DE1120069B - Process for the production of structures colored in the mass with pigments from high-melting polymers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY
GERMAN Ml PATENT OFFICE

kl. 29 b 3/60

INTERNAT.KL. D 01 f

EDITORIAL NOTES 1120069

C 19380 IVc / 29b

REGISTRATION DATE: JULY 10, 1959

NOTICE
THE REGISTRATION
ANDOUTPUTE
EDITORIAL: DECEMBER 21, 1961

The dyeing of high-melting organic substances in bulk, such as polyamides or polyethylene terephthalates, makes such high demands on the thermal stability of the dyes to be used that inorganic pigments have hitherto mainly been used for this purpose. However, these have the Disadvantage of low color strength, in addition, the dyed fibers obtained with it are fairly cloudy hue. Efforts are therefore made to replace the inorganic pigments with organic ones. Until now However, only very few organic dyes are known which at the melting point of the mentioned Masses are not destroyed, for example copper phthalocyanine and chlorinated copper phthalocyanines.

It is therefore a valuable addition to the art that it has now been found that 1,9-pyrazole anthrones excellent for the production of mass-colored structures from high-melting Polymers such as polyamides, polyacrylonitrile ^ Polyethylene terephthalates or polyethylene, are suitable.

Suitable pyrazole anthrones for the present process there are both those with one and those with two anthrone cores (dipyrazole anthronyls) into consideration. Of the first-mentioned group, in particular, the compounds of the formula may be mentioned

N — N —R method of manufacture of structures made of high-melting polymers colored with pigments in the mass

Applicant: CIBA Aktiengesellschaft, Basel (Switzerland)

ίο Representative: Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse and Dipl.-Chem. Dr. rer. nat. E. Frhr. v. Pechmann, patent attorneys, Munich 9, Schweigerstr. 2

Claimed priority: ^X 5 Switzerland of July 11, 1958 (No. 61 632)

Dr. Hans Altermatt and Dr. Jacob Koch,

Basel (Switzerland) have been named as the inventor

isomeric dipyrazole anthronyls of the formulas

35

called, where R is a low molecular weight alkyl radical, for example a methyl, ethyl or isopropyl group means. The compounds of the formulas are also used

R ₁

N-NH

NH

and

45

wherein R ₁ and R _{3 are} hydrogen atoms or identical or 50 different alkyl, cycloalkyl or aralkyl radicals, for example methyl, ethyl or isopropyl groups. Of particular interest are the two mean.

109 750/543

All of the compounds are known and can be obtained by known methods. After the customary manufacturing processes, a mixture of the two isomers is always obtained, of which the red Dipyrazole anthronyls of the formula (1) are distinguished by high lightfastness. Since the same in organic Solvents and conc. Sulfuric acid are less soluble than the isomers of formula (2), leave them separate relatively easily. If you are satisfied with dyeings of lower light fastness, so you can also use the isomer mixtures.

The material to be colored is conveniently in the form of powder, grains or chips with the dry Dye powder mechanically mixed in such a way that the surface of these particles with a layer of the Dye is coated. The dye is expediently in finely divided form. To particularly good ones Results lead to the use of dye preparations consisting of a fine powder of the coloring material, which contains the dye in an even distribution. Such preparations can for example according to Belgian patent 567 953 by dispersing a pigment in the solution of a polyamide in formic acid and precipitation of the pigmented polyamide by adding water.

The plastic particles loaded with pigments are then melted and carried out according to known methods spun or otherwise deformed, for example into foils. The polymers can also by Addition of the dye before, during or immediately at the end of the polycondensation process of the monomers to be colored.

The dyeings obtained according to the process are characterized by high purity and excellent quality Lightfastness.

In the following examples, unless otherwise stated, the parts mean parts by weight, the percentages by weight and the temperatures are given in degrees Celsius.

C ₂ H ₅

N-N

N-N

(1) dye

Color of the dyed polyamide threads

R.

N-N

'Ij

N-N

R ₁ = R ₂ = CH ₃

RT> / "I TT

= K ₂ = i ~. ₂ ri ₅

R ₁ = R ₂ = -

R ₁ = R ₂ = CH ₂ CH ₂ CH ₂ CH ₃

R ₁ = R ₂ = CH ₂ - CH ₂ - O - CH ₃

R ₁ = CH ₃ , R ₂ = -CH (CH ₃ ) ₂

/ CH ₃
R ₁ = - CH: _v

^X CH ₃

Red red red red red red

R ₂ =

R ₁ = -CH ₂ -CH

R ₂ = - CH ₂

Red

Red

40

example 1

99 parts of polyamide from hexamethylenediamine and adipic acid are in the form of chips with a Part of the finely divided dye of the formula

Ν — Ν

N-N

45

R ₃ = R ₄ = H
R ₃ = R ₄ = CH ₃

Yellow orange

55

N-N -R

breaded dry. These chips are spun as usual, for example in the grate spinning process, at 290 to 295 ° _r. The thread obtained in this way is dyed ruby red, and the dyeing has excellent light and wet fastness.

In the table below are a number of others Called dyes, soft polyamide according to the above process in the shades given in column II to dye.

v-

R = -CH ₃

= CH (CH ₃ ) ₂

Yellow yellow yellow

5 dye colour
the colored
polyamide
threads N-NH {' Y ι'' ^X -
ί j ' yellow O N-NH I i
I ■ ί
■ I olive \ \
O NH ₂

Example 2

99 parts of polyethylene terephthalate chips are mixed with one part of finely divided dye of the formula (1) breaded dry. These chips are melted by the usual methods at 285 ° and the Spun mass. This gives a polyester thread which is colored ruby red and whose coloring is excellent Possesses fastnesses.

Example 3

99 parts of polyethylene chips are mixed dry with 1 part of finely divided dye of the formula (1). In an injection molding machine moldings are produced at 180 °, which are colored red and their coloring has excellent fastness properties.

Example 4

15 parts of polyamide from hexamethylenediamine and adipic acid become formic acid in 100 parts by volume (84.5%) dissolved, then an aqueous dispersion containing 3.75 parts of the dye used in Example 1, added in 25 parts of water and the mixture with vigorous stirring in a thin stream Poured parts of water. The red precipitate is filtered off, washed neutral and dried. That so ίο The red preparation obtained contains 20% dye, which is homogeneously distributed in the preparation.

96 parts of polyamide from hexamethylenediamine and

Adipic acid are breaded with 4 parts of this preparation according to the information in Example 1 and peeled off. A ruby red dyeing of excellent light and wet fastness is obtained.

Claims (2)

PATENT CLAIMS: 1. A process for the production of structures colored with pigments in the mass, such as threads, fibers or films, from high-melting polymers, characterized in that the melt of the polymers when shaped have colored pigments of water-solubilizing groups free of pyrazole anthrones. 2. The method according to claim 1, characterized by the use of the pyrazolanthrone formula N-N N-N wherein R ₁ and R _{2 are} hydrogen atoms or identical or different alkyl, cycloalkyl or aralkyl radicals. © 109 750/543 12.61