US2548546A - Pyranthrone composition comprising an inorganic halogenate and process for dyeing - Google Patents

Description

Patented Apr. 10, 1951 PYRANTHRONE COMPOSITIONTCDMPRISINGT AN INORGANIC HALOGENATEAND PROG-v ESS FOR DYEING Jerry M.'. Mecco, Somerville,1. N J.-., assignor to American. Cyanamid Company, New York,,. N: -Y., acorporationof Maine.

No'Drawing: Application November'30, -1949 Serial No. 130,360?

and} it, and. itsedib'romo. derivative. (o: 1.. 1098),

are. well. known vat dyesof golden-orange color. When these dyes are dyedfby ordinary vat dyeing processes,.,whieh involve a strongalkaligsuch. as' sodium hydroxide and a reducing agent, such as sodium hydrosulfite, there is a loss'iii strength and brilliance, whenathe' dyeing operation is carriedout. at. high. temperatures. On the. other hand,. high temperature dyeing presents... such large, practicall economic advantages, that. the properties of thesetwo. dyes, for dyeing. at high temperatures, approaching that" of boiling, water, has .hampered their economic exploitation.

High temperature dyeing. usually. improves dye penetrationand/or; level'ness,. particularly with such fabrics as nylon; The fast-dyeing which is possible. at high temperatures also makes various continuous andi semi' continuous processes. possible.

In referring to a "dye bath"it' shouldbe under stood that we are considering'the situation at" the time the dye is aflixedtmthe fabric. In many processesthedyestuif is present ina dye bath .or vat .in solutioni'n the form ofithe reduced leuco comp,ound',andfthe goods are introduced into this bath. In other processes, such as,,for example,

pigment dyeingjprocesses; which lend themselves to continuous and semi-continuous processesof the package: dyeing; variety, the. dyestufi may "be originallyincorporated loosely in the'fiber in the;

form of a" pigmentand'then" reduced" by; the dye 50' in. the-fiber Throughout. -thisr2case; the term 55 12;-Claims. (Cl; 8-34).

2. dyebath? willtbe used-to cover both types. of situation.

We. have found 'that the addition of an inorganichalogenate, suchas .chlorates, bromates,.and iodates, removes v:the disadvantage noted inordinary high-temperaturadyeing with pyranthrone,v and its. halogenated derivatives. A all. off the alkali metal halogenatesbehave in thesamemanner, sodiumchlorate is,-,. ordinarily,. used becausev ofitslowcost- The particular metal cation, however, does not .appearto enterinto the. mechanism,, by which the halogenates:achievetheir iinproved'i. results. Therefore, practically, sodium halogen.- ate. is preferred. a

It .islnotknownhow thehalogenate operatesl'in. preventing. loss .of strength vand brilliance in. high temperature. dyeing. with. pyranthrone; and; ac.- cordingly, the present invention. is. not intended to. be limited. to. any, theory. of. action. In particular, the phenomena. which. underlies the.pres.-- ent invention areall'the-moremysterioushecause,. as. is. described: and claimed. in my. copending, application .SerialTNo. 1301357,filed'November 30', 1949; inorganic halogenates. exert a: similar action" with vatj dyestuffs, which are sensitive to. over reduction or decomposition athigh temperatures. In. the. caseiofthese. dyes; which are easily, decomposed or over reduced; it is. possible that the halogenate may, a'ctas somef kindv of'a reduction buffer. In'the caseiofpyra'nthrone and 'its'ha1o'-- genated. derivatives; however, such an explanation .is not'tenablabecause it is a known characteristic of these dyes .thatthey do not show any appearance of decompositionorover'reductionin" bathsup to the. boiling.point ofwa'ter. In'spite of this. well known stability; of" the dye'stufisythe,v halogenates exert their beneficial" action to a marked degree. It is obvious" that'fact'orsotheT than prevention of oven-reduction or decomposition at high. temperatures. must. be. involved.

Whatthese. other factors. are, however, hasistill. not. been. determined" The advantages. of. therpresentv inventionare. obtained bothwithpyranthrone andits halogenated derivatives. The. degree of improvement,. however, is considerably. greater." with dibromopyranthrone than with .pyranthrone. itself..

