CA1227909A

CA1227909A - Polyesters or polyethers carriers for use in dyeing textiles

Info

Publication number: CA1227909A
Application number: CA000459686A
Authority: CA
Inventors: Serge Boisvert
Original assignee: INDUSTRIES TECHNO-CHEM LTEE (LES)
Current assignee: INDUSTRIES TECHNO-CHEM LTEE (LES)
Priority date: 1984-07-25
Filing date: 1984-07-25
Publication date: 1987-10-13

Abstract

ABSTRACT OF THE DISCLOSURE

The present invention relates to a method of dyeing or printing synthetic fibres, wherein the fibres are treated with a dye material including a carrier for the dye material, according to the invention the carrier is selected from the group consisting of aromatic polyesters and polyethers which are obtained by the reaction of: a) a n-alkylene, thioalkylene, polyalkylene polyol or a functional derivative thereof with at least one aromatic carboxylic acid or a functional deriv-ative thereof; or b) an aliphatic dicarboxylic acid or a functional derivative thereof with at least one aromatic alcohol or a functional derivative thereof. The invention also relates to a composition for use as a carrier which comprises the aromatic polyesters or polyethers defined above, in association with an emulsifying agent, if desired an addi-tional polyglycol ether. The chemicals have a low degree of toxicity, an excellent biodegradability and an extremely low odor.

Description

79~;~

The invention relates to aromatic polyesters or polyethers which are obtained by reaction of:
a) One n-alkylene, thioalkylene, polyalkylene polyol or a functional derivative thereof or else one I, ethylenically saturated or unsaturated aliphatic dicarboxylic acid or a functional derivative thereof and b) at least one aromatic carboxylic acid or a functional derivative thereof or else at least one aromatic alcohol or a functional derivative thereof. More particular-lye the invention relates to the use of these aromatic polyp esters or polyethers in the in the dyeing of synthetic fires.
The water insoluble compound resulting from the condensation of a glycol with at least one molecule of aromatic acid or, the water insoluble compound resulting from the condensation of an aliphatic dicarboxylic acid with at least one molecule of an aromatic alcohol preferably have to be blended with proper emulsifiers in order to render them easily emulsifiable in warm water. These emulsifiable products which, inter alias are usable as dyeing and printing assistants, possess interesting properties.
It is known that the standard carriers and adjutants which are used in the dyeing of synthetic fires cause serious environmental problems as a result of their smell, high vote-utility, toxicity and/or biodegradability. The drawbacks of the conventional carriers (dye accelerators) are very well known to the textile industry and are also a major concern for the environment authorities. For the purpose of this invention, "carrier" will be defined as follows:
A water insoluble compound or a water insoluble blend of compounds which when blended with proper emulsifying agents, is rendered easily water emulsifiable. This easily water emulsifiable compound when added to a dye bath I

at a concentration varying from 0.5 to 8.0% on the weight of the material to be dyed and upon applying heat, will be positively absorbed by the fire and will swell the same to a greater extent -than water alone at same temperature.
This swelling effect of the fire will greatly promote dye penetration, dye leveling and dye exhaustion at same tempt erasure. In addition to that effect, the emulsifiable sub-stance, when absorbed by the fire, will have a greater solvent cry effect for the distaffs than - the fire alone at same temperature.
It is an object of this invention to provide the textile industry with chemicals having a low degree of toxic-fly, an excellent biodegradability and having also an extremely low odor.
The present invention relates to a method of dyeing synthetic fires, wherein the fires are treated with a dye lo -I

material including a carrier for the dye material. According to the invention the carrier is selected from the group consisting of aromatic polyesters and polyethers which are obtained by the reaction of:
a) a n-alkylene, thioalkylene, polyalkylene polyol or a functional derivative thereof with at least one aromatic carboxylic acid or a functional derivative thereof; or b) an unsaturated aliphatic dicarboxylic acid or a functional derivative thereof with at least one aromatic alcohol or a functional derivative thereof.
The invention also relates to a composition for use as a carrier which comprises the aromatic polyesters or polyp ethers defined above, in association with emulsifying agent , if desired an additional polyglycol ether.
Types of n-alkylenediols which are suitable for component (a) are principally those with 2 to 6 carbon atoms, e.g., ethylene glycol, diethylene glycol, 1,2-propanediol, trim ethylene glycol, tetramethylene glycol, pentamethylene glycol and hexamethylene glycol. Ethylene glycol is particular-lye preferred m e thioalkylene dills with a molecular weight bet-wren 110 and 400, and particularly thiodiethylene glycol, are particularly suitable as the polyol of group (a).
The polyalkylene glycols and the n,alkanediols are particularly preferred in group (a). These have for example the formula:
H ( n on em (I) wherein n is an integer from 2 to 4 and m is an integer from 1 to 10 and, if n is 1, -C Hen represent an unbranched chain or especially the formula:

Ho ( n'H2n' em' (2) wherein n' is 2 or 3 and m' is an integer from 1 - 10.

