DE1769449B - Process for removing dyeings and prints with non-fiber-reactive disperse dyes on hydrophobic fibers - Google Patents

Description

The present invention relates to a process for stripping off non-fiber-reactive disperse dyes !! Dyeings or prints produced on hydrophobic fibers, which is characterized in that the dyed fibers are mixed with nonionic compounds of the polyglycol ether series, which have a water solubility of at least 3% at 20 C and contain a hydrophobic radical with 12 to 26 carbon atoms per polyglycol ether chain Amount of at least 0.5% (based on the weight of the dyed fibers) treated ^{at temperatures above 160: C.}

As colored hydrophobic, fully synthetic or semi-synthetic organic fibers come over 160 C resistant fibers into consideration: z. B. aromatic Polyester fibers, e.g. B. from polyethylene terephthalate or from condensation products of terephthalic acid and 1,4-bis (hydroxymethyl) cyclohexane. Polyamide fibers, e.g. B. from the specialist body in S.F.V., 15 (1960), pp. 8/9, listed types of nylon. Polyurethane fibers e.g. 3. from the condensation products of 1,4-butanediol and hexamethylene diisocyanate: polyacrylonitrile fibers z. B. made of pure polyacrylonitrile or from copolymers of acrylonitrile and vinyl chloride, vinyl acetate or vinyl pyridine: cellulose polyester fibers z. B. from cellulose triacetate or cellulose tri- (acetate propionate). The colored fibers can in the form of individual threads or fibers, tapes or fabrics, alone or in admixture with one another or with animal fibers such as wool, e.g. B. polyester wool, with vegetable fibers, z. B. Cotton or linen, with regenerated cellulose fibers. z. B. viscose rayon or with so-called "Polynosic" fibers (fibers made from regenerated cellulose with high wet and tear strength) are present.

The dyeings and prints to be peeled off can have been colored with any non-fiber-reactive disperse dyes. z. B. with those described in the literature listed on page 2 of Swiss Patent 386 982, or with alkali-unstable disperse dyes, e.g. from British Patent 843 643, 841 927, 800 200 or 606 008.

As nonionic compounds of the polyglycolithic compounds come z. B. in question: the addition products of butylene oxide. Propylene oxide or preferably Ethylene oxide to a hydrophobic compound with 12 to 26 carbon atoms. The hydrophobic Compound can be an aliphatic acid. z. B. a fatty acid having 12 to 22 carbon atoms. or an amide derivative of such an acid, an alcohol, an amine or a thiol compound. whereby both the saturated and the unsaturated and / or branched types come into question, e.g. B. an alcohol. a synthetic alcohol, an Fcttamin. a synthetic mono- or diamine or a synthetic one Thiol compound with 12 to 22 carbon atoms, or a monoalkyl or dialkyl phenol or naphthol having a total of 12 to 26 carbon atoms or an oil containing hydroxyl groups. like castor oil. being. Such connections are e.g. in the book by N. Schoenfeldt. Surface active Ethylene oxide adducts (1959).

The number of ethylene oxide groups must min- ^fi 5 dcstens be so great that the polyglycol ether at 20 "C in water to mindes'.tns 3% is soluble. Eg with a hydrophobic compound such as lauryl alcohol, the number of Älhylenoxidgruppen at least about 5 to 6, for nonylphenol, for example, about 8. The maximum number is, for example, about 100 to 120 per hydrophobic radical ) or a carboxyalkoxy group

(HOOC-CH ₂ -O-, HOOC-CH ₂ -CI - O-)

be replaced.

The following are examples of suitable polyglycol ethers:

Pole suitable as examples
the following are mentioned:

A lauryl octaalycol ether,

B tridecyl-fO - CH ₄ I ₈ - OH.

C 2,6,8-trimethyl-4-nonyl (OCH ₄ ) ,, - OH.

D CetyH OC H ₄ J ₁ -, - OH.

