WO1999028546A1

WO1999028546A1 - Process for dyeing wool-containing fibre materials

Info

Publication number: WO1999028546A1
Application number: PCT/EP1998/007348
Authority: WO
Inventors: Ulrich Strahm; Peter Aeschlimann
Original assignee: Ciba Specialty Chemicals Holding Inc.
Priority date: 1997-11-27
Filing date: 1998-11-17
Publication date: 1999-06-10
Also published as: AU1338899A

Abstract

A process is described for dyeing wool-containing fibre materials with anionic dyes, which comprises dyeing these materials in the presence of a wool protective agent comprising at least one compound of formula (1), wherein X is -NR-, -O- or -S-, A is an aliphatic radical containing 1 to 18 carbon atoms, phenyl or naphthyl, and R is hydrogen or an aliphatic radical containing 1 to 6 carbon atoms, or X-A is hydroxy or morpholino. This process gives rub-fast, level dyeings without any loss in the quality of the wool.

Description

Process for dyeing wool-containing fibre materials

The present invention relates to a process for dyeing wool-containing fibre materials using specific wool protective agents.

It is known to dye wool-containing fibre materials, in particular wool/polyester blends, in the presence of assistants so as to counteract fibre damages that occur in particular in high-temperature dyeing. Many of the known assistants contain formaldehyde or release formaldehyde when heated, which is toxicologically unsafe. Moreover, at dyeing temperatures around and above about 120° C wool in many cases also adversely affects the disperse dyes used for dyeing the polyester component.

Surprisingly, an improved process for dyeing, especially for high-temperature dyeing, wool- containing fibre materials has now been found which is based on the use of a novel class of wool protective agents.

Accordingly, this invention relates to a process for dyeing wool-containing fibre materials with anionic dyes, which comprises treating these materials in the presence of a wool protective agent comprising at least one compound of formula

• " (1 )

CI wherein

X is -NR-, -O- or -S-,

A is an aliphatic radical containing 1 to 18 carbon atoms, phenyl or naphthyl, and

R is hydrogen or an aliphatic radical containing 1 to 6 carbon atoms, or X-A is hydroxy or morpholino.

A defined as aliphatic radical containing 1 to 18 carbon atoms is, for example, a Cι-C₁₈alkyl radical, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, pen- tyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, heptadecyl or octadecyl, which alkyl radical can be substituted, for example, by hydroxy, alkoxy or sulfo, and the alkyl chain can be interrupted from C₂ once or from C₃ several times, e.g. by oxygen, sulfur, ami- no, carbonamido, aminocarbonyl, ureido, sulfonamido, aminosulfonyl, carboxy, and carbo- nyloxy.

A defined as phenyl may be further substituted, for example by CrC₄alkyl, C C₄alkoxy, sulfo, sulfatoethylsulfoxy or carboxy.

A defined as naphthyl can be further substituted, for example by C C₄alkyI, C C₄alkoxy, sulfo, sulfatoethylsulfoxy or carboxy.

A is preferably linear or branched OR substituted C_rC ₈alkyl, more preferably CrC₈alkyl, wherein the alkyl chain can be interrupted from C₂ by one or from C₃ by several radicals -Q-, or linear or branched C₂-C₁₈alkyl, more preferably C₂-C₈alkyl, wherein the alkyl chain is interrupted by one or several radicals -Q- , wherein -Q- is -O-, -S-, -NR₂-, -CONR₂-, -NR₂CO-, -NR₂-CO-NR₃-, -SO₂NR₂-, -NR₂SO₂-, -COO-, -OCO-, -NR₂COO- or -OCOO-, Ri is hydrogen or C C₄alkyl, R₂ is hydrogen or C C₄alkyl, and R₃ is hydrogen or C C₄alkyl.

A defined as C C₁₈alkyl, CrC₈alkyl, C₂-C₁₈alkyl or C₂-C₈alkyl may additionally be mono- or polysubstituted by e.g. carboxy, carbonamido or sulfonamido.

R defined as aliphatic radical containing 1 to 6 carbon atoms is, for example, a C C₆alkyl radical, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, pentyl or hexyl, which alkyl radical may be substituted, for example, by hydroxy, alkoxy or sulfo.

X is preferably -NR-, wherein R is hydrogen or an aliphatic radical containing 1 to 6 carbon atoms.

R is preferably methyl and, more preferably, hydrogen.

R_T defined as Cι-C₄alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl or isobutyl. R₂ and R₃ defined as d-C₄alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert- butyl, or isobutyl.

Ri is preferably methyl and, more preferably, hydrogen.

R₂ is preferably hydrogen.

R₃ is preferably hydrogen.

-Q- is preferably -O-, -S- and -NR₂-, wherein R₂ is hydrogen or C C₄alkyl.