I

Polyethylene glycols with a molecular weight between about 150 and about Lowe, in particular between about 150 and about 400, above all the polyethylene glyeols within this range and with lower molecular weights, are particularly suitable in group (a). In this connection, the values for m, in formula

(2) are between 3 to 5 and 8 to 9.
Triethylene glyeol may be cited as a suitable glycol in respect of which m, in formula (2) has values between 3 and 5. Good results may also be obtained with polyethylene glycols lo which have a molecular weight of lo to 200 and a value for m, in formula (2) of 8 to 9.
Particularly preferred glycols in group (a) are those of the formula:
Ho - (C Ho I) 2 - H (3) wherein n, is 2 or 3 and my is 1 or 2.
Ethylene glycol, diethylene glycol, propylene glycol have a particularly interesting utility:
If in group (a) an aliphatic diearboxylie acid is used instead of a glyeol, then the condensation reaction is carried out with a component of group (b) which is an aromatic alcohol. In this ease the component of group (a) has for example the formula - C - R - C - X (4) O O
wherein represents alkaline of l to carbon atoms.
Examples of suitable dicarboxylie acids with an alkaline group of l to 8 carbon atoms include Masonic, Suzanne, gloater, adipic, pummel sub Eric azalea and Saab acid.
Types of aromatic carbolic acids which can be used in group (b) include those where the earboxyl group is Sue attached directly to a Bunsen or naphthalene rink, or a functional derivative thereof.
Particularly preferred acids in this case include those of the formula:
IX

X - I C KIWI
C - X or Y (5) C /
X
wherein X is hydrogen, halogen, methyl group or other low molecular weight aliphatic group and Y is the carboxylic acid group.
If only one aromatic carboxylic acid is used, then a low molecular weight aliphatic acid may additionally be used.
apples of suitable aromatic carhoxylic acids include benzoic, salicylic, cresotinic, phthalic and talk acids, 1-8 naphthalic acid android or a functional derivative thereof. An example of additional aliphatic acid includes for example acetic acid. In group (b) an aromatic alcohol is used instead of an aromatic carboxylic acid; then, the condensation reaction is carried out with an aliphatic dicer-boxlike acid. In this case, the aromatic alcohol shall have for example, the formula X

X I C C -- Y

X - C C C - X or Y

wherein X is hydrogen, halogen, hydroxyl, methyl group or other low molecular weight aliphatic group and Y is a hydroxyl or an alcoholic group. If only one aromatic alcohol is used, then a low molecular weight aliphatie alcohol may additionally be used.
Examples of suitable aromatic alcohols, include bouncily alcohol, phenol, crossly or a functional derivative thereof, and the additional aliphatic, alcohol may for example include methanol, ethanol, etc...
Typical examples of the products resulting from the above condensations are illustrated below:
a) Low molecular weight polyols condensed with at least one aromatic carboxylic acid.
a diethylene glycol dibenzoate O C00(CH2)2-0-(CH2)2-00C O (6) a-2) - propylene glyeol dibenzoate O C00-fH2-CH2-OOC O (7) SHEA

a-3) - glycerol tribenzoate O C00-CH2-CH-CH200C O (8) ox C

a-4) - ethylene glycol bonniest acetate a-5) - bisdiethylene glycol phthalate diacetate C00(CH2)2 C 3 (pa) 7~3¢1'5~

b) Low molecular weight dicarboxylic acids with an aromatic alcohol.
b-l) - Di-Benzyl succinate O CH200CCH2CH2COOCH2 0 (10) b-2) - Methyl, Bouncily succinate O SCHICK ( SHEA ) COUCH ( 11 ) Preferred polyesters according to the present invention include the divesters obtained by the condensation of ethylene glycol, diethylene glycol, triethylene glycol or propylene glycol with benzoic acid or a functional derivative thereof Also preferred are the divesters obtained by the condensation of succinic, glutaric and adipic acid with bouncily alcohol, or phenol or a functional derivative thereof.
As stated before, these divesters or low molecular weight polyesters are not soluble in water as such but are however either sparingly or else totally soluble in aliphatic, aromatic and chlorinated solvents.
In order for these polyesters to be useful for the coloration of textiles, they have to be blended with appropriate emulsifiers and/or solvents or delineates in order to make them easily emulsifiable in water.
Formulas that have proved to be of interest are as follows:
dyeing of polyester fires (regular type) at the boil and under pressure:

~Z;2~9~

70% Diethylene glycol dibenzoate 20.5% Solves 100 4.0% Oleic acid DUD. (12) 0.5% Monoethanolamine 5.0/~ Nonyl phenol with 6 moles of ethylene oxide.
By using the above formula, a textile dyeing company will eliminate most of the environmental problems associated with the use of conventional carriers (dye accelerators). These conventional dye carriers are normally based on a single or on a blend of the following solvents prepared with the adequate emulsifiers:
- Methyl, ethyl, propel or bottle bonniest - Biphenyl dissolved in Zillion or SolvessoT 100 - 1-2-4 Trichlorobenzene - Methyl cresotinate - N-Butyl phtalimide - Methyl biphenyl - Methyl naphtalene All the above products are well known in the textile industry to cause severe problems either because of the smell, high volatility, toxicity or biodegradability When a compound according to the invention, particularly diethylene glycol dibenzoate is used as a replacement for these substances, none of these problems are encountered.
The efficiency of the above formula (12) was compared to that of the other substances currently being used in the following respects:
a) Dye acceleration b) Leveling c) Biodegradability I

d) Smell e) Toxicity Table l illustrates the results of evaluations with ratings from l to 5, l being the worst and 5 being the best.
a) Dye Acceleration - fabric:
Regular Diablo knitted polyester fabric properly scoured.
- dye bath:
4.0% Disperse Blue 56 OWE Dye accelerator lo 0.5 g/L Acetic acid 56%
0.5 g/L Sequestering agent 0.5 g/L Anionic dispersing agent The dyeings were started at 60C and then raised at the boil at a rate of 2C~minute. They were then boiled for one hour and rinsed.
b) Dye Levellin~
- fabric Regular Diablo knitted polyester fabric properly scoured and dyed with:
4.0% Disperse Blue 56 0.5 gel Acetic Acid 56% (13) 0 5 g/L Sequestering agent 0.5 g/L Anionic dispersing agent The dyeing was started at 60C and then raised at 130C at a rate of 2C/minute. It was maintained at 130C
for 60 minutes and it was then cooled to 80C and rinsed.
This was the prepared fabric to carry our dye leveling test.
Four our Dye Leveling Test, 2 1/2 grams of above dyed material was placed together with 2 l/2 grams of properly 79~

scoured undyed material in a clean beaker containing:
- dye leveling solution Dye accelerator ~12 4.0%
Acetic acid 56% 0.5 g/L (14) Anionic dispersing agent 0.5 g/L

LO 20:1 The dye leveling test was started at 60C and raised at 130C at a rate of 2C/minute. It was maintained at 130C for 20 minutes. It was then cooled down to 80C and the dyed samples were rinsed.
The difference in depth between the previously dyed and undyed materials indicated the efficiency of each substance as a dye leveling agent.

Lo Jo rl I I I I Lo o En _ Jo Jo I Lo I I Lo e Jo Us _ I
.. , . .. , a) Jo so .,, rq U O Jo .
l Jo I I Lo a) I, It I
O
I Al r I Do Or on O X Jo I Lo on I I +
o Lo Lo O
~:~ O
I hen Lo do Lo on n Lo n do IQ I
I: O O d' d' UP
,1 ~,~ O
U
O
O
Al Al h O
o a En v m, a a) Al O
a o Jo e o o o O Id O N r l ED O id N O N
N (D O I I I (U
a) m ,1 Al m m I Jo m z m Jo I I I I
ox m I m -1' a? I) Jo I Al I) a) (I) - rl LO m ; a b) Dyeing of polyester fires (deep Diablo type) at the boil.
40% Diethylene Glycol Dibenzoa-te (15) 600/o Alkyd and Alkyd Aureole Polyglycol Ethers.
It has been stated by the polyester fire manufac-tuners that this (deep Diablo type of) polyester fire virtually eliminates the need to have a carrier in the dye bath consequently removing all problems of pollution of the environment. It was however stated that the need for a leveling agent is still there.
The chemical suppliers have consequently turned to products that would form aggregates with the distaffs in the dye bath consequently keeping more dye in suspension and for a longer time throughout the dyeing cycle. This however, has the serious drawback that the final exhaustion of the dye bath is usually poor consequently reproducibility is poor and also but most important, physical differences in the fires due to previous heat treatments are not properly covered Formula) has the following advantages over the products known to those skilled in the art.
a) perfectly on tone exhaustion b) excellent dye bath exhaustion c) excellent migration or leveling of the distaffs.
do excellent coverage of the physical differences within the fires.
To prove these advantages, the following tests were carried out.
a) Strike or acceleration test.
by Final exhaustion.