OCHOH

y ₄ P
F stearyHO - CH ₄ ), ₅ - OH, G octylphenyl- (OCH ₄ ), ₀ - OH, H octylphenyHO - CHj ₁₀ - OH. I nonylphenyl- (OCH ₄ ), ₅ -OH. K Nonylphenyl- (OCH ₄ ) ₉ _ _IO - OH. L di (isoamyl) phenyl (OCH ₄ ) p - OH, M dioctyl phenyl (OCH ₄ ) ₄₀ - OH. N-nonyl-phenyl- (OCH ₄₎ -, ₀ - OH. O UC ₁₇ -H ₃₅ -CO-NH ₂ + 12 (CH ₄ O). P tert -dodecyl SH + 10 (C ₂ H ₄ O). Q 01CyI- (OCH ₄ J ₁₅ -O-CH ₂ -COOH as sodium salt.

In polyglycol ether B, tridecyl means the Resl of the tetramethymonanol obtained from tetrapropylene by the oxo synthesis.

Preferred polyglycol ethers are the addition products of about 8 to 100 moles of ethylene oxide and unsaturated alcohols such as oleyl alcohol. or ar unsaturated acids such as oleic acid, e.g. B. the oleyl polyglycol ethers with 20 to 60 C ₂ H ₄ O groups. how

Oleyl- (OC ₂ H ₄ ) ₂₅ -OH, (R) oleyl- (OC ₂ H ₄ I ₄₀ -OH (| and olcyl- (OC ₂ H ₄ ) _h0 - OH (?) And the oleoyl poly glycol ethers with 8 to 50 C ₂ H ₄ O groups, such as oils OyI- (OC ₂ H ₄ ) ,, - OH (D) and the addition products of 25 to 200 mol of ethylene oxide with 1 mo of castor oil. Ζ. Β Castor oil + 32 (C ₂ H ₄ O) (v). Castor oil +40 (C ₂ H ₄ O) (W) castor oil +46 (C ₂ H ₄₀ ) (X) to castor oil + HO (CjH ₄ O) (Y). These castor oil derivatives

as triglycerides each contain three hydrophobic unsaturated radicals with 18 carbon atoms each and ji three PolyglyVoliitherkcltcn with 8 to about 70 Ethy each lcnoxide groups.

The amount of non-ionic compounds or compounds, as they are mostly mixtures refers to the weight of the colored egg hydrophobic fibers, which has to be taken into account for mixed fabrics and also for prints; you amount 0.5 to 40%. advantageously 1.0 to 35% of the weight de colored fibers.

You can z. B. the dyed fibers with an aqueous solution of the nonionic compound at low or slightly elevated temperatures, ζ. Ε at 15 to 5CTC, plop or sprinkle and mi or without intermediate drying at temperature

i 769

over 160. ζ. B. at ISO up to 230 C. treat. Not only dilute but also concentrated aqueous solutions of the nonionic compounds and even the nonionic compounds themselves are suitable for spraying, provided they are sufficiently thin. In this second embodiment, the amount of nonionic compounds is advantageously 2.0 to 20% of the weight of the dyed fibers. The concentrations in the padding liquor vary in inverse proportion to the squeeze effect. The duration of treatment is z. B. at least 1 minute, preferably 2 to 5 minutes, at 180 to 230 ^c C.

In order to remove the peeled off dyes from the fiber, the dyeings treated in this way can unc Prints still need to be rinsed and dried. "

The lightening effect can be achieved by varying the amount and type of non-ionic compounds as well as by varying the temperature and the duration, so that it is possible any desired degree of lightening, e.g. B. from 5 to practically 100 "ή to achieve.

In order to achieve a degree of lightening of, for example, 5 to 50 °, small amounts are generally sufficient, for example up to about 5%. of the polyglycol ethers to be used, while door degrees of heating from 70 to practically 100%, the required amounts are 5 to 40%. In amounts of about 15 to 40%, preferred oleyl polyglycol ethers and castor oil polyglycol ethers are able to completely decolorize the fibers by the thermosol process at 180 to 230.degree.

