dioxazine with a vibration mill, and then treating it with an organic solvent to transfer it to a β-type pigment (Japanese Patent Publication No. Sho 62-122).
No. 60). Among them, the solvent salt milling method is the most general pigmenting method, and the obtained pigment has the most excellent characteristics. However, it is disadvantageous in that the pigmentation time is long and that a great amount of heat energy is required for recovering the grinding aid and the organic solvent.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a method for producing a β-type dioxazine pigment having excellent suitability for various uses such as coloring power and gloss, and improved productivity which is the above-mentioned conventional drawback. It is a thing.

[0004]

The present invention is a method of wet-milling crude dioxazine with an organic liquid consisting of at least one inorganic salt and at least one of alcohols or polyols as a grinding aid, and the dioxazine derivative is converted to the above crude dioxazine. The present invention relates to a process for producing a β-type dioxazine pigment, which comprises adding 0.2 to 20 parts by weight to 100 parts by weight and milling.

The dioxazine derivative represented by the general formula (1) in the present invention is shown in Production Example 3 of JP-B-1-34268. That is, a water cake of a monochlorosulfonate of dioxazine obtained by using chlorosulfonic acid was added to ice water to reslurry, and then an amine component was added and stirred at 10 ° C to 20 ° C for 3 hours, followed by filtration and washing with water, Further, the hydrochloric acid generated with a dilute aqueous alkali solution is washed, filtered, washed with water, and dried. Representative amine components include biperidinomethyl, dimethylaminoethyl, diethylaminoethyl, dimethylaminopropyl, diethylaminopropyl, dibutylaminopropyl, piperidinoethyl, pipecolinenoethyl, morpholinoethyl, piperidinopropyl, pipericonopropyl, diethylaminohexyl. , Diethylaminoethoxypropyl, diethylaminobutyl, dimethylaminoamyl, N, N-methyl-lauryl-aminopropyl, 2-ethylhexylaminoethyl, stearylaminoethyl, oleylaminoethyl, p-dimethylaminoethylsulfamoylphenyl, p- Diethylaminoethylsulfamoylphenyl, p-dimethylaminopropylsulfamoylphenyl, p-diethylaminoethylcarpamoylphenyl Which are the amine of.

The phthaloimidomethyl group-containing dioxazine can be obtained, for example, as follows. That is, dioxazine violet was added to 15 times by weight polyphosphoric acid with stirring, N-methylolphthalimides were added at 80 ° C., the mixture was stirred at 120 ° C. for 5 hours, and then poured into water, filtered, washed with water, dry. Instead of N-methylolphthalimides, equimolar amounts of formaldehyde and phthalimides may be added.

The phthalimidomethyl group-containing dioxazine of the present invention is a compound represented by the following general formula (2) or a phthalimidomethyl group having a halogen atom, a nitro group, an amino group, a sulfone group, a carboxyl group or an alkyl group at any position of the benzene ring. It may be a compound substituted with a group or the like.

[Chemical 1] (In the formula, Q represents a dioxazine residue, and m represents an integer of 1 to 4.)

The dioxazine sulfonic acid alkylamine salt of the present invention is a compound represented by the following general formula (3). Q- ^{_{[SO 3 - N + (R 1}} , R 2, R 3, R 4) ] _m (3) [In the formula, Q is dioxazine residue, R ₁ to R ₄ is a hydrogen atom or a branched Optionally an alkyl group having 1 to 30 carbon atoms (however, all of R _{1 to} R ₄ are not hydrogen atoms), and m represents an integer of 1 to 4. ]

The compound of the general formula (3) can be obtained, for example, as follows. The water slurry of the dioxazine monochlorosulfonate obtained in the general formula (1) is hydrolyzed by making it weakly alkaline, then the amine component is added and the mixture is stirred at 70 ° C. for 1 hour, filtered, washed with water, and dried. To do. Typical examples of the amine component are so-called cationic surfactants such as aliphatic amines such as octylamine, laurylamine and coconut oil fatty acid modified amines, guanidine, alkylpyridinium halides and aromatic amines such as higher alkylaniline.

The crude dioxazine is obtained by heating p-benzoquinones and an aromatic amine in a high-boiling point organic solvent to cause condensation ring closure. In the present invention, crude dioxazine which has been subjected to dry pulverization with a vibration mill or the like after synthesis may be used.

In the present invention, the organic liquid includes alcohols such as n-propyl alcohol, n-butyl alcohol, isopropyl alcohol and isobutyl alcohol, or ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol. , Polyols such as polyethylene glycol and glycerin. The inorganic salt is preferably water-soluble such as sodium chloride, sodium sulfate and calcium chloride.

The amounts of organic liquid and inorganic salt based on 100 parts of crude dioxazine are preferably 100 to 300 parts and 500 to 1000 parts, respectively. In the present invention, the dioxazine derivative is used in an amount of 0.2 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of crude dioxazine. It is also preferable from the viewpoint of exerting it.

