Anticrease finishing composition and use thereof in the dyeing or whitening of textile material which contains polyester fibres

The invention relates to a novel anticrease finishing composition which comprises at least PA0 (A) an O-cyanoethylated compound of the formula EQU (1) R(O--CH.sub.2 CH.sub.2 CN).sub.n, PA0 wherein R is an n-valent aliphatic, cycloaliphatic or araliphatic radical, and n is 1 to 5, and PA0 (B) a carboxylated polypropylene oxide adduct, or salt thereof, which adduct is obtainable from PA1 (a) an aliphatic diol having an average molecular weight of at most 2600, PA1 (b) an aliphatic dicarboxylic acid, or anhydride thereof, containing 4 to 10 carbon atoms, PA1 (c) an adduct of propylene oxide and an at least trihydric aliphatic alcohol containing 3 to 10 carbon atoms, and PA1 (d) a fatty acid containing 8 to 22 carbon atoms, and optionally, PA0 (C) an aliphatic alcohol containing 5 to 18 carbon atoms, a siloxane-oxyalkylene copolymer, or a mixture thereof, and/or PA0 (D) a polar solvent. The novel composition is used in dyeing or whitening textile material which contains polyester fibres.

The present invention relates to novel anticrease finishing compositions 
and to the use thereof in the dyeing or whitening of textile material 
which contains polyester fibres. 
Anticrease finishing agents which are already commercially available are 
hydrophobic, plasticiser-like substances. On account of their low HLB 
value, they have the property--if they do not actually foam themselves--of 
at least stabilising foam resulting from residual surfactants or dye 
dispersants. The HLB value stands for the hydrophilic/lipophilic balance 
in a molecule. 
Carboxylated polypropylene oxide adducts which are employed as anticrease 
agents are known e.g. from German Offenlegungsschrift No. 30 00 370. These 
products do not themselves foam, but they stabilise the foam of 
dispersants so strongly that it is scarcely possible to use them for 
dyeing polyester fibres in certain jet dyeing machines, e.g. in a short 
liquor jet dyeing machine. 
Surprisingly, there has now been found a novel, non-foaming composition 
which may be used as anticrease finishing agent in dyeing textile material 
which contains polyester fibres. 
Accordingly, the present invention provides a novel dyeing assistant 
composition which comprises at least 
(A) an O-cyanoethylated compound of the formula 
EQU R(O--CH.sub.2 CH.sub.2 CN).sub.n, (1) 
wherein R is an n-valent aliphatic, cycloaliphatic or araliphatic radical, 
and n is 1 to 5, preferably 1, and 
(B) a carboxylated polypropylene oxide adduct, or salt thereof, which is 
obtainable from 
(a) an aliphatic diol having an average molecular weight of at most 2600, 
(b) an aliphatic dicarboxylic acid, or anhydride thereof, containing 4 to 
10 carbon atoms, 
(c) an adduct of propylene oxide and an at least trihydric aliphatic 
alcohol containing 3 to 10 carbon atoms, and 
(d) a fatty acid containing 8 to 22 carbon atoms. 
In addition to components (A) and (B), the composition of the invention may 
also contain 
(C) an aliphatic alcohol containing 5 to 18 carbon atoms, a 
siloxane-oxyalkylene copolymer, or a mixture thereof, and/or 
(D) a polar solvent. 
Components (A), (B), (C) and (D) may be in the form of individual compounds 
or mixtures. Preferred compositions comprise all components (A), (B), (C) 
and (D). 
An aliphatic radical R is preferably the hydrocarbon radical of an 
unsaturated or preferably saturated aliphatic monoalcohol containing 3 to 
24 carbon atoms. This hydrocarbon radical may be straight chain or 
branched. Examples of aliphatic saturated alcohols are: propanol, 
isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl 
alcohol, isoamyl alcohol, tert-amyl alcohol, neopentyl alcohol, hexanol, 
2-methylpentanol, 2-ethyl-hexanol, trimethylhexanol, 5-methyl-heptan-3-ol, 
octan-2-ol, trimethyl nonyl alcohol, decanol, lauryl alcohol, myristyl 
alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, arachidyl 
alcohol, behenyl alcohol or alfols. Some representatives of alfols are 
alfol (8-10), alfol (10-14) and alfol (16-18). Examples of unsaturated 
aliphatic alcohols are: allyl alcohol, butenol, dodecenyl alcohol, 
hexadecenyl alcohol or oleyl alcohol. The alcohol radicals may be present 
individually or as mixtures, and may be mono-, di- or triethoxylated. 
An aliphatic radical R may also be derived from a polyhydric aliphatic 
alcohol which contains at least 2, preferably 2 to 5, hydroxyl groups and 
preferably 2 to 9 carbon atoms, e.g. from a alkylenediol having an 
alkylene radical of 2 to 6 carbon atoms, such as ethylene glycol, 1,3- or 
1,2-propylene glycol or 1,5-pentanediol, as well as glycerol, 
trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, 
mannitol or sorbitol. These polyhydric alcohols can also be etherified 
with 1 to 6 moles of ethylene oxide or propylene oxide or mixtures 
thereof. 
An aliphatic radical R is preferably alkenyl or, most preferably, alkyl, 
each of 3 to 22 carbon atoms. 
A cycloaliphatic radical R is preferably derived from cyclopentanol, 
cyclohexanol, cyclododecanol, p-nonylcyclohexanol or hydroabietyl alcohol, 
whereas an araliphatic radical is preferably derived from benzyl alcohol, 
phenylethyl alcohol or phenoxyethanol, and the benzene nucleus may also be 
substituted by lower alkyl, e.g. methyl, ethyl or isopropyl, or by lower 
alkoxy such as methoxy, ethoxy or isopropoxy, or by halogen. 