The Polyglykoläthjr can be aHein or also mixed with mi; throw other surface-active compounds used; suitable such Connections are e.g. B. polyethylene glycols. like the addition products of z. B. 3 to 14 moles of ethylene oxide of ethylene glycol (like the polyethylene glycols with an average molecular weight of 200. ΓΌ0. 400 and 600); also anionic compounds, such as aromatic sulfonic acids, e.g. B. alkylarylsulfonic acids (Mono- and polyalkylbenzenesulfonic acids. Mono- and polyalkylnaphthalene-sulfonic acids. Preferably those with a total of 18 to 21 carbon atoms, as well as dinaphthylmethanedisulphonic acid: others suitable anionic compounds are the condensation products, e.g. B. the invention 4.s Used polyglycol ethers with the salts of HaIojzcnulcan carboxylic acids like haloacetic acids. .; - Halopropionic acids or of alkene carboxylic acids. how Acrylic acid. The anionic compounds mentioned are preferably used as alkali metal or ammonium salts used.

Those carrying a terminal carboxyalkyl group Polyglycol ethers can partially or wholly contain the polyglycol ethers used in accordance with the present invention replace, as they have the same Abzich-Uiikung as mentioned before show. The polyethylene glycols and the courtiers of aromatic sulfonic acids, which in themselves show no or only a slight pull-off effect, are advantageously added in such amounts, that they are about 15 to 35%, preferably 20 to 30%. make up the mixture; be there just as good results are obtained as with the same amount of the polyglycol ethers to be used according to the invention alone. In some cases the results are even improved; h .. the peeled color is whiter than a color peeled off with the polyglycol ether alone, or the effect occurs faster one. z. B. after only one minute instead of after 2 minutes if you start the treatment at 180 to 230 C.

The peeled off dyeings and prints can be used directly as such, or they can over-colored with the same or with other disperse dyes and so in depth of color or in Correct the hue. Also faulty, e.g. B. uneven, colorations can be corrected by they are first strongly lightened and then re-colored to the desired color depth.

Compared to the use of carriers (so-called carriers), the peeling method according to the invention has some advantages:

1. relatively small amounts of the non-ionic compounds are sufficient to produce a significant To create a lightening effect,

2. The non-ionic compounds are practically non-volatile and remain practically odorless even at the highest application temperatures (difference to the liquid and volatile carriers such as polychlorobenzenes, methyl anthranilate, etc.).

3. They do not affect the lightfastness of the dyeings and prints removed (difference to 2- or 4-hydroxy-l, l'-diphenyl),

4. A simple wash with water is sufficient to put them together with the removed dye to be removed completely (difference to 1,1'-diphenyl. 2-hydroxy- and 4-hydroxy-1,1'-diphenyl).

Compared to the peeling process described in German Patent 742 424, the inventive Method has the unexpected advantage that with a significantly shorter peeling time and, mostly with dry heating, better peeling results can be achieved, vobci it continuously can be carried out.

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

example 1

A 1% strength is impregnated with the dye 2 - bromine - 4.6 - dinitro - 2 '- acetylamino - 4' - N, N - bis ^ (, i'-acctoxyüthyli-amino-S'-ethoxy-], l'-azobcnzol (T) on a jacket material made of polyethylene terephthalate / cotton (67/33 intimate mixture) made coloring with a solution of 50 g! of the PoIv glycol ether I. squeezes it to a weight increase of 70% over dry weight, dries it hot 130 and treated them for 2 minutes at 220 with hot air on a pin tensioning frame. On that the fabric is only washed with hot water and dried on the wide washing machine. Opposite to of the original navy blue color, the degree of lightening is about 50%. The brightened one Coloring can now be done without any disadvantage with any conventional disperse dye Exhaust method or the thermosol method over-colored and corrected in the color tone or in the color depth.