More specifically, the method for producing the β-type dioxazine pigment according to the present invention will be described. The crude dioxazine, the dioxazine derivative and the inorganic salt are charged into a kneader such as a kneader and uniformly mixed, and then alcohols or polyols are added. Gradually inject, grind the contents into a dough, grind, and after grinding, treat the contents with water or dilute aqueous acid to dissolve alcohols or polyols and inorganic salts, filter, wash with water, dry, Smash.

[0014]

【Example】

Production Example 1 15 parts of dioxazine was added to 100 parts of chlorosulfonic acid at 10 to 20 ° C., stirred at 60 to 70 ° C. for 3 hours, poured into 1000 parts of ice water, filtered and washed with water to obtain dioxazine monochloro. A sulfonated water cake was quantitatively obtained. The water cake of the chlorosulfonate was added to 300 parts of ice water to reslurry, 20 parts of N, N-dibutylaminopropylamine was added, and the mixture was stirred at 10 ° C to 20 ° C for 3 hours, filtered, and washed with water. Then 3000 of this water cake
22 parts of N, N-dibutylaminopropylsulfamoyldioxazine was obtained by adding 0.1 part of 0.1% aqueous sodium hydroxide solution, stirring for 1 hour, filtering, washing with water and drying.

Production Example 2 Pipecolinoethylamine was used in place of N, N-dibutylaminopropylamine of Production Example 1, and pipecoline ethylsulfamoyldioxazine 2 was similarly used.
I got one copy.

Production Example 3 220 parts of polyphosphoric acid was heated to 80 ° C., and 15 parts of crude dioxazine violet was added thereto and stirred to dissolve. Next, add 7 parts of N-methylol phthalimide and add 12 parts.
Stir at 0 ° C for 5 hours, then add to water, filter, wash with water,
After drying, 19 parts of phthalimidomethyldioxazine was obtained.

Production Example 4 The water cake of the dioxazine monochlorosulfonate obtained in Production Example 1 was added to 300 parts of water and reslurried, and sodium carbonate was added to adjust the pH to 10,
The mixture was stirred at 0 ° C for 2 hours. Add sodium carbonate to bring the pH back to 10 and add 7 parts of laurylamine acetate to give 7
After stirring at 0 ° C. for 1 hour, the mixture was filtered, washed with water, and dried to obtain 22 parts of dioxazinesulfonic acid laurylamine salt.

EXAMPLE 1 Crude dioxazine 100 was added to a 2000 liter kneader.
Parts, N, N-dibutylaminopropylsulfamoyldioxazine 5 parts, and crushed sodium chloride 700 parts were charged and uniformly mixed, and then diethylene glycol 130 was added.
Parts gradually and keep the contents dough-like, 70 ~ 8
Mill for 5 hours at 0 ° C. Continuously, the content is 0.5%
The mixture was placed in 4000 parts of hydrochloric acid, stirred at 80 ° C. for 60 minutes, filtered and washed with water, and the obtained wet cake was dried at 80 to 90 ° C. to obtain 102 parts of dioxazine pigment (a) having a specific surface area of 96 m ² / g. It was

Example 2 In the same manner as in Example 1 except that the dioxazine derivative in Example 1 was replaced with pipecolinoethylsulfamoyldioxazine, 102 parts of a dioxazine pigment (b) having a specific surface area of 96 m ² / g was obtained. .

Example 3 In the same manner as in Example 1 except that the dioxazine derivative in Example 1 was replaced with phthalimidomethyldioxazine,
102 parts of a dioxazine pigment (c) having a specific surface area of 95 m ² / g was obtained.

Example 4 In the same manner as in Example 1 except that the dioxazine derivative in Example 1 was replaced with a dioxazinesulfonic acid laurylamine salt, 102 parts of a dioxazine pigment (d) having a specific surface area of 93 m ² / g was obtained. .

COMPARATIVE EXAMPLE 1 N, N-dibutylaminopropylsulfamoyldioxazine in Example 1 was omitted, and the same as in Example 1 except that 97 parts of the dioxazine pigment (e) having a specific surface area of 79 m ² / g. Got

Example 5 Pigments (a) to (e) obtained in Examples 1 to 4 and Comparative Example 1 were added to a nitrocellulose varnish for gravure ink.
Were mixed so that the pigment content was 10%, and the gravure ink was adjusted. The results of evaluation of the viscosity, color tone, tinting strength and gloss are shown in Table 1, and compared with (e), and (a) ) To (d) were excellent in fluidity, sharpness of color tone, tinting strength and gloss.

[Table 1]

Example 6 An alkyd melamine-based baking coating varnish was prepared using Examples 1 to
4 and the pigments (a) to (e) obtained in Comparative Example 1 were blended so that the pigment content was 6%, and the paint was adjusted. The results were evaluated for viscosity, color tone, tinting strength and gloss. Is shown in Table 2, and compared with (e),
(D) was excellent in fluidity, sharpness of color tone, tinting strength and gloss.

