US2470080A

US2470080A - Method of dyeing with metallized dyes

Info

Publication number: US2470080A
Application number: US677526A
Authority: US
Inventors: Henry E Millson; Mooradian Shannon
Original assignee: American Cyanamid Co
Current assignee: Wyeth Holdings LLC
Priority date: 1946-06-18
Filing date: 1946-06-18
Publication date: 1949-05-10
Anticipated expiration: 1966-05-10

Description

Patented May 10, 1949 UNITED STATES ATENT OFFICE METHOD OF DYEING WITH METALLIZED DYES Cyanamid Company, ration of Maine New York, N. Y., a corpo- No Drawing. Application June 18,1946, Serial No. 677,526

20 Claims.

This invention relates to an improved process of dyeing". metallized dyes. More particularly, the invention relates to the use of an improved leveling agent or dyeing assistant in the process.

Fibers and fabrics, particularly basic nitrogenous materials such as wool, have been dyed with metallized dyes by various processes, in one of which the dye is metallized to form a metal complex and then dyed onto the fiber from a bath. The other processes involve simultaneous dyeing and metallizing, the so-called metachrome process, and processes in which the dye and metal salt are applied separately, the so-called top and bottom chrome process. The present invention relates only to the first process in which preformed metallized dyes are used.

It has been common to dye basic nitrogenous materials such as wool from a strongly acid dye bath with metallized dyes. A relatively strong acid bath has been necessary, and even with a large amount of acid the process has often resulted in dyeings which are not sufiiciently level. This has greatly restricted the field of utility of premetallized dyes, both of the completely metallized type and the so-called half metallized compl'exes which contain less than the maximum amount of metal capable of entering into chemical combination in the complex.

The difl'lculties involved in producing level shades have resulted from a number of factors, an important one being the inadequate or excessively slow penetration of the dye into the fiber. This poor penetration has led in the past to considerable experimentation. It was soon found that cationic surface active agents improved the penetration of metallized dyes in the fibers. This increased the strength of the dyeing but it led to another serious difiiculty, namely, scum formation. The metallized dyes are acid, and in the strong acidbath tend to react with cationic surface active agents to produce insoluble compounds forming a scum, which scum in many cases adhered locally to portions of the fabric and resulted in specky dyeing. Various procedures have been adopted to keep the scum in dispersed form so that the specks would not be too large. However, the palliatives used in the past have still left much to be desired.

Other factors are present in metallized dyeing which produce undesirable results. The high strength of acid used tends to attack the fiber with loss in tensile strength, and often with the production of a harsh hand.

The present invention is based on the observed factsthat a'particular type of non-ionic surface active agent, which may be prepared by reacting an alkylene oxide with an alkylol amide of a thermally polymerized drying oil acid, permits overcoming the disadvantages \which have hitherto served to limit the field of utility of premetallized dyes. In the first place, the non-ionic surface active agents used in the present invention are effective in promoting penetration, even though they are in no sense cationic surface active agents.

The increased penetration producesan equal or 10 better levelness in less time and permits markedly increased color value. Exhaustion of the bathis also improved. 7

Another very important advantage of the present invention is that it has been found that when the dyeing assistants of the present invention are used the amount of sulfuric acid in the dyebath can be very markedly reduced. The less acid dyebath reduces, and in many cases eliminates entirely, damage to the fiber. Tensile strength is affected but little, if any, and a much softer hand is obtained.

The advantages of the present invention are obtained without the drawbacks of scum formation, which has made the use of cationic surface active agents alone unsuitable in many cases:

Surprising amounts of the surface active agents of the present invention can be added to the dyebath without precipitation, even when the bath contains such salts as alkali metal metaphosphates, ammonium sulfate, sodium sulfate, and the like. The agents are also very stable in the presence of acid, and the dyebath can be kept" for a reasonable time without serious decomposition.