Very suitable cyanoethylated compounds have the formula 
EQU R.sub.1 --O--CH.sub.2 CH.sub.2 CN (2) 
wherein R.sub.1 is an aliphatic radical of 3 to 22 carbon atoms or a 
phenoxyethyl radical which is unsubstituted or substituted by halogen, 
lower alkyl or lower alkoxy. 
Lower alkyl and lower alkoxy in the definition of the radicals of the 
cyanoethylated compounds are usually those groups or group components 
which contain 1 to 5, preferably 1 to 3, carbon atoms, e.g. methyl, ethyl, 
n-propyl, isopropyl, n-butyl, sec-butyl or amyl, or methoxy, ethoxy or 
isopropoxy. 
Halogen in connection with all substituents is e.g. fluorine, bromine or, 
preferably, chlorine. 
Typical representatives of the cyanoethylated compounds employed in this 
invention are those of the formulae: 
EQU C.sub.2 H.sub.5 --OCH.sub.2 CH.sub.2 CN (3) 
EQU C.sub.4 H.sub.9 O--CH.sub.2 CH.sub.2 CN (4) 
EQU (CH.sub.3).sub.2 CH--CH.sub.2 O--CH.sub.2 CH.sub.2 CN (5) 
##STR1## 
EQU C.sub.6 H.sub.13 O--CH.sub.2 CH.sub.2 CN (7) 
EQU C.sub.8 H.sub.17 O--CH.sub.2 CH.sub.2 CN (9) 
EQU C.sub.12 H.sub.25 O--CH.sub.2 CH.sub.2 CN (12) 
EQU (CH.sub.3).sub.3 C--CH.sub.2 O--CH.sub.2 CH.sub.2 CN (13) 
EQU R'--O--CH.sub.2 CH.sub.2 CN 
wherein R'=alfol radical (8-10), (10-14), (12-14), (12-18) or (16-18) 
EQU C.sub.18 H.sub.37 O--CH.sub.2 CH.sub.2 CN (16) 
EQU NC--CH.sub.2 --CH.sub.2 --O--CH.sub.2 CH.sub.2 --O--CH.sub.2 CH.sub.2 CN 
(17) 
EQU NC--CH.sub.2 CH.sub.2 --O--CH.sub.2 CH.sub.2 --S--CH.sub.2 CH.sub.2 CN (18) 
##STR2## 
Among these representatives, especially preferred compounds are those of 
the formulae (8), (11), (12), (13), (14) and (23). 
The compounds of the formulae (1) to (25) are prepared in a manner which is 
known per se. The preferred procedure is to react an alcohol of the 
formula R--OH, wherein R has the given meaning, with acrylonitrile. The 
reaction is conveniently carried out in an aqueous medium, e.g. in 
alcoholic medium, in the presence of an alkali metal hydroxide or alkali 
metal alcoholate or of a quaternary base such as trimethylbenzyl ammonium 
hydroxide, and in the temperature range from 10.degree. to 60.degree. C. 
The polypropylene oxide adducts used as component (B) may be in the form of 
free acids or salts, e.g. alkali metal or ammonium salts. Representative 
alkali metal salts are, in particular, the sodium and potassium salts, and 
representative ammonium salts are ammonium, trimethylammonium, 
monoethanolammonium, diethanolammonium and triethanolammonium salts. The 
sodium or ammonium (NH.sub.4) salts are preferred. 
The carboxylated polypropylene oxide adduct is obtained preferably from 1 
to 3 moles, preferably 1 mole, of component (a), 2 to 4 moles, preferably 
2 moles, of component (b), 1 mole of component (c) and 0.5 to 2 moles, 
preferably 0.7 to 1 mole, of component (d). 
Component (a) is preferably a diol of the formula 
EQU HO--(CH.sub.2 --CH.sub.2 --O).sub.m ( 26) 
wherein m is 1 to 50, preferably 10 to 40. Examples of such diols are 
ethylene glycol, diethylene glycol or polyethylene glycols having an 
average molecular weight of 450 to 2300, preferably 650 to 1800. Further 
aliphatic diols may also be 1,3- or 1,2-propylene glycol or 
1,5-pentanediol. 
The aliphatic dicarboxylic acid employed as component (b) may be saturated 
or ethylenically unsaturated. Examples of suitable saturated dicarboxylic 
acids are succinic acid, glutaric acid, adipic acid, pimelic acid, suberic 
acid, azelaic acid or sebacic acid or their anhydrides, in particular 
succinic or glutaric anhydride. 
Ethylenically unsaturated dicarboxylic acids are preferably fumaric acid, 
maleic acid or itaconic acid, and also mesaconic acid, citraconic acid and 
methylenemalonic acid. The preferred anhydride of these acids is maleic 
anhydride, which is also the preferred component (b). 
Component (c) is, in particular, an adduct of propylene oxide and a 
trihydric to hexahydric alkanol containing 3 to 6 carbon atoms. This 
alkanol may be straight chain or branched. Typical examples of such 
alkanols are glycerol, trimethylolpropane, erythritol, pentaerythritol, 
mannitol or sorbitol. 
The reaction product employed as component (c) may be prepared e.g. by 
addition of about 2 to 20 moles, preferably 4 to 12 moles, of propylene 
oxide to 1 mole of the trihydric to hexahydric alcohol. Adducts of 4 to 8 
moles of propylene oxide and 1 mole of pentaerythritol have proved 
particularly suitable. 
