US3619106A

US3619106A - Process for dyeing keratinic fibers with water-soluble polysulfhydryl polymers

Info

Publication number: US3619106A
Application number: US873627A
Authority: US
Inventors: Gregoire Kalopissis; Constantin Aretos; Roger Charle; Jean Gascon
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1964-03-23
Filing date: 1969-11-03
Publication date: 1971-11-09
Anticipated expiration: 1988-11-09

Abstract

The process of dyeing keratinic fibers comprising first treating the fibers with an aqueous solution of water-soluble keratinic fiber reactive polysulfyhdryl polymer which has -SH groups that react with the keratinic fiber, said polymer being present in amounts of about 0.1-10 percent by weight of the aqueous solution then dyeing the keratinic fibers with a dye composition selected from the group consisting of reactive dyes and metallized monoazo acid dyes.

Description

United States Patent [72] inventors Gregoire Kaloplssls Paris; Constantin Aretos, [say-Les Moulineaux; Roger Charle, Soisy sur Montmorency; Jean Gascon, Parts, all of France 121] App]. No. 873,627 [22] Filed Nov. 3, I969 [45] Patented Nov. 9, 1971 Soclete Anonyme dlte: LOreal Paris, France [32] Priorities June 19, 1964 [33] France Aug. 5, 1965, France, No. 27,374; Mar. 23, I964, Luxembourg, No. 45,729; Nov. 6, 1964, Luxembourg, No. 47,298; .lan.7 1965, Luxembourg, No. 47.746; Mar. 8, 1965, Luxembourg, No. 45,729 Continuation-impart 01 application Ser. No. 441.311, Mar. I9, 1965, now abandoned and a continuation-impart of 565,371, July I5, 1966, now abandoned.

[73] Assignee [54] PROCESS FOR DYEING KERATINIC FIBERS WITH WATER-SOLUBLE POLYSULFHYDRYL POLYMERS ll Claims. No Drawings 52 us. c1 8/31. 8/1 D. 8/10. 8/54. 8/1276. 8/128. 260/78. 260/785. 260/79, 260/561.424/70, 424/335. 424/365 Primary Exuminer- Donald Levy Assistant Examiner- Patricia C. Ives A1mrneyHolcombe. Wetherill and Brisebois ABSTRACT: The process of dyeing keratinic fibers comprising first treating the fibers with an aqueous solution of watersoluble keratinic fiber reactive polysulfyhdryl polymer which has SH groups that react with the keratinic fiber. said polymer being present in amounts ofabout 01-10 percent by weight of the aqueous solution then dyeing the keratinic fibers with a dye composition selected from the group consisting of reactive dyes and metallized monoazo acid dyes.

PROCESS FOR DYEING KERATINIC FIBERS WITH WATER-SOLUBLE POLYSULFHYDRYL POLYMERS This application is a continuation-in-part application Ser. No. 441,3 ll filed Mar. 19, I965 and application Ser. No. 565,371 filed July I5, 1966, both now abandoned.

This invention relates to the dyeing of keratinic textile materials and particularly to a dyeing process which can be carried out at ambient temperatures. The term textile materi als" as used herein includes material in fibrous form and material in the form of fabrics, for instance woven, nonwoven or knitted fabrics.

it is known that, when dyeing keratinic textile materials, particularly wool, it is necessary to operate at temperatures in the neighborhood of boiling point if it is desired to exhaust the dye bath almost completely, which is one of the essential conditions for an economically acceptable dyeing process. Moreover it is desirable to be able to dye wool with dyestuffs which have valuable properties in dyeing other fibers such as cotton. For example reactive" dyestuffs have already been known for some years, by means of which it is possible to dye cellulosic textile materials under good conditions, the advantage of the use of these dyestuffs being their intensity and the luminosity of their coloration, and their fastness.

Efforts have already been made to employ such dyes for dyeing wool, but it has hitherto not been possible to obtain really satisfactory results, even by the use of adjuvants and by working at temperatures in the neighborhood of boiling point.