Compounds which are particularly interesting for the novel process are those of formula (1), wherein -X-A is the following radicals:

-NHCH₂CH₂SCH₂CH₂OH₎ -NHCH₂CH₂CONHCH₂CH₂OH, -NHCHaCHgCHaCONHCHzCHsOH, -NHCH₂CONHCH₂CH₂CH₂OH, -NHCH₂CONHCH₂CH₂CH₂θH, -NHCH₂CON(CH₂CH₂θH)₂, -NHCH₂CH₂NHCOCH₂CH₂CH₂OH, -NHCHaCHzCHgNHCOCHgCI-feCHgOH, -OH, morpholino, -NH-C₆H₅-Sθ₂-CH₂CH₂-OSθ₃H, -N(CH₃)-C₆H₅, -N(CH₂CH₂OH)-C₆H_5> -NH-C₆H₅COOH,

-N(CH₂SO₃H)-C₆H₅, -NHCH₂CH₂CH₂CONHCH₂CH₂CH₂OH or ^"NH_rtΩ— SO₃H .

Compounds which are particularly important for the novel process are those of formulae

CL r _/N.r _/NH-CH-C OH ₍3)

CI

CH-ChLOH I ^{2 2}

CI

"X X^ ^CH₂CH₂OH (5),

CI

CH, -^5- ^ CH₂CH₂OH (6),

CI

Compounds which are very particularly important for the novel process are those of formulae (2), (3),(16), (17), (18) and (19).

The compounds of formula (1) used in the novel process are prepared by methods known per se by reacting, for example, a trichlorotriazine of formula

with an equimolar amount of a compound of formula

HX - A (21),

wherein X and A have the meaning given for formula (1 ), and by isolating the resulting end product of formula (1).

Wool-containing fibre material can be dyed by customary dyeing processes. Dyeing is carried out, for example, by pretreating the wool-containing fibre material first with a wool protective agent in an aqueous bath and then dyeing it by adding the dye to this bath. It is also possible to treat the goods to be dyed simultaneously with the wool protective agent and the dye in an aqueous bath.

It has been found useful to use the wool protective agent in an amount from e.g. 0.1 to 20 % by weight, preferably from 0.1 to 10 % by weight, particularly preferably from 1 to 10 % by weight and, very particularly preferably, from 1 to 6 % by weight, each based on the weight of the goods to be dyed.

The wool-containing fibre material is preferably wool as such and also wool/polyester blends. Normally, the wool is dyed by itself with the anionic dyes, and blends of wool and polyester fibres are preferably dyed with anionic dyes and disperse dyes. The novel process is preferably used for dyeing wool/polyester fibre blends.

Anionic dyes suitable for the novel process are those dyes which are described in Colour Index, 3^rd Edition (3^rd revision 1987 inclusive Additions and Amendments to No. 85) under "Acid Dyes". These dyes are, for example, carboxylic acid group- and/or in particular, sulfo- nic acid group-containing monoazo, disazo, nitro, anthraquinone, metal complex and triphe- nylcarbonium dyes.

Disperse dyes suitable for the novel process are those dyes which are described in Colour Index, 3^rd Edition (3^rd revision 1987 inclusive Additions and Amendments to No. 85) under "Disperse Dyes". These dyes are, for example, carboxylic acid group- and/or sulfonic acid- group-free nitro, amino, aminoketone, ketonimine, methine, polymethine, diphenylamine, quinoline, benzimidazole, xanthene, oxazine or coumarine dyes and, preferably, anthraquinone and azo dyes, such as mono- or disazo dyes.

The fibre materials may be in a wide range of forms of presentation, e.g. in the form of yarns, flocks, slubbing, knitwear, such as knitgoods, in the form of bonded fibre fabric or, preferably, wovens.

The blended fibre fabrics are preferably fibre blends of wool and polyester, usually at a ratio of 20 to 50 parts by weight of wool to 80-50 parts by weight of polyester. The fibre blends preferred for this process contain 45 parts by weight of wool and 55 parts by weight of polyester fibres.

In addition to containing the dye, water and the wool protective agent, the dyebath may contain further customary additives. To be mentioned are, for example, mineral acids, organic acids and/or salts thereof which serve to adjust the pH of the dyebath, and also electrolytes, levelling and wetting agents, antifoams as well as - for dyeing wool/polyester blends - dis- persants, it being possible to forego the routine addition of carriers. The dyebath has a pH of e.g. 4 to 6.5 and, preferably, of 4.5 to 5.8. The novel process is usually carried out in the temperature range from e.g. 60 to 135°C.

The polyester/wool fibre blends are advantageously dyed in a single bath from an aqueous liquor by the exhaust process. Dyeing is preferably carried out by the so-called high-temperature process in closed, pressure-resistant apparatus at temperatures above 100°C, conveniently in the range from 110 to 135°C, preferably from 118 to 130°C, most preferably from 125 to 130°C, under normal or elevated pressure.