The fatty acid employed as component (d) may be an unsaturated or a 
saturated acid, e.g. caprylic acid, capric acid, lauric acid, myristic 
acid, palmitic acid, stearic acid, arachidic acid, coconut fatty (C.sub.10 
-C.sub.16) acid, behenic acid, decenoic acid, dodecenoic acid, 
tetradecenoic acid, hexadecenoic acid, oleic acid, linolenic acid, 
ricinolic acid, eicosenic acid, docosenic acid or clupanodonic acid. 
Preferred fatty acids are oleic acid, coconut fatty acid, tallow fatty 
acid, palmitic acid or, in particular, stearic acid. 
Preferred polypropylene oxide adducts are obtained from the following 
components: 
(a.sub.1) an aliphatic diol of the formula 
EQU HO--CH.sub.2 CH.sub.2 O).sub.m.sbsb.1 H, (27) 
wherein m.sub.1 is 10 to 40, preferably a polyethylene glycol having an 
average molecular weight of 900 to 1800, preferably from 1500 to 1600, 
(b.sub.1) a saturated or an ethylenically unsaturated aliphatic 
dicarboxylic acid, or anhydride thereof, containing 4 to 10 carbon atoms, 
preferably maleic anhydride, 
(c.sub.1) an adduct of propylene oxide and a trihydric to hexahydric 
alkanol containing 3 to 6 carbon atoms, and 
(d.sub.1) a saturated or unsaturated fatty acid of 12 to 22 carbon atoms, 
preferably coconut fatty acid, oleic acid, palmitic acid and, most 
preferably, stearic acid. 
Typical representatives of these adducts are reaction products of: 
1. 1 mole of the condensation product of 1 mole of pentaerythritol and 4 to 
8 moles of propylene oxide, 2 moles of maleic anhydride, 1 mole of 
diethylene glycol and 1 mole of coconut fatty acid, 
2. 1 mole of the condensation product of 1 mole of pentaerythritol and 4 to 
8 moles of propylene oxide, 2 moles of maleic anhydride, 1 mole of 
polyethylene glycol having an average molecular weight of 1500 and 0.8 
mole of stearic acid, 
3. 1 mole of the condensation product of 1 mole of pentaerythritol and 4 to 
8 moles of propylene oxide, 2 moles of glutaric or succinic anhydride, 1 
mole of polyethylene glycol having an average molecular weight of 1500 and 
1 mole of coconut fatty acid, 
4. 1 mole of the condensation product of 1 mole of pentaerythritol and 4 to 
8 moles of propylene oxide, 2 moles of maleic anhydride, 1 mole of 
polyethylene glycol having an average molecular weight of 900 and 1 mole 
of stearic acid, 
5. 1 mole of the condensation product of 1 mole of pentaerythritol and 8 
moles of propylene oxide, 2 moles of maleic anhydride, 1 mole of 
polyethylene glycol having an average molecular weight of 1500 and 0.7 
mole of oleic acid or palmitic acid. 
The adducts 1 to 5 may be in the form of free acids or salts, in particular 
sodium salts or ammonium salts. 
The preparation of the polypropylene adducts is carried out by known 
methods. One process for the preparation of these products comprises 
reacting component (a) with components (b), (c) and (d) and, if desired, 
converting the reaction product into a salt. The reaction of component (a) 
with components (b), (c) and (d) may be conducted in the presence of an 
acid catalyst and/or of an organic solvent which is inert to the 
reactants, and in the temperature range from 80.degree. to 150.degree. C., 
preferably from 90.degree. to 130.degree. C. Sulfuric acid or 
p-toluenesulfonic acid may be used as catalyst. Examples of suitable 
organic solvents are benzene, toluene or xylene. 
When a dicarboxylic acid is used as component (b), the different components 
may be reacted simultaneously. If component (b) is the anhydride of an 
aliphatic dicarboxylic acid, then the esterification is conveniently 
carried out stepwise. In a first step, the diol (component a)) is reacted 
in the presence of a polymerisation inhibitor, e.g. 
di-(tert-butyl)-p-cresol, with the anhyride by heating to 
90.degree.-130.degree. C. to give the bis-monoester of the dicarboxylic 
acid, which is then further esterified in a second step, with the addition 
of an acid catalyst and, if desired, in the presence of an inert organic 
solvent, e.g. benzene or toluene, with the adduct of component (c) and a 
fatty acid (component (d)), following which the ester product which still 
contains carboxyl groups may be converted into a salt by addition of a 
base, such as ammonia or an alkali metal hydroxide. Depending on their 
composition, the resultant adducts are solid to liquid, highly viscous 
products. They may therefore be in the form of waxes, pastes or oils, and 
are normally colourless or slighty yellow or brown in colour. 
Preferred compositions comprise at least the following components: 
(Aa) an O-cyanoethylated compound of the formula 
EQU R.sub.2 --O--CH.sub.2 CH.sub.2 CN (28) 
wherein R.sub.2 is an aliphatic radical of 6 to 22 carbon atoms or a 
phenoxyethyl radical which is unsubstituted or substituted by halogen, 
methyl or methoxy, and 
(Bb) a carboxylated polypropylene oxide adduct or salt thereof, which 
adduct has been prepared from the above components (a.sub.1), (b.sub.1), 
(c.sub.1) and (d.sub.1). 
In addition to containing components (A) and (B), the novel composition may 
also contain, as component (C), an aliphatic alcohol containing 5 to 18 
carbon atoms or a siloxane-oxyalkylene copolymer, or a mixture of such 
compounds. Component (C) acts in particular as foam inhibitor. 
