DE1619402A1 - Process for dyeing fiber material made of synthetic polyamide - Google Patents

Description

New, complete application documents intended for the Druolr der Offenlegungsschrift. . File number: P 16 19 402.8-45
U * sign: 21 153-BR / H

CIBAAKTIENGESEL LS C HA FT, BA SE L is GHWEI Z)

Case 5Q62 / E.

Process "for dyeing synthetic fiber material

Polyamide. : -

The present invention relates to a method for Dyeing of synthetic polyamide fiber material with water-soluble 1: 2 metal complex dyes that do not contain any have free, acidic water-solubilizing groups.

0098377 2007

New documents ^ 7 | iAi * 2N

The characteristic of the process is that the fiber material with an acidic dyeing preparation is brought into contact at elevated temperature, which a) at least one reaction product of a higher molecular weight aliphatic amine with ethylene oxide and b) contains at least one nonionic dispersant.

All fiber materials are suitable as synthetic polyamide fiber material which is dyed according to the invention based on synthetic polyamide. Preferred examples are polyamides made from adipic acid and hexa-. triethylenediamine (nylon 6,6), from ε-caprolactam (nylon 6) or from ω-aminoundecanoic acid (nylon 11) mentioned. Fibers made from ω-amino-enanthic acid are less common, but also suitable (Nylon 7), from ω-aminopelargonic acid (nylon 8) or from Sebacic acid and hexamethylenediamine (nylon 6,10).

Water-soluble 1: 2 Me- 'suitable according to the invention metal complex dyes that do not have free acidic water-solubilizing agents Have groups, have a cobalt or, in particular, a chromium atom as the central atom. With the central atom two complex-forming components are connected, at least one of which is a dye molecule, preferably however, both dye molecules are. Suitable dye molecules are above all azo dyes in the ο, ο'-position to the azo bridge one substituent each capable of complex formation exhibit. The two of them can work on the complex

009837/2007

The dye molecules involved in the formation are the same or apart from one another be different and have only one or more azo bridges. Comes as complex-forming substituents for example the hydroxyl, amino, carboxyl, carbomethoxy or methoxy group. Particularly suitable are, for example, dyes with one of the following groupings; OiO'-diaminoazo-, o-oxy-o'-aminoazo-, o-carboxy-o'-oxyazo-, o-carboxy-o'-aminoazo-, o-carbomethoxy-o'-oxyazo-, o-carbomethoxy-o'-aminoazo-, and in particular the o, o'-dioxyazo group. As water-solubilizing groups do not come dissociating, from acidic groups, such as 2.B-. the sulfonic acid or carboxyl groups not involved in the complex formation, functionally derived groups into consideration. Such derivatives are, for example, sulfonamide or alkyl sulfone groups.

The dyeing preparations with which the fiber material is brought into contact contain two different ones Tools (a) and (b). Both auxiliaries have a higher molecular weight hydrophobic radical and at least one hydrophilic polyethylene glycol chain. They make a difference in the way that the polyethylene glycol residues are connected to the hydrophobic residue.

The auxiliaries (a) are derived from higher molecular weight aliphatic amines which have at least one amine nitrogen atom are connected to the polyethylene glycol chains. Both mono- and polyamines can be used here.

009837/2007

BATH ORIGINAL

Among the polyamines are the diamines, especially propylenediamine, particularly preferred, with at least one nitrogen atom being at most secondary. The higher molecular weight aliphatic The remainder can be unsaturated, but is preferably saturated and has 12 to 22, preferably 16 to 18, carbon atoms on. Examples of such aliphatic radicals are lauryl, palmityl (cetyl), stearyl, arachidyl, Behenyl, called oleyl radical, unsaturated radicals other than the oleyl radical also coming into consideration. the Polyethylene glycol chains are expediently built up with ethylene oxide. They usually contain between 5 and 30, but preferably between 7 and 20 moles of ethylene oxide per Mole amin. These amine polyethylene glycols can be used as such in the process according to the invention. You can but also exist as quaternary ammonium salts, the quaternization with customary quaternizing agents, e.g. with Epichlorohydrin, dimethyl sulfate or chloroacetamide is made. Both the production and the quaternization take place according to methods known per se. The amine polyethylene glycols described can either be used individually or as Combinations are used.