Example 2

One with 0.8% of a brominated 1,5-diamino-4.K-dihydroxyanthraquinone (T) on a poplin

1

Pure polyethylene terephthalate produced dyeing with an aqueous liquor containing 20 g 1 of the polyglycol ether E padded, squeezed to a weight gain of 60%, dried and during Heated to 215 minutes for 2 '/, minutes. The one with hot water S The dye that has been washed and dried on a hot flue has a degree of lightening of about 70% compared to the original blue color and can be over-colored without difficulty. Replaces one obtains the polyglycol ether E by one of the polyglycol ethers A to D and F to P. also a clear brightening.

Example 3

A dye made with 1 "η of the red dye 4-nitro-4'-N-ethyl- is Ν-, ι'-hydroxyäthylamino-ll '-azobenzene (T) on cellulose triacetate fabric is done with a solution of 200 g of 1 of the polyglycol ether V at 18 up to 20%, squeezed off to a dry weight increase of 4% and heated for one minute to 200. After oiling with hot and cold water and drying, the coloration is 80% lighter.

Good lightening effects are obtained as well. when dyeing with the dyes l- (4'-Hydroxyphcnylazo) - 4 - phenylazobenzene (4). 1 - Amino-2 - [2 '- (2 "- ethoxyethoxy) - ethoxy] - 4 - hydroxy - anthraehinone (Rat) (T) or I.S-dihydroxy ^ .S-diamino-2- (4'-ethoxyphenyI) -anthraquinone (6) in treated in the manner described above or one of the polyglycol ethers W. X or Y used.

Example 4

Fine with 1% of the dye (T) on polyamide-66-Gcwcbc Coloring produced is treated in the manner described in Example 3 'game 3.

Practically 100% of the dye is removed.

The dyeing is etched onto polyamide 66 fabric by staining on polyamide 6 fabric and carrying out the treatment for one minute at 180. so the drawdown effect is about 90%. d. h .. only 10% of the original remains on the fabric amount of dye present.

A very good repelling effect is also obtained. if you dye with the yellow-brown dye 2,6-dichloro-4-nitro-4'-N -,; - cyanoethyl-N -,; - acelo \\ ethyl - amino - 1.1 '- azobenzene (s) or with the dyes I - (4-hydroxyphenyla / o) - 3.6-dimethoxy-4-phcnylazobcnzol (orange) <J). (?) or (6) insert.

Example 5

Fine with 1% of the navy blue dye 2-ßroni-4.6-dinitro-2'-acctylamino-4'-N.N-bis - (, .'-acctoxyiithyl) -amino-5'-ethoxy-1.1 '-azobenzene® on polyethylcntrephthalate gcwcbc is obtained at room tcmpcratu. with an aqueous solution containing 200 g / l of the polyglycol ether dinonylphynyl-dodecaglycol ether (Z), impregnated, squeezed off to a liquor pick-up of about 70% and treated for 2 minutes at 220 ". The hot and Dyeing, rinsed with cold water and dried, shows a degree of lightening of about 75 to 80%; d. i.e., remain from the original amount of dye about 20 to 25% back on the polyester fabric.

If one treats a dyeing with the same dye on that by condensation in the same way of terephthalic acid with 1,4-bis (hydroxymethy1) -

449,

cyclohexane obtained polyester fiber, a very similar result is obtained.