The surface active agents usable in the present invention are not claimed here, as they constitute the subject matter of the copending application of Jack T. Thurston and Ruth B. Warner, Serial No. 677,524, filed June 18, 1946. In general the products are alkylol amides of heat polymer ized, unsaturated fatty acids which have been reacted with a comparatively large number of" allrylene oxide molecules.

It is well known that lower alkyl esters of drying oilacids are converted by heating to dimers.

These dimers are essentially organic dicarboxylic acid esters of the cycloaliphatic series, from which the free dim-erized acids may be obtained in the usual way. Clear and comprehensive descriptions of these compounds and methods of preparing the same will be found in the literature,

for instance in the article by-Theodore F. Bradley and William B. Johnston in Industrial and.

Engineering Chemistry, vol. 32 (1940) No. 6,. pp.

5 802-809. In applicants specification and claims the phrase thermally dimerized drying oil'lacids?! has been used to describe compounds such as disclosed in the above article.

Among the common drying oil acids which are effective in producing compounds for use in the present invention are those obtained from soybean oil and linseed oil. The average fatty acid composition of linseed oil, for example, is given in Laboratory Letters, Spencer Kellogg and Sons, Inc. (1940), page 80, linoleic acid 60.4%, linolenic acid 22.8%, other acids 12.7%, and glyceryl radical 4.1%. In other words, linseed oil consists largely of glycerides of octadecadienic and octadecatrienic acids. The dimer of an octadecadienic acid is stated by Bradley and Johnston in the above mentioned article, to be a monocyclic compound represented by the following structure or isomers thereof :0-(011910 I OH is f onaonm-on The dimer of an octadecatrienic acid is stated to be a dicyclic compound represented by the following structure or isomers thereof:

II H H o HCH 0 The first step in preparing the surface active agents usable in the present invention consists of reacting the thermally dimerized drying oil acid with a lower alliylol amine having at least one free amine hydrogen, that is to say, a primary or secondary alleylol amine. Excellent products can be obtained with monoethanol amine, diethanol amine or other alkylol amines, such as propanol amines. If desired, esters of the thermally dimerized drying oil acids may be used in place of the free acids. A complete description of methods for forming the alkylol amine-thermally dimerized drying oil acid reaction product will be found in the examples to follow, in particular Examples 1, 5, 11, 13, 16.

The reaction products of the dimerized drying oil acids or esters with alkylol amines are believed to be the bis-allrylolamides of the dimerized acids which would have, for instance when ethanolamine is the amine used, the formula a. lower alkylene oxide such as ethylene oxide,

or propylene oxide. Complete details of suitable procedures for performing this reaction are given in the examples to follow. The exact number of alkylene oxide molecules which react is not critical. Optimum results are obtained with about 31 molecules, but improved results can be produced with products having as little as 16 or 18 molecules. Products having more than about 31 molecules of alkylene oxide are also useful.

It is not desired to limit the present invention to any particular theory of the exact constitution of the surface active agents used. It seems probable that they are ether amides of the polymerizeol fatty acids. There is much evidence to support this view because their behavior is quite different from related compounds which are esters. However, for the purpose of the present invention it is sufficient that the surface active agents are eiTective and the invention isnot intended to be limited to any particular theory of chemical constitution.

The invention will be described in greater detail in conjunction with the specific examples. The parts are by weight.

Example 1 Fifty-six parts by weight of dimerized cottonseed fatty acid are dissolved in 31 parts of xylene and 125 parts of monoethanolamine are added. The mixture is heated under a reflux condenser with a water trap until the distillation of water is almost complete, after which an additional 12 parts of monoethanolamine are added. Reflux is continued until no more water is evolved,

. after which the xylene is distilled off at li0150 C. under a pressure of 20-30 mm. of mercury. The bis-ethanolamide of the dimerized acid is obtained as a dark, viscous liquid.