We have now devised a process by means ofwhich keratinic textile materials can be satisfactorily dyed, especially using reactive dyestuffs, while avoiding the difficulties referred to above. The process of the invention is one in which the textile material is treated with an aqueous solution ofa polysulphydryl polymer before the dyestuffis applied to the said material. If desired the textile material after treatment with the said polymer can be rinsed with water and hydroextracted before the dyestuff is applied to it. The process permits woolen materials to be dyed with reactive dyestuffs in an acceptably short time and with an almost complete exhausting of the dye bath.

in accordance with the invention, it is preferable, but not essential, for the polymer solution to have a basic pH, for example from 7 to l0, This basic pH can be obtained, for instance by the addition of an alkali-metal base, ammonia or an amine. lt is also preferable, after the textile material has been hydroextracted to remove water and rinsed with water, to treat it with an acid so as to insolubilize the polysulphydryl polymers in situ before the dyestuffis applied.

The acid can be, a mineral or organic acid, for instance sulfuric or acetic acid. A suitable concentration has been found to be an NH solution.

According to the invention, the keratinic textile fibers may be immersed in the polymer solution for a period of about to 60 minutes, the solution being, for example, at ambient temperature or at a temperature in the neighborhood thereof, for instance l530 C.

The concentration of the polysulphydryl polymers in the said solution may vary within wide limits, but it is generally between 0.1 percent and I0 percent, the preferred concentration being 0.5 percent to 2 percent.

It is to be understood that the basic pH of the polymer solution and the intermediate immersion in an acid solution do not constitute essential features of the invention, but we have found that the mere presence of polysulphydryl polymers in the keratinic material appreciably increases the quality of the dyeing that can be effected with reactive dyes.

The polysulphydryl polymer can be for instance one having a repeated structural unit of the formula:

in which:

R, denotes an alkylene radical (preferably two to four carbon atoms long), optionally substituted by lower alkyls which may have up to four carbon atoms, by a carboxyl radical or by 5 a carbalkoxy radical;

R represents a hydrogen atom or a lower alkyl, for instance methyl or ethyl;

R and R (which can be the same or different) each represents a hydrogen atom, or a lower alkyl, a phenyl, lower alkoxy radical, and R may represent either a hydrogen atom or the radical OCOCH COOCH;, or CN.

Preferred polysulphydryl polymers of formula (I) are those in which R, and R both represent a hydrogen atom and R, represents either the radical OCOCH;, COOCH or CN. and polysulphydryl polymers in which R represents a hydrogen atom, R represents a methyl radical and R, represents the radical COOCH Except where the context requires otherwise, the terms lower alkyl" and "lower alkoxy" used in this specification refer respectively to alkyl and alkoxy radicals of l-6, especially one to four carbon atoms, such as methyl, ethyl, methoxy and ethoxy.

in which:

R represents a hydrogen atom or a lower alkyl, for instance methyl or ethyl, or a lower hydroxyalkyl, for instance -CH CH -OH;

R represents a hydrogen atom or a methyl radical;

q is an integer from two to six inclusive;

p is zero or one;

R, and R, (which can be the same or different) each represents a hydrogen atom, or a lower alkyl, a phenyl or lower alkoxy radical; and

R represents a hydrogen atom, or the radical -C-EN, or COOCH Preferred polysulphydryl polymers of formula ll are those in which R, and R each represent a hydrogen atom and in which R represents the radical -OCOCH ,CEN or COOCH;,, and polysulphydryl polymers in which R represents a hydrogen atom, R represents a methyl radical and R represents the radical COOCH Further suitable polysulphydryl polymers are those having in their molecules both SH groupings and alkyl and aminoalkylene groupings and having a repeated structural unit ofthe formula:

OCOCH (III) in which:

R and R (which can be same or different) each represents a hydrogen atom, or a lower alkyl, a phenyl or a lower alkoxy radical; and

R represents a hydrogen atom, or the radical OCOCH;,, COOCH or (EN;

is a radical represented by the following formula:

in which:

R represents a hydrogen atom or a lower alkyl radical;

R represents either hydrogen, a lower alkyl radical or a radical of the formula r and r being identical or differm lower alkyl radicals, or together with the nitrogen atom depicted constitute a heterocycle, for instance morpholine or piperidine ring; and

m is one, two, three or four.

The proportions of substituents Q and Q may vary within very wide limits, for example from 1 percent to 99 percent preferably from 20 percent to 80 percent.

Preferred polymers of formula III are those in which R and R each represent a hydrogen atom, and R represents the radical OCOCH,, CE N or COOCH;,; and polymers in which R represents a hydrogen atom, R represents a methyl radical and R, represents the radical -COOCH Among the so-called reactive" dyes which can be used in accordance with the invention, there may be mentioned for instance, those sold under the following trade names:

Procion by l.C.l.