~2;~7~

c) Migration test.
fabric:
Fortrel 416, FortrelTM 426 and TreviraT 815 carpets properly scoured dyeing formula:
Disperse yellow 54 0.007% (16) Disperse red 60 0.005%
Disperse blue 56 0.0030/O
Acetic acid 56% 0.50 g/L
lo Anionic dispersing agent 0.50 g/L
A) Strike or Acceleration Test All the tests were run starting from fresh baths:
a) No addition b) Lowe Product of formula 15 c) 1~0% Product of prior art I
d) 1.0% Product of prior art (2) The times and temperatures of dyeings were as follows:
1) 30 seconds at 80C
2) 2 minutes at 80C

3) 2 minutes at 85C

4) 60 seconds at 90C

5) 2 minutes at 90C

6) 5 minutes at 90C
I lo minutes at 95C
8) 30 minutes at 95C
B) Final Exhaustion The dye baths of dyeings I above were kept and to each one of them was added the same amount of undyed scoured fabric.

79~

The dye baths were then exhausted for 60 minutes at 100C.
C) Migration Test:
The dyeing formula was as per (14) but no accelerator was added to the dye bath. The dyeings were carried for 1 hour at 100C.
Formula for leveling test:

Acetic Acid 56% 0.5 g/L
(17) Leveling agent x % OW
1) No leveling agent 2) owe Product formula 15 3) owe Product formula 15 I 1~0% Product from prior art (1) 5) owe Product from prior art (1) 0% Product from prior art (2)

7) OWE Product from prior art (2) 5 grams of fabric dyed as per (14) was added together with 5.0 grams of undyed scoured fabric.
LO 20:1 The leveling test was carried for one hour at 100C.
On these three particular fires product formula 15 showed definite superiority in all respects and the results of these tests are confirmed in a few carpet mills in Canada.
c) Printing of polyester, acetate, and triacetate fires with disperse dyes OWE Diethylene Glycol Dibenzoate (18) 10% Alkyd and alkyd aureole polyglycol ethers.
It has been shown that an addition of 10-20 g/L

30 of product (18) in a printing paste will improve the color I

value of the steamed, pressure steamed or thermosoled fabrics by a percentage of up to OWE. Also the brilliance and the appearance of the printed fabric are markedly improved.
The main advantages of the products according to this invention, preferably glycol dibenzoate or tribenzoates are their extremely low volatility, good solvent properties of disperse distaffs and also excellent plasticizing effect for the different gums used in textile printing which allow greater mobility of the distaffs particles within the gums 10 to reach more easily the fire.
A typical printing paste would consist of:
3 - 5.0% Guard gum derivative or allegiant 1 - OWE Disperse distaffs (19) 1 - 3~0 g/L Citric Acid 1 - 2.0 g/L Ludigol 10 - 20 g/L Product 18 d) Printing of paper to be used in the transfer printing of synthetic fires.
OWE Glycerol tribenzoate or Triethylene Glycol Dibenzoate owe Solves 100 or other (20) 10% ~lkyl and/or alkyd aureole polyglycol ether When composition (20) is added directly to the printing paste to be applied on paper it will solidify upon drying and cooling of the paper and will remain in the printed area without premature transfer to other unprinted areas of the paper.
Then, when these printed portions of the paper are transferred onto a Textile material by a heat treatment, product (20) will greatly enhance the color transfer and d~Z;2 I assay improve also the brilliance of the then printed fabrics.

e) Atmospheric dyeing of nylon 6 and nylon 6-6 with acid dyes.