The alcohols may be used as individual compounds or in admixture with one 
another. They may be straight chain or branched, saturated or unsaturated, 
and they will normally be liquid at room temperature. Typical examples of 
such alcohols are: n-amyl alcohol, n-hexanol, trimethylhexanol, 
2-ethyl-n-hexanol, octyl alcohol (octanol mixture of isomers), nonyl 
alcohol, decyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl 
alcohol, cetyl alcohol, stearyl alcohol or oleyl alcohol, and also the 
alfols, e.g. alfol (6-10), alfol (8-10), alfol (10-14), alfol (12), alfol 
(16) and alfol (18). Preferred alcohols are alkanols of 5 to 10 carbon 
atoms, with 2-ethyl-n-hexanol being particularly preferred. 
Further suitable optional components (C) are commercially available 
surface-active hydrophilic adducts of an organopolysiloxane and ethylene 
oxide and/or propylene oxide. 
The organopolysiloxanes employed as starting materials for obtaining such 
adducts are, in principle, commercially available silicone oils which are 
described in German Auslegeschrift No. 20 31 827. Among these silicone 
oils, polydimethylsiloxanes are preferred. The siloxane-oxyalkylene 
copolymers suitable for use as optional component (C) may be obtained e.g. 
from halogen-substituted organopolysiloxanes, in particular 
polydimethylsiloxanes and alkali metal salts of polyoxyalkylene, e.g. 
polyethylene and/or propypropylene glycols. 
These siloxane-oxyalkylene copolymers are polyether siloxanes which 
advantageously have a cloud point in the range from about 
20.degree.-70.degree. C., preferably from 25.degree.-50.degree. C. The 
glycol content consisting of oxyethylene groups or oxyethylene and 
oxypropylene groups is advantageously from 35 to 85% by weight, preferably 
from 40 to 75% by weight, based on the total weight of the polyether 
siloxane. 
A preferred embodiment of component (C) is accordingly a block polymer of a 
polydimethyl siloxane and ethylene oxide, or of a copolymer of ethylene 
oxide and propylene oxide, which block polymer has a cloud point of 
20.degree.-70.degree. C., preferably from 25.degree.-50.degree. C. Such 
block polymers or polyether siloxanes may be illustrated by the probable 
formula 
##STR3## 
wherein q is 3 to 50, preferably 3 to 25, r is 2 or 3, s is 0 to 15, t is 
1 to 25, x.sub.1 is 3 to 10 and R.sub.3 is alkyl of 1 to 4 carbon atoms, 
preferably methyl. Such polyether siloxanes are described e.g. in German 
Auslegeschrift No. 1 719 328 and in U.S. Pat. Nos. 2,834,748, 3,389,160 
and 3,505,377. 
Further polyether siloxanes which may be used as component (C) have the 
probable formula 
##STR4## 
wherein each of R.sub.4 and R.sub.5 is alkyl of 1 to 4 carbon atoms, 
preferably methyl, a' is 1 to 20, b' is 2 to 20, c' is 2 to 50, d' is 1 or 
2, preferably 1, and m' is 2 to 5, and the groups C.sub.m' H.sub.2m' 
O.sub.d' are preferably ethylene oxide groups or mixtures of ethylene 
oxide groups and propylene oxide groups. Such siloxane compounds are 
described in German Auslegeschrift No. 1 795 557. 
A suitable component (C) which corresponds to the probable formula (29) and 
has a cloud point of 32.degree. C., is e.g. SILICONSURFACTANT L 546.RTM. 
(registered trademark of Union Carbide). This silicone compound is used 
preferably in conjunction with 2-ethyl-hexanol. 
In addition, the assistants of this invention may contain, as polar solvent 
(D), a water-miscible organic solvent. The addition of solvent improves 
the solubility of the composition. Examples of water-miscible organic 
solvents are aliphatic C.sub.1 -C.sub.4 alcohols such as methanol, 
ethanol, the propanols or isobutanol; alkylene glycols such as ethylene 
glycol or propylene glycol; monoalkyl ethers of glycols such as ethylene 
glycol monomethyl, monoethyl or monobutyl ether, and diethylene glycol 
monomethyl or monoethyl ether; ketones such as acetone, methyl ethyl 
ketone, cyclohexanone or diacetone alcohol; ethers and acetals such as 
diisopropyl ether, diphenyl oxide, dioxane, tetrahydrofurane, and also 
tetrahydrofurfuryl alcohol, pyridine, acetonitrile, .gamma.-butyrolactone, 
N-methylpyrrolidone, N,N-dimethyl formamide, N,N-dimethyl acetamide, 
tetramethyl urea, tetramethylene sulfone etc. Mixtures of these solvents 
may also be used. The preferred solvent is water. 
The compositions of this invention advantageously contain 
10 to 60% by weight of component (A), 
20 to 50% by weight of component (B), 
0 to 15% by weight, preferably 1 to 10% by weight, of component (C), and 
0 to 60% by weight, preferably 10 to 45% by weight, of component (D), 
in each case based on the weight of the total mixture. 
The novel compositions may be prepared by simple stirring of components 
(A), (B) and optionally (C) and/or (D), to produce homogeneous clear 
formulations which are stable at room temperature. 
The novel formulations are used in particular as anticrease finishing 
agents in dyeing linear polyester fibres or blends of polyester fibres and 
cotton or wool. They increase the rate of diffusion of the dyes in the 
fibres and thereby increase the dye yield. Moreover, they have a foam 
inhibiting effect. 
Accordingly, the present invention also provides a process for dyeing 
textile material which contains polyester fibres with disperse dyes, or 
for whitening such material with fluorescent whitening agents, which 
process comprises dyeing or whitening said material in the presence of the 
composition of the invention. 
