DE2215691A1 - Method of dyeing in organic solvents - Google Patents

Description

Patent attorneys

Dipl.-Ing. P. Wirth

Dr. V. Schmied-Kowarzik

Dip !. ! \ a. G, D;:; -.; - erib.srg

D. P. VAJ -.held, Dr. D. Gude \

C Ftcii'itui UtA., Gr. Eschenheimer sir. 39.

Case 150-3135 / Z, Basel, Switzerland

Method of dyeing in organic solvents

The subject of the invention is a further development of the method according to main patent No, patent application No. P. 21.03.764-9. ... (Case 150-5135), for production of dyeings with dispersions of organic dyes in liquid organic compounds.

It has been found that you can get high quality dyeings on textile fibers or threads or the textile materials made from them made of synthetic polyamides or basic modified, hydrophobic, high molecular weight, organic substances are obtained when these are mixed with dispersions of .acid

Dyes or reactive dyes in liquid organic 209843/1112

Case

Compounds, in the presence of alkyd resins, which are dissolved in the liquid organic compounds , impregnated and the impregnations obtained are fixed

Among the substrates made of synthetic polyamides are in particular fiber fleece, threads, woven or knitted fabrics made of synthetic polyamides ( e.g. nylon 6, nylon 7 *, nylon 10, nylon 11, nylon 66, nylon 76, nylon 226, nylon 6IO or nylon 6/66) to understand · Known base modified substances are, for example, base modified polypropylene or base modified polyacrylonitrile, or base modified copolymeric polyacrylonitrile.

The "Color Index" (Second Edition, 1956, Vol. 1, pages 1001-1404) provides information on acidic dyes. Among reactive dyes, in particular dyes are understood here to mean the molecule at least one group of the formula

Shark

N N

Hal

Hal-

Il I

N N

I.
Z

or

Hal

209843/1112

Case

where Hal is fluorine, chlorine or bromine

Y is hydrogen, fluorine or chlorine and Z is an optionally substituted amino

group or an alkoxy group,

contains, but also, for example, compounds with one or more substituents of the formula

-SO ₂ -CH ₂ -CH ₂ -O-SO ₅ H, -SO ₂ -CH = CH ₂ ,

-SO ₂ -NH-CH ₂ -CH ₂ -O-SO H,

-SO ₂ -NH-CH ₂ -CH ₂ -X,

-CO-CH = CH ₀ , -CO-C = CH ₀ ,

d. 1 d

Shark

-CO-C = CH ₀ , -CO-CH = CH-X, 1 c

CH ₃

-CO-C = CH-CH, -CO-CH = C-CH ^,

x x

-CO-C = CH-X, -CO-CH = CH-CH ₀ -X, CH,

-CO-CH ₂ -X, -CO-CH ₂ -CH ₂ -X or -CO- (JiH-CH -X,

x ² 209843/1112

- 4 - Case

wherein χ is chlorine or bromine.

These dyes can contain carboxylic acid and / or sulfonic acid groups and be metallized

In the present case, the alkyd resins only serve as dispersants. When grinding the dyes with the organic compounds in the absence of alkyd resins, the production is of dispersions not possible, the dyes precipitate immediately.

Mixtures that are up to 30 percent by weight are preferably ground Contain dye. The dispersions obtained in this way remain for a very long time and even at elevated levels Temperatures are stable and are generally increased by adding more organic liquid before dyeing approx. 0.01 to 4 percent by weight of pure dye diluted.