OWE Dibenzyl Succinate or ~ibenzyl (21) Adipate 20~0% Chlorinated (or aromatic) hydrocarbon OWE Fatty amine ethoxylate (35-50 Eye.) Mixture (21) when incorporated to a dye bath at a concentration between 2 and OWE OW has been found to allow a perfectly level dyeing due to good coverage of physical differences within the fires and due also to excellent compatibilizing effect on the distaffs and this result was obtained at 80C.
Example of a formula:
fabric:
pylon 6-6 knitted fabric, properly scoured.
dyeing formula:
Acid blue 25 1.0% OW (22) MOP 2.0 g/L
TOP 0~5 g/L
Product 21 2.0% OW
The dyeing was started at ~0C and raised to 80C
at a rate of 1C/Minute~ It was then dyed for one hour at 80C~
Then it was cooled down and ringed.
f) Continuous dyeing of nylon 6-6 and nylon 6 mixed by steam or by dry heat.
No tests were performed for this process but we can assume that product (21) would show equal benefits in this process as compared to atmospheric dyeing.

Claims

The embodiments of the invention in which an exclus-ive property or privilege is claimed are defined as follows:-

1. In a method of dyeing or printing synthetic fibres, wherein the fibres are treated with a dye material including a carrier for said dye material, the improvement wherein said carrier is selected from the group consisting of aromatic polyesters and polyethers which are obtained by the reaction of:
a) n-alkane, a n-alkylene, thioalkylene, polyalkyl-ene diol or polyol or a functional derivative thereof with at least one aromatic carboxylic acid or functional derivatives thereof; or b) a saturated or unsaturated aliphatic dicarboxylic acid or a functional derivative thereof with at least one aromatic alcohol or a functional derivative thereof.

2. A method according to claim 1, wherein said carrier comprises the reaction product of a n-alkylenediol with at least one aromatic carboxylic acid or a functional derivative thereof.

3. A method according to claim 2, wherein said n-alkyl-enediol has 2 to 6 carbon atoms.

4. A method according to claim 1, wherein said diol or poliol is selected from the group consisting of ethylene glycol, diethylene glycol, 1,2-propanediol, glycerine, tri-methylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, polyethylene glycols having a molecular weight ranging between about 150 and 1,000 and polypropylene glycols having a molecular weight ranging between 150 and 400.

5. A method according to claim 1 (a), wherein said n-alkylene and polyalkylene polyols have the following formula:

HO-(CnH2nO)m-H
wherein n is an integer from 2 to 4 and m is an integer from 1 to 10.

6. A method according to claim 1, wherein said polyol polyalkylene glycols are selected from the group consisting of polyethylene glycols having a molecular weight between about 150 and about 1000 and polypropylene glycols having having a molecular weight between about 150 and 400.

7. A method according to claim 1(a), wherein said aromatic carboxylic acid has at least one carboxyl group directly attached to benzene ring.

8. A method according to claim 1(a), wherein said aromatic carboxylic acid has the following formula:

wherein X is selected from hydrogen, halogen, methyl group and low molecular weight aliphatic group, and Y represents the carboxylic acid group.

9. A method according to claim 7 , wherein said aroma-tic carboxylic acid is selected from the group consisting of benzoic, salicylic, cresotinic, phthalic and toluic, 1-8 naphthalic acids and functional derivatives thereof.

10. A method according to claim 1(b), wherein said aliphatic dicarboxylic acid has the formula:

wherein R represents alkylene of 1 to 8 carbon atoms, and X represents OH.

11. A method according to claim 10, wherein said alipha-tic dicarboxylic acid is selected from the group consisting of malonic, succinic, glutaric, adipic, pimelic, azelaic and sebacic acids.

12. A method according to claim 10, wherein said aromatic alcohol has the formula:

wherein X is selected from hydrogen, halogen, hydroxyl, low molecular weight aliphatic group, and Y represents a hydroxyl or alcoholic group.

13. A method according to claim 12, wherein X represents methyl.

14. A method according to claim 12, wherein said aromatic alcohol is selected from the group consisting of benzyl al-cohol, phenol, cresol, or a functional derivative thereof.

15. A method according to claim 1, wherein said carrier is selected from the group consisting of diethylene glycol dibenzoate, propylene glycol dibenzoate, glyceryl tribenzoate, ethyleneglycol benzoate acetate, dibenzyl succinate and methyl benzyl succinate.

