US2683646A - High-temperature vat dyeing baths using manganese compounds - Google Patents

Description

Patented July 13, 1954 UNITED STATEfi... ATENT I OFFICE-J1 HIGH-TEMPERATURE VAT DYEING BATHS USING MANGANESE COMPOUNDS Frederick Fordemwalt, Middlescx, N. J., assignor 1 to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing.- Application November 1, 1952,

Serial No. 318,343

13 Claims. (Cl. 834) This invention relates to improved-reduction" baths containing alkali metal hydrosulfite and over-reduction buffers and the'compositions for producing them.

In ordinary vat dyeing there is used a reduc-:

tion bath to transform the vat dye into its leuco form. This reduction bathis strongly alkaline.

and for the reducing material generally usesa metal hydrosulfite, usually sodium or zinc hydrosulfite. shown themselves sensitive to over-reduction in dyeing at elevated temperatures. This constituted a serious drawback in the cas of the sensitive dyes, as there is a great economic advantage in dyeing at high temperature. In Patents 1548;543

and 2,548,544, both dated April 10,1951; andlll Numerous vat dyes in the past have Patent 2,576,846, dated November 27, 1951, there a have been described processes for the high temperature dyeing of vat dyestufis which are sensi tive to over-reduction using certain over-reduction buifers. In the two patents dated April- 10, 1951, the inorganic nitrites and halogenates are described and claimed, and in Patent-2,-5'76,846, dated November 27, 1951, organic nitrogen compounds in which the nitrogen is attached 'b'yat least one co-valent bond to oxygen and by at least one co-valent bond to an element other -than oxygen or nitrogen are described and claimed:

These compounds stabilized the dyestuffs and prevented over-reduction. The same compounds were also found to improve the dyeing with oer-1 tain pyranthrone vat dyestuffs'whichare'not" sensitive to over-reduction. Processes using"? nitrites and halogenates in the dyeing-of these described solve the problem presented by over--- reduction of sensitive vat dyestuffs in high tern-H perature dyeing and improve the :dyeingof the.

pyranthrone dyestuffs referred to above.--.H0w-= ever, this greatly improved resultwas obtained. at

the expense of increased hydrosulfite consumption and while the consumption'of hydrosulfite is not so great as to renderthe improved dye processes uneconomical, the cost of the increasedhydrmsulfite consumption is nevertheless sufficient" so that reduction of the excessive consumption economically desirable.

The mechanism w h ults n increased hjyable when thebath containsonly-thestabilizing drosulfite consumption "is not fullydetermined;

but appears to be due at least-in part-to chemical reaction with the stabilizeror over-reduction."

buffer.

According to the present invention, I have' found that if a substantial amount of manganese compound is introduced into the bath,.the excessconsumption of hydrosulfite at high temperatures is very greatly reduced and as aresult on stand-- ing the hydrosulfite concentration is much-higher than if the bath contained no manganese-ions; It is not known just howthe presence of the manganese compound reduces-excessive-hydro-' sulfite consumption and therefore the-invention is not restricted to a particular theory'of how-it behaves. It is possible that a manganese salt or complex of the hydrosulfite may be formed which is less'reactive with the stabilizers or overreduction buffers than the alkali salts.- -*However; though this may be a factor, it seems probable: that it is not the only factor because manganese ions are effective in amounts very materially less" than the stoichiometrical equivalents-necessary for forming manganese hydrosulfite:

The preparation of baths has been described above in terms of adding ingredients to the bath. In manycases this is preferable, :but it is also possible to produce-compositions.containingmhe' vat dyestuff and the manganese. suchrcomposis;

tions contain suflici'ent manganese so that when a vat dye bath is prepared in the normal manner the manganese counteractsthe' hydrosulfiteconsumption. Thusrit is possi-blezto marketia com- The' over-reduction buffers are substantial equivalents and .thepresent invention is therefore applicable regardless of whether ther'e-is a single bufier'present or a mixture of two or more Of them.

While manganese compounds of the'presentinvention mayalsobe used withother compounds having the same effect, namely; magnesium compounds and trialkanolamine's, theseother compounds are not claimed perse in this case but constitute the subject matter of the copending applications of Jerry M. Mecco,'Serial No.-258,281, filed November 26, l951,'and Serial No.-253;282;

filed November 26, 1951, both now abandoned.

The operation of the present invention is not limited to vat dyeing'baths in which the vat dye Similar is actually incorporated into the bath.

savings in hydrosulfite consumption-are obta'in agent or over-reduction buffer and the hydrosulfite as in the case of certain pigment dyeing processes.

The invention will be described in greater detail in conjunction with the following specific examples, the parts being by Weight unless otherwise specified.

Example I A dye bath was prepared to contain 400 parts of a solution composed of the following materials: 10.0% 30 B. caustic soda, 0.75% sodium nitrite, 8.7% of a 1% dispersion of a commercial paste of the vat dye having Color Index No. 1113, 80.55% water.

