US2638404A - Method of dyeing nitrogenous fibers with metallized azo dyes - Google Patents

Description

Patented May 12, 1953 METHOD OF DYEING NITROGENOUS METALLIZED AZO FIBERS WITH DYES Henry Edmond Millson, Plainfield, and Shannon Mooradian,

Somerville, N. J., American Cyanamid Company,

assignors to New York,

N. Y., a corporation of Maine No Drawing. Application February 10, 1951,

Serial No. 210,426

10 Claims. (Cl. 8 43) This invention relates to the use of the reaction product of substituted triazines with low-molecular weight epoxides as dye assistants for metallized dyes in dyeing processes.

Fibers and fabrics, particularly basic nitrogeneous materials such as wool, nylon, aralac, etc., have been dyed with metallized dyes by various processes, in one or which the dye is metal-, lized in theform of a metal complex and then dyed onto the fiber from a bath. The compounds of this invention are advantageous for use in this process as well as other processes such as the metachrome process which involves simultaneously dyeing and metallizing, or the so-called top and bottom chrome process in which the dye and metal salts are applied separately.

It has been common practice to dye basic nitrogeneous materials 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 sufficiently level. The disadvantage of dyeing any fabric in a solution of a strong inorganic acid is obvious. Chemically, both wool and nylon are high-molecularweight polyamides and in a boiling acid solution we have ideal conditions for the hydrolysis of the amide linkage. It is not surprising, therefore, that some hydrolysis does take place in the acid dye bath with the production of a lower molecular weight product that is reflected in decreased tensile strength and a harsh hand.

Although the dye chemist has recognized for years that strong, completely ionized acids should not be present in the dye bath, their use was continued because no other method was known that would produce as level dyeings. The dyeibath was always a compromise between increasing the acid, the temperature and bath time to improve the dyeing, and decreasing the acid, the temperature and bath time to avoid excessive damage to the fabric. This has greatly restricted the field of utility of premetallized dyes, both of the completely metallized type and the socalled half-metallized complexes which contain less than the maximum amount of metal-capable of entering into chemical combination in'the complex. r v i The difficulties 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 increasedthe strength of the dyeing, but it led to another serious difiiculty, name- 1y, scum formation. The metallized dyes contain acid groups and in the strong acid bath tend to react with cationic surface active agents to produce insoluble, compounds forming a highly colored 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.

We have now discovered a class of nonionic substituted triazines which, when used according to the process of this invention, result in a level'dyeing but do not form objectionable scum in the dye bath. These compounds are polyalkylene oxide derivatives of 2-alkyl guanamines which, in the case of ethylene oxide derivatives, conform to the general formula in which R is an aliphatic hydrocarbon radical containing at least 7 carbon atoms anda: plus 3 may vary between 9 and 98 depending upon the amount of alkylene oxide that is condensed. Although the above formula illustrates the product formed by the condensation of guanamine with ethylene oxide, it will be recognized that glycidol may be substituted for all or part of the ethylene oxide. Furthermore, various other alkylene oxides inay be used, such as propylene oxide, isobutylene oxide and-.tetramethylene oxide.

It is possible to vary the ratio of alkylene oxide to substituted guanamine through a wide range, depending on the properties desired in the dyeing assistant. In general, We prefer to condense between aboutiO and '75 moles of alkylene oxide with 1 mole of substituted guanamine.

1118's i much 'asthepolyalkylene oxide chain is respon- -56 'sible for the water-solubilityof the dye assistant,

it will be recognized that the tendency to form scum will be reduced as the amount of alkylene oxide present in the molecule is increased. When the alkylene oxide condensed is ethylene oxide, and the ratio of ethylene oxide-to substituted guanamine drops "belowfi or 'to l,"a"condition is obtained where the dye assistant is so insoluble that objectionable scum interferes with its use.

The strength of the dyeing is an inversefunction of the amount of alkyleneoxide condensed with the substituted guanamine and therefore, the particular dye assistant which .may beused to greatest advantage will beacompromise"between obtaining satisfactory. soliibility andmaximum strength of dyeing.

The hydrocarbon chain R as mentioned above, may be varied between 7 and fi carbon atoms. We have found that when the aliphatic hydrocarbon constituent contains less than 7 *carbon atoms, the resulting compound is no longer effective as a. dyeing assistant.