300 parts of tertiary butanol, 190 parts of bisethanolamide of the dimerized acid and 20 parts of triethylamine are heated together with stirring. Ethylene oxide is bubbled through the resulting solution, which is maintained at '70-80 C. until 244 parts are absorbed. A reflux condenser is provided, cooled with ice water to prevent escape of unreacted ethylene oxide. When the addition is complete the reaction mixture is refluxed for several hours until the temperature reaches -95 C., after which the solvent and. volatile material are stripped at reduced pressure (20-30 mm).

Example 2 A dye bath is made up of 300 parts of water and 0.1 part of chromium complex of the azo dyestufi" from diazotized anthranilic acid and 1- (4-sulfophenyl) -3-methyl 5 pyrazolone. Two parts of 10% sulfuric acid are added and 5 parts of wool yarn thoroughly wet out are then introduced into the bath. 7.5 parts of a 1% solution of the product of Example 1 is then added and the bath brought slowly to the boil and main- Example 3 A dye bath is made up of 4000 parts of water heated to F. and 100 parts of wool fabric gradually introduced and maintained for a sufficient time to assure thorough wetting. 5 parts A dark, viscous liquid is obtained.

2 parts of the product of Example 1 dissolved in warm water are then added, the temperature of the dye bath raised to the boil gradually, and boiled for a sufficient time to complete dyeing. Thereupon the dye bath is run off, the wool fabric rinsed in cold water, and dried.

The goods dyed are level, free of skitteriness, and showed no oil blotches. The shade of the fabric is strong, approximately 20% stronger than the same dyeing effected under identical conditions and without surface active agent. The latter, in addition to the weaker strength, is

uneven, skittery, and shows the presence of oilblotches due to the oil present in the undyed material.

When the dyeing is effected without the surface active agent but with double the amount of sulfuric acid, approximately the same strength and levelness is obtained as with the surface active'agent and half the amount of acid. However, the fabric is definitely harsher, mechanically weaker, andpoorer in fabric texture to felting.

Example 4 A dye bath is made up of 300 parts of water and 0.4 part of the chromium complex of the azo dyestuif obtained from diazotized l-amino- 2-hydroxy-6-nitro-naphthalene-e-sulfonic acid coupled to 2-naphthol. 0.5 part of calcined Glaubers salt and 0.1 part of 56% acetic acid is then added, whereupon 5 parts of thoroughly wet out wool yarn is introduced into the dye bath. parts of a 1% solution of the product of Example 1 is introduced and the temperature raised to 180 F., whereupon 0.075 part of formic acid are added, the temperature raised to the boil, the bath boiled for a short time, 0.1 part sulfuric added and the boil continued for about twice the length of time until dyeing is complete.

A similar dyeing is effected without the condensation product, all other factors being the same. As measured on a spectrophotometer the dyeing with the condensation products present in the dye bath is 25% stronger in color value, more level, and a better shade of black.

Example 5 The procedure of Example 1 is followed, but the dimethyl ester of dimerized linseed oil acids is used in place of the dimerized cottonseed fatty acids, the amide formation under a nitrogen atmosphere. As the ester is liquid the xylene is omitted. Ethylene oxide absorption continues as in Example 1 until about 23.5 molecules of ethylene oxide have been absorbed. The product is a dark red oil.

Example 6 A dye'bath is made up of 300 parts of water and 0.1 part of well dissolved chromium complex of the azo dyestuif obtained from diazoti zed' 4* nitro-Z-amino-phenol coupled to 1-(4'-sulfophenyl)-3-methyl-5-pyrazolone. 3-parts of 10% ammonium sulfate solution are then added with a parts of calcined Glaubers salt. parts of a 1% solution of the'product of Example 5 are added and 5 parts of thoroughly Wet out wool yarn then introduced. The bath is then slowly brought to the boil, boiled for a short time, 0.5 part of 56% acetic acid added, boiling'continued for about the same length of time, followed by an addition of another 0.1 part of 56% acetic acid and the boiling then continued for the same time until the dyeingis complete. The yarn is removed, rinsed and dried, and presents a bright dyeing which is level and of excellent color value.