It is .an advantage. of. the present invention that. the amount of..inorganichalogenate.to.:be.. used.is,. not? critical. 'I here;is-,-.of, course a lower limit; and. it. has been. found that when. thes amount 01:. halogenate; is.- less-than oneequa-rter by weight: of.- the: content". of -actual.-- dyestuft in r the bath-, the; improvements are notesuificientlm marked i to be of; practical. value. Abova-this-s minimum; results.-

improve for a while, with increasing amounts of halogenate, but soon reach the point at which greater amounts of halogenate do not give any improvement. This point is approximately 16 parts by weightqthalogenate to 1 part of dye. However for practical operation, the improvement obtained with much smaller amounts (for example, from 1 to 3 parts of halogenate per part of dye), so closely approach the maximum improvement obtainable, thatllarger amounts of halogenate do not produce sufiicient improvement to justify the additional cost. Even the upper limit of 16 parts of halogenate does not'represent the maximum amount which can-be-used, without destroying the improvement in strength and bril- 4 in warm water to remove the excess acid, soaped at the boil for ten minutes in 0.1 soap and 0.1% soda ash solution, rinsed and dried. The color was a bright orange and the yarn was dyed a full shade. I 1

A second dyeing was made liketh'e above except the 1.5 parts of sodium chlorate were omitted from the dye bath. The material dyed in this liance, which is the purpose of..the present .in-

vention. Even when 50 parts of halogenate. to 1 of dye are used, the improvements are still to be noted; but, of course, such enormous amounts of halogenate are only of theoretical interest.

Another advantage of the present invention is that the manipulative techniques of high temperature dyeing are not, in any way changed by its'use. Dyeing conditions remain the same as do dyeing times; and the only change is that the shades obtained are stronger and brighter.

I The optimum amount of inorganic halogenate who used depends, to some extent, on the temperature of the dye bath and on the time during which dyeing takes place. In general, the faster the dyeing, the smaller the amount of halogenate whichcan caused to give results so closely approximating the optimum results, as to make larger amounts of halogenate practically unnecessary. When dyeing time is longer, as is customary; additional amounts of hydrosulfite are added to makeup for hydrosulfite oxidized by mean, or by other factors.

It is an advantage of the present invention that it'may be applied in several ways. ample, vat dye baths can be made up by adding all of the ingredients, that is, dye, alkali, reducing agent and halogenate, to produce a finished bath. Another method which has the practical advantage of makingit unnecessary for the dyer to control closely the" proportion of all ingredients going into the dye bath, is to blend with the dyest'u'fi a suitable amountof'halogenate to form'a p'owder'or a paste. This blend, which constitutes a new article of manufacture included within the scope of the present invention, may be sold; The dyer may then prepare his bath with the dyestuff blend, the alkali and thelr'educing agent in any convenient order.

The invention, will be illustrated in greater detailin conjunction with the following specific examples. Parts are by weight.

Example 1 10 parts of cotton yarn were dyed in a bath containing about 0.09 part of the real dye having Qolor Index 1098, three parts of sodium hydros'uliite, 1.5 parts of sodium chlorate in 400 parts o'f water. -The bath'was heated for five minutes at about 200' F.-during which time the vat dye was reduced, after which thecotton yarn was entered and dyed for 60 minutes at about 200 F. The dyed yarn was then removed, and the excess dye liquor extracted from the yarn. The remaining dye on the yarn was then oxidized for five minutes in the air at room temperature, after which it was immersed in an oxidizing solution consisting oi 0.1% sodium peroxide (100 volumes) and 0.1% glacial acetic acid'solution for ten minutes at 140 F; The dyed yarn was then rinsed For ex- .repeatedexcept the dye having Color Index No.

1096- and 1.5 parts of sodium hydrosulfite were added after 5minutes and another 1.5 parts were added after minutes. The color value of the yarn dyed'ii'ithis'bath is a stronger and brighter orange than that of the yarn dyed in the control sample in which no sodium chlorate is present.

Example 3 'Ten parts of cotton yarn were dyed in a bath containing 0.09 part of the real dye having Color Index No. 1096, 3 parts of sodium hydroxide, 3

parts of sodium hydrosulfite, 1.5 parts of potas- Example 4 The procedure of the preceding example was repeated except the dye having Color Index No. 1098 and 1.5 parts of sodium hydrosulfite were .added after 5 minutes and another 1.5 parts were added after. 20 minutes. The color value of the yarn dyed in this dyebath is much'stronger and brighter orange than that of the yarn dyed in the control sample in which no potassium bromate is present.

