DE2148347B2 - Process for the production of pigment preparations for the dope coloring of polyacrylonitrile - Google Patents

Description

It has long been known to add basic dyes to polyacrylonitrile fibers from aqueous solutions to dye. However, the use of pigments for this purpose wins due to the better fastness properties pigments and the more efficient and cheaper working methods for coloring more and more Meaning. It is necessary to disperse the pigments very finely in the spinning mass, so that a Optimum in terms of color strength and levelness of the color and technical problems such as clogging the filter or the spinneret and thread breaks due to coarse agglomerates are excluded. In German Patent 1,225,858 describes a process in which pigments are mixed with polyvinyl acetate or a copolymer or polymer mixture consisting predominantly of polyvinyl acetate Grind in a double trough kneader or in an attritor mill and then added to the spinning solutions will.

The use of polyvinyl acetate, which serves to stabilize the pigment dispersion and a Intended to prevent reagglomeration of the pigment, however, it can change the physical properties the fiber material lead.

Patent No. 62 443 of the Office for Invention and patent system in East Berlin describes a process for the production of pigment preparations, which do not contain any substances that impair the properties of the fiber. The pigment preparations are there by the separate or joint aqueous pearl milling of pigment and Polymer and subsequent co-flocculation obtained.

Another possibility for the production of powdery pigment preparations with the desired Its properties are the kneading of the pigment with a highly viscous paste made of polymer and solvent and then removing the solvent by evaporation.

For immediate consumption one can also use pigment dispersions by bead milling the pigment in the appropriate spinning solvent and stabilize the dispersion with polymer solution.

All the processes listed here for the production of pigment preparations or for fine distribution of pigments for polyacrylonitrile pulp dyeing have the disadvantage that they are technically due to the use of MahJ and kneading devices are very complex.

The present invention relates to a process for the production of pigment preparations for the spinning pulp dyeing of polyacrylonitrile and its modifications, which is characterized in that in the production or formation of the pigments, pure polyacrylonitrile or mixed polymers are produced after the dispersion polymerization process, as

ίο Carrier material clogs and the pigments in the usual Way worked up.

The production of such pigment preparations is done in such a way that one during the production or Forming the pigments these with the required

x5 amount of polyacrylonitrile pure or mixed polymer stirred and the pigment treated in this way worked up in the usual way. The polyacr »'! Nitrurein- or Copolymer is advantageously used in the form of its moist presscake, as it is obtained in the dispersion polymerization.

It is not necessary here to disperse the press cake, for. B. pearl milling, in a dispersion form to bring theeD particle size of the pigment fineness corresponds. If applicable, proves an additional use of small amounts of surface-active auxiliaries to achieve optimal Pigment preparations as advantageous. Both nonionic or alkoxylated alkylphenols are used for this purpose Fatty alcohols as well as special cationic or anionic auxiliaries are possible. With a number of Pigments, for the production or formation of which already require surfactants, are not necessary further addition of surface-active auxiliaries to the preparation.

Both pure polyacrylonitrile and copolymers, which in addition to Acrylonitrile also contain one or more other copolymerizable monoolefinic monomers. Suitable copolymerizable monoolefinic compounds are, for. B. in the German Auslegeschrift 1 292 310.

The amount of added carrier material is 20 to 80, preferably 30 to 60 percent by weight, based on on the finished preparation.

The time of preparation is different for the individual pigments, as it depends on the type of production or the formation is dependent. Azo pigments are prepared in such a way that the aqueous press cake of polyacrylonitrile is added before or after the coupling. With pigments that after the coupling reaction has ended, it is formed by heating to temperatures of up to 100 ° C. and / or above the polyacrylonitrile can also be added before or after heating. The additional The use of surface-active auxiliaries is not necessary here. The separation of the preparation takes place, as in the production of the pure pigment, by suction, washing and drying and subsequent grinding. Pigments that are subjected to salt grinding for the purpose of fine division, is prepared by adding water and the required polyacrylonitrile press cake as well as low Submit amounts of surface-active auxiliaries and introduce the pigment-salt mixture with stirring. The salary extract is expediently carried out at an elevated temperature (60 to 80 ° C.). The processing of the preparation takes place analogously to the azo pigment preparations described above.

