DE1920357A1 - Process for dyeing textile material with different dye affinities from synthetic polyamide fibers - Google Patents

Description

Basel, Switzerland

Patent attorneys

Dr. W. Schalk, Dipl.-Ing. P. Wirth

Dipl.-Ing. G. Dannenberg

Dr. V. Schmied-Kowarzik

Dr. P. Wcinhold, Dr. D. Gudel

6 Frankfurt / M., Gr. Eschenheimer Str. 39

Process for dyeing textile material with different dye affinity from synthetic polyamide fibers.

It is known that textile material has different dye affinity dyeing synthetic polyamide fibers streak-free by doing the same thing before dyeing a pH value from 3 to 4 and temperatures of preferably 70 ° treated to 80 ° with an aqueous solution, which a sulfated, higher molecular weight fatty acid or a sulfated one Esters of the same, optionally in a mixture with oxethylated amines, which have a higher molecular weight fatty residue own.

In this known dyeing process, the pretreatment bath cooled to 50 ° after the pretreatment and only then added the dye and an acid-binding agent, after which it is colored at the boil. This known method therefore requires a relatively large amount of energy and time.

It has been shown that following the procedure described below Invention on the said material strip-

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can get free and particularly beautiful coloring without that you have to cool the pretreatment bath before adding the dye needs.

The present invention now relates to a process for level dyeing textile material of different. Dye affinity from synthetic polyamide fibers with anionic dyes, which synthetic polyamides normally dye streaky, characterized in that the dyed material is at a pH of J> to 5 and at Temperatures from 70 ° to 13> 0 ° C with the aqueous solution of a surface-active compound containing sulfuric acid ester or sulfonic acid groups

pretreated and on the treatment bath, which still contains the textile material, without cooling it, an optionally quaternized, at least one aliphatic, saturated or unsaturated, optionally heteroatom-containing radical with 12 to ^ O carbon atoms, at least one basic nitrogen atom and at least 20-200 ethenoxy groups containing basic compound and the material the color, and the dyes are added and then under the above temperatures and pH values colors. The dye can be added to the bath at the same time as or after the basic compound.

. 909887/1536 ..

As surface-active, sulfuric acid ester or sulfonic acid groups containing compounds are embossed: alkylarylsulfonic acids, alkanesulfonic acids, amides from higher-

molecular fatty acids and aminoalkyl sulfonic acids, sulfated, higher molecular weight fatty acids or their esters.

As sulfated, higher molecular weight fatty acids or their Esters come into question sulfation products of the oil resp.

Elaidic acid or ricinoleic acid and their alkyl esters, for example the methyl, ethyl, propyl or butyl esters, or the glycerol ester of these fatty acids, for example castor oil. Sulphation products which have a high degree of sulphation, preferably those with a degree of sulphation of more than 70 %, are particularly suitable.Compounds which contain at least one basic nitrogen atom and at least 20-200 ethenoxy groups in the molecule are, for example, those of the following formulas I-IV.

- alkylene

m-1

(D

^. co

Alkylene

9 0933 77

-X-

- alkylene

m-1

(in)

N - alkylene - N

(IV)

wherein R and R ₁

one aliphatic, saturated or unsaturated, optionally heteroatoms, such as O, S or -CO-NH-, containing radical with 12 to JO, preferably ΐβ to 2k , carbon atoms,

an aliphatic saturated or unsaturated, optionally containing heteroatoms Remainder with 1 to JO carbon atoms,.

909887/153 6 BATH ORIGINAL

each of Α., A ₂ and A ~ is a polyethenoxy chain, where the

The sum of the ethenoxy groups for the three chains is at least 20 and at most 200,

each of A ^, and A ₁ - a polyethylene oxide chain, where the sum

the ethenoxy groups for the two chains is at least 20 and at most 200,

at least one of the symbols X ,, Xp and X- one by one

Alkyl or hydroxyalkyl radical with 1 to 20 carbon atoms or by a phenyl radical monosubstituted or by a polymethylene chain or by 2 optionally substituted alkyl radicals, each with 1 to 18 Carbon atoms disubstituted ethylene group,

and the other two a simple bond or a through

an alkyl · or hydroxyalkyl radical having 1 to 20 carbon atoms or by a Phenyl radical monosubstituted or optionally by a polymethylene chain or by 2 substituted alkyl radicals with 1 to 18 carbon atoms each disubstituted Ethylene group,

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η 1, 2, 5, 4, 5 or 6

and - m is 1, 2, 3, 4, 5, 6 or 7

and the alkylene radical has 2 or 3 carbon atoms contains.