The amount in which the composition of the invention is added to the 
dyebaths or whitening liquors varies from 0.5 to 10% by weight, preferably 
from 2 to 8% by weight, based on the weight of the material to be dyed. 
Suitable polyester fibre material which can be dyed or whitened in the 
presence of the novel composition is e.g. material made from cellulose 
esters, such as cellulose 21/2-acetate and cellulose triacetate fibres, 
and especially linear polyester fibres. 
Linear polyester fibres are to be construed as meaning synthetic fibres 
which are obtained e.g. by condensation of terephthalic acid with ethylene 
glycol or of isophthalic acid or terephthalic acid with 
1,4-bis-(hydroxymethyl)cyclohexane, as well as copolymers of terephthalic 
acid and isophthalic acid and ethylene glycol. The linear polyester used 
up to now almost exclusively in the textile industry is that derived from 
terephthalic acid and ethylene glycol. 
The fibre material can also be employed as blends with another or with 
other fibres, e.g. blends of polyacrylonitrile/polyester, 
polyamide/polyester, polyester/cotton, polyester/viscose and 
polyester/wool. 
The textile material to be dyed or whitened can be in different states of 
processing, preferably piece goods, such as knits or wovens. 
The disperse dyes to be used, which are soluble in water to only a very 
limited degree and are present in the dye liquor for the most part in the 
form of a fine dispersion, may belong to the most diverse dyestuff 
classes, for example to the acridone, azo, anthraquinone, coumarin, 
methine, perinone, naphthoquinone-imine, quinophthalone, styryl or nitro 
dyes. Mixtures of disperse dyes may also be used in the process of the 
invention. 
In the process of this invention, polyester/wool blends are preferably dyed 
with commercially available mixtures of anionic dyes and disperse dyes. 
The anionic dyes are e.g. salts of heavy metal-containing dyes or 
preferably of metal-free mono-, dis- or polyazo dyes including formazane 
dyes, as well as anthraquinone, xanthene, nitro, triphenylmethane, 
naphthoquinone-imine and phthalocyanine dyes. The anionic character of 
these dyes can be imparted by metal complexing alone and/or preferably by 
acid salt-forming substituents such as carboxylic acid groups, sulfuric 
acid ester and phosphoric acid ester groups, phosphonic acid groups or 
sulfonic acid groups. These dyes can also contain in the molecule reactive 
groups which form a covalent bond with wool. 
Particularly interesting dyes are 1:1 or 1:2 metal complex dyes. The 1:1 
metal complex dyes preferably contain one or two sulfonic acid groups. As 
metal they contain a heavy metal atom, e.g. a copper, nickel or especially 
chromium atom. 
The 1:2 metal complex dyes contain, as central metal atom, a heavy metal 
atom, e.g. a cobalt or especially a chromium atom. Attached to the central 
atom are two complexing components, at least one, but preferably each, of 
which is a dye molecule. In addition, both dye molecules participating in 
the complexing can be identical or different. The 1:2 metal complex dyes 
can contain e.g. two azomethine molecules, a disazo and a monoazo dye 
molecule or preferably two monoazo dye molecules. The azo dye molecules 
can contain water-solubilising groups, e.g. acid amide, alkylsulfonyl, or 
the above mentioned acid groups. Preferred metal complex dyes are 1:2 
cobalt or 1:2 chromium complex dyes of monoazo dyes which contain acid 
amide or alkylsulfonyl groups or altogether a single sulfonic acid group. 
Mixtures of anionic dyes may also be used. 
Blends of polyester and cotton are normally dyed with combinations of 
disperse dyes and vat dyes, sulfur dyes, leuco vat ester dyes, direct dyes 
or reactive dyes, and the polyester constituent is dyed beforehand, 
simultaneously or subsequently with disperse dyes. The vat dyes are higher 
fused and heterocyclic benzoquinones or naphthoquinones, sulfur dyes and, 
in particular, anthraquinoid or indigoid dyes. Examples of vat dyes which 
may be employed in the process of this invention are listed in the Colour 
Index, 3rd Edition (1971), Vol. 3, pp. 3649-3837 under the heading 
"Sulphur Dyes" and "Vat Dyes". Suitable direct dyes are e.g. those listed 
under the heading "Direct Dyes", C.I. (1971), 3rd Ed., Vol. 2, pp. 
2005-2478. The leuco vat ester dyes are obtainable e.g. from vat dyes of 
the indigo, anthraquinone or indanthrene series by reduction e.g. with 
iron powder and subsequent esterification e.g. with chlorosulfonic acid, 
and are listed under the heading "Solubilised Vat Dyes", C.I. (1971), 3rd 
Ed., Vol. 3. Reactive dyes will be understood as meaning the customary 
dyes which form a covalent bond with cellulose, e.g. those listed under 
the heading "Reactive Dyes" in C.I. (1971), 3rd Ed., Vol. 3., pp. 
3391-3560. 
The novel assistant compositions may also be used in the whitening of 
undyed synthetic fibre materials with fluorescent whitening agents which 
are dispersed in water. 
The fluorescent whitening agents may belong to any class of such compounds. 
In particular they are coumarins, triazole coumarins, benzocoumarins, 
oxazines, pyrazines, pyrazolines, diphenyl pyrazolines, stilbenes, styryl 
stilbenes, triazolyl stilbenes, bisbenzoxazolyl ethylenes, stilbene 
bis-benzoxazoles, phenylstilbene oxazoles, thiophene bis-benzoxazoles, 
naphthalene bis-benzoxazoles, benzofuranes, benzimidazoles and 
naphthalimides. 