In the case of naphthalenetetracarboxylic acid, dioxazine, quinine forms into threads, one obtains brilliant, fast-to-rubbing

acridon or phthalocyanine pigments, the colors are highly transparent.

Preparation also in the manufacturing or for- Similar good products are obtained when one has the

mation process, e.g. B. in the formation of the pigment PAC press cake before the precipitation of the Dome Compo-

grain or the desired crystal modification 5 nente into the mixture of water, glacial acetic acid and emulsified

submitted by heating in aqueous or solvent-based gator or the same after the precipitation to the

Systems or in the hydrolysis of salts or salt suspension of 2,5-dimethoxy-4-chloroacetoacetani-

like addition compounds as well as in the umlids and carries out the coupling reaction,
dissolving the pigments.

In this way, preparations with Ge io B e i s η i e 1 ^ are obtained

hold from 20 to 80%, preferably 40 to 70% P-

Pigment. 40.8 parts of 4-amino-benzamide are used in 1600 parts

The method is suitable for the preparation of water and 88.5 parts of hydrochloric acid (37%) dissolved and at

of inorganic and organic pigments. 12 ° C with 52 parts of sodium nitrite solution (40%) diazo-

which benefits in purely aqueous or organic solvents 15. 6 parts are added to the diazonium salt solution

containing aqueous systems, or glacial acetic acid, 13.6 parts of crystalline sodium acetate and

be formed, e.g. B. azo pigments, perylenetetra- 3 parts of an oxyethylated with 20 moles of ethylene oxide

carboxylic acid or naphthalenetetracarboxylic acid pig-stearyl alcohol.

ments, dioxazines, phthalocyanines, quinacridones, 99 parts of 2-oxynaphthoic acid-o-phenetidide

Indigoids, anthraquinone dyes, iron oxide as well as 20 in 2800 parts of water and 73.5 parts of sodium hydroxide solution

Titanium dioxide pigments. (33%) dissolved and at 13 to 15 ° C to the diazonium

The powdery preparations according to the invention allowed to run in saline solution. After the coupling reaction, which is particularly suitable for dyeing the spinning pulp, 272 parts of a PAC polyacrylonitrile fibers and their modifications are added. The presscake (36%) is added, the mixture is stirred for 1 hour at room temperature by simply stirring in at the respective temperature and the suspension is heated to 98 ° C. After the spinning solvent, for example dimethylformamide, dimethyl 1 to 2 hours of heating at 98 ° C., it is suctioned off , sulfoxide or dimethylacetamide, the residue being washed with water and the pigment particle size in the resulting suspension dried at 60 ° C. 240 parts of a 60 percent ion 0.02 His 2 μίτι is obtained. The advantage of this pigment-containing preparation with excellent performance over already known ones is that the 3 "dispersing properties.
arising during manufacture or formation. .
Primary grain of the pigment is protected and in the B e 1 s ρ 1 e 1 3
Preparation is retained, while in the case of the initially 50.4 parts of 5-nitro-2-amino-anisole, the pigment agglomerates formed by the isolation and 1200 parts of water and 118 parts of hydrochloric acid (37%) drying are stirred through 35 using the methods mentioned (40%) are digested again at 0 to 10 ⁰ C sodium 51.8 parts Elaborate methods nitrite solution.

have to. Thus, the pigment and the preparation are divided into 105.3 parts of 5- (2'-hydroxy-3-naphthoylamino) -

a work step without additional apparatus benzimidazolone in 500 parts of water by

Effort made. Addition of 109 parts of sodium hydroxide solution (33%) dissolved and

In the following examples, parts of Ge 40 mean with stirring at 5 ° C simultaneously with the diazonium

parts by weight and percent weight percent. salt solution in a mixture of 2700 parts of water,

146.4 parts of sodium hydroxide solution (33%), 90 parts of glacial acetic acid

Example 1 and 18 parts of a 10% aqueous emulsion

.101.2 parts of 3,3'-dichloro-4,4'-diamino-diphenyl be concentrate from 25 parts of a Halbsulfoden with about 250 parts of water and 195 parts of hydrochloric acid 45 chlorination of a hydrocarbon fraction with boiling acid (37%) stirred and with 138 parts of sodium limits 180 to 330 ° C obtained alkylsulfoamidonitrite solution (40%) diazotized at 0 to 10 ° C. 240 parts of sodium acetic acid and 75 parts of mineral oil 2,5-Dimethoxy-4-chloroacetoacetanilide are allowed to run in at 25 ° C.