16. A method according to claim 1, wherein said carrier also includes a polyglycol ether.

17. A composition for dyeing or printing synthetic fibres which includes dispersed dyestuffs, acid donor and a carrier, said carrier comprising an aromatic polyester or polyether which is obtained by the reaction of:
a) n-alkane, a n-alkylene, thioalkylene, polyalkyl-ene diol or polyol or a functional derivative thereof with at least one aromatic carboxylic acid or functional derivatives thereof; or b) a saturated or unsaturated aliphatic dicarboxyl-is acid of a functional derivative thereof with at least one aromatic alcohol or a functional derivative thereof and an emulsifying agent.

18. An aqueous bath for the coloration of polyester fibres wherein the fibres are treated with a dye bath consist-ing of disperse dyestuffs, acid donor, dispersing agent, sequestering agent and carrier wherein the carrier is selected from the group consisting of aromatic polyesters or polyethers which are obtained by the reaction of a n-alkane, n-alkylene, thioalkylene, polyalkylene diol or polyol or a functional derivative thereof with at least one aromatic carboxylic acid or a functional derivative thereof.

19. An aqueous printing paste for the printing directly or by transfer of synthetic fibres wherein the fibres are treated with a paste containing disperse dyestuffs, thick-ening agent, antioxidant, acid donor, and carrier, said carrier being selected from the group consisting of aromatic polyesters or polyethers which are obtained by the reaction of a n-alkane, thioalkylene, polyalkylene diol or polyol or a functional derivative thereof with at least one aromatic carboxylic acid or a functional derivative thereof.

20. An aqueous bath for the coloration of polyamide fibres wherein the fibres are treated with a dyebath consist-ing of anionic dyestuffs, pH control agent, non ionic levell-ing agent, sequestering agent and carrier, carrier being selected from the group consisting of aromatic polyesters or polyethers which are obtained by the reaction of a saturated or unsaturated aliphatic carboxylic acid or a functional derivative thereof with at least one aromatic alcohol or a functional derivative thereof.

21. The bath of claim 18 wherein said acid donor is an inorganic or organic acid, inorganic or organic acidic salt or any buffering system which has the ability to maintain the pH slightly acidic.

22. The bath of claim 20 wherein said pH control agent is inorganic or organic acid, inorganic or organic salt or any buffering system which has the ability to maintain the pH anywhere between 1.5 and 7.8 depending on the fibre or the conditions of dyeing.

23. The bath of claim 18 wherein the dispersing agent is a sulfonated naphthalene formaldehyde condensate, ligno-sulfonate or sulfonated or carboxylated polyester or poly-acrylate.

24. The bath of claim 18 or 20 wherein the sequestering agent is the sodium salt of ethylene diamine tetraacetic acid, nitrilotriacetic acid, diethylene triamine tetraacetic acid, polyphosphates, polyphosphonates.

25. The aqueous printing paste of claim 19 wherein the thickening agent comprises alginate, starch derivatives, guar derivatives or synthetic thickeners.

26. The bath of claim 18 which includes a non ionic levelling agent which is a fatty amine ethoxylate or fatty diamine ethoxylate.

27. The composition of claim 17 which includes a blend of a non ionic and/or anionic emulsifying agents, said blend being used with or without diluents or co-solvents.

28. The composition of claim 27 wherein said emulsifying agents are selected from the group comprising alkoxylated alkyl phenols, alkoxylated alkyl naphthols, alkoxylated fatty amines, alkoxylated sorbitol derivatives, alkoxylated diamines, alkoxylated esters, sulfonated oils, sulfonated alkyl benzene, sulfonated alkyl naphthols, soaps of fatty acids: sulfated, phosphated or carboxylated alkoxylated alkyl phenols, alk-oxylated alkyl phenols, alkoxylated alkyl naphthols and alk-oxylated fatty alcohols.

29. The composition of claim 27 wherein said diluents or co-solvents are selected from the group comprising non chlorinated and chlorinated aliphatic solvents, non chlorin-ated and chlorinated aromatic solvents, low molecular weight alcohols and low molecular weight glycols or polyols, all being aliphatic.

30. The bath of claim 18 wherein said diol or polyol are selected from the group consisting of ethylene glycol, diethylene glycol, 1-2 propanediol, glycerine, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexame-thylene glycol, polyethylene glycols having a molecular weight ranging between about 150 and 1,000, polypropylene glycols having a molecular weight ranging between about 150 and 400.

31. The bath of claim 18 wherein said aromatic car-boxylic acids are selected from the group consisting of benzoic, salicylic, cresotinic, phthalic, toluic, 1-8 naph-thalic acid anhydride, chlorobenzoic acid or derivatives thereof.