The auxiliaries (b) belong to the group of non-ionogenic dispersants and are polyethylene glycol derivatives of higher molecular weight fatty acids or higher molecular weight aliphatic, cycloaliphatic or aromatic

009837/2002

■ - 5 -

aliphatic mono- or polyoxy compounds. They have at least 14 carbon atoms in the hydrophobic part. • All of these compounds can be unsaturated, but they are preferably saturated in character. For example, the aliphatic radicals listed under (a), corresponding carboxylic acids and alcohols are suitable. Other suitable compounds are, for example, also higher molecular weight alkylphenols, such as pentadecylphenol. Dihydroabietyl alcohol, higher molecular weight sorbitan esters, such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate or sorbitan monooleate, and castor oil are particularly suitable. The reaction of these compounds with ethylene oxide takes place according to methods known per se. As a rule, K to JO moles of ethylene oxide per mole of acid or oxy compound * give effective products. Carboxylic acids and monooxy compounds preferably contain 10 to 40 moles of ethylene oxide per mole, while polyoxo compounds preferably contain 5 to 25 moles of ethylene oxide per hydroxyl group. The reaction products of 15 moles of ethylene oxide with 1 mole of Oley1 alcohol or dihydroabietyl alcohol, of 10 moles of ethylene oxide with 1 mole of stearyl alcohol, of 17 moles of ethyl oxide with 1 mole of cetyl alcohol, of 20 moles of ethylene oxide with 1 mole of one of the sorbitan esters listed above and 65 moles of ethylene oxide with 1 mole of castor oil. ·

O09837 / 2ÖOT

The proportions of the auxiliaries a: b vary within relatively narrow limits and amount to e.g. IsO, 2 up to 1: 1.5 * but preferably 1: 0.4 to 1: 0.8 »the quantitative ratio of the two auxiliaries together, i.e. from a + b, to the dye can be at least 1: 4 and preferably with 1: 1.4 to 1: 0.3 can be stated, i.e. the total amount of auxiliaries a + b should not be less than 1/4 of the amount of dye be.

The dyeing preparations are in accordance with the procedure angry. They advantageously have a p n value of 1 to 5 *, but preferably 2 to 4. This acidity can be caused by organic or inorganic acids. For example, ant, vinegar, sulfur and preferably phosphoric acid. But potentially acidic salts, such as ammonium sulfate, can also be used will.

The polyamide fiber material is dyed by methods known per se, preferably by the exhaust process. For example, the dyed material is added to the dye liquor at room temperature, then the Bath temperature increased to boiling temperature, followed by a is dyed at this temperature for a longer period of time. The finishing is carried out as usual by rinsing and drying »

The advantage of the present method is that the material-related streaky coloring of the poly

00 9 83 7/2007

Γ «I

amide fiber fabrics and knitted fabrics are avoided without ^ stains appear “Until now, it was not possible to use non-ionogenic or cationic auxiliaries to address this disadvantage of the Iv2-Meta1! complexes in dyeing bypassing polyamide.

In the following examples, parts are parts by weight and percentages are percentages by weight.

0098 37/2007

example 1

10 parts of textured NylQn-6,6-Fllaflientgewirke are immersed in the following liquor, which has a liquor ratio of 1:40 »and a temperature of 20 ° C:

0.2 part of 1: 2 chromium complex with two dye molecules of the formula

OH HO Cl.