The alkyd resins required for the production of durable dispersions are for example in "Encyclopedia of Polymer Science and Technology "(John Wiley and Sons, London, Sidney, 1964), Vol. 1, pp 663-734. These Alkyd resins are oligomeric polyesters made from organic polyhydroxy compounds with mainly polybasic ones Acids. The acid number is due to an excess

209843/1112

Polyalcohols are kept small, i.e. below about 25. Examples of suitable polyalcohols are glycerol, pentaerythritol, trimethylolpropane and trimethylolethane. Examples of suitable acids are ortho-, iso- or terephthalic acid and other aromatic and in some cases saturated dicarboxylic acids. Most of these alkyd resins also contain triglycerides in the form of non-drying vegetable oils, in which case the resins are often used dissolved in xylene because of their high viscosity. Quick-drying oils with an iodine number above about 100, for example alkyd resins containing linseed oil, can lead to an undesirable finishing effect on the substrate; Organic liquids are preferably those in which the dyes are not noticeably soluble at room temperature, that is to say less than 5 g / l, preferably less than 2 g / l. Its boiling point should be between about 80 ° and 170 ⁰ C. Examples of such liquids are: saturated aliphatic hydrocarbons, aromatic hydrocarbons or unsaturated hydrocarbons (2,2,5-trimethylhexane, xylene, vinylbenzene), higher alcohols (cyclohexanol, isobutylcarbinol or trimethylene glycol), higher ethers (iso-

209843/1 1 12

amyl ether, ethoxytoluene, furan or 1,1-diethoxyethane), higher-boiling compounds that contain one or more carbonyl groups (butanol, acetophenone), acids (propionic acid), higher-boiling esters (propyl acetate, butyl formate or, preferably, halogenated hydrocarbons (chlorobenzenes, Tetrachlorethylene, trichlorethylene, tetrachlorethylene, Trichlorotrifluoroethane), compounds that contain one or more nitrogen atoms (nitroethane, acetonitrile, Methacrylonitrile, dimethylformamide, triethylamine or pyridine), but also compounds containing sulfur or metal contain (thiophene, thiodiethylene glycol) or compounds that are a combination of the elements or groups mentioned contain.

The dispersions are prepared by grinding the dyes with the liquid organic compounds in which the alkyd resins are dissolved. The grinding is usually carried out in ball or sand mills; the suitable apparatus is generally known to the person skilled in the art. Milling is carried out until the size of the dye particles is between about 0.01 to 10 ^ i or, preferably, between 0.1 to 5 ji .

209843/1112

It is of course advantageous to use the dyes in pure form, that is to say without the dyes only for dyeing, padding or Printing in an aqueous medium cheap coupage means to use. This can do the otherwise necessary washing and Rinsing of the dyeings and prints are omitted in many cases.

The amount of alkyd resin used is generally between 0.05 and 5, preferably between 0.2 and 2 parts by weight per part by weight of dye. Larger amounts of alkyd resins have no coloring advantages.

It can be advantageous to use other auxiliaries in the preparation of the dispersions, e.g. alkylene oxide adducts, especially those of the general formula

HO- (CH ₂ CH ₂ O) _a - (CHCH ₂ O) _b - (CHgCHgO) _c -H,

where a is an integer from 5 to 50, b is an integer from 2 to 50 and c is an integer from 5 to 50,

whose molecular weight is between about 500 and 5OOO, to add.

209843/1112

The dyeing is done from so-called short or long liquor. When dyeing in a long liquor one turns in general less than 10 g of pure (uncoupled) dye per liter, when dyeing from a short liquor up to about 40 g per liter.

When dyeing from a long liquor, this is optionally pretreated Substrate brought into the already heated to dyeing temperature or into the cold liquor. In the latter In this case, the bath is then made according to a specific program, similar to exhaust dyeing from an aqueous dispersion or solution, brought to dyeing temperature. The fixing always takes place during the dyeing process, which generally lasts between 10 minutes and 2 hours, where, because of the increased exhaust or fixing speed, higher dyeing temperatures, if necessary by using pressure vessels, preference will be given. Short fleets are mostly in continuous operation Dyeing devices applied. The substrate, usually a textile web, textile yarn or textile thread, is so during a short time, about 10 seconds to 5 minutes, passed through the heated, short liquor and then in one with superheated or saturated steam or with hot

209843/1112

Air-filled chamber fixed. The fixation takes about 30 seconds to about 5 minutes, depending on the chamber temperature. Both the steam and the steam come as steam organic liquid in the bath, as well as another suitable solvent vapor or water vapor into consideration. This treatment, too, can optionally be carried out under increased pressure.