Cibacron by ClBA,

Drimarene Z by Sandoz,

Reactone by Geigy,

Remazol by Hoechst and Levafix by Bayer.

The reactive dyes may, for example, possess in their molecules reactive groupings such as the following types:

Dichloro-s-triazine, Monochloro-s-triazine, Diand trichloropyrimidines, Vinylsulphone, Ethylenimine, Epoxide and Epichlorhydrin The process of the present invention is also applicable to dyestuffs which do not belong to the class of reactive dyes. Examples of such dyestuffs are metalliferous dyes. Among the so-called "metalliferous dyes" which can be used in accordance with the invention, there may be mentioned for instance those sold under the following trade names:

Neolan Green BL 13425) Neolan Blue 2R (Acid Blue 154) Neolan Black 2R (15691) and the other" "metalliferous dyes" described in the Color Index, 4366, second Edition, 1956 under the trade name of Neolan (ClBA).

The dyeing of keratinic material which has been bleached can take place at ambient temperatures. However, in the case of some dyes which possess only low reactivity and in the case of the dyeing of unbleached materials, it may be advantageous to use higher temperatures,

The numerous experiments carried out by us have shown the excellent quality of the dyeing effected in accordance with the invention. Thus, the colorations obtained have high fastness (especially wet fastness) as may be verified by boiling dyed samples for 3 to 4 minutes with a solution of acetic acid, 1 percent ammonia or ethanol or dimethylformamide. Moreover, the dyeing effects produced are extremely even, though it is unnecessary to employ a considerable volume of bath for a given weight of textile material. in practice, satisfactory results have been obtained by using from 6 to 7 liters of bath per kilogram of treated material.

It has been observed that the temperature at which the textile material which has been treated with polysulphydryl polymer is introduced into the dyeing bath has an appreciable influence on the speed at which exhausting of the dye bath can be obtained. The consequence of the variation of the temperature at which the dyeing bath is maintained are of particular interest because, in the case of dyestuffs naturally having good levelness, it is desirable to increase the dyeing speed and consequently the speed at which the bath is exhausted, while in the case where the dyestuffs concerned have medium or poor levelness, it may be desirable to reduce the temperature of the bath in order to reduce the dyeing speed, this reduction being accompanied, as is known, by an improvement of the levelness.

We have also observed that excellent results are obtained by using the process according to the invention even if small quantities of polysulphydryl polymers are employed as compared with the weight of keratinic fibers. Thus, the dye bath can be practically completely exhausted in 60 minutes at a temperature of 50 C. when using keratinic material previously treated with polysulphydryl polymer these fibers then containing only 0.5 percent of combined SH radicals calculated on their total weight. Under these temperature conditions, an increase of the polymer content and of the SH radical content is unnecessary for obtaining better results.

By way of comparison, keratinic fibers dyed under the same temperature conditions and with the same quantities of dyestuffs, but having undergone no pretreatment with a polysulphydryl polymer result, at the end of 60 minutes, in an exhausting of the dye bath of only between 25 percent to 50 percent of the dyestuff, depending upon the nature of the latter. This degree of exhausting is clearly not sufficient for industrial application.

The keratinic material can be subjected first to an oxidizing treatment, for example with hypochlorite or hydrogen peroxide. However, where the keratinic material has not been bleached a preferred form of the process of the invention consists in the following steps:

I. immersing the material in a basic solution of polysulphydryl polymer at a temperature which may be from 20 to 50 C.,

2. preferably after rinsing with water and treatment with a dilute acetic acid, immersing it in a dye bath containing a reactive dyestuff, for example at a temperature of 50 C.,

3. raising the temperature to boiling point and maintaining this temperature for a period of the order of 60 minutes,

4. rinsing the keratinic material, optionally after it has been treated in the residual dyeing bath brought to a pH of 7 with a dilute ammoniacal solution, so as to wash out the small quantity of dyestuff which is not fixed to the fibers.

In this mode of carrying out the process according to the invention, which is concerned more especially with the dyeing of keratinic textile materials and in particular wool, which have not undergone any bleaching treatment, vat dyeing is effected, as is also the case in the conventional process for dyeing wool with the aid of reactive dyestuffs.

Compared with the conventional process, the following advantages are obtained which are particularly important.