The following polyglycol ethers show very similar behavior:

Dinonylphenyl pentadecaglycol ether .. Λ Λ

Stearic acid ι-16 C ₃ H ₄ O \ B

Stearic acid 1- 26 C ₂ H ₄ OAC

Stearic acid amide +22 CiFl ₄ OAD

Stearic acid amide +29.5 C ₂ H ₄ O Λ Ε

Polyglycol ether H
Polyglycol ether K
Polyglycol ether L.

while the polyglycol ethers

Stearic acid +6.2 CH ₄ OAF

Stearic acid + 10 C ₂ H ₄ OAG

Polyglycol ether C
Polyglycol ether I.

have a lightening effect vu.i about 60%, the Polyglycol ether

oleic acid +6.3 CH ₄ OAH

Stearic acid +40 C ₂ H ₄ OAI

Polyglycol ether M
Polyglycol ether N

show a thinning effect of about 90%, d. h .. the peeled off colorations only have one Strength of about 10% of the original dyeings, and in the case of the following polyglycol ethers the lightening effects in brackets (as a percentage of the original color) are observed:

Polyglycol ether O 97%

Polyglycol ether Q 98%

Very similar results are obtained by staining polyester uses which have been made with the following dyes:

2-nitro-1,1'-diphenylamine-4-sulfonic acid phylamide (Yellow),

2-chloro-4-nitro-4'-N - /, '- cyanoethyl-N- / i'-acctoxyethylamino-1,1 '-azobenzene (scarlet red).

2-cyano-4-nitro-4'-N- _/ ; -cyanoethyl-N- _/ ; -acctoxyethylamino-1,1 '-azobenzene (red).

I-Cyano- ^ nitro- ^ - N-Uthyl-N-cyanoethylamino-1.1 '-azobenzene (bluish tinge).

2-chloro-4-nitro-2'-acetylamino-4'-N, N-bis - (, i'-acetoxyethyl) -amino-1.1 '-azobenzene (ruby red).

101

Examples 6 to

% dyeings of the dye (9) on Polyäthylcntercphthalatgewcben are impregnated with aqueous solutions at 18 to 20, the increasing amounts the polyglycol ethers listed below or a mixture of a polyglycol ether and a contain other surface-active bodies, squeezed to 70% liquor uptake and to 220 ° heated, then rinsed thoroughly and dried.

example

Polyglycol ethers crowd additive crowd time of g'l Heating 125 Minutes 200 AH 2 AH 2

Peelable

continuation

example

13th
14th
15th
16
17th
18th
19th
20th

'
34
35
36
37
38
39
40
41
42
43
44
■ 46 47

Polvgkkolather

AK

AK

AL

AL

AL

AL

AL

AT THE

AT THE

R.
R.
R.
R.
R.
R.
R.
R.
R.
R.
R.
R.
R.
R.
R.
R.
R.
R.
R.
R.
R.
R.
R.
R.
R.
R.
R.
R.
Q
0

Quantity ...... f .. ¹ ..

125 200 125 200 125 200 200 200 200 100 200 50 100 200 200 200 60 90 112 112 112

112 112 112 135 135 135 135 135 135 157 157 157 157 157 157 180 180 180 180 180 180 200 150 150 150 150 210 210 160 160

additive

lull of the crowd I Krhilzcns ' ^Λ

I I I

II

II

II

III

III

50 50 50

50 50 50

50 50 50

50 50 50 50 50 50 50 50

Minutes

2 2 2 2 2 2 2 2

2 2 2 I.

2 2 2 1

2 3

2 3 I.

2 3 1

2 3 1 2

3 1

2 3 1

elTect

97

99

95

99

95

99

99

99

95

Sf

90

60

90

97

65

95

65

95

55

95

98 to

60

95

98

65

98

99

70

97

99

75

99 100

80

99 100

90

99 100

90

99 100 100

99

100

> 99

100

95 100

95

98

IS

example

68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101

kolä'ther
crowd
h ^gl 8th crowd ³ olygly \ """
200 additive 50 L. 100 I. 100 B. 100 rv 100 B. 125 IV V 125 V 125 - - V 125 17.5 V 125 Ml 17.5 V 125 III 17.5 V 150 St. V 150 __ ._. V 150 - - V 150 - 17.5 V 150 III 17.5 V 150 III 17.5 V 175 III - V 175 - - V 175 - - V 175 - 17.5 V 175 III 17.5 V 175 III 17.5 V 200 III - V 200 - - V 200 - - V 200 - 17.5 V 200 III 17.5 V 200 III 17.5 V 225 III - V 22S - - V 250 - - V 250 - - V 275 - - V 275 - - V 300 - - V 300 - - V 150 - 50 V 150 III 50 V III