In some cases it can be advantageous to add small amounts to the dyebaths (about 2 to 20 parts per 1000 parts Solvent) of a neutral, inert acid derivative, e.g. an amide, in particular one which is different from a carboxylic acid with 1 to 3 carbon atoms derived amide, for example dimethylformamide or dimethylacetamide or Add phosphoric acid tri- (dimethylamide).

When dyeing with reactive dyes that. responsive Contain halogen, hydrogen halide is released. Should it be necessary to use this acid in order to avoid possible fiber damage To prevent this, the dye liquor can, as already stated, an acid amide or, if appropriate, to bind an amine which is soluble in the corresponding organic liquid is added ,.

209843/11 12

Those obtained in the dyeing process according to the invention The dyeings are in no way inferior to the dyeings obtained in the usual way in terms of fastness and brilliance The levelness of the colorations is even better in many cases. For the dyeing method of the present invention, the following can be used Advantages compared to the dyeing process from aqueous solution or dispersion are mentioned:

No water consumption, therefore no wastewater pollution;

The heat of evaporation of organic liquids is lower than that of water, thus saving energy;

The time required for staining and fixing is generally less.

Compared to the dyeing process with water-in-oil or oil-in-water emulsions The method according to the invention is characterized, among other things, by the easy possibility of recovery of organic liquids.

Since it is usually not necessary with the method according to the invention is to work with solvent mixtures, which leads Recovery to pure solvents by simple distillation.

209843/1112

- 11 - Case 150-3133 /%

In the following examples, parts are parts by weight and percentages are percentages by weight. The temperatures are given in degrees Celsius.

example

1 part of the dye of the formula

is mixed in 4 parts of perchlorethylene with 1 part of a mixture of 45 parts of alkyd resin, 27 * 3 parts of ethyl glycol acetate and 27.3 parts of ethyl acetate, ground in a ball mill to a fine dispersion and mixed with 10 parts of perchlorethylene. The alkyd resin used is a phthalic acid glycerol ester with 43.5 % phthalic anhydride and 33 % coconut oil content. The acid number is between 6 and 10.

209843/1112

- 12 - Case 150-3133 / Ζ,

In a liquor consisting of 3 parts of the dispersion thus obtained, 15 parts of a 7 percent solution of ethyl cellulose in perchlorethylene, 1 part of dirnethylacetamide and 80 parts of perchlorethylene, a nylon 6 filament fabric is produced. padded, squeezed off to 70% dry weight increase, dried, fixed for 1 minute at 210 ° in hot air, in perchlorethylene and, after drying, rinsed in water. A level yellow dyeing with excellent fastness properties is obtained in this way.

Practically the same coloring results are obtained if, instead of the alkyd resin used with 33 % coconut oil content, one with 76 % glycerol phthalate and 24 % peanut oil, 82 % glycerol phthalate and 18 % castor oil or 69 % pentaerythritol phthalate and 31 % coconut oil is used.

Instead of the dye indicated above, it is also possible to use the dyes of the following formulas:

2-methyl-4- (2'-chloro-4'-methylaminotriazinyl-6 * -amino) -4 ^lt -chlor-l, ^lt -azobenzene (yellow),

4- (2 ', 4 ■, 5' -trichloropyrimidyl-6 '-amino) -3 "-me thoxynaphthyll, 1" -azonaphthalene (Red),

209843/1112

- 13 -. Case 150-3133 / Z ^

4- ^(2! 4 ', ^5-difluoro-f -chlorpyrimidyl ^{6-t-N-methylamino)} -2 ^{tl methyl-4-chloro-n} l, l "azobenzene (yellow),

l- (2 ^l , 4 ^t -dichloropyrimidyl-5 ^l «-carbonylamino) -3-methoxy-4-dimethylaminoanthraquinone (violet),

1- (Benzthiazolyl-2-mercapto) -5-vinyl-carbonylaminoanthraquinone (blue),

1- (3'-Methy1-4'-chloroacetylaminophenylazo) -4-hydroxynaphthalene (reddish yellow),