First, the time for which the wool is immersed in the solution which has been brought to boiling temperature is appreciably reduced, whereby the harmful effect of such a treatment on the appearance and handle of the textile product obtained is considerably limited. (lt is known that a prolonged treatment of wool at boiling temperature produces undesirable matting.) Secondly, the dyeing process according to the invention renders possible a better fixation on the keratinic fibers of the reactive dyestufi's employed. This results in a better quality of the dyeing effect obtained.

Experiments carried out have shown that textile fibers (such as wool) which have been dried after having undergone an impregnation with polysulphydryl polymer by the process according to the invention may be stored for the necessary time without any disadvantage. It is thereafter sufficient to dip these fibers into a dye bath in order to continue the perfonnance of the process of the invention.

The invention is illustrated by the following examples.

EXAMPLES The following solutions A to S are examples of compositions of the invention containing illustrative water-soluble polysulphydryl polymers which can be used to impregnate textile materials prior to dyeing. The use of these solutions is exemplified in examples 1-49 below.

Solution A polysulphydryl polymer obtained by reacting 1 gram mol of B-mercaptoethylamine per gram mol structural unit of the ethylene-maleic anhydride copolymer which has a specific viscosity of 0.1 in a 1 percent solution of the resin in dimethyl formamide at 25 C. sold under the trade name Resin DX 840-11" 3 g. NH OH solution (22 B.) 6 cc. Water......q.s. for 100 cc. Solution B polysulphydryl polymer obtained by reacting 1 gram mol of B-mercaptoethylamine per gram mol structural unit of the maleic anhydride-styrene copolymer which has a molecular weight of about 1,600 sold under the trade name Resin SMA 1000 A 3 g. NH OH solution (22 B.) 6 cc. Water q.s. for 100cc. Solution C polysulphydryl polymer obtained by reacting 1 gram mol of B-mercaptoethylamine per gram mol structural unit of the maleic anhydride-styrene copolymer which has a molecular weight of about 400-600 sold under the trade name Resin SMA 4000 A" 3 g.

NH OH solution (22 B.) 6 cc.

Water.....q.s. for 100 cc. Solution D polysulphydryl polymer of Solution B NH OH solution (22 B.) 6 cc.

Water q.s. for 100 cc.

Solution E polysulphydryl polymer resulting from the action of 1 gram mol of B-mercaptoethylamine per gram mol structural unit of a styrene-maleic anhydride copolymer having a molecular weight of about 3,000 formed by reacting equimolar amounts of styrene and maleic anhydride 3 g. NH OH solution (22 B.) 6 g. Water...... q.s. for 100 cc. Solution F polysulphydryl polymer of Solution A 1.5 g. NH,Ol-l solution for a pH of 9.5 Water q.s. for 100 cc.

Solution G polysulphydryl polymer of Solution B 1.1 g. NH OH solution for a pH of 9.5 Water.......q.s. for 100 cc.

Solution H polysulphydryl polymer of Solution C 3 g. NH.OH solution for a pH of 9.5 Water q.s. for 100 cc.

Solution 1 polysulphydryl polymer obtained by reacting 1 gram mol of cysteine per gram mol structural unit of Resin SMA 1000 A 5 g. NH OH solution for a pH of 9.5 Water q.s. for cc. Solution J polysulphydryl polymer of Solution A 6 g. NH OH solution (22 B.) for a pH of 9.5

Water q.s. for 100 cc. Solution K polysulphydryl polymer obtained by reacting 1 gram mol of N-(fi-aminoethyl)thioglycolamide per gram mol structural unit ofResin DX 840-11 3 g. NH OH (22 B.) pH 9.5 Water q.s. for 100 cc.

Solution L polysulphydryl polymer obtained by reacting 1 gram mol of B-mercaptoethylamine per gram mol of structural unit acrylonitrile/maleic anhydride copolymer 0.9 g. ammonia(22 B.) 1.8 cc. Water..... q.s. for 100cc. Solution M polysulphydryl polymer resulting from the condensation of 1 gram mol of fi-mercaptoethylamine and 1 gram mol of n-butylamine with 2 gram mol of structural unit Resin DX 840-1 1" 3 g. ammonia (22B.) 6 cc. Water q.s. for 100 cc.