Example 5 Ten parts of cotton material-were dyed in a bath containing 0.09 part of the real dye having Color Index No. 1096, 3 parts of sodium hydroxide, 3 parts of sodium hydrosulfite, 1.5 parts of potassium iodate in 400 parts of water. The bath was reduced for 5 minutes at 200 F. after which the cotton was entered and dyed for 60 minutes at 200 F. The dyeing was bright orange and the cotton was dyed a full shade.

A second dyeing was made exactly as above except the 1.5 parts of potassium iodate were omit-' ted from the dyebath. The cotton material dyed in this bath was a weaker shade of orange.

Example 6 Three parts of the dye having Color Index 1098 and containing about 18.5 %"real dye were mixed with 3 parts of sodium chloratek This mixture was then added to 1170 parts of water'at 160 F. To this was added 35"parts of' 30 Bet sodium hydroxide, after which the temperature was. again adjusted to 160 F. and 9' parts of sodium hydrosulfite added and dissolved. The temperature was maintained at 160 F. for 15- minutes, after which time the color was reduced. This will be referred to as thestandard leuco solution. 400 parts of this reduced dye solution were then transferred to a separate dye beaker.

Twenty parts of natural cotton yarn were prewet with approximately solution of pine oil soap,'the excess removed by squeezing, and the yarn then entered into the 400 parts of reduced vat dye and dyed at 160 F; for 15 minutesi -The dyed yarn was then removed and the excess dye liquor extracted. The remainingdye onthe yarn was, then oxidized for five minutes inthe air at room temperature, after which it was immersed in an oxidizing solution consisting of 0:1 sodium peroxide (100vo1umes)'- and 0:1% glacial acetic acid solution for minutes at'140" F; The dyed yarn was then rinsed in warm water to remove the excess glacial acetic acid, soa'ped at the boil for ten minutes in 0.1% soap and 0.1% soda ash solution, rinsed and dried.

A, control dye bath was prepared exactly like the above except the sodium chlorate was omitted. This was used to make a control dyeing using the same procedure as above. Theyarn dyed in the bath containing the sodium chlorate was stronger, redder and brighter than the con trol dyeing.

Example 8 The procedure of Example '7 was. repeated. ex.- cept the dyeing was made, for 1 hour 45 minutes after which the difference between the dyeing made in the bath containing the sodium chlorate and the control dyeing was even greater than that indicated in the preceding example.

Example 9 The procedure of Example 1 was repeated except rayon was used in place of the cotton and the resultswere similar to those obtained in Example 1.

ExampleIO;

The= procedure-0t the preceding example was repeated exceptlinen was used inplace of the rayon and the results were similar to those obtained in the precedin example.

Example 11 The procedure of the preceding example was repeated except nylon was used and the temperature was raised to the boil. The dyeing made in the bath containing the sodium chlorate was strong and bright whereas the dyeing made in the control bath was dull and yellow.

Example 12 The procedure of Example 1 was repeated except 0.025 part sodium chlorate was used instead of the 1.5 parts used in Example 1. The results showed an improvement in the appearance of the dyeing made in the bath containing the sodium chlorate over that made in the control bath but this difierence was not as great as was obtained in Example 1.

Example 13 A dyeing was made at a temperature of about 250 F. (approximately 50 pounds pressure) on 2.5 parts of bleached, unmercerized cotton in the apparatus described in U. S. P. 2,405,167 using a dye bath containing 0109- part ofreal dye having Color Index No. 1098, one partof sodium chlorate,

A goodstrong, bright reddish-orange shadewas obtained. I A. control dyeing in which, no sodiumchlorate was present, but. otherwise made as, above, had a dull yellow shade.

. Example 14 '500 parts ofNojZOs, Z-ply, natural cotton yarn in package form were wet'out' with 7000 parts of a solution of a surface-active anionic-ma terial which had been preheated to 190 F. This was then dyed in a dye bath containing nine parts of real dye having Color Index No. 1098,15 parts of a surface-active anionic material and: 22.5- parts of sodium chlorate in a liter of water, mak-' ing adye bath volume 0f8000 parts.

The dye dispersion was-first heated to 190 F; and then circulated through the wet-out package for ten minutes, after which 200 parts of: 30 B: sodium hydroxide which had-been preheated. to 190 F. were added to the dye bath and circulated for five minutes, after which parts of solid sodium hydrosulfite were. added and circulated for 25 minutes. The spent dye bath was then flushed with water from the machine, the dye was oxidized with 2% of 100-volume. hydrogen,

the dyebath. The package-dyed in the control bath was 'dull and yellower.