* 'tr *

CH, ENT "

-r **. σι

0.24 parts orthophosphoric acid

0.04 part of condensation product of 7 moles of ethylene oxide with one mole of palmitylamine [auxiliary (a) 3

0.08 part of condensation product of 20 moles of ethylene oxide with one mole of an amine mixture consisting of

• 25 % hexadecylamine
70 % octadecylamine
5 % octadecenylamine

[Aid (a) 3

0.09 part of condensation product of 15 moles of ethylene oxide with one mole of dihydroabiety alcohol

[Aid (b)].

The p "value of the liquor is 2.5 to 3. Within Minutes, the bath temperature is increased to about 100 ° C and

dyed the fabric for 2 hours at this temperature,

009837/2007

Then it is rinsed in cold water and dried, A streak-free, level blue coloration is obtained.

Instead of the above dye, the 1: 2 chromium complex with two dye molecules of the formula

(2) HO

OH

= N-0 I scarlet fever

O = N I

the 1: 2 cobalt complex with two dye molecules der formula

HO:

be used.

Similar results are also obtained if the above combination of tools (a) is replaced by the following combinationsί. _;

00983 7/2007

0.04 part of condensation product of 7 moles of ethylene oxide with a mole of findtylamine

0.08 part of condensation product of 15 moles of ethylene oxide with a mole of an amine chemical the end

25 % hexadecylamine 70 % octadecylamine 5 % octadecenylamine

or 0.06 part of condensation product of 7 moles of ethylene

oxide with one mole of palmitylamine

0.06 part of condensation product of 8 moles of ethylene

oxide consisting of one mole of an amine ash the end

25 % hexadecylamine 70 % octadecylamine 5 % octadecenylamine

or by 0.12 part of condensation product of 12 mol of ethyl

lenoxide with one mole of stearyl amine.

Component (b) can also be used without impairing the results

0.06 part of condensation product of 15 moles of ethylene oxide with one mole of oleyl alcohol

or 0.09 part condensation product of 65 moles of ethylene

oxide with a mole of castor oil

be replaced.

Example 2

10 parts of text-tared nylon 6i6 filament knitted fabric are in the following liquor, which has a liquor ratio of 1:40 and a temperature of 40 ° C

0.12 parts of any of those listed below Dyes. "

0.2 parts Orthophosphosilure *

0.12 part of condensation product of 8 moles of ethylene oxide with one mole of hydrogenated sebum amine (aid (a))

0.08 part of condensate product of 15 MpI of ethylene oxide with one mole of dihydric alcohol [Aid (b) l

The bath temperature is up to 2 µm within 50 minutes Boiling point increased and the tissue at for 90 minutes colored at this temperature. Then it is cold Rinsed with water and dried. A streak-free, level coloring.

The dyeings were carried out with the following dyes:

1: 2- ^ cobalt complex with two dye oils of the

formula

009837 / 2Ö & 7

OH

blue

υπ η ₂ «

XJ  <~>

ON. \

1: 2 chromium complex with two dye molecules of the formula

(5)

HO OH> -Ν - <^>

• N — N — C

Orange red

O = N

S0,0H, Η, Ο 3 3 3

1: 2 cobalt complex with two dye molecules of the Formula

OHH O .

NO ₂

1: 2 chromium complex with two dye molecules of the

formula

OHH O

Gray

009837/2 0

1619AG2

Example J5

10 parts of textured knitted fabric are dyed according to the information in Example 1 or 2 the following table shows the fleet. '-.'-

0 0 9837/2007

relationship P.
σ * Parts acid Share tools 0.09 0.09 0.09 P to ρ ρ ρ ppp
00 OCTNVJI 4! » Vj) KJ H 0.08
0.04 0.12
0.12 Color
material H "ρ * 1: 0.75 CO CQ CQ CQ
4 * Vj) Kl H σ * er ¹ tf c *
4 * · .Vj) KJ H 0.09 60 '0. 0.12 0.12 No.
Parts KJ 1: 1.14 1: 0.75 O
Mt O
O
VD * O
H
- KJ O
- H
KJ Vj) 1: 1.14 1: 0.75 ο 0.09 0.12 O
ro ro • 1: 1.14 1: 0.75 O
Vj) 0.12 O
"ro H
■ ί * VJl 1: 1.14 1: 0.75 O
Vj) 0.12 O
ro ro
4 * 1: 1.14 1: 0.75 O
Vj) 0.12 O -J 1: 1.14 1: 0.75 O
Previous year O
ro ro
■ £ - 03 1: 1.14 H
Ö O
VJ) O
KJ KJ H
»Β
O ο
Vj) O
KJ KJ