Mixtures of fluorescent whitening agents may also be used in the practice 
of this invention. 
The amount of dye or fluorescent whitening agent to be added to the liquor 
depends on the desired colour strength. In general, amounts of 0.01 to 10% 
by weight, preferably 0.02 to 5% by weight, based on the weight of the 
textile material employed, have proved advantageous. 
The compositions to be employed in the practice of this invention may also 
be used in admixture with known carriers based on e.g. di- or 
trichlorobenzene, methyl or ethyl benzene, o-phenylphenol, benzylphenol, 
diphenyl ether, chlorodiphenyl, methyl diphenyl, cyclohexanone, 
acetophenone, alkylphenoxy ethanol, mono-, di- or trichlorophenoxy ethanol 
or mono-, di- or tri-chlorophenoxy propanol, pentachlorophenoxy ethanol, 
alkylphenylbenzoates or, in particular, based on diphenyl, methyl diphenyl 
ether, dibenzyl ether, methyl benzoate, butyl benzoate or phenyl benzoate. 
The carriers are used preferably in an amount of 0.5 g/l to 2 g/l of liquor 
or 5 to 30% by weight, based on the composition. 
Depending on the textile material to be treated, the dyebaths or whitening 
baths may contain, in addition to the dyes or fluorescent whitening agents 
and compositions of the invention, also wool protecting agents, oligomer 
inhibitors, antifoams, emulsifiers, levelling agents, retarders and, 
preferably, dispersants. 
The purpose of the dispersants is in particular to obtain a good dispersion 
of the disperse dyes. Suitable dispersants are those customarily employed 
in dyeing with disperse dyes. Preferred dispersants are sulfated or 
phosphated adducts of 15 to 100 moles of ethylene oxide or preferably 
propylene oxide with polyhydric aliphatic alcohols containing 2 to 6 
carbon atoms, e.g. ethylene glycol, glycerol or pentaerythritol, or with 
amines containing 2 to 9 carbon atoms and at least two amino groups or one 
amino group and one hydroxyl group, as well as alkylsulfonates containing 
10 to 20 carbon atoms in the alkyl chain, alkylbenzenesulfonates with 
straight or branched alkyl chain containing 8 to 20 carbon atoms, e.g. 
nonyl- or dodecylbenzenesulfonate, 
1,3,5,7-tetramethyloctylbenzenesulfonate or octadecylbenzenesulfonate, and 
alkylnaphthalenesulfonates or sulfosuccinates, such as sodium 
dioctylsulfosuccinate. 
Particularly suitable anionic dispersants are lignosulfonates, 
polyphosphates and, preferably, formaldehyde condensation products of 
aromatic sulfonic acids, formaldehyde and, optionally, of mono- or 
bifunctional phenols, e.g. of cresol, .beta.-naphtholsulfonic acid and 
formaldehyde, of benzenesulfonic acid, formaldehyde and 
naphthalenesulfonic acid, of naphthalenesulfonic acid and formaldehyde, or 
of naphthalenesulfonic acid, dihydroxydiphenylsulfone and formaldehyde. 
The preferred anionic dispersant is the disodium salt of 
di-(6-sulfonaphthyl-2)-methane. 
Mixtures of anionic dispersants may also be employed. Normally the anionic 
dispersants will be in the form of their alkali metal salts, ammonium 
salts or amine salts. These dispersants are preferably employed in an 
amount of 0.1 to 5 g/l of treatment liquor. 
Depending on the dye and substrate to be employed, the dyebaths or 
whitening baths may also contain in addition to the compositions of the 
invention, conventional additives, advantageously electrolytes such as 
salts, e.g. sodium sulfate, ammonium sulfate, sodium or ammonium 
phosphates or sodium or ammonium polyphosphates, metal chlorides or metal 
nitrates such as calcium chloride, magnesium chloride or calcium nitrates, 
ammonium acetate or sodium acetate and/or acids, e.g. mineral acids, such 
as sulfuric acid or phosphoric acid, or organic acids, preferably lower 
aliphatic carboxylic acids, such as formic acid, acetic acid or oxalic 
acid. The acids are used in particular for adjusting the pH value of the 
dyebaths employed in the invention. The pH value is ordinarily in the 
range from 4 to 6.5, preferably from 4.5 to 6. 
Dyeing or whitening is performed advantageously from an aqueous liquor by 
the exhaust method. The liquor ratio can accordingly be chosen within a 
wide range, e.g. from 1:4 to 1:100, preferably from 1:6 to 1:50. The 
dyeing or whitening temperature is at least 70.degree. C. and is 
ordinarily not higher than 140.degree. C. Preferably it is in the range 
from 80.degree. to 135.degree. C. 
Linear polyester fibres and cellulose triacetate fibres are preferably dyed 
by the high temperature process in closed and advantageously also 
pressure-resistant machines at temperatures above 100.degree. C., 
preferably in the range between 110.degree. and 135.degree. C., and 
optionally under pressure. Examples of suitable closed dyeing machines are 
circulating liquor machines such as cheese dyeing and beam dyeing 
machines, winch becks, jet dyeing or rotary dyeing machines, muff dyeing 
machines, paddles or jiggers. Cellulose 21/2-acetate fibers are preferably 
dyed at temperatures from 80.degree. to 85.degree. C. 
The dyeing process of the present invention can be carried out such that 
the material to be dyed is either briefly treated first with the dyeing 
assistant and then dyed, or preferably simultaneously with the assistant 
and the dye. The goods are preferably run for 5 minutes at 
60.degree.-80.degree. C. in the bath which contains the dye, the 
composition and optionally further ingredients, and which is adjusted to a 
pH value of 4.5 to 5.5, then the temperature is raised over 15 to 35 
minutes to 110.degree.-135.degree. C., preferably to 130.degree. C., and 
the bath is left for 15 to 90 minutes, preferably for 30 minutes, at this 
temperature. 