Solution N polysulphydryl polymer obtained by reacting 1 gram mol of B-mercaptoethylamine and 1 gram mol of N,N- diethypropylenediamine with 2 gram mol of structural unit methyl mcthacrylate/maleic anhydride copolymer 2.3 ammoiia (22 B.) Water q.s. for Solution 0 polysulphydryl polymer obtained by reacting 1 gram mol of B-mercaptoethylamine and 1 gram mol of n-butylamine with 2 gram mol of structural unit vinyl acetate/maleic anhydride copolymer 3.2 g. ammonia (22 B.) 6.4 cc. Water q.s. for 100 cc.

Solution P polysulphydryl polymer obtained by reacting 1 gram mol of N-(B-aminoethyl)thioglycolamide with 1 gram mol of structural unit ofResin DX 840-1 1 1.2 g. ammonia (22 B.) 2.5 cc. Water q.s. for 100 cc.

ammonia (22 B.) 2 cc. Water..... q.s. for 100 cc.

EXAMPLE 1 10 g. of wool fabric are treated with a solution A by immersion at ambient temperature for 20 minutes. After hydroextraction, the fabric is dyed by immersion in a dyestuff solution containing:

C.l. Reactive Red 2 (Procion Brillian Red M-SBS) 0.2 g. glacial acetic acid 2 cc. Water q.s. for 200 cc.

This dyeing takes place at ambient temperature for 30 minutes. After copious rinsing with water and hydroextraction the boiling usual for wool dyeing is performed.

An attractive dark red coloration is obtained.

EXAMPLE 2 g. of wool fabric are treated with solution C by immersion at ambient temperature for 20 minutes. After hydroextraction, the fabric is dyed by immersion in a dyestuff solution containing:

C]. Reactive Blue 2 0.2 g. glacial acetic acid 2 cc.

water q.s. for 200 cc.

This dyeing takes place at ambient temperature, for 20 minutes. After copious rinsing with water and hydroextraction, the usual boiling for wool dyeing is carried out.

An attractive royal blue coloration is obtained.

EXAMPLE 3 g. of wool fabric are treated with solution B by immersion at ambient temperature for minutes. After hydroextraction and rinsing with a N/lO sulfuric acid solution, the fabric is dyed by immersing in a dyestuff solution containing:

CJ. Reactive Yellow l4 (Remalol Yellow 6) 0.2 g. glacial acetic acid 2 cc.

water q.s. for 200 cc.

This dyeing takes place at ambient temperature for 45 minutes. After copious rinsing with water and hydroextraction, the usual boiling for wool dyeing is carried out.

An attractive canary yellow coloration is obtained.

EXAMPLE 4 10 g. of wool fabric are treated with solution A by immersion at ambient temperature for 20 minutes. After hydroextraction and rinsing with a N/ l0 acetic acid solution the fabric is dyed by immersion in a dyestuff solution containing:

C.|. Reactive Red 20 0.2 g. glacial acetic acid 2 cc. water q.s. for 200 cc.

This dyeing takes place at ambient temperature for 30 minutes. After copious rinsing in water, and hydroextraction, the usual boiling for wool dyeing is carried out.

An attractive dark pink coloration is obtained.

EXAMPLE 5 l0 g. of wool fabric are treated with solution E by immersion at ambient temperature for 20 minutes. After hydroextraction and rinsing with N/lO acetic acid solution, the fabric is dyed by immersion in a dyestuff solution containing:

C.l. Reactive Brown I 0.2 g. glacial acetic acid 2 cc. crystallized anhydrous sodium sulfate I g.

water q.s. for 200 cc.

This dyeing takes place at ambient temperature for 20 minutes. The fabric is copiously rinsed with water, hydroextracted and boiled in the manner usual for wool dyeing.

An attractive light brown coloration is obtained.

tion, the fabric is rinsed with a N/lO acetic acid solution and dyed by immersion in a dyestuff solution containing:

C.l. Reactive Red 7 0.2 g. glacial acetic acid 2 cc. water q.s. for 200 cc.

This dyeing takes place at ambient temperature for 40 minutes. The fabric is copiously rinsed in water, hydroextracted and boiled in the manner usual for wool dyeing.

An attractive buttercup yellow coloration is obtained.

EXAMPLE 7 10 g. of wool fabric are treated with solution A by immersion at ambient temperature for 10 minutes. After hydroextraction, the fabric is rinsed with a N/lO acetic acid solution and dyed by immersion in a dyestuff solution containing:

C.L Reactive Red 0.2 g. glacial acetic acid 2 cc. water q.sl for 200 cc.