1- (Naphthyl-2'-azo) -2-methyl-4- (3 ^{! I} -vinylsulfonylbenzoylamino) -benzene (orange),

4- (2 '-methylsulfonyl-4 "-chloro-5" -methylpyrimidyl-6-amino). ^-3-methoxy-l l, l ^t azobenzene (yellow),

NaSO

OCH ₃

ο6ήΓ JL ν ' ³ Λ _ν /

j (yellow) ^C 6 ^H 5

Cl

2 O 9 Ö 4 Ί / IM? (Red).

example Part of the formula dye

Case 150-3133 / 2

O NH

SO ₂ NHCH ₂ CH ₂ OH

is mixed in 2 parts of perchlorethylene with 1 part of a mixture of 50 parts of alkyd resin (with 68 % glycerol phthalate and 32 % coconut oil) and 50 parts of xylene, ground in a sand mill to a fine dispersion and mixed with 6 parts of perchlorethylene.

A nylon 6 taffeta fabric is impregnated with a liquor consisting of 5 parts of the dispersion obtained in this way and 95 parts of perchlorethylene, squeezed off to 70 % dry weight increase , dried at 120 °, fixed with hot air for 1 minute at 210 ° , with perchlorethylene, for Removal of the alkyd resin, rinsed and dried.

2 Π i) B 4 I / 1 I 1 2

Case

After washing as is customary in practice, a blue dyeing with excellent wash, light and rubbing fastness properties is obtained.

Instead of the above-mentioned alkyd resin, the alkyd resins mentioned in the first example can be used, the staining results are practically identical.

According to the working instructions of Example 2, the following dyes can also be colored:

SO oh oh

= N- / 1 VT / - *

0 NH

Cl ρ

5 ^ « ^v iU CH- * Λ

209843/1112

5 F.

Case

S O..II

NO ₀

The] '\: rbutoi'fe d (-r i'ol ^ onden Pornieln can also be colored according to the specifications of Br · 3 game 2. After drying at 120 °, however, in superheated steam for 1 minute or approx. l8o °, fixed.

30 Well

Cl

NH -in

Cl Cl

OH

CH.,

(yellow),

(yellow),

0 «8 4 3 / ί 1 1 2

Case 150-113'i / '- /. J

CH
\

JO Well

HO- / C?
N - /

H ₅ C ₂ -CO-OC N _ CH-

(Red),

(Red),

)) - CH ₂ -N

SO. N / A

CH

= 1 N-CH

0-

(greenish blue)

209i43 / 1tt2

(bluish red),

0 NIIC, IL
6th

O NH-CH,

SO-Al Ά

(Mau),

OH

HO-C-CH, N-N-C-CO-NH-CH ₂ CH

1: 2 Co complex

OHH O

N = N- (Oi

So ₂ -NH-CH ₂ CH ₂ CH ₂ OCH

1: 2 Co complex

(bordeaux)

OH

OH

_N = K

NHCOCH-;

CH.

1 ;? Cr complex

(Brown).

Claims (2)

- 19 - 'Case P a t e η. t a η s ρ r ü c Ii e 1. Further training in the process according to the main patent No,,, Patent err /, ι dung NoJ βλ . ⁽ V. \ .'S - '. Vi (Ca :; c ISO- yi'X-) for dyeing textile fibers or threads or other hot (eatellton textile materials made of hydrophobic, high-molecular or, -; r-ni.see substances, characterized in that one; Juix: tread - from synthetic polyamides or basic r.iodif j.siertan, hydrophobic, hoohm ·. lekulercn, ο rc an ir.-el κ-, η ntoficn with dispersions of acidic; Farüstovfon or Ji 'a'.: tivfarl ■ · »Btofl 'en in liquid rrftanisehen compounds, in Gt - 0; in the presence of A13: ydharKen itnpräfjjni.ort and fixes the received Iinprä ^ nierungen -t " 2. l) ie ßeinä .'- c rntjritaiiEjv ^ uch 1e / fcal * fjnei. Colorations and Prints « The IVitentaBwlt ? O98 4 3/11 '2
BATH ORiGINAL.