DE1494563C - Process for the production of solid pigment preparations for spin dyeing of polyamides. Eliminated from: 1266443 - Google Patents

Description

1 2

While fibers made from regenerated cellulose can be processed in organic solvents by grinding

The pigments in question are spun-dyed in a relatively simple manner in, for example, methanol,

can by adding aqueous suspensions of pigments- ethanol, isopropanol, acetone or dimethylform-

th of the likewise aqueous viscose or copper oxide amide can be obtained relatively easily in such a way that the pigment

ammonia solution, there is a fine dispersion of the polyamide 5 ment in the relevant solution

fiber has a significant difficulty in that it does not contain solvent. As mills they can

it is common to use foreign matter during the spinning process, in addition to the usual vibratory

the dyes or pigments or colloid mills required for coloring are used,

th to be introduced into the spinning melt. Another It is advisable to use at least part of the liquid

The difficulty is that it is desirable to use part of the polyamide,

would be, the coloring substances as soon as possible before Since most polyamides are sensitive to oxygen

to be added to the spinning process of the spinning mass, so that it is advisable to close with the exclusion of oxygen

to work from one color without too much malfunction. This is expediently done by displacement

another can be changed. the air present in the pressure vessel

For the actual coloring (with inclusion of nitrogen or, if desired, also with solution white, black and gray), preparations are desired, medium steam. Depending on the type and amount of the same fiber-forming solvent used as a carrier substance, temperatures of relatively little substance from which the polyamide fibers are made can be more than 100 ^° C. sufficient to completely dissolve the polyamide, but which advantageously dissolve a comparatively large amount of dye. If you work in a relatively concentrated, finely to colloidly distributed form. 20 trated approach, or if you wish to use the procedure in

Methods have already become known that can be completed in a short time, so it is advisable to do so

which allow the manufacture of such preparations. They cause higher temperatures.

necessary but complicated or not very difficult After the polyamide is completely in solution

Stable apparatus, such as kneaders or is gone, the mixture is cooled, whereby the

Roller mills around which the absolutely necessary fine 25 polyamide together with the pigment precipitates. It can be

Distribution of the dye in the spinning mass to be determined by microscopic examination that

workmanship. Surprisingly, the pigment in terms of degree of dispersion

It has now been found that solid pigment preparations cannot be treated in a closed vessel

for the spin dyeing of polyamides is changed, but that the pigment is now in

that can be achieved if fiber-forming polyamides are distributed with 30 polyamide in the same finely dispersed form

finely dispersed dispersions of pigments in with water, as they were previously in the organic dispersion

ser miscible organic solvents with high-passed.

at least 5 carbon atoms in the closed structure. The product obtained in this way can be used in any way

barrel to temperatures between 100 and 200 ⁰ C he is freed from the solvent of the reaction mixture

heat until the polyamide has dissolved, one on 35 den, z. B. by filtering off and evaporating the remaining

100 parts preparation used more than 10 parts pigment adhering solvent, or by distilling off

and then let the mixture cool down and the solvent alone.

Precipitated polyamide containing finely dispersed pigment It is particularly advantageous if the dispersion

freed from solvent. does not contain any foreign substance that has yet to be washed out

The fiber-forming polyamides used for this must be 4 °. The present proceedings thus lead in lying process the superpolyamides into consideration, easier way to pigment preparations, which for the as they are suitable for example from ε-caprolactam, from co-amino spin dyeing of polyamides. Included Undecanoic acid, from hexamethylenediamine and adipine, as already mentioned, is supposed to be the ratio of pigment acid or can be produced from analogous starting materials to polyamide so that the finished are. Mixed polyamides are also used in preparations containing at least 10% pigment. the Tracht, for example from ε-caprolactam and hexa-pigment content can easily be increased methylenediamine and adipic acid. One uses the values, e.g. B. 40 to 60% are brought, but It is advisable to observe polyamides in comminuted form, so that if the pigment is selected too high Cutlet. part of which fine distribution can be lost.

Both inorganic and 50 pigments can be used as pigments

Soot or titanium dioxide, cadmium yellow, mercadmium- sufficiently fine distribution, e.g. B. in powder form,

yellow, iron oxide, chromium oxide, or organic pig- so that grinding is usually possible with the finished preparation

ments z. B. copper phthalocyanine, highly chlorinated copper is unnecessary.

ferphthalocyanine, anthraquinone, azo and di- In the following examples, the parts mean

oxazine pigments, as well as colored hydrocarbons, such as 55 unless otherwise stated, parts by weight,

Rubicen, or colorless UV-absorbing pig- the percentages percentages by weight, and the temperatures

elements, such as optical brighteners, in question. . are given in degrees Celsius.