To this were added 4 parts of a solution of manganous chloride (MnCl2-4H2O). The bath was heated to the boil and then 12.5 parts of sodium hydrosulfite were added.

The temperature was maintained at the boil for 23 minutes, at which time the bath was found still to contain 5 parts of hydrosulfite as determined by titration with a standard indigo solution. At the end of 30 minutes, a swatch of 80 x 80 bleached unmercerized cotton print cloth was introduced into the bath and dyed for minutes at the boil. The result was an excellent strong blue dyeing.

In a similar bath which contained no man ganese salt, the hydrosulfite concentration during the dyeing period decreased to less than 1.2 parts in 10 minutes time, and no hydrosulfite remained after 18 minutes. A swatch of cotton cloth, similar to the above, which was introduced into the bath at the end of 30 minutes remained essentially undyed.

Example 2 The procedure of Example 1 was repeated except only 3 parts of the manganese chloride solution were used. The bath contained 3,6 parts of hydrosulfite after 23.5 minutes and the cotton cloth introduced at the end of 30 minutes became strongly dyed as compared to a control dyeing which was essentially undyed.

Ezvample 3 The procedure of Example 1 was repeated except only 2 parts of the manganese chloride solution were used.

After eleven minutes, the bath still contained 8.5 parts of hydrosulfite whereas a similar bath without the manganese salt had less than 1.2 parts of hydrosulfite after 10 minutes.

Example 4 A dye bath was prepared to contain 4 oz./gal. sodium hydroxide, 4 oz./gal. sodium hydrosulfite, 1 oz./ga1. sodium nitrite, 0.1 oz./gal. of a commercial paste of the blue vat dye having Color Index No. 1113 and 0.25 oz./gal. of hydrated manganese chloride. The rate of hydrosulfite consumption at the boil was approximately 0.16 oz./gal./min. In a corresponding bath with no manganese salt present, the hydrosulfite consumption was more than twice as rapid.

Example 5 A dye bath (having no dye present) containing 4 oz./gal. sodium hydroxide, 1 oz./gal. sodium nitrite, and 4 oz./gal. sodium hydrosulfite was held at a temperature of approximately 200 The hydrosulfite consumption amounted to approximately 03 oZ./gal./min. In a corresponding bath which contained, in addition 0.12

oz./gal. of hydrated manganous chloride, the r e of hydrosulfite consumption was only about 0.1 oz./gal./min.

Emample 6 A dye bath which contained 4 oz./gal. sodium hydroxide, 0.1 oz./gal. sodium nitrite, 4 oz./gal. sodium hydrosulfite, and 0.1 oz./gal. of a commercial paste of the orange vat dye having Color Index No. 1098 was heated to approximately 200 F. for 30 minutes. At the end of this time, the hydrosulfite content was approximately 3.3 oz./gal. and 1 oz./gal. sodium nitrite was then added. The hydrosulfite consumption then became about 0.7 oz./gal./min.

Ercample 7 The procedure described in Example 6 was repeated except the bath contained, in addition, 0.2 oz./ga1. hydrated manganese chloride. The hydrosulfite consumption in this case was only about one-fourth as rapid as under the conditional of Example 6.

Example 8 The procedure described in Example 7 was re peated except that the dye used was the pink vat dye having the formula: 6,6dichloro-4,4- dimethyl 2,2bis(thio)naphthene indigo. The hydrosulfite consumption was approximately the same as that observed under the conditions described in Example '7.

Example 9 A dye bath containing 4 oz./gal. of sodium hydroxide, 1 oz./gal. of sodium nitrite, 0.08 oz./gal. of a commercial paste of the green vat dye having Color Index No. 1101, and 0.07 oz./gal. manganese sulfate technical grade was heated to approxi mately 200 F. and 4 oz./ gal. sodium hydrosulfite were then added. The rate of hydrosulfite consumption in this bath was only about one-half as great as in a corresponding bath which contained no manganese salt.

A piece of x 80 bleached unmercerized cotton cloth introduced into the bath at the end of 30 minutes and dyed for 10 minutes became heavily dyed. A piece of similar cloth introduced into the corresponding bath which contained no manganese salt remained undyed.

Example 10 The procedure of Example 9 was repeated using manganese resinate instead of manganese sulfate. The results were generally similar to those described in Example 9.

Example 11 The procedure of Example 9 was repeated using 0.03 oz./gal. hydrated manganese chloride instead of the manganese sulfate.

The results were generally similar to those described in Example 9.

Example 12 The procedure of Example 9 was repeated using 0.01 oz./gal. hydrated manganese chloride instead of the manganese sulfate. Again, a good dyeing was obtained with the bath which contained the manganese salt.