relationship P.
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OD -J σ \ vji ■ ** sjj ro H Varb-
material VXJ ?
σ * 1: 0.75 CO CO CO CO
• J ». SjJ Ν »Η he he he ¹ he
4k vjj ro H 0.044 No.
Parts O H
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Vj) 1: 0.75 2 * 0 0.033 ο ο
ο ro
ro
VJI fei H
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G.
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Oil O
(VJ 0.033 0.044 ο
"θ VjJ
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rvj 0.033 0.05 ο
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O ** ■
rvj
VJl H
Vj) II H
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ro 'O
O
H ο
G O
G ro
CTi «■ 1: 1 H
H
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To O
G
H 0.03 O
O VjJ
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O 'ro
cn H
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KJ O O

relationship P.
σ * Parts acid O O
VJI 0.15 O
VjJ ' Share tools ρρρρρρρρ
00 * ^ 3 O ^ ^ JH "f ^ * V / i ΓΟ Η * '
t 0.16 ο
σ \ Color
material H
co σ H
O
-J CO CQ CQ CQ
■ Ρ * VjJ PO H O cf σ * cc σ *
+ ». vjj ro H O
Ιψ
© Kr.
Parts a H . H
Ö O
PO 0.05 © 1: 4 1: 0.75 O
PO ο
ο
VJl © © 1: 1.14 H
VJl O
PO O
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VO ©
FV ©
"η ro
rv ro 1: 1.14 H
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VJl 0.09 "η ©
H ro
rv ro 1: 1.14 H
♦ ·
O
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VJl 0.09 OK _r 12 © PO 1: 1.14 H
O
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O
VO ©
fm
H iv
rv H
H H
Ö
VJl 0.08 ©
1"·
PO PO H
H 0.08 O
PO PO

I. I.

CP O

US »'■

relationship Cf Parts acid Share tools ppp PP PPP
00 * "* 3 O ^ VT! - (^ ^ 3 IV ^ I * ™ ' • material ; IV)
UI : cf. H
ο
UI co ta ca tn
4 ^ U) IW H Cf Cf Cf Cf
45 * UJ ro H 0.034
0.103 ω hi IV)
CA ■■ η " , P.
UI O
UJ 0.103 0.114
0.343 P ■
ro to ' H ■ H
Ö ■ ■ ■ ". * °
UJ 0.343 0.06
0.17 ο '
ro ro
4 * ■ ■ I IV)
CD σ \ ■ Ή
Ul O
UJ 0.17 0.034
0.102 & IV)
KD ■■■ ·. · <
.. η ■ _t H
ο ■
-j
Ul ■ ■ ■ ¹ O
UJ 0.102 0.026
0.077 O
<· Ns
ro '■■ ■ '■' Ή '
** ■
UJ 1: 0.75 , '*. ■■■■■ ο
• ■ ■■.:: - ■; UJ, ο
ο. ^: ■ '
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-J 0.017
0.051 O
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UJ 0.051 P '',
- ro
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-p »

a, reaction product of one mole of hydrogenated tallow fatty amine with 7 moles of ethylene oxide.

a ₂ Reaction product of one mole of tallow amine with 20 moles of ethylene oxide and quaternized with epichlorohydrin

a, reaction product of one mole of tallow fatty amine with 7 Mol of ethylene oxide and quaternized with epichlorohydrin

au reaction product of one mole of dodecylamine with 20 moles of ethylene oxide

a ^ Reaction product of one mole of N-aminopropyl soy fatty amine with 8 moles of ethylene oxide

ag Reaction product of one mole of hydrogenated tallow amine with 8 moles of ethylene oxide

a "Reaction product of one mole of hexadecylamine with 7 moles of ethylene oxide

ag reaction product of one mole of hexadecylamine with 15 Moles of ethylene oxide