Such and other suitable compounds are e.g. Swiss patents 317-900, 353.013, 363.ΟΟ6, 373.012, 388.903, 401.900 and 409.991.

Special mention should be made of the

Addition products of ethylene oxide or of propylene oxide and ethylene oxide with higher molecular weight mono- or polyamines such as Oleyl, cetyl, stearyl and behenylaniinoethylamine or -propylamine and its quaternization products. The oxethylated amines can be used as such or in the form their quaternization products are used. Suitable quaternizing agents are e.g. dimethyl sulfate, diethyl sulfate, Methyl chloride, benzyl chloride, methyl or ethyl benzenesulfonate, methyl or ethyl para-methylbenzenesulfonate, etc. Depending on the amount of the quaternizing agent, one can only. one, several or all basic nitrogen atoms quater- '■■ kidneys.

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The pretreatment is carried out in a liquor, which by acetic acid, formic acid or sulfuric acid on one pH has been adjusted from 3 to 5 and can be around 10 to Take 30 minutes.

The amount of surfactant, sulfuric acid ester or

Compound containing sulfonic acid groups may, for example, be 0.5

up to 5 "Ι» des

Be the paser weight; in the. However, generally suffice about 0.7 to 2%, of the basic compound, one can also 0.5 to 5 $> of Fasergewichtesj but preferably using about 0.7 to 1.5%. " These quantities always relate to the 100 % active substance. The dyeing may be carried out at the boil or at temperatures above 100 ⁰ C under pressure.

Dyes that normally streaky dyeing textile material made of synthetic polyamide fibers are, for example, the 1: 2 chromium or 1: 2 cobalt complex dyes, such as the 1: 2 chromium or 1: 2 cobalt complex compound of 1- (2'- Hydroxy 5'-methylaminosulfonylphenylazo) -2-hydroxynaphthalene, the so-called fulling dyes, such as 1,4-bis (4 ^l - (4 ^ll -chlorophenoxy) -2'-sulfophenylamino) anthraquinone or l-hydroxy-2- (2 ^1- phenoxy-5'-chlorophenylazo) -8- (4 "-methyl-phenylsulfonylamino) -naphthalene-3,6-disulfonic acid, and the acidic full-color dyes such as l-amino-2-bromo-4- [) \ ' -methylphenylamino) anthraquinone-2-sulfonic acid. 9 0 9 8 8 7/1536

These deliver according to the process according to the invention. streak-free dyeings with good light and wet fastness.

In the following examples, the parts are parts by weight, the percentages are percentages by weight and those indicated therein Temperature degrees Celsius degrees.

Example 1 .

100 parts of a streaky coloring. G.ev / ehes made of nylon-66 are treated for 30 minutes in 4000 parts of a boiling aqueous liquor adjusted to pH 4-5 with acetic acid, which contains y, J> parts of an 80% sulphated ricinus oil with an active substance content of J> 0 fo , contains. After that, the liquor without cooling down. 1.4 parts of the adduct of 100 moles of ethylene oxide and 1 mole of behenylamino-3-propylamine were added. 1 part of the dye Acid Blue 127 C ^ 1135), Color Index II 1 ⁽ J56, is then added to the boiling liquor and stained in it for 1 hour. The result is a streak-free, level, wash, sweat and lye-like blue coloration .

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- Of -

Instead of the sulphated castor oil you can use

Use the same amount of 95 % sulfated oleic acid or 1.8 parts of 75% sodium dibutylnaphthalenesulfonate or 1.4 parts of 98% sodium dodecylbenzenesulfonate with similar success.

You also get similar effects if you instead of the oxethylated behenylaminopropylamine the same amount an addition product of 30 mol of ethylene oxide 1 mole of monocetyl or monostearylaminoethylaminoethylamine or 1 mole of a mixture of fatty amines with 18-22 Carbon atoms im.Alkylrest or the same amount of an adduct of 20 moles of ethylene oxide and 1 mole of coconut amine or 25-80 mol of ethylene oxide on 1 mol of oleyl, cetyl,

1 mol, or stearylamine or from 90-120 mol of ethylene oxide to ^ eicosyl, docosyl or tetracosylamine, or from 80-200 mol of ethylene oxide to 1 mol of hexadecyl, octadecyl, eicosyl, docosyl or tetracosyl-3-aminopropylamine, used. According to the same Pärbemethode also obtained very good staining with the 1: 2 cobalt complex compound of l- (2'-hydroxy-3 ¹ -acetylamino-5'-methylphenylazo) -2-hydroxy-5 ~ nitrobenzene or l- (2 ^l -Hydroxy-5 ^l -methylaminosulfonylphenylazo) -2-hydroxynaphthalene or with the 1: 2 chromium complex compound of 1- (>' -chlorophenyl ) -3-methyl-4- (2 ¹ -carbo: cy-4 * -arainosulfonylphenylazo ) -5-pyrazolone, from 0- (2 '

