DE1919120A1 - Process for uniform, streak-free dyeing of synthetic polyamide fiber material - Google Patents

Description

Patent attorneys Mönditn 2, Brauhaussfrab ^ U 1-3015

J.R. OtiSY A.O., Β ** · *., 3ohw * i »

Process for uniform, streak-free dyeing of synthetic polyamide fiber material

The present invention provides a method for uniform, streak-free dyeing of synthetic fiber material Polyamide of different dye affinity, as well as that according to these processes. colored fiber material. .. · "· ■

It has been found that fiber material made of synthetic polyamide with different dye affinity, such as textured polyamide fiber material, e.g. Banlon, can be dyed very evenly and without streaks if this fiber material is at a pH of 2 to 7 and at temperatures of 30 to 130 ⁰ C, preferably 40 to 95 ° C, with the aqueous solution of an auxiliary mixture which is composed of "a) at least one anion-active compound of the formula 1,

(SO ₃ X) _n

in the

R is an alkyl radical with 8 to 18 carbon atoms,

X is a cation and. .

η is a number from 1 to 2,

b) at least one cation-active, optionally quaternized Compound which has at least one basic nitrogen atom to which at least one polyglycol ether chain and at least one aliphatic radical with 10 to 18 carbon atoms are bonded, the molecule having 8 to 20 groupings of the formula II

- C - C - 0 - (II)

has, as well as optionally

009848/1890

• - ■

c) further customary in dyeing auxiliaries is pretreated, then at temperatures from 30 to 100 ⁰ C dissolved anionic dye and the color in the heat, preferably at the boil or at temperatures above ⁰ C are added to 100 under pressure, completes. ,

Anion-active compounds of the formula I are known per se and e.g. and 1,043,043 methods described can be prepared by appropriately substituted diphenyl ethers together with a sulfonating agent, such as sulfur trioxide or chlorosulfonic acid, in a solution of a polychlorinated aliphatic hydrocarbon converts or the diphenyl ether compound in a saturated aliphatic Hydrocarbon dissolves and then with the sulfonation agent brings in contact.

Have as particularly valuable in the process according to the invention anion-active compounds of the formula I have been found in which R is an alkyl radical with 9 to 12 carbon atoms., X is an alkali metal ion, like the lithium or potassium ion, but preferably the sodium ion, or the Aifmoniumion and η denotes the number 2. Disulfonated Compounds of the formula I, which are obtained by sulfonating 4-dodecyldlphenyl ether are particularly preferred.

The cation-active, optionally quaternized compounds b) which can be used in the process according to the invention are likewise known per se and can be prepared in a manner known per se, for example by reacting corresponding aliphatic amines, particularly long-chain primary alkylamines, their alkyl or alkenyl; has a remainder of 10 to 18 carbon atoms, such as dodecyl, octadecyl or octadecenylamine, or di- and triamines, such as dodecylpropylenediamine, octadecylethylenediamine and octadecyldiethylenetriamine, with alkylene oxides, for example propylene oxide, but above all with customary ethylene oxide, and, if appropriate, subsequent reaction with quaternary agents , such as methyl, ethyl or benzyl halides, diethyl sulfate and especially dimethyl sulfate. Cation-active compounds b) which can be used according to the invention can also be obtained by reacting the above-mentioned alkylamines with 1 to 2 equivalents of styrene oxide, 0

009848/1890 ..- "- ■

up to 2 equivalents of propylene oxide and 1 to 19 equivalents of ethylene lenoxyd and, if necessary, subsequent quaternization

«Considered products.

Cation-active compounds of the formula III are preferred,

R-,

R,

Tl h

CH -CH-O

CH-CH-O

I I

(CH ₂ -CH ₂ -O) _n - H (CH ₂ -CH ₂ -O) - H

in the
R ₁

an alkyl or alkenyl radical with 10 to 18 carbon atoms, especially the octadecenyl or octadecyl radical, R ~ a lower alkyl radical with 1 to 4 carbon atoms, especially the methyl group,
from Y-. and Y ₂ one Y is hydrogen and the other Y is hydrogen or

the phenyl radical,

m 0 or 1,. '. ,.

η and ρ whole numbers, the sum of which is 6 to 18, especially 11 to 18,

is, and

A is the equivalent of an anion, especially methosulfate ion, mean.