In our Patent No. ..2',4'7.0,'080 which issued May I0, "1949 to "American "CyanamidCompany, we have described a particulartype'o'f nonionic 'surface active agent preparedby"therea'ction of an alkylene oxide with analkan'dliamide of a thermallypdlymerizeddrying oil acid. These'reagents were efie'ctivein producing betterlev'elness in'less time and markedly increased "the 'cdl'or value when they"were present in'the dyebath. "The substitutedguananiine condensates ofthe present invention'show some ver dmportent additional advantages over the dye assistants re'ferredto above "in that they are "most efficient 'in" the presence of an organic acid. "Itis'now ,pra'cticalfor required in the 'dye'bath ibyithe'mu'ch more weakly ionized organic acids. Thusa' solution is oiferedto one'problem' which has plagued'the dyeindustry'ever since the first synthetic dye was obtained by Perkins. This "substitution of a Weaker organic acid for sulfuric"acidwilrgreatly reduce damage to the fiber. Tensile strength of the'dyed fiber will'be improveda'nda'mueh' softer hand is obtained.

t" is "an advantage of the :dyeing assistants of the present "invention that "they may"be"used without "the drawback of scum formation "which had previously made the use "of cationic surface active agents unsuitable as dyeing assistants. Effective amounts of the surface active agents of the present invention can be added to the dye bath without precipitation, even: when the bath contains such salts as ammonium sulfate, sodium sulfate, and the like. "These-agents, in the quantities used, are stable in the presence of acid and permitthe dye bath -tobe kept fora reasonable time without serious decomposition.

It is an advantage of the present invention that no prdblem is involved .in regulating the concentration of these .dye assistanta'asLthey may be-added to .the dye bath in small portions to obtain'maximum effectiveness with-.a..minimum of precipitation and scum "formation. .Thisenables one to vary the .concentrationlover'a wide range. In addition, .the dyeass'istants bfthis series may be .tailor-madeby regulating the amount of ethylene oxide present in the molecule .to avoid scum formation in dye. solutionsof normal concentration.

We haveifound thatthese nonionic surface active Idye assistants are particularly well adapted for the dyeing of loose yarns, such :ascarpet yarn, rawstock, slubbing .and knittingayamsand wool -with-.a low.twistinv general.

We have found that the substituted uanamines of the present invention reduce the time required for dyeing by as much as one-half, which decreased bath time represents a considerable economic saving. As we have pointed out above, it has long been recognizedthat dyeing in acid solutions at the boiling point is detrimen- -ta1 to the fabric and that the damage is related to the time during'which the fabric is subjected to 'these conditions. An even greater advantage of the decrease'd'bath time, therefore, is the resulting .improvementin the physical properties :of'theriyedfabric.

'Thefollowing specific examples will further i'llustrate the-inanner in which the present invention may be practiced. Parts are by weight.

' Example 1 v Stearoguanamine was prepared by the method described in Example 2 of U. S. Patent No. 2,309,679 and then condensed with the following quantities of ethyleneoxide:

A 1l.moles ethylene oxide B-25 molesethylene oxide C-35-mo1es ethylene oxide 13-50 moles ethylene oxide -3100 moles ethylene oxide It should be noted that the amount ofstearoguanamine is 1- molein each-case. The-reaction between-the ethylene oxide andstearoguan'amine proceeded smoothly at '1 1'0-'-220 i C.

Example 2 A dye bath was :prepared using. 250 cc. water, 0.1g. of the chromium l'com'plex of the azo dye obtained by coupling :diazotized -1-amino-2-hydroxynaphthalene-id-sulfonic acid to beta-naphthol, ddgiofiformic acid and-I01 gof the surface active agent prepared as -Example 1A. Five grams of wool, :.pre-'wet with water, were then introduced .into the vdye bath at about--F., the bath:slowlyraisedto the boil with intermittent turning of .the"wo'ol, and dyed for about 1 /2 hours -.at the boil. The water that evaporated during the boiling was replenished frequently in orderto keep the aliquor-wool ratio practically constant. "When the dyeing was completed, the wool: wasremo'ved, rinsed and-air-d-ried. A second dyeing was prepared Jin the same manner, except the product of Example 1A was not added to the dye bath. This was used as a control dyemg.

The shade of the wool dyed in the bath in which the surface active agent was present was more level and much stronger than that of the wool dyed in the control bath.

Example 3 Example 2 was rep'eated except that thetime of::dy.eing wasrlimitedto f'crty-five minutes. The shade of .the wool J-dyed in the presence of the surface :active agent more level and stronger than thataof .WoZJLdyedin the control bath for .li ihours.

Example .4

The general proeedure ofrfixample2 was repcated; except #05; g. of iformi'cuacid .was used instead of .0:4= g. :formica'cid. The. result Was gen- ':erally similar-to that obtained .in Example 2.