This dyeing takes place at ambient temperature for 30 minutes. After copious rinsing in water, the fabric is hydroextracted and boiled in the manner usual for W001 dyeing.

An attractive orange-maroon coloration is obtained.

EXAMPLE 8 10 g. of wool fabric and synthetic fibers are treated with solution F by immersion at ambient temperature for 20 minutes. After hydroextraction, the fabric is rinsed with a N acetic acid solution and dyed by immersion in a dyestuff solution containing:

C.l. Reactive Blue 19 0.2 g. glacial acetic acid 2 cc. water q.s. for 200 cc.

This dyeing takes place at ambient temperature for 60 minutes. After copious rinsing in water and hydroextraction, the boiling usual for W001 dyeing is carried out.

An attractive vivid blue coloration is obtained.

EXAMPLE 9 25 g. of wool yarn are treated with solution G by immersion at ambient temperature for IS minutes. After hydroextraction, the fabric is rinsed with a sulfuric acid solution and dyed by immersion in a dyestuff solution containing CAI. Reactive Red 9 0.2 g. glacial acetic acid 2 cc. water q.s. for 200 cc.

This dyeing takes place at ambient temperature for 60 minutes. After copious rinsing in water and hydroextraction, the boiling usual for wool dyeing is carried out.

An attractive scarlet red coloration is obtained.

EXAMPLE l0 12 g. of wool fabric are treated with solution I by immersion at ambient temperature for 60 minutes. After hydroextraction, the fabric is rinsed with a N/lO acetic acid solution and dyed by immersion in a dyestuff solution containing:

C.l. Reactive Black 4 0.2 g. glacial acetic acid 2 cc.

anhydrous crystalline sodium sulfate 0.5 g. water q.s. for 200 cc.

This dyeing takes place at ambient temperature for 30 minutes. After copious rinsing in water and hydroextraction. the boiling usual in wool dyeing is efiected.

An attractive intense black coloration is obtained.

EXAMPLE 1 l 10 g. of wool yarn are treated with solution A by immersion at ambient temperature for 30 minutes. After hydroextraction, the fabric is rinsed with a N/l acetic acid solution and dyed by immersion in a dyestuff solution containing:

C.l. Reactive Blue I glacial acetic acid water 0.2 g. 2 cc.

EXAMPLE l2 8 g. of wool fabric are treated with solution 0 by immersion at ambient temperature for 10 minutes. After hydroextraction, the fabric is dyed by immersion in a dyestuff solution containing:

C.l. Reactive Red 8 0.2 g. glacial acetic acid 2 cc.

water q.l. for 200 cc.

This dyeing takes place at ambient temperature for minutes. After copious rinsing in water and hydroextraction, the boiling usual in wool dyeing is carried out.

An attractive bright red coloration is obtained.

EXAMPLE 13 20 g. of wool yarn are treated with solution C by immersion at ambient temperature for 45 minutes. After hydroextraction, the fabric is rinsed with a N/lO acetic acid solution and dyed by immersion in a dyestuff solution containing:

C.l. Reactive Yellow 2 0.2 g. glacial acetic acid 2 cc.

water q.s. for 200 cc.

This dyeing takes place at ambient temperature for 45 minutes. After copious rinsing in water and hydroextraction, the boiling usual in wool dyeing is carried out.

An attractive bright yellow coloration is obtained.

EXAMPLE l4 10 g. of wool yarn are treated with solution B by immersion at ambient temperature for l5 minutes. After hydroextraction, the fabric is rinsed with a N/IO sulfuric acid solution and dyed by immersion in a dyestuff solution containing:

C.l. Reactive Red l2 0.2 g. glacial acetic acid 2 cc. anhydrous sodium sulfate 0.5 cc. water q.s. for 200 cc.

This dyeing takes place at ambient temperature for 45 minutes. After rinsing in a excess of water and hydroextraction, the boiling usual in wool dyeing is effected.

An attractive red coloration is obtained.

EXAMPLE l5 8 g. of wool fabric are treated with solution A by immersion for 20 minutes at ambient temperature. After hydroextraction, the fabric is rinsed with a N/lO acetic acid solution and dyed by immersion in a dyestuff solution containing:

C.l. Reactive Brown I 0.2 g. glacial acetic acid 2 cc.

watcr q.s. for 200 cc.

This dyeing takes place at ambient temperature for 60 minutes. After copious rinsing in water and hydroextraction the boiling usual in wool