The sum of the coefficients η and ρ means an average value, and there are mixtures of analogous compounds with polyalkyleneoxy substituents of different chain lengths.

Anionic dyes suitable for the process according to the invention can belong to a wide variety of dye classes. For example it concerns the technically important dye classes of the azo, anthraquinone, phthalocyanine, nitro or Formazan dyes, which may also contain complex-bound metals such as copper, nickel, chromium or cobalt. Monoazo dyes are primarily suitable as azo dyes, for example those of the phenylazobenzene, phenylazo- * naphthalene, phenylazohydroxy- or aminopyrazole, phenylazoacyloacetylafylamide, or those of the analogous naphthylazo series, where

009848/1890

the aromatic nuclei can be suitably substituted. Further Dis- and polyazo dyes are also suitable. The azo dyes, which also include the formazan dyes, can be metallized, primarily with chromium or cobalt., but then also by copper or nickel, whereby 1 or 2 molecules of dye per metal atom are involved in the complex.

The pH of the dyebath is adjusted to the desired value by adding an acid such as acetic acid, formic acid or sulfuric acid Brought value. The pretreatment of the fiber material in the dyebath containing the auxiliaries according to the definition preferably lasts 5 to 30 minutes. The weight ratio of anion active to the cation-active compound is expediently Γ: Γ up to 10 rl.

After the pretreatment you can determine the acidity of the liquor Addition of an acid-binding agent, such as an alkali metal hydroxide, -carbonates or -hydragenscarbonates, of ammonium hydroxide, disodium- or dipotassium phosphate, sodium or potassium acetate, as well as hexamethylenetetramine to reduce.

An advantageous embodiment of the process according to the invention consists in the pretreatment at boiling temperature carries out, then the pre-dissolved dye is added and the dyeing is completed at the same temperature. After dyeing the dyed material is expediently rinsed in the usual way, if necessary, treated and dried to improve the wet fastness properties.

In general, the anion-active compounds are used in amounts of 0.1 to 5 percent by weight, based on the amount to be treated Fiber material, preferably in amounts of 0.2 to 2 percent by weight, the cation-active compounds in amounts of 0.01 to 2 Percent by weight, preferably in amounts of 0.05 to 0.5 percent by weight .

The dye bath, for example, can be used as a customary auxiliary in dyeing Urea, thiourea, thiodiethylene glycol or hydrophilic compounds with limited solubility in water, e.g. Butyl or benzyl alcohol.

U09848 / 1890

BATH ORIGINAL

-D-

Fiber-affine textile protection agents, which slit the textile material to be dyed, are also suitable as further additives.

As a fiber material made of synthetic polyamide, which according to the According to the process according to the invention, there are, for example, condensation products of hexamethylenediamine and adipic acid (Nylon 6.6) or sebacic acid (nylon 6.10) or mixed condensation products, e.g. from hexamethylenediamine, adipic acid and ε-caprolactam (Nylon 6.6 / 6), also the polymerization products from £ -caprolactam, known under the trade names Nylon 6, Perlon, Grilon or Enkalon, or from o-aminoundecanoic acid (nylon 11 or Rilsan). These fibers can be used at any processing stage, e.g. in the form of threads, yarns, Knitted and woven fabrics.

The method according to the invention is characterized in that also on streak-colored polyamide fiber material with per se poorly leveling dyes are obtained with extensive exhaustion of the dyebath level and streak-free dyeings.

In the examples below, the temperatures are given in degrees Celsius.

ORIGINAL

009848/1890

example 1

0.1 ml of 40% acetic acid is added to 200 ml of softened water and 0.1 g of a mixture consisting of 0.076 g of a 45 puff aqueous Solution of the disodium salt of dodecyldiphenylether disulfonic acid, 0.0075 g of a compound of the formula

Ί G)

3 _XV (CH ₂ CH ₂ O) _n H

2 2 'p

SO ₄ CH ₃

η + ρ = 10 and 0.0165 g of water.

In the resulting liquor, 5 g of knitted fabric made of textured polyamide 6 yarn are treated for 10 minutes at 40 °. Then you bet the liquor a solution of 0.025 g of the dye of the formula

NaO ₃ S 0.009 g of the dye of the formula

SO ₃ Na

and 0.007 g of the dye of the formula

V-NH-COCH,

in 10 g of water.