S S T T V V

200 200 200 200 150 150

V VI

50 50

3 duration of
Heating
Minutes Deduction
effect 2 90 I. 97 2 98 up to 99 1 80 2 98 3 99 1 95 2 98 3 98 up to 99 1 80 2 98 3 99 1 96 2 99 3 99 1 95 2 > 99 3 > 99 1 97 2 99 3 99 1 96 2 100 3 100 I. 98 2 99 3 100 1 99 2 100 I. 99 2 100 1 100 2 100 1 100 2 100 I. 99 2 100 1 99 2 100 1 80 2 100 2 99 99

The polyglycol ethers used are AK. AL and AM correspond to the formulas

oleic acid + 10 C ₇ H ₄ O AK

Oleylamine + 8 C ₂ H ₄ O AL

3-stearylaminopropylamine + 90 C ₂ H ₄ O AM

The following surface-active compounds (referred to in the table as additives) were used in a mixture with a polyglycol ether.

109551/473

9 pounds

! 54

I sodium dinaphthylmethanedisulphonic acid.
II Sodium dodecylbenzenesulfonate.

III Sodium dibutylnaphthalenesulfonic acid.

IV tridecyl- (OC ₂ Hjg - 0 - CH ₂ - COONa., V polyethylene glycol with a molecular weight of 300.

VI polyethylene glycol with a molecular weight of 600.

In II the dodecyl radical is branched.

In IV, tridecyl means the remainder of the tetrapropylene tetramethylnonanol obtained by the oxo synthesis.

Example 102

A 1% coloration of the dye (Ts (T) on polyethylene terephthalate fabric with a solution containing 125 g / l of polyglycol ether W, it squeezes to a liquor pick-up of 70%. treats 2 minutes at 220 ". rinses them with hot and cold water and dry them. The peeling effect is 98%. If you increase the polyglycol ether content to 200 g / l. this increases the pull-off effect to 100%.

One color peeled off with the yellow dye of the formula: 98 to 99% peel effect at 200g
Polyglycol ether W.

Claims (5)

Claims: NHCOO-C2H4 QH, N-CH = C CN CN is deducted 100% with 125 g / l of the polyglycol ether W. With dye mixtures, e.g. B. colorings produced with the mixture of 66% of the dye (K 17% of the dye (Π and 17% of the dye (f)) are also very good brown 1. A process for stripping off dyeings or prints produced with non-fiber-reactive disperse dyes on hydrophobic fibers, characterized in that nonionic compounds of the polyglycol ether series are applied to the dyed fibers. which have a water solubility of at least 3% at 20'C and each polyglycol ether chain contain a hydrophobic radical with 12 to 26 carbon atoms, in an amount of at least 0.5% (based on the weight of the dyed fibers) in a thin liquid form or an aqueous solution and then the Fibers treated with or without intermediate drying at temperatures above 160 ^{r C.} 2. The method according to claim 1, characterized in that the nonionic compounds the series of polyglycol ethers mixed with the condensation products of such polyglycol ethers with the salts of haloacetic acids, / f-halopropionic acids or acrylic acid used. 3. The method according to claim 1, characterized in that the nonionic compounds the series of polyglycol ethers mixed with the condensation products of ethylene glycol used with 3 to 14 moles of ethylene oxide. 4. The method according to claim 1, characterized in that the treatment at Performs temperatures of 180 to 230 ° C for at least one minute. 5. The method according to claim 1, characterized in that the nonionic compounds of the polyglycol ether series used in a mixture with salts of aromatic sulfonic acids.