The dyeings are finished by cooling the dyebath to 60.degree.-80.degree. 
C., rinsing them with water and, if desired, effecting a reductive 
afterclear in alkaline medium in conventional manner. The dyeings are then 
once more rinsed and dried. When using carriers, the dyeings are 
conveniently subjected to a heat treatment, e.g. a thermosol treatment, in 
order to improve the lightfastness. This heat treatment is preferably 
carried out in the temperature range from 160.degree. to 180.degree. C. 
over 30 to 90 seconds. When using vat dyes for the cellulose constituent, 
the goods are first treated with hydrosulfite at a pH of 6 to 12.5 and 
then with an oxidising agent, and finally given a washing off. 
The process of the invention gives level and intense dyeings which are 
distinguished by good dye yields. In particular, level dyeings are 
obtained, and the material has a crease-resistant rating of 2-5 according 
to the Monsanto standard and has a level appearance and an attractive soft 
handle. In addition, the fastness properties of the dyeings, e.g. 
lightfastness, crockfastness and wetfastness, are not impaired by the use 
of the composition of the invention. Further, no troublesome foaming 
occurs during dyeing in the presence of the composition of the invention.

In the following Preparatory and Application Examples, parts and 
percentages are by weight, unless otherwise indicated. The indicated 
amounts of dye refer to commercially available, i.e. diluted, product, and 
the indicated amounts of the components of the composition refer to pure 
substance. Five-figure Colour Index (C.I.) numbers refer to the 3rd 
Edition of the Colour Index. 
PREATORY EXAMPLES 
Example A 
150 g of polyethylene glycol having an average molecular weight of 1500, 
19.6 g of maleic anhydride and 0.3 g of di-(tert-butyl)-p-cresol are 
heated to 130.degree. C. and the mixture is stirred for 3 hours at 
130.degree. C. The reflux cooler is replaced by a distillation receiver 
and then 60 g of a condensation product of 1 mole of pentaerythritol and 8 
moles of propylene oxide, 22 g of stearic acid and 0.5 g of 99% sulfuric 
acid are added, and the mixture is kept for 5 hours under vacuum at 
130.degree. C.. while small amounts of water are distilled off. The melt 
is cooled to about 60.degree. C. and 2 g of 30% sodium hydroxide solution 
are added to neutralise the sulfuric acid. An ester condensation product 
having an acid number of 7 is obtained. This condensate is dissolved in 
580 g of water and the solution is adjusted to pH 6.5-7 by addition of 30% 
sodium hydroxide solution. A 30% viscous solution of the polypropylene 
oxide adduct is obtained. 
Example B 
The procedure of Example A is repeated, but using 10.6 g of diethylene 
glycol instead of 150 g of polyethylene glycol, and 15.6 g of coconut 
fatty acid instead of 22 g of stearic acid. A 30% viscous emulsion of the 
carboxylated polypropylene oxide adduct is obtained. 
Example C 
The procedure of Example A is repeated, but using 20 g of succinic 
anhydride instead of 19.6 g of maleic anhydride, and 15.6 g of coconut 
fatty acid instead of 22 g of stearic acid. A 30% viscous solution of the 
polypropylene oxide adduct is obtained. 
Example D 
The procedure of Example A is repeated, but using 100 g of polyethylene 
glycol having an average molecular weight of 1000 instead of 150 g of 
polyethylene glycol 1500. A 30% viscous solution of the polypropylene 
oxide adduct is obtained. 
Example E 
The procedure of Example A is repeated, but using 21.8 g of oelic acid 
instead of 22 g of stearic acid. A 30% viscous solution of the 
polypropylene oxide adduct is obtained. 
Example F 
2 cm.sup.3 of a 30% methanolic potassium hydroxide solution are added 
dropwise at room temperatures over 20 minutes to 144.3 g of 
3,5,5-trimethylhexyl alcohol and 53.5 g of acrylonitrile, while keeping 
the temperature below 40.degree. C. with periodic cooling. The reaction 
mixture is stirred for 3 hours at 40.degree. C., then a further 1 cm.sup.3 
of 30% methanolic potassium hydroxide solution is added. The reaction 
mixture is kept for a further 2 hours at 40.degree. C., and then cooled to 
25.degree. C. The reaction product is then neutralised with acetic acid 
and kept for 60 minutes at 50.degree. C. under vacuum. Yield: 198 g of an 
adduct of the formula 
##STR5## 
in the form of a clear, colourless liquid. 
The cyanoethylated compounds of the formulae (3) to (13) and (15) to (25) 
are also prepared in this manner. 
APPLICATION EXAMPLES 
Example 1 
100 g of texturised polyester knitted fabric are dyed in 2.4 liters of 
water on a laboratory jet dyeing machine with the following ingredients: 
2 g of a dye of the formula 
##STR6## 
5 g of ammonium sulfate 2 g of a mixture of a polyglycol oleate and a 
polyadduct of 9 moles of ethylene oxide and 1 mole of p-tert-octylphenol 
0.2 g of 85% formic acid and 
6 g of a composition (1) consisting of 30% of a compound of the formula 
##STR7## 
30% of the product prepared in Example A (30%) 2% of a 
siloxane-oxyalkylene copolymer (C.sub.1) having a viscosity of 1200 mPas 
at 20.degree. C. and a cloud point of 32.degree. C., and 
38% of water. 