009848/1890

With constant movement of the textile material you increase the Temperature of the dyebath within 45 minutes to the boiling point and colors with gentle boiling for a further 45 minutes. On that the dyed material is rinsed warm and cold and dried.

In this way, a streak-free and level brown coloration is obtained.

If, in this example, the 0.076 g of the 457 _c aqueous solution of the sodium salt of dodecyldiphenylether disulfonic acid is replaced by the same amount of one of the anion-active compounds listed in the second column of Table I below and the rest of the procedure described in Example 1, similarly good ones are obtained Colorations on the said material.

Table I.

Example no. Anion-active compound 2 Diammonium salt of the dodecyl diphenyl ether
disulfonic acid 3 Sodium salt of Dodecyldiphenyläthennono-
sulfonic acid 4th Sodium salt of nonyldiphenylether disulfone
acid

BATH ORIGINAL

0098 4 8/1890

Example 5 ,

0.075 ml of 40% acetic acid are added to 400 ml of water at approx. 40 ° and 0.2 g of a mixture consisting of 0.152 g of a 45% aqueous solution of the disodium salt of dodecyldiphenylether disulfonic acid, 0.015 g of a compound of the formula

CH,

CH ₂ CHO (CH ₂ CH ₂ O) H

SO ₄ CH ₃

η + ρ - 18
and 0.033 g of water.

10 g of knitted fabric made of textured polyamide 6.6 yarn are added to the resulting liquor, and the temperature of the liquor is increased with constant ' Rapidly move the fabric to boiling point and cook for 30 minutes. Then 0.050 g of the dye is added to the liquor Formula,

Cl

0.018 g of the dye of the formula

SO ₃ Na

and 0.014 g of the dye of the formula

0 NH-CH (CH ₃ ) ₂

SO-Na

009 8 48/18 STO

pre-poured in | <Q g of water and cook for another 60 minutes until the Dye is attached to the textile material. Then it is rinsed warm and cold and dried. The resulting brown color is calm, doesn't matter and material-related differences in affinity are perfectly balanced,.

Without! The addition of the above auxiliary mixture you get at otherwise the same working method an uneven and strongly streaky coloring.

If you replace the 0.015 g of the compound in the above example formula

CH ₉ CHO (CH ₂ CH ₂ O) H

... η - + ρ * iß

by the same amount of one of those in the second column of the following The cation-active compounds listed in Table II and otherwise proceed as described in the previous example is obtained similarly on knitted fabrics made of textured polyamide 6.6 yarn calm and streak-free colors.

Table II

0eisp}? L No. - Cation-active compound η + p -10 ^ iCHeH ₂ PiH
CJ, _C H * ■
'■ ■■ ^ (CH ₉ CH ₉ O) H
² 4 P 8th Ί / (CH ₉ CHJ) H η * ρ * m 8th / (CH ₉ CH ₉ O) H.
CH -H ^l * ⁿ '"

009848/1890

ORIGINAL SUSPECTED

13191

continuation Example no. Ϊ Cation-active compound

^c iA ₅ f

'(CH ₀ CE ₅ O) H 2 2 ρ

η * ρ + ζ ~ 20

10

2 2η

IDH ₇ CHJ) H

11th

Vi η »βη" Λ

η + ρ- * 10

■ α ¹

η + ρ = 10

Example 1 $ .

Put muffs made of polyamide 6-> textured yarn in an open dyeing device (faekapparat). An approx. 40 ° warm liquor is separated, the, based on the textile material weight, 2.0% 40% acetic acid and contains 3.0% of the auxiliary mixture used in Example I, prepared (liquor ratio approx. I: 15). ;

This liquor is pumped into the dyeing device. Then, pan quickly increases the temperature of the liquor to 96 ° and treats the dyed material at this temperature for 30 minutes. The pH value of the dyebath is then increased to β.0 by adding aqueous ammonia solution. After the liquor is mixed well, sets .man, mi based the fabric weight, 0.5% of dye of the formula - _.----....;

ORIGINAL INSPECTED

pre-dissolved in 10 times the amount of water and stains for a further 60 minutes at 96 °. Then the red-colored goods are rinsed warm and cold and dried. '

A knitted fabric made from the yarn dyed in this way is free of stripes and uniform.