D ₁ reaction product of one mole of pentadecylphenol with 15 moles of ethylene oxide

do; Reaction product of one mole of oleic acid with a

Moles of polyethylene glycol of approximate molecular weight 1500.

b-, reaction product of one mole of gel säunireoTbitanester with 20 moles of ethylene oxide.

b ^ Reaction product of one mole of dihydroabietyl alcohol with 15 moles of ethylene oxide

s,. Orthophosphoric acid
S ₂ acetic acid
S ^ formic acid

Si ₁ sulfuric acid - · _m
⁴ 009837/2007

Similar good results are achieved if instead of the nylon 6,6 filament knitted fabric one of Nylqn-6 or a. non-textured filament knitted fabric or - nylon 6,6 or nylon 6 fabric is used.

009837/2007

Claims (14)

Claims 1. Process for dyeing synthetic polyamide fiber material with water-soluble Ii2 metal complex dyes, which have no free, acidic water-solubilizing groups, characterized in that the Brings fiber material with an acidic dye preparation at elevated temperature, which (a) at least a reaction product of a higher molecular weight aliphatic amine with ethylene oxide and (b) at least one nonionic Dispergator contains « 2 »Method according to claim 1, characterized in that that one stains at a p "value of 2 to 4. ti 3. The method according to claim 2, characterized in that dyeing in the presence of phosphoric acid. 4. The method according to any one of claims 1 to jj * marked ,, that one dyes by the exhaust process. ■ 5. Process according to one of Claims 1 to k, characterized in that dyeing is carried out with 15 2-chromium or cobalt complex dyes. ■ 6. The method according to any one of claims 1 to 5, there- characterized in that the auxiliary means (a) implementation , 009837/2007 products from 5 to 30 moles of ethylene oxide and one mole of one saturated fatty amine or fatty amine mixture with 14 to Carbon atoms used. ■ · 7 »Method according to claim 6, characterized in that that one reaction products of 7 to 20 moles of ethylene oxide and one mole of a saturated fatty amine or fatty amine mixture with 16 to 18 carbon atoms used. 8. The method according to any one of claims β or J, characterized in that mixtures of different fatty amine / ethylene oxide conversion products are used. 9 · The method according to any one of claims 1 to 8, characterized in that the auxiliary (b) reaction products from 4 to 70 moles of ethylene oxide and one Moles of an aliphatic having at least 14 carbon atoms Carboxylic acid or an aliphatic, cycloaliphatic or aromatic-aliphatic mono- or polyoxy compound containing at least 14 carbon atoms used. ■ 10. The method according to any one of claims 1 to 8, characterized in that as auxiliary (b) reaction products of 4 to 70 moles of ethylene oxide and one mole of one higher molecular weight sorbitan ester or castor oil is used. 11. The method according to claim 9. » characterized, that the reaction product of 10 to 40 mol of Aethylßn- 009837/2007 ': oxide and one mole of dihydroabietyl alcohol are used. 12. The material colored according to any one of claims 1 to 11. 13 · To carry out the procedure after a of claims 1 to 11 suitable dyeing auxiliaries, characterized in that marked 'that they a) .at least one reaction product of a higher molecular aliphatic amine with ethylene oxide and b) contain at least one nonionic dispersant, the proportions of the Components a) and b) are 1: 0.2 to 1: 1.5 and from a + b to the dye are at least -1: 4 ". 14. dyeing aid according to claim I3, characterized characterized in that the quantitative ratio of the components a) and b) 1: 0.4 to 1: 0.8 and the quantitative ratio of a + b to the dye is 1: 1.4 to 1: 0.3. 009837/2007