The liquor ratio in the novel process can be chosen from a wide range and is, for example, from 1 :1 to 1 :100, preferably from 1 :10 to 1 :50 and, more preferably, from 1 :10 to 1 :20.

The fibre blends can also be dyed by the standard carrier dyeing process at temperatures below 106°C, e.g. in the temperature range from 75 to 98 °C, in the presence of one or more than one carrier.

The dyeing of the wool or of the polyester/wool fibre blends can be carried out such that the goods to be dyed are treated first with the wool protective agent and, if appropriate, the carrier, and then dyed. The procedure may also be such that the goods to be dyed are treated simultaneously with the wool protective agent, the dyes and optional assistants. The preferred procedure comprises putting the textile fibre blend material into a bath that contains the wool protective agent and, if required, additional customary assistants and which has a temperature of 40-50°C, and treating the material for 5 to 15 minutes at this temperature. Afterwards, the temperature is raised to about 60 to 70°C, the dye is added, the dyebath is slowly heated to dyeing temperature and dyeing is carried out for about 20 to 60 minutes, preferably for 30 to 45 minutes, at this temperature. At the conclusion, the liquor is cooled to about 60°C and the dyed material is finished in customary manner.

By means of the novel process it is possible to dye wool or wool/polyester fibre blends at high temperature, for example in the range from 120 to 135° C, without yellowing and with markedly reduced shrinkage, the wool component being perfectly protected, i.e. the important, fibre-technological properties of the wool are preserved, such as tear resistance, burst strength and stretch. Dyeing the polyester/wool blend above 120° C increases the degree of exhaustion of the disperse dye on polyester, thus reducing the contamination of the wool component with disperse dye and positively affecting, inter alia, the wool component's fastness to washing and light.

It is also to be highlighted that the polyester component in blends does not show any yellowing and no loss in colour strength.

The novel process also has the advantage of reducing the setting, which is achieved through the presence of a compound of formula (1 ) in the dyebath. The term "setting" denotes an undesirable fixation of the wool fibres occurring during the dyeing process which is caused by the rearrangement of the disulfide bridges in the wool. Such undesirable fixations can show, for example, as a deformation (flattening) of the wool yarn on spools, as a compacting of the wool fibre and as a loss in volume of the wool.

The antisetting effect of a wool protective agent can be determined, inter alia, in accordance with A.M. Wemys and M.A. White, Proc. Ind. Japan-Australia, Joint Symp. on Objective Measurement, Kyoto (1985), page 165, by punching out circles from woollen test fabric, folding these circles in the middle and sewing them together at the edges. The test samples are then dyed compressed in the presence of the wool protective agent. The samples are then opened and one thread each is pulled out. After a relaxation time in warm water, the angle of the threads is measured. The more the previously compressed yarn has opened and the more the angle approximates 180°C, the better the antisetting effect of the wool protective agent. An angle of c. 120 to 180°C and, preferably, of 140 to 180° C indicates a good antisetting effect.

The invention is illustrated by the following Examples. Temperatures are given in degrees Celsius and parts and percentages are by weight, unless otherwise stated.The ratio of parts by weight to parts by volume is the same as that between the kilogramme and the litre.

Example 1 :

100 parts by weight of a blended fabric, consisting to 55% of polyester and to 45% of wool, are pretreated for 5 minutes at 40° C in a circulation apparatus with a liquor comprising 2.0 parts by weight of the compound of formula

0.5 part by weight of a sulfated fatty amine polyglycol ether,

1.0 part by weight of a commercially available assistant mixture based on carboxylic acid aromatic and phosphoric acid aromatic compounds, and 2.0 parts by weight of sodium acetate in 1200 parts by weight of water, which liquor is adjusted to pH 5.5 with acetic acid. The liquor is then heated over 30 minutes to 130° C, adding at 70° C 2.0 parts by weight of a dye mixture consisting of 1.6 % by weight of the dye of formula

60.0 % by weight of the dye of formula

5.0 % by weight of the dye of formula

O_zN- = N— ft - N(CH₂CH₂OCOCH₃)₂ (102),

CN

4.0 % by weight of the dye of formula

3.3 % by weight of the dye of formula

15.0 % by weight of the dye of formula

10.0 % by weight of sodium sulfate. Dyeing is then carried out for 40 minutes at 120° C and the dye liquor is then cooled to 60° C. The dyed goods are then washed in customary manner, giving a rub-fast, level, red, tone-in-tone dyeing without any loss in the quality of the wool.