Example 15 900 parts of the real dye, having Color Index No. 1098, were ground and dry-blended with 250 parts of potassium chlorate. Ten parts of'cotton were dyed in. a bath containing, 0.115 part of this blend, 3 parts of sodiumthydroxide, and 3 parts-of sodium hydrosulfite in'400'partsofwater using the general method of-E'xamp'le 1. Theresultant dyeing was stronger, redder and brighter than a control dyeing made from a bath containing the same amount of real dye, alkali and hydrosulfite but omitting the potassium chlorate.

Example 16 Example 17 960 parts of the dye having Color Index No.

1096 and 2,400 parts of sodium bromate were ground and dry blended to give a homogeneous mixture. Ten parts of rayon yarn were dyed in a bath containing 0.35 part of this blend, 3 parts of sodium hydroxide, and 3 parts of sodium hy- Ten parts of cotton drosulfite in 400 parts of water by the general method used in Example 1. The yarn dyed in the bath containing the sodium bromate was redder and brighter than the control dyeing.

Example 18 Example 19 462.5 parts of the 20% wet press cake containing about 92.5 parts of the dye having Color Index No. 1098 and 400 parts of sodium chlorate were stirred together and then made up to 1,000 parts with water. One part of this paste was substituted for the one part of the paste of the preceding example, the dyeings were made as in the preceding example, and the results were satisfactory.

Example 20 The procedure of the preceding example was repeated except part of the water needed to bring the paste to 1,000 parts was replaced with glycerine to give a glycerine content of %10% on the final weight. Dyeings made with pastes containing glycerine were quite satisfactory.

Example 21 The procedure of the preceding example was repeated except the glycerine was replaced by ethylene glycol. Cotton yarn dyed with this paste is commercially satisfactory.

Example 22 The procedure of the preceding example was repeated except the wet press cake was dispersed with parts of the sodium salt of di-sulfo-dinaphthyl methane, the humectant then added and the paste made up to 1,000 parts. Cotton yarn dyed in a bath containing one part of this 8 paste but otherwise dyed as in Example 19 gave satisfactory results.

I claim:

1. A method of vat dyeing fibrous material to which alkali metal salts of the leuco vat pyranthrone dye are substantive with a pyranthrone dye, which comprises dyeing the material at high temperature approaching the boiling point of water in a bath containing the dyestuif, strong alkali, reducing agent, and an amount of an inorganic halogenate at least onequarter the weight of the real dyestufi.

2. A method according to claim 1 in which the halogenate is sodium chlorate.

3. A method according to claim 2 in which the dyestuif is pyranthrone.

4. A method according to claim 2 in which the dyestufi is dibromopyranthrone.

5. A method according to claim 1 in which the dyestuif is pyranthrone.

6. A method acording to claim 1 in which the dyestufi is dibromopyranthrone.

7. As a new article of manufacture a blend of a pyranthrone vat dyestuff with an amount of an inorganic halogenate at least one-quarter the weight of the real dyestuff.

8. An article of manufacture according to claim '7 in which the halogenate is sodium chlorate.

9. An article of manufacture according to claim 8 in which the dyestufi is pyranthrone.

10. An article of manufacture according to claim 8 in which the dyestuff is dibromopyranthrone.

11. An article of manufacture according to claim 7 in which the dyestuif is pyranthrone.

12. An article of manufacture according to claim 7 in which the dyestufi is dibromopyranthrone.

JERRY M. MECCO.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,029,999 Grieshaber Feb. 4, 1939 2,146,646 Nusslein Feb. '7, 1939 2,383,393 Kienle Aug. 21, 1945

Claims (1)

1. A METHOD OF VAT DYEING FIBROUS MATERIAL TO WHICH ALKALI METAL SALTS OF THE LEUCO VAT PYRANTHRONE DYE ARE SUBSTANTIVE WITH A PYRANTHRONE DYE, WHICH COMPRISES DYEING THE MATERIAL AT HIGH TEMPERATUE APPROACHING THE BOILING POINT OF WATER IN A BATH CONTAINING THE DYESTUFF, STRONG ALKALI, REDUCING AGENT, AND AN AMOUNT OF INORGANIC HALOGENATE AT LEAST ONEQUATER THE WEIGHT OF THE REAL DYESTUFF.