A similar dyeing procedure is followed with no surface active agent added but all other factors kept the same. Theresulting dye is quite inferior in brightness, levelness and strength of shade.

Example 7 A dye bath is made up of 300 parts of water and 0.1 part of chromium complex of the azo dyestuif obtained by coupling diazotized i-nitro- Z-amino-phenol to l-(4'-sulfophenyl) -3-methyl- 5-pyrazolone. 2 parts of 10% sulfuric acid are then added and 5 parts of wool yarn thoroughly wet out introduced into the dye bath. 7.5 parts Example 8 The procedure of Example 7 was followed but the dyestuif is replaced by the same amount of the chromium complex of the azo dye obtained by coupling diazotized l-amino-2-naphthol-4- sulfonic acid on 2-ethoxy-benzoyl acetonitrile.

The wool is dyed a bordeaux shade.

Example 9 The procedure of Example 2 is followed but the metallized dye of that example is replaced by the chromium complex of the azo dyestuff obtained from diazotized 5-nitro-2-amino-phenol coupled to Z-amino naphthalene-5,7-disulfonic acid.

Example 10 The procedure of Example 6 is followed using 0.1 part of the mixture of the chromium complexes of diazotized picramic acid coupled to lnaphthol-5-sulfonic acid, diazotized 4-nitro-2- amino phenol coupled to l-naphthol-5-sulfonic acid, and diazotized 1-amino-2-naphthol-4-sulfonic acid coupled to 2-naphthol.

Example 11 The procedure of Example 1 is followed but dimerized soyabean fatty acids are substituted for the dimerized cottonseed fatty acids. The product obtained is a reddish brown viscous oil, the absorption of the ethylene oxide being about 31 mols.

Example 12 A dye bath is made'up of 300'parts of water and 0.4 part of the cobalt complex of. the: azo. dye obtained by coupling 4-nitro-2-aminophenol Thereupon to 1-(4'-sulfophenyl) 3 methyl-5-pyrazolone. 0.5 part of calcined Glaubers salt and 0.1 part of 56% acetic acid is then added, whereupon 5 parts of thoroughly wet out wool yarn is introduced into the dyebath. parts of a 1% solution of the product of Example 11 is introduced and the temperature raised to 180 E, whereupon 0.075 part of formic acid are added, the temperature raised to the boil, the bath boiled for a short time, 0.1 part sulfuric acid added and the boil continued for about twice the length of time until dyeing is complete. A level orange shade is obtained.

Example 13 The procedure of Example 11 is followed but the dimethyl ester of dimerized linseed fatty acids is replaced by the corresponding dimethyl ester of tung oil fatty acids. An amber color viscous oil is obtained.

Example 14 The procedure of Example '7 is followed but instead of using the condensation product of Example 5 a corresponding amount of the condensation product of Example 13 is used in the dye bath. Wool is dyed the same shade, the dyeing possessing the same characteristics of brightness and levelness.

Example 15 The procedure of Example 8 is followed but instead of using the condensation product of Example 5 a corresponding amount of the condensation product of Example 13 is used in the dye bath. Wool is dyed the same shade, the dyeing possessing the same characteristics of brightness and levelness.

Example 16 200 parts of dimerized cottonseed fatty acids and 60 parts of normal propanolamine are refluxed in 120 parts by volume of xylene with stirring, water being stripped off in a trap as it is formed. The temperature is maintained at about 135-148 C. until formation of the di-normal propanolamide of the dimerized acid is obtained. The completion of the action can be determined by cessation of water formation. The xylene and excess normal propanolamine are then distilled off under a slight vacuum, producing a viscous greenish-black oil.