The above ingredients are first dissolved or dispersed in water and added 
to the dyebath at 70.degree. C. The dyeing temperature is then raised over 
60 minutes to 127.degree. C. and the goods are dyed for a further 60 
minutes at this temperature. The bath is then cooled to 20.degree. C. over 
4 minutes and the goods are then rinsed and dried. A level blue dyeing is 
obtained. 
The dyed goods have a rating of 3 according to the Monsanto standard (test 
of crease resistance). The rating is only 1 without the addition of 
composition (1). 
Example 2 
100 kg of a polyester/wool (55:45) blended fabric are treated on a winch 
beck with a dye liquor which contains 
1 kg of a mixture (7:3) of the dyes of the formulae 
##STR8## 
0.8 kg of the sodium salt of ethylenediaminetetraacetic acid 4 kg of the 
reaction product of naphthalenesulfonic acid and formaldehyde 
2 kg of an amphoteric fatty amine polyglycol ether sulfate and 
3 kg of composition (1) 
in 4000 liters of water. The temperature is then raised to 107.degree. C. 
over 30 minutes and the goods are dyed for 1 hour at this temperature. The 
bath is then cooled to 20.degree. C. and the fabric is then rinsed and 
dried. A level, fast, yellow dyeing is obtained. Compared with a dyeing 
obtained on a fabric without the addition of composition (1), a 30% 
greater dye yield is obtained on the polyester constituent of the fabric 
dyed according to this Example. The dyebath does not foam during the 
entire duration of the dyeing procedure. 
According to the Monsanto standard, the dyed goods are rated 2-3. 
Example 3 
A high temperature dyeing machine which contains 100 kg of 
polyester/cellulose (67:33) fabric in 3000 liters of water of 60.degree. 
C., is initially charged with the following ingredients: 
2 kg of a mixture of the dyes of the formula 
##STR9## 
6 kg of ammonium sulfate and 0.6 kg of a fatty alkylbenzimidazole 
sulfonate. 
Then 4 kg of composition (1) are added. The pH of the dyebath is adjusted 
to 5 with 85% formic acid and the goods are allowed to circulate for 15 
minutes. The temperature is then raised to 125.degree. C. over 50 minutes 
and the goods are treated for 90 minutes at this temperature. The bath is 
then cooled to 70.degree. C. and the following further ingredients are 
added in order to develop the vat dye: 
9 kg of 30% sodium hydroxide solution 
9 kg of 40% hydrosulfite and 
5 kg of sodium chloride. 
The goods are subsequently treated for 45 minutes at 70.degree. C., then 
rinsed, oxidised with hydrogen peroxide, rinsed again, and dried. A level, 
fast, orange dyeing is obtained. 
A comparison with a dyeing obtained without the addition of composition (1) 
shows that a 20% greater dye yield is obtained on the polyester 
constituent of the fabric dyed in accordance with this Example. The 
dyebath does not foam during the entire duration of the dyeing procedure. 
According to the Monsanto standard, the rating is 3-4. 
Example 4 
100 kg of the polyester fabric are wetted at 60.degree. C. in 800 ml of 
water in a jet dyeing machine. The following ingredients are then added: 
2200 g of a dye of the formula 
##STR10## 
2000 g of an ammonium salt of the formula 
##STR11## 
1600 g of ammonium sulfate and 3000 g of a composition (2) consisting of 
30% of a compound of the formula 
EQU (CH.sub.3).sub.2 --CH--CH.sub.2 O--CH.sub.2 CH.sub.2 CN (5) 
30% of the product obtained in Example E 
20% of propylene carbonate and 
20% of water. 
The dyebath is then adjusted to pH 5.5 with formic acid and heated to 
125.degree. C. over 45 minutes and the goods are then dyed for 60 minutes 
at this temperature. The bath is then cooled and the goods are rinsed and 
dried. A level, crockfast, blue dyeing is obtained. According to the 
Monsanto standard, the dyed goods have a rating of 3.5. Without the 
addition of composition (2) the rating is only 1. 
A level, crockfast, blue dyeing is also obtained by using, in this Example, 
the same amount of the following compositions (3) or (4) instead of 
composition (2): (3) Composition consisting of 
25% of a compound of the formula (23) 
##STR12## 
40% of the product prepared according to Example C 1% of a 
siloxane-oxyalkylene copolymer (C.sub.1) having a viscosity of 1200 mPas 
at 20.degree. C. and a cloud point of 32.degree. C., 
5% of isobutanol and 
29% of water. 
(4) Composition consisting of 
20% of a compound of the formula (11) 
##STR13## 
45% of the product prepared according to Example B 20% of isobutanol and 
15% of water. 
Example 5 
10 g of polyethylene glycol terephthalate fabric are treated for 5 minutes 
at 40.degree. C. in a dyeing apparatus with a liquor which contains 
0.2 g of composition (1) and 
0.01 g of a dispersion of a fluorescent whitening agent of the formula 
##STR14## 
in 200 ml of water and which has been adjusted to pH 5.5 with 85% formic 
acid. The liquor is then heated over 30 minutes to 110.degree. C. and the 
goods are dyed for 30 minutes at this temperature. The liquor is then 
cooled to 40.degree. C. over 15 minutes and the goods are subsequently 
rinsed and dried at 70.degree. C. A brilliant, level white effect with an 
excellent degree of whiteness is obtained. 
Example 6 
The procedure of Example 5 is repeated, but using a liquor which, instead 
of the fluorescent whitening agent of the formula (108), contains the same 
amount of a fluorescent whitening agent of the formula 
##STR15## 
Level, brilliant white effects are also obtained.