Example 5 {I he procedure :of Example 12 was repeated, using again 0.5 :"g. of formic acid and :substituting for the dye of Example 2 the chromiuma'complex of the azo dye obtained by coupling, diazotized 1-amino-2-hydroxy-naphthalene-.4-sulfonic acid to 1-hydroxy-naphthalene-8esulfonic acid.- Again the color value of the dyeing obtained from the bath in which the surface active material was present was much stronger and the shade was more level than the dyeing obtaine in the control bath.

Example 6 Example 7 The procedure of Example 2 was repeated, 11S? ing 0.5 g. of formic acid and the chromium complex of the azo dye obtained by coupling diazotized 2-amino-4-chlor-phenol-6-sulfonic acid to 1-phenyl-3-methyl-5-pyrazolone. When the color value of the dyeing was determined by means of a spectrophotometer and the control sample was assigned a value of 100%, the color'value of the sample dyed in the presence of the product of Example 1A was'165%.

Example 8 Example The procedure of Example 8' was repeated, except that 0.1 g. of the surface active material described in Example 13 was used instead of the dye assistant of Example 1A. The dyeing made in thebath inwhich the surface active material was present'was' substantially equal to that in Example 8 and notably superior tothat made in the control bath.

Example 10 The procedure of Example 8 was repeated, except 0.1 g. of the product described in Example 10 was used. The dyeing obtained in-the bath containing the surface active material was slightly more level and somewhat weaker than the dyeing obtained in Example 8 which employed the surface active agent of Example 1A. Both dyeings, however, were markedly superior to the control dyeing.

Example 11 The procedure of Example 8 was repeated, substituting 0.1 g. of the product described in Example 1D. The results were very similar to those obtained in Example 9.

Example 12 The procedure of Example 8 was repeated, sub- 6 stituting the-surface active agent described Example 1E. The wool dyed in the bath containing this product was notably stronger and much more level than the control dyeing. It was also more level than the dyeing obtained in Example 8. However, the shade was somewhat weaker than that obtained in Example 8.

This series of examples from 8 to 12 illustrates the principle mentioned above, namely, that increasing the amount of ethylene oxide improves the levelness of the dyeing and decreases the color value.

Example 13 .The procedure of Example 2 was repeated, substituting 0.1 g. of the product of'Ex'ample 1C for the product of Example 1A. The dyeing made in the bath in which the surface active material was present was much stronger and more level than the dyeing made in the control bath. 1

Example 14 l I The procedure of Example 2 was repeated, substituting the dye assistant of Example 10' and decreasing the amount to 0.025 part A,). The wool dyed in this bath was slightly weaker in color than that of Example 13, but was stronger than the wool dyed in the control bath.

Example 15 The procedure of Example 2 was repeated, using 0.15 g. of the surface active agent described in Example 10. Wool dyed in the bath containing 0.15 g. of dye assistant was stronger and more level than wool dyed in the control bath.

Example 16 Example 17 A dye composition'was prepared consisting of 29 parts of the chromium complex of the azo dye obtained'by coupling diazotized 1-amino-2-hydroxy-naphthalene-4-sulfonic acid to l-hydroxynaphthalene-B-sulfonic acid, 35 parts of the chromium complex of the azo dye obtained by coupling diazotized 1-amino-2-hydroxy-naphthalene-4-sulfonic'acid to beta naphthol, 17 parts ofthe chromium complex of'the azo dye obtained by coupling diazotized l-amino-2-hydroxy-naph thalene-4-su1fonic acid to 1-phenol-3-methyl- 5-pyrazolone, and 19 parts of Glaubers salt. A dye bath was prepared, using 250 cc. water, 0.1 g. of the dye mix described above, 0.5 g. of formic acid and 0.1 g. of the product of Example 1A; A control dyeing was also made in the absence of any surface active material.

The color value of the dyeing as made in the two baths was then determined by means of the spectrophotometer and the dyeing made in the presence of the dye assistant had a value of about 250% based on for the control sample.

Example 18 a-Ethylhexanoguanamine was prepared according to the method described in Example 11 of U. S. Patent No. 2,309,679 and then condensed with 25 mol equivalents of glycidol to give a product that was readily soluble in water. This dye assistant was then used according to the awesome Adye bath: was preparedw ith 300:cc'. oi' wate1: and 0.4 g. of the cobalt complex of the azo-dye obtained by coupling 4-nitro-.2-amino-phenol to 1 (4' -sulfo-phenyl) =3'-'me'thyl=5pyrazolone. To this bath was added :5 2g; of calcinednG laub'ens salt,- -0. 1 cc. of 55 acetic acid and firigs of *;t-hor-. oughlywet-out woollyarn. cc. of:a 1%*solution of the product of Example 1 was introduced and the temperature raised*to:1805.l7.; whereupon 0.075 .gpof formic acid'waseadded. Therdy'eing was continued at the boiling point until a satisfactory shade had beenbbtained.