As a water-miscible organic solution

Medium with a maximum of 5 carbon atoms come from example L.

for example, low molecular weight alcohols, ketones, 60-75 parts of polyamide chips made from hexamethylenediamine

Lactones, lactams or bases, amides or sulfoxides and adipic acid and 450 parts of a methanolic

into consideration, e.g., methanol, ethanol, isopropyl alcohol dispersion containing 25 parts / 3-copper phthalocyanine

hol, acetone, γ-butyrolactone, dimethylformamide, di- in finest distribution, are slowly

methyl sulfoxide and pyridine. If desired, the vessel can be set to 165 to 170 ° with the exclusion of oxygen

mixtures of the liquids mentioned are also heated. After an hour it is left to cool

turn. These solvents are expediently in the polyamide with entrainment of the pigment in

practically anhydrous condition used. Form of a fine powder precipitates, which after the

The dispersions of pigments in the said filtering and drying a pigment content of

25%. The pigment is evenly distributed in the preparation and has the same fineness as in the methanolic dispersion.

Instead of ß-copper phthalocyanine you can use use the following pigments with the same success: chlorinated copper phthalocyanine, dipyrazole anthronyl, the linear quinacridone, cadmium yellow, carbon black, titanium dioxide, the pigment of the formula

CH _S

CO

CO-C

C _R H ₅

or the colored hydrocarbons Rubicene or Periflanthen.

B e i s ρ i e 1 2

Containing 75 parts of polyamide chips made from hexamethylenediamine and adipic acid and 450 parts of a suspension 425 parts of dimethylformamide and 25 parts of ^ -Kupferphthalocyanin in finest distribution, are slowly heated to 200 ° in a stirred pressure vessel with exclusion of oxygen. After an hour it will 'Allowed to cool, the polyamide precipitating in the form of a fine powder with the pigment being carried away.

ίο The preparation prepared according to Example 1 has a Pigment content of 25%.

Example 3

75 parts of polyamide chips made from ε-caprolactam and 450 parts of a methanolic dispersion containing 25 parts of finely divided indanthrone slowly heated to 165 to 170 ° in a stirred pressure vessel with exclusion of oxygen. After a Hour is left to cool, with the polyamide

so precipitates in the form of a fine powder with entrainment of the pigment. After filtering and drying, a preparation is obtained which has a pigment content of 25 ° / _0th

With the same success, a polyamide made from ω-aminoundecanoic acid can also be used instead of the polyamide as made from ε-caprolactam be used.

Instead of indanthrone, the dyes of the formulas

C ₂ H ₅ O ^

- COHN

Cl

N I

( Y -

Cl NHCO- / N

OC ₂ H ₅

H ₃ C

CH ₃

Cl f> - NHCOCH - _COCH3

OCH ₃

Ii

Cl CH ₃ CO-CH-CONH

Il
N

CONH - ;;

- NHOC

"Χ / OCH ₃

-Cl

'ΙΓ

Cl

/ -N ^s - N '

C - '.

or nigrosine black bases can be used. Example 4

75 parts of polyamide from hexamethylenediamine and adipic acid and 100 parts of a methanolic Suspension containing 25 parts of copper phthalocyanine finely divided and 75 parts of methanol, are slowly excluded in a stirred pressure vessel heated by oxygen to 165 to 170 °. After one hour, the mixture is left to cool while stirring, with the polyamide precipitates with entrainment of the pigment in the form of a fine powder which has the same properties as the powder produced according to Example 1 has.

Example 5

75 parts of polyamide chips made from ε-caprolactam and 500 parts of a methanolic dispersion containing 25 parts / I-copper phthalocyanine in extremely fine distribution, are slowly heated to 140 ° in a stirred pressure vessel with exclusion of oxygen. After 2 hours it will left to cool, whereby the polyamide precipitates out with entrainment of the pigment, which after filtering off and drying has a pigment content of 25%, ao

Claims (2)

Patent claims: 1. Process for the production of solid pigment preparations for spin dyeing of polyamides, characterized in that fiber-forming polyamides are mixed with finely dispersed dispersions of pigments in water-miscible organic solvents with a maximum of 5 carbon atoms (vlenstoffatomen in a closed vessel to temperatures "between 400 and 200 ° C heated until pxlasPoiyainidjgelöstihat to give 100 parts Präparatemeh ¥ t4i ^s; used io ;. (percentages by weight pigment t, and-thereafter the mixture is allowed to cool: umi · precipitated pigment preparation of the 'solvent removed' DAS. ' . 2. The method according to claim 1, characterized in that that one works with the exclusion of oxygen.