in 800 parts of water and 109.2 parts of sodium hydroxide solution. After the coupling reaction has ended, the

(33%) dissolved and the solution while stirring at pH 5 to 50 with dilute sodium hydroxide solution to weak

14 ° C to a mixture of 1000 parts of water, acidified and the suspension in an autoclave

684 parts of glacial acetic acid and 4 parts of one with 20 moles heated to 130 ° C for 3 to 4 hours. After leaving

Ethylene oxide run in oxyethylated stearyl alcohol cool to 80 ° C with stirring 291 parts of a

calmly. In this suspension of the coupling component 37.5% PAC press cake entered and 1 hour

the solution of the diazotized 3,3'-di-55 is slowly added at 80.degree. You vacuum, wash it

chloro-4,4'-diamino-diphenyls and then 618 parts of a residue with water and dried at 60 ° C. It

aqueous press cake (36.7%) of polyacrylonitrile, 280 parts of a 60% pigment preparation

as obtained in the manufacture of the dispersion poly, which can be easily stirred into the

merization process is incurred (can be dispersed in the following spinning solvent,

play called PAC press cake). Stir 60. . . .

1 hour at room temperature and heated to 85 ° C. ^p

After 15 minutes of heating to 85 ° C, the mixture is filtered. 408 parts of a 36.7% -

the residue washed with water and at 60 ° C PAC press cake in 1600 parts of water and

dried. There are suspended in this way 567 parts of a 3 parts sodium naphthenate and under

yellow pigment preparation with 60% pigment obtained, 65 stirring 937.5 parts of one in a rolling or vibrating

the mixture of 16% perylene (3,4,

allows solvent to disperse. By introducing the 9,10) -tetracarboxylic acid-bis- (3 ', 5'-dimethyl-anilide) and

Dispersion in the spinning mass and then added 84% sodium sulfate. It will then on

80 ° C and stirred for about 30 minutes. The mixture is filtered through a suction filter and washed with ßtwa 10,000 parts of water at 80 ⁰ C until salt-free. The press cake is dried milled at 60 ⁰ C in a circulating air cabinet and on a pin mill. The powder obtained contains 50% pigment and can be easily and completely dispersed in the respective spinning solvent by simply stirring in with a dissolver.

Example 5

If the ground pigment-salt mixture in Example 4 is replaced by a corresponding sodium sulfate ground of 4,4'-7,7'-tetrachlorothioindigo and proceeding as in Example 4, one obtains a Pigment preparation with equally good application properties.

Example 6

160 parts of a 37.5% PAC press cake and 6 parts of one o.xyäthylierten with 15 moles of ethylene oxide Nonylphenols are stirred into about 3000 parts of water. 359 parts of the ethanol-moist potassium addition compound of 8,17-dioxo-bis-benzimidazo (2,1-b: 2 ', l'-i) benzo (lmn) -3,8) -phenanthroline (C.I, Vat Orange 7, No. 71105) with a pigment content of

ίο 39% are added to the suspension, the potassium addition compound hydrousizes to the pigment. The pH is then adjusted to 8 with 5N HCl and the mixture is then ^{stirred at a temperature of 60 °} C. for about 30 minutes. The batch is filtered off using a suction filter, washed neutral and dried in a circulating air cabinet at 60 ° C. By grinding on a pin mill, a powdery pigment preparation with a pigment content of 60 % is obtained.

Claims (2)

Patent claims: 1. Process for the production of pigment preparations for the dope coloring of Pure polyacrylonitrile and mixed polymers, characterized by the fact that at the production or formation of the pigments, pure polyacrylonitrile or mixed polymers according to the dispersion polymerization process, added as a carrier material and optionally surface-active auxiliaries and the Worked up pigments in the usual way. 2. Use of pigment preparations, produced according to claim 1, for dyeing spinning pulp of acrylic fibers or their modifications.