"Example "21 :A dyeing was-made as in Example :Z BXOEDUX'ZhE copper cemplex of the .dyeobtainedrbydiazotiz ing ortho-phenetidineand coupling with :Sch-ae-" fers salt is substituted for the chromium complex of Example 2. ni'ust 'colored shade having excellent color value was 'obtained.

Ewa'mple 22 By a reaction similar --to that described in Example 1, istearogua-namine was preparedand condensed with mols ofpropyleneoxide.

To a dye bath containing 0.1 part of the propylene oxide condensationprepared above, 4-

parts: of 16% hydroxy acetic'acida and i ;1 .-;-part of the chromium complex of the azo dyestufffrom diazotized anthranolic acid and =1'-='(4 '-"-sulfophenyl) -3 methyl.-5-pyrazolonein .300, parts not water --were :added 5 gparts of wool gyairn whicl'i had been thoroughly =-wet out. The loath was brought slowly*to the :boil and'maintainecl at .:the boil for sufiicient time to-complete-the dyeing.

Yarn which was dyed. in controlexperi-ment without theadvantage of thisdye assistantzwas' not level.

E'fitample 23 Example L '2 was repeated substituting g. .of nylon for the wool. N h

.lNylon dyedin a control bath was muchmeaker 'a dye bath containing.ime'tallized:dye; formic aorta-and an amountsuificient to be e1 ctive but msufiicientito eause scum ienna "on and excessivepreciliitatit in in the b'ath yL'guam amine; lkyh-eroup hen .g' an aliphatic hydro'earbon chain of- I-'= t0 17'carben atoms and said 2-alkyl guanaminehaving' polyalkylene oxide chains attached to the amino nitrogens, said pol-yailkyl'eneoxidechains-containing "at least 1 1 but'notmorethan100-etiier"oxygenatoms separated*by"'at least-'2 butnot more than 3 carbon atoms," aiidsa'idflye bath being further characterized"by thea'bsen'ce of mineral acids.

The method of claim 1 which the material to be dyed is Wool.

i. The method 'of 'clainrB inwhich said polyalkylene oxide chainluiswa ilpolyethylene oxide chain.

*5. The methodof fclaim"'1 which'the 2-allryl gcanamineisystea'rogizananrme.

7. "The metho'cl according "to "claim 1 in which said .2 -alkyljg'uanamine is'lauroguan'amine.

"8. 'The method'of claim! in which said polyalkylen'e oxide'chainsjare'fpolyglycidol' chains.

fQH'Ihe'mthnd of'claim"i iniwhi'ch said polyalkyl'ene "dxi'd'e'ehain's "contain between 40 and ethylene oxide units.

10. The method accbrdingto claim 9 in which the material to tbe dyed is wool.

EDMOND" MILLSON. SHANNON MOORADIAN.

*References Cited *in" the file of "this patent U 'NI'I'ED V i STKTES PKTENT'S Name Date 2,040,796 Rittin hausen one: may :12, 1936 2,470,080 Millson We; May 10, 1949 OTHER REFERENCES l Ameri'can Dyestufif Reporter for March 6, i950; pagesxl5-2 -f't0 1-54; inclusive, a-rticle vby Luttrirrghaus.

Claims (1)

1. A METHOD OF DYEING NITROGENOUS FIBERS WITH METALLIZED AZO DYES SOLUBLE IN ACID BATHS, WHICH COMPRISES SUBJECTING THE MATERIAL TO BE DYED TO A DYE BATH CONTAINING METALLIZED DYE; FORMIC ACID; AND AN AMOUNT SUFFICIENT TO BE EFFECTIVE BUT INSUFFICIENT TO CAUSE SCRUM FORMATION AND EXCESSIVE PRECIPITATION IN THE BATH, OF A 2-ALKY GUANAMINE; SAID ALKYL GROUP BEING AN ALIPHATIC HYDROCARBON CHAIN OF 7 TO 17 CARBON ATOMS AND SAID 2-ALKYL GUANAMINE HAVING POLYALKYLENE OXIDE CHAINS ATTACHED TO THE AMINO NITROGENS, SAID POLYALKYLENE OXIDE CHAINS CONTAINING AT LEAST 11 BUT NOT MORE THAN 100 ETHER OXYGEN ATOMS SEPARATED BY AT LEAST 2 BUT NOT MORE THAN 3 CARBON ATOMS; AND SAID DYE BATH BEING FURTHER CHARACTERIZED BY THE ABSENCE OF MINERAL ACIDS.