Example 13 A dye bath which contained 4 oz./ga1. NaOH, 0.1 oz./gal. of a commercial paste of the blue vat dye having C. I. No. 1113, 2 oz./gal. of hydroxylamine hydrochloride and 0.01 oz./gal. of hydrated manganese chloride was heated to approximately 200 F. and 4 oz./gal. of sodium hydrosulfite added. At the same timea secondw bath was prepared in exactly thesame way :ex-

cept no maganese salt was added. The rate of hydrosulfite consumption, as measured'by titration with standard indigo, .was over twice as fast in the bath which contained no manganese as it was in the bath to which the manganese salt had been added.

A swatch of 80 x 80 cotton introducedinto the first bath at the end of eleven minutes became heavily dyed while a swatch introduced at the same time into the bath to which no manganese had been added remained essentially undyed.

Example 14 A bath which contained 4 oz./gal. of NaOI-I, 0.04 oz./gal. of a commercial paste of the blue vat dye having C. I. No. 1113 and 2 oz./gal. of NaClO3 was heated to approximately 200 F. and 4 oz./ gal. of sodium hydrosulfite added.- The rate of hydrosulfite consumption in this bath was approximately 0.19 'oz./ga1./min. In a corresponding bath to which 0.01 oz./gal. of hydrated manganese chloride had been added th hydrosulfite consumption was less than one-half as great.

Example In a bath prepared as described in Example 14 but with no dye present, the rate of hydrosulfite consumption was approximately-0.22 oz./gal./min.

without the manganese and only about one-half that fast in the bath which contained the manganese salt.

Example 16 A bath which contained 4 oz./gal, of NaOI-I and 2 oz./ gal. of hydroxylammonium sulfate was heated to about 200 F, and 4 oz./gal. of sodium hydrosulfite added. The rate of hydrosulfite consumption, measured by titration with a standard indigo solution, was approximately 0.33 oz./gal./min In a corresponding bath to which had been added 0.01 oz./gal. of hydrated manganese chloride the hydrosulfite consumption was only about 0.22 oz./ gal. /rnin.

Example 17 Two dye baths were set up, each containing a oz./gal. of NaOI-I, l oz./gal. of NaNOz, 0.1

oz./ gal. of a commercial paste of the blue vat dye having C. I. No. 1113 and 4 oz./gal. of zinc hydrosulfite. One of the baths contained, in addition, 0.03 oz./ gal. of hydrated manganese chloride.

Titrations with standard indigo showed that, r

in the bath which did not contain the manganese compound, the hydrosulfite consumption was about more rap-id than it was in the other bath in which the manganese ions were present.

Example 18 ExampleIQ parts of the real dye having Color Index No. 1106 in the'form'of a press cake were dispersed with 5 parts of disodiumdisulfodinaphthylmethane. To this were added 50 parts of manganous chloride after which the mixture was passed through a high *speedmixer. This gave a vat dye composition containing the 'manganous salt.

A dye bath was prepared to contain 5 parts of the above paste, 4 Qa/galNaOH, 1 oz./gal. sodium nitrite and 4 oz./gal.'sodium hydrosulfite. When cotton was dyed in this dye bath at a temperature of 200 F., the rate at which the hydrosulfite was consumed was less than the rate of consumption in a similar dye bath-in which no manganous salt was present.

Example 20 The following dye mixtures were prepared using 100 parts of the dye having ColorIndex No. 1105 in the form of a dispersed press cake as in the preceding example:

100 parts dye-25 parts manganous chloride 100 parts dye12 parts-manganous chloride 100 parts dye6 parts manganous sulfate 100 parts dye-13 parts manganous sulfate When these were dyed on cotton by the pro cedure of Example 19, good blue shades were obtained.

If desired, the dyes having Color Index Nos. 1112, 1113, 1098, 1101, may be used in place of the dye having Color Index No. 1106. 1

Example 21 100 parts of the dye of Example 19 in the form of a press cake were dispersed as in Example 19 and then colloidized by the general procedure of ,U. S. Patent No. 2,090,511,'except that 50 parts of manganese chloride were used to replace 50 parts of cerelose. The product was a colloidized vat dye containing a manganese salt.

This powder was used to make a 5% dyeing by the procedureof Example. 19 and no difference was noted.

Example 22 The procedure of the precedingiexample'was' repeated except the manganese salt-was added to the defiocculated press cake before colloidizing. It was then blended with the requisite quantity of sugar.

Dyes having Color Index Nos. 1106, 1112, 1098, 1101 and 1117 were colloidized by the methods outlined above and in Example 21 and the colloidized powders were substituted for the paste in making dyeings according to the process described in Example 19. The results were satisfactory.

Example 23 Two dye baths were set up, each containing 4 oz./gal. of NaNOz, 0.1 oz./gal. of a commercial paste of the blue vat dye having Color Index 1113, and 4 oz./gal. of zinc hydrosulfite. One of the oaths contained, in addition, 0.03 oz./gal. of man-- ganese chloride.