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aminosulfonylphenylazo) -aceto-acetylamino-octane, from 1- (4 ¹ <-Cyanophenyl) -j5-methyl-4- (2 '-hydroxy-4' -methylaminosulfonylphenylazo) -5-pyrazolone or from l- (2 '-Hydroxy-5'-methylsulfonylphenylazo) -2-hydroxy-8-acetylaminonaphthalene, or with the dyes l-amino-4- (2 ', 4 ¹ , 6'-trimethylphenyl-amino) -anthraquinone-2-sulfonic acid, -1 -Amino-4-phenylaminoanthraquinone-2-sulfonic acid, 1,4-bis (2 ', 4 ¹ , 6'-trimethyl- ^' - sulfophenylaminoJ-anthraGhinone, 1- (4 '- (4 "- cyclohexyl-phenoxy ) -phenylazo) -2- (2 ^f '', 4 ^{t! l} , 6 ^{! ll} -trimethylphenylamino) -8-hydroxy-naphthalene-6.2 ^l -disulfonic acid, l-amino-2- (4'-amylphenoxy) -4- (2 ¹¹ , 4 ", 6" -trimethylphenylamino) anthraquinone-2 ', 3 ^f V-disulfonic acid, 1-acotyl-2-hydroxy-4-methyl-6- (4' -chlorophenylamino) -5 -azobenza) ithrone-2'-sulfonic acid.

For s ρ ie 1 2

100 parts of a streaky nylon-6 fabric are treated for 30 minutes in 5000 parts of a boiling, aqueous liquor which has been adjusted to pH 4-5 with acetic acid and which contains 4 parts of an 80 % sulfated castor oil from

gt.

Thereafter, the liquor without cooling 1.4 parts of the adduct of 90 mol of ethylene oxide to 1 mol Araehinyl-3-aniinopropylamine added and the nylon fabric moved about 5 minutes in the fleet. Then one adds same - also without cooling - 1 part of the dye Acid Blue 113 (26360), Color Index II I956 and colors in it by boiling for an hour. This gives a streak-free, level, blue coloration of good light and color Wet fastness.

Instead of the oxethylated arachinylaminopropylamine can the same amount of that according to Example VI of Swiss Patent 388.903 is also used with similar success. available quaternized adduct of 85 moles of ethylene oxide with 1 mole of the adduct of 2 moles of propylene oxide to 1 mole of the alkylaminopropylamine described there.

Similar effects are obtained if instead of the sulfated castor oil 1.4 parts of 85 S ^ -iges oleoylmethyltauride sodium used.

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In the above examples, the dye can also be used simultaneously with the basic compound added to the bath by adding the basic compound and the dye together be dissolved in a small amount of water and this solution is then added to the bath.

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Claims (6)

A process for level dyeing textile material of different paraffin affinity made from synthetic polyamide fibers with anionic dyes which normally dye synthetic polyamides in streaks, characterized in that the dyed material is dyed at a pH of J> to 5 and at temperatures of 70 ° to 1300C with the aqueous Solution of a surface-active compound containing sulfuric acid ester or sulfonic acid groups: pretreated and on top of the treatment bath, which still contains the textile material, without cooling it, an optionally quaternized, at least one aliphatic, saturated or unsaturated, optionally heteroatom-containing radical with 12 to 20 carbon atoms, at least one basic Basic compound containing nitrogen atom and at least 20-200 ethenoxy groups and adding the dye or dyes and then coloring it under the temperatures and pH values given above. 909887/1536 subclaims 1. The method according to claim, characterized in that with a solution of a sulfated castor oil whose degree of sulfation is about 70 % or more than 70 %, is pretreated. 2. The method according to claim, characterized in that the degree of sulfation is at least $ 95 with a solution of a sulfated oleic acid, pretreated. 3. The method according to claim and the subclaims 1 and 2, characterized in that the - at least one basic nitrogen atom and 20-200 ethenoxy groups Compound containing - the adduct of 100 moles of ethylene oxide with 1 mole of behenylaminopropylamine is. . 4. The method according to claim and the subclaims 1, 2 and 3, characterized in that the pretreatment and the dye is added at the boiling point. 909 8 8 7/1536 5. The method according to claim and the subclaims 1, 2, 2 and 4, characterized in that at one pH value of 4.5-5 is pretreated. 6. The method according to claim and the sub-claims "1, 2, 5, 4 and 5 * characterized in that with Milled dyes is dyed. The patent attorney / J 909887/1536