[Table 2]

Example 7 Pigment (a) obtained in Examples 1 to 4 and Comparative Example 1 was added to a rosin-modified phenolic resin-based offset ink varnish.
~ (E) are mixed so that the pigment content is 20%, and the offset ink is adjusted. The results of evaluation of the viscosity, color tone, and tinting strength are shown in Table 3 and compared with (e). (A) to (d) were excellent in fluidity, sharpness of color tone and coloring power.

[Table 3]

Example 8 Example 1 was applied to a water-soluble acrylic gravure ink varnish.
~ 4 and the pigments (a) to (e) obtained in Comparative Example 1,
The gravure ink was prepared by mixing so that the pigment content was 16%, and the results of evaluation of the viscosity, color tone, tinting strength, and gloss are shown in Table 4, and compared with (e), (D) was excellent in fluidity, sharpness of color tone, tinting strength and gloss.

[Table 4]

[0027]

The dioxazine derivative during wet milling is
It is considered that the alcohols or the polyols improve the wetting to the crude pigment particles, lower the surface free energy of the pigment particles, and improve the grinding effect by the crystal growth preventing effect. Further, in addition to atomization of the pigment by improving the grinding effect, the fluidity improving effect of the dioxazine derivative in various applications improves suitability for color tone, coloring power, gloss and the like. Furthermore, the β-type dioxazine pigment obtained by the method of the present invention has a specific surface area of about 95 m ² / g, which is 80% of that obtained without using the dioxazine derivative.
It is about 20% larger than around m ² / g. Therefore, it is characterized in that the hue is clear, the coloring power is large, and the gloss is good in applications such as printing ink and paint.

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[Procedure amendment]

[Submission date] June 14, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0005

[Correction method] Change

[Correction content]

The dioxazine derivative represented by the general formula (1) in the present invention is shown in Production Example 3 of JP-B-1-34268. That is, a water cake of a monochlorosulfonate of dioxazine obtained by using chlorosulfonic acid was added to ice water to reslurry, and then an amine component was added and stirred at 10 ° C to 20 ° C for 3 hours, followed by filtration and washing with water, Further, the hydrochloric acid generated with a dilute aqueous alkali solution is washed, filtered, washed with water, and dried. Representative amine components include biperidinomethyl, dimethylaminoethyl, diethylaminoethyl, dimethylaminopropyl, diethylaminopropyl, dibutylaminopropyl, piperidinoethyl, pipecolinoethyl, morpholinoethyl, piperidinopropyl, pipecolinopropyl, diethylaminohexyl, Diethylaminoethoxypropyl, diethylaminobutyl, dimethylaminoamyl, N, N-methyl-lauryl-aminopropyl, 2-ethylhexylaminoethyl, stearylaminoethyl, oleylaminoethyl, p-dimethylaminoethylsulfamoylphenyl, p-diethylaminoethyl Sulfamoylphenyl, p-dimethylaminopropyl sulfamoylphenyl, p-diethylaminoethylcarbamoylphenyl Which are the amine of.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction content]

The phthalimidomethyl group-containing dioxazine can be obtained, for example, as follows. That is, dioxazine violet was added to 15 times by weight polyphosphoric acid with stirring, N-methylolphthalimides were added at 80 ° C., the mixture was stirred at 120 ° C. for 5 hours, and then poured into water, filtered, washed with water, dry. Instead of N-methylolphthalimides, equimolar amounts of formaldehyde and phthalimides may be added. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] May 20, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

Claims (3)

[Claims] 1. A method of wet-milling crude dioxane with an organic liquid comprising at least one inorganic salt as a milling aid and alcohols or polyols, wherein a dioxazine derivative represented by the following general formula (1) is used. A method for producing a β-type dioxazine pigment, which comprises adding 0.2 to 20 parts by weight to 100 parts by weight of the crude dioxazine and milling. Q- _{[SO 2 -NH (CH 2) m} N (R 1, R 2) ] _n (1) (In the formula, Q is dioxazine residues, R _1, R ₂ is a substituted or unsubstituted alkyl group , Or a heterocycle which may contain a nitrogen atom, an oxygen atom or a sulfur atom in R _{1 and} R ₂ , m represents an integer of 1 to 4, and n represents an integer of 1 to 4.) 2. A method of wet-milling crude dioxazine with an organic liquid consisting of at least one inorganic salt and at least one alcohol or polyol as a grinding aid, wherein 100 parts by weight of said dioxazine containing phthalimidomethyl group is used. A method for producing a β-type dioxazine pigment, which comprises adding 0.2 to 20 parts by weight to the above and milling. 3. A method of wet milling crude dioxazine with an organic liquid consisting of an inorganic salt as a milling aid and one or more of alcohols or polyols,
A process for producing a β-type dioxazine pigment, which comprises adding 0.2 to 20 parts by weight of dioxazine sulfonic acid alkylamine salt to 100 parts by weight of the crude dioxazine and milling.