Titrations with standard indigo showed that, in the bath which did not contain the manganese compound, the hydrosulfite consumption was about 50% more rapid than it was in the other bath in which the manganese ions were present.

Example 24 A dye bath was prepared to contain 50 parts of a 1% slurry of the vat dye having Color Index No. 1113, 15.8 parts of 30 B. NaOI-lf, 1.5 parts of NaNOz, 130 parts of H20 and 2.6 parts of a 3% solution of KMnO4. This was heated to 196 F. and there were then added 6 parts of sodium hydrosulfite. The bath was stirred frequently while the temperature was held at 197-198 F. The amount of hydrosulfite was determined at intervals by titration with soluble indigo. After minutes a swatch of 80 x 80 cotton was introduced and dyed for 6 minutes. A strong bluecolor was obtained and after 18 minutes the bath still contained approximately two parts of hydrosulfite.

Another dyebath was prepared as above with the omission of the 2.6 parts of the potassium permanganate solution. After five minutes the hydrosulfite was practically gone. After seven minutes the dye started to precipitate in the bath, and the swatch of cotton introduced at the end of ten minutes and dyed for six minutes remained essentially uncolored.

Example A dye bath was prepared to contain 0.5 part of a commercial paste of the vat dye having Color Index No. 1113 and containing 0.1 part real dye, 6.0 parts of NaOH, 1.5 parts of NaNOz, 0.12 parts of MgSO4'7I-I2O, 0.078 part of mm and 200.0 parts of water.

The bath was heated to approximately 200 F. and held at that temperature. 6.0 parts of Na2S2O4 were added and the bath stirred frequently.

Titration with a standard solution of soluble indigo showed that at the end of 12 minutes there were still approximately 3.5 parts of hydrosulfite remaining in the bath.

A similar bath was prepared omitting the magnesium sulfate and the potassium permanganate and after 10 minutes the hydrosulfite was entirely consumed.

I claim:

1. A reducing bath suitable for high temperature vat dyeing comprising an aqueous solution of caustic alkali and metal hydrosulfite, a stabilizer against over-reduction of vat dyes selected from the group consisting of inorganic nitrites, inorganic halogenates and nitrogen compounds in which a nitrogen atom is attached by at least one co-valent bond to oxygen and by at least one co-valent bond to an element other than oxygen or nitrogen and at least 0.0005 mol of a manganese compound per mol of metal hydrosulfite.

2. A bath according to claim 1 containing a vat dyestufi capable of over-reduction at elevated temperatures.

3. A bath according to claim 1 containing a pyranthrone vat dyestuif.

4. A bath according to claim 1 in which the stabilizer is alkali metal nitrite.

5. A bath according to claim 2 in which the stabilizer is alkali metal nitrite.

6. A bath according to claim 5 in which the vat dyestuff is a vat dyestufi of the indanthrone series.

7. A bath according to claim 3 in which the stabilizer is alkali metal nitrite.

8. A bath according to claim 1 in which the stabilizer is a nitrogen compound linked by at least one co-valent bond to oxygen and by at least one co-valent bond to an atom other than oxygen or nitrogen.

9. A bath according to claim 8 containing a vat dyestufl capable of over-reduction at elevated temperatures.

10. A bath according to claim 9 in which the nitrogen compound is a hydroxylamine compound.

ll. A bath according to claim 10 in which the vat dyestufi is a dyestufi of the indanthrone series.

12. A bath according to claim 1 in which there is present in addition to the manganese compound at least one compound selected from the group consisting of soluble magnesium compounds and trialkanolamines.

13. A bath according to claim 12 containing a vat dyestuff capable of over-reduction at elevated temperatures.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,584,202 Theobald May 11, 1926 2,067,927 Kern Jan. 19, 1937 2,067,928 Kern Jan. 19, 1937

Claims (1)

1. A REDUCING BATH SUITABLE FOR HIGH TEMPERATURE VAT DYEING COMPRISING AN AQUEOUS SOLUTION OF CAUSTIC ALKALI AND METAL HYDROSULFITE, A STABILIZER AGAINST OVER-REDUCTION OF VAT DYES SELECTED FROM THE GROUP CONSISTING OF INORGANIC NITRITES, INORGANIC HALOGENATES AND NITROGEN COMPOUNDS IN WHICH A NITROGEN ATOM IS ATTACHED BY AT LEAST ONE CO-VALENT BOND TO OXYGEN AND BY AT LEAST ONE CO-VALENT BOND TO AN ELEMENT OTHER THAN OXYGEN OR NITROGEN AND AT LEAST 0.0005 MOL OF A MANGANESE COMPOUND PER MOL OF METAL HYDROSULFITE.