100 parts of the oil are mixed with 100 parts of butyl alcohol and 10 parts of triethylamine and heated under a reflux condenser at 80-86 C. while ethylene oxide is passed in until 170 parts are absorbed, corresponding to about molecules of ethylene oxide per molecule of the propanol amide. The temperature is then raised to 95- 105 C. for several hours and solvent and volatile material distilled off. A brown viscous oil is obtained.

Example 17 The procedure of Example 7 is followed but the condensation product of Example 5 is replaced by a similar amount of the condensation product of Example 16. The result is a bright, strong, level orange dyeing the wool.

When a dyeing is made in a similar dye bath without the condensation product, the result is inferior in brightness, strength and levelness.

Example 18 The procedure of Example 5 is followed but the addition of ethylene oxide is stopped when about 18 mols per mol of ethanolamide have been absorbed. The product is an" oil having an appearance similar to that of Example 5.

Example 19 The procedure of Example 7 is followed but the condensation product of Example 5 is replaced by the same amount of the product of Example 18. A bright, full strength, level shade of orange is obtained on the wool.

When the dyeing is made in a similar dye bath without addition of condensation product, it is inferior in brightness, strength and levelness.

Example 20 The procedure of Example 13 is followed but the addition of ethylene oxide is stopped when about 18 mols have been absorbed per mol of ethanolamide. The product is a viscous oil similar in appearance to that of the product of Example 13.

Example 21 The procedure of Example 7 is followed, substituting for the condensation product there used the same quantity of the condensation product of Example 20. A bright, level, good strength orange dyeing is obtained on wool.

When a dyeing is made in a similar dye bath without adding any condensation product, it is inferior in brightness, strength and levelness.

Example 22 The procedure of Example 2 was followed but instead of using wool the synthetic fiber obtained from formaldehyde and casein, and known under the trade name of Aralac, is used in place of the wool. Dyeing shows the same shade and qualities of brightness and levelness.

Example 23 The procedure of Example 6 is followed but the condensation product of No. 1 is used and the chromium complex is replaced by an iron complex of the azo dye obtained by coupling 4-nitro- 2-amino phenol on 1-(4-sulfophenyl) -3-methyl- S-pyrazolone. A level dyeing of olive brown shade is obtained.

Example 25 The procedure of the preceding example is followed but the iron complex of the dye is replaced by the copper complex. A level dyeing reddish orange shade is obtained.

Example 26 The procedure of Example 24 is followed but the iron complex of the dye is replaced by the nickel complex. A level dyeing of bright yellowish orange shade is obtained.

Example 27 The procedure of Example 22 is followed using nylon instead of aralac. The dyeing shows the same shade and qualities of brightness and levelness.

We claim:

1. A method of dyeing with metallized dyes soluable in acid baths which comprises subjecting the material to be dyed to a dyebath containing the metallized dye and an amount, sufiicient to be effective but insufficient to cause scum formation and extensive precipitation in the bath, of a water soluble condensation product of at least 16 to 18 mols of a lower alkylene oxide with a lower alkylolamide of a thermally dimerized drying oil acid.

2. A method of dyeing wool with metallized dyes soluble in acid baths which comprises subjectin the material to be dyed to a dyebath containing the metallized dye and an amount, sufficient to be effective but insufficient to cause scum formation and extensive precipitation in the bath, of a water soluble condensation product of at least 16 to 18 mols of a lower alkylene oxide with a lower alkylolamide of a thermally dimerized drying oil acid.

3. A method of dyeing with metallized dyes soluble in acid baths which comprises subjecting the material to be dyed to a dyebath containing the metallized dye, an amount, sufficient to be efiective but insufficient to cause scum formation and extensive precipitation in the bath, of

a water soluble condensation product of at least 16 to 18 mols of a lower alkylene oxide with a lower alkylolamide of a thermally dimerized drying oil acid, and an amount of acid materially below that giving level dyeing with the same dyestuff in the absence of said condensation product.