Example 2:

The procedure of Example 1 is repeated, but replacing 2.0 parts by weight of the compound of formula (2) with the same amount of one of the compounds of formulae

CH₂CH₂OH

CH₂CH₂OH (5),

T II

CI

CI M ^ NH-(CH₂)₃-CONH-(CH₂)₃OH i T

^Nγ^N (11),

CI Cl Λ\ - , NH-(CH₂)₂-NHCONH-(CH₂)₂OH

X Y (12), ^Nγ^N

CI

CI

/^~Λ (18) or

>-

''

which also gives dyeings having good properties and without any adverse effect on the quality of the wool. Example 3:

The procedure of Example 1 is repeated, but adjusting the pH of the liquor not to 5.5 but to 4.5, which also gives dyeings having good properties and without any adverse effect on the quality of the wool.

Example 4:

100 parts by weight of a woollen fabric having a m² weight of 180 g are treated for 10 minutes at 50° C in 1000 parts by weight of an aqueous liquor comprising 4.0 parts by weight of ammonium sulfate, 4.0 parts by weight of the compound of formula (2), and 0.5 part by weight of a naphthalenesulfonic acid condensate, which liquor is adjusted to a pH of about 6 with acetic acid. Subsequently, 3.0 parts by weight of the dye of formula

are added and treatment is continued for another 5 minutes. The dye liquor is then heated over about 45 minutes to about 98° C and the woollen fabric is dyed at this temperature for 60 minutes. The liquor is then cooled to about 60° C. The dyed woollen fabric is then rinsed and dried in customary manner, giving a rub-fast, level, blue dyeing without any loss in the quality of the wool.

Example 5:

The procedure of Example 4 is repeated, but replacing 4.0 parts by weight of the compound of formula (2) with the same amount of one of the compounds of formulae (3) to (19), which also gives dyeings having good properties and without any adverse effect on the quality of the wool.

Claims

What is claimed is

1. A process for dyeing wool-containing fibre materials with anionic dyes, which comprises treating these materials in the presence of a wool protective agent comprising at least one compound of formula

wherein

X is -NR-, -O- or -S-,

2. A process according to claim 1 , wherein A is ORi-substituted C C₁₈alkyl, wherein the alkyl chain can be interrupted from C₂ by one or from C₃ by several radicals -Q- , or C₂-C₁₈al- kyl, wherein the alkyl chain is interrupted by one or several radicals -Q- , wherein -Q- is -O-, -S-, -NR₂-, -CONR₂-, -NR₂CO-, -NR₂-CO-NR₃-, -SO₂NR₂-, NR₂SO₂-, -COO-, -OCO-, -NR₂COO- or -OCOO- , and R_t is hydrogen or d-C^lkyl, R₂ is hydrogen or d-dalkyl, and R₃ is hydro-gen or C C₄alkyl.

3. A process according to claim 2, wherein A is OR substituted C C₈alkyl, wherein the alkyl chain can be interrupted from C₂ by one or from C₃ by several radicals -Q-, or C₂-C₈alkyl, wherein the alkyl chain is interrupted by one or several radicals -Q- , wherein -Q- is -O-, -S-, -NR₂-, -CONR₂-, -NR₂CO-, -NR₂-CO-NR₃-, -SO₂NR₂-, NR₂SO₂-, -COO-, -OCO-, -NR₂COO- or -OCOO- , and R^ is hydrogen or C_rC₄alkyl, R₂ is hydrogen or CrC₄alkyl, and R₃ is hydrogen or C C₄alkyl.

4. A process according to any one of claims 1 to 3, wherein X is -NR-, and R is hydrogen or an aliphatic radical containing 1 to 6 carbon atoms.

5. A process according to any one of claims 1 to 4, wherein -Q- is -O-, -S- or -NR₂- , and R₂ is hydrogen or d-C₄alkyl.

6. A process according to claim 1 , which comprises using one of the compounds of formulae

CI -N ^ . NH-(CH₂)₃-CONH-(CH₂)₃OH I T

^N╬│^N (11).

CI

CI ╬¢ ^ . NH-(CH₂)₂-NHS0₂-(CH₂)₄OH r T (15),

CI

7. A process according to any one of claims 1 to 5, which comprises using from 0.1 to 20 % by weight of the compound of formula (1), based on the weight of the fibre.

8. A process according to any one of claims 1 to 5, which comprises applying the compound of formula (1) to the fibre before or during a dyeing process.

9. A process according to any one of claims 1 to 8, wherein the wool-containing fibre materials consist of wool/polyester fibre blends.

10. A process according to claim 9 for dyeing wool/polyester fibre blends by the exhaust process.

11. A process according to claim 1 , which comprises using a wool protective agent comprising at least one compound of formula (1).

12. Use of a compound of formula (1) according to claim 1 as wool protective agent for dyeing wool-containing fibre materials with anionic dyes.

13. The dyed wool-containing fibre materials, which are treated with the compounds according to claim 6.