Example 14

0.5 g of the water in Example 5 is added to 300 ml of water at 70 ° auxiliary mixture used and 0.2 ml of 85% formic acid. In the resulting liquor, 10 g of tricot made of polyamide 6.6 textured yarn are pretreated for 15 minutes at 70 °. Then the Float 0.04 g of dye of the formula

2 Well

(' Vn = ν

dissolved in 4 ml of water, added and the liquor within 20 minutes heated to a boil. "Then it is stirred continuously the material to be dyed for one hour at cooker temperature, whereupon the brown color obtained is rinsed and dried.

The resulting coloration ^ ^Wt: \ tekirit borrowed "quieter than one without addition of the above aufgefünVtetf ^^ lr'smlit ^ ^ strength sdhes Restrained Ausfär ^ · environment.

009848/1890

Claims (9)

Claims 1. A method for uniform, streak-free dyeing of fiber material made of synthetic polyamide of different dye affinity, characterized in that the fiber material at a pH of 2 to 7 and at temperatures of 30 to 130 ⁰ C with the aqueous solution of an auxiliary mixture , the end a) at least one anionic compound of the formula I, (So ₃ X) _n ^(I) in the .' R is an alkyl radical with 8 to 18 carbon atoms, X is a cation and η is a number from 1 to 2, b) at least one cation-active, optionally quaternized Compound which has at least one basic nitrogen atom to which at least one polyglycol ether chain and at least one aliphatic radical with 10 to 18 carbon atoms are bonded, the molecule having 8 to 20 groupings of the formula II - C - C - 0 - (II) has, as well as optionally. c) there are other auxiliaries customary in dyeing, pretreated, then ^{dissolved anionic dye is added at temperatures of 30 to 100 ° C.} and the dyeing is completed in the heat. 2. The method according to claim 1, characterized by the use an anion-active compound of the formula I in which R is an alkyl radical with 9 to 12 carbon atoms, X is an alkali metal ion or the ammonium ion and η is the number 2. -, 3. The method according to claims 1 and 2, characterized by the Use of a cation-active compound of the formula III, 00984 8/1890 r ■ * in the YY Λ
* K®A ^ - ™ - ⁰ Zm - (CH ₂ -CH ₂ -O) _n - H R, CH-CH- _{O (CH 2} -CH ₂ -O) -H 1 * 2 (IH) R is an alkyl or alkenyl radical with 10 to 18 carbon atoms, R _{2 is} a lower alkyl radical with 1 to 4 carbon atoms, from Υ, and Y _{2 is} one Y hydrogen and the other Y hydrogen or the phenyl radical,
m 0 or 1, η and ρ integers, the voice of which is 6 to 18, and A mean the equivalent of an anion. 4. Process according to Claims 1 to 3, characterized by the use of anion-active and cation-active 'compound in one mutual weight ratio from 1: 1 to 10: 1. 5. Process according to Claims 4, characterized in that the pretreatment is carried out at a temperature between 40 and 95 ^° C. 6. The method according to claims 1 to 5, characterized in that the dyeing is carried out at boiling temperature. 7. The method according to claims 1 to 5, characterized in that the dyeing is carried out at temperatures above 100 ⁰ C under pressure. 8. The method according to claims 1 to 5 *, characterized in that the pretreatment is carried out at the boiling temperature, the pre-ItJsten dye is added therein and the dyeing is completed at the same temperature. 1S9Ö - 14 - 9. To gleichinässigen, streak-free dyeing of fiber material made of synthetic polyamide of different Farbstoffäffinität by pretreatment thereof at a pH from 2 to 7 and at temperatures of 30 to 13O ⁰ C, followed by the addition at temperatures of 30 to 100 ⁰ C of dissolved anionic Dye and completion of the dyeing in the heat, suitable aqueous solution of an auxiliary mixture, which is characterized in that it contains a) at least one anionic compound of the formula I, in the . R is an alkyl radical having 8 to 18 carbon atoms, X is a cation and η is a number from 1 to 2, b) at least one cation-active, optionally quaternized compound, which has at least one basic nitrogen atom to which at least one polyglycol ether chain and at least one aliphatic Rest having 10 to 18 carbon atoms are bonded, the molecule having 8 to 20 groupings of the formula II - C - G - 0 ■ - (II) has, as well as optionally c) contains other auxiliaries customary in dyeing. ORIGINAL INSPEOTID £ i§S§4§ / 1i§§