4. A method of dyeing wool with metallized dyes soluble in acid baths which comprises subjecting the material to be dyed to a dyebath containing the metallized dye, an amount, suflicient to be effective but insuflicient to cause scum formation and extensive precipitation in the bath, of a water soluble condensation product of at least 16 to 18 mols of a lower alkylene oxide with a lower alkylolamide of a thermally dimersized drying oil acid, and an amount of acid materially below that giving level dyeing with the same dyestuff in the absence of said condensation product.

5. A method of dyeing with metallized dyes soluble in acid baths which comprises subjecting the material to be dyed to a dyebath containing the metallized dye and an amount, sufficient to be effective but insufficient to cause scum formation and extensive precipitation in the bath, of a water soluble condensation product of about 31 mols of a lower alkylene oxide with a lower alkylolamide of a thermally dimerized drying oil acid.

6. A method of dyeing W001 with metallized dyes soluble in acid baths which comprises subjecting the material to be dyed to a dyebath containing the metallized dye and an amount, sufl'icient to be effective but insufiicient to cause scum formation and extensive precipitation in the bath, of a water soluble condensation product of about 31 mols of a lower alkylene oxide with a lower alkylolamide of a thermally dimerized drying oil acid.

7. A method of dyeing with metallized dyes soluble in acid baths which comprises subjecting the material to be dyed to a dyebath containing the metallized dye, an amount, suiflcient to be efiective but insuificient to cause scum formation I Number and extensive precipitation in the bath, of a water soluble condensation product of about 31 mols of a lower alkylene oxide with a lower alkylolamide of a thermally dimerized drying oil acid, and an amount of acid materially below that giving level dyeing with the same dyestufi in the absence of said condensation product.

8. A method of dyeing wool with metallized dyes soluble in acid baths which comprises subjecting the material to be dyed to a dyebath containing the metallized dye, an amount, sufficient to be effective but insufficient to cause scum formation and extensive precipitation in the bath, of a water soluble condensation product of about 31 mols of a lower alkylene oxide with a lower alkylolamide of a thermally dimerized drying oil acid, and an amount of acid materially below that giving level dyeing with the same dyestuff in the absence of said condensation product.

9. A method according to claim 1 in which the alkylene oxide is ethylene oxide and wherein the alkylol groups of said alkylolamide are hyclroxyethyl.

10. A method according to claim 2 in which the alkylene oxide is ethylene oxide and wherein the alkylol groups of said alkylolamide are hydroxyethyl.

11. A method according to claim 3 in which the alkylene oxide is ethylene oxide and wherein the alkylol groups of said alkylolamide are hydroxyethyl.

12. A method according to claim 4 in which the alkylene oxide is ethylene oxide and wherein the alkylol groups of said alkylolamide are hydroxyethyl.

13. A method according to claim 5 in which the alkylene oxide is ethylene oxide and wherein the alkylol groups of said alkylolamide are hydroxyethyl.

14. A method according to claim 6 in which the alkylene oxide is ethylene oxide and wherein the alkylol groups of said alkylolamide are hydroxyethyl.

15. A method according to claim "I in which the alkylene oxide is ethylene oxide and wherein the alkylol groups of said alkylolamide are hydroxyethyl.

16. A method according to claim 8 in which the alkylene oxide is ethylene oxide and wherein the alkylol groups of said alkylol amide are hydroxyethyl.

1'7. A method according to claim 1 in which the metallized dye is a chromium complex of a metallizable azo dye.

18. A method according to claim 2 in which the metallized dye is a chromium complex of a metallizable azo dye.

19. A method according to claim 3 in which the metallized dye is a chromium complex of a metallizable azo dye.

20. A method according the metallized dye is a chromium complex metallizable azo dye.

HENRY E. MILLSON. SHANNON MOORADIAN.

to claim 4 in which of a REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date 2,040,796 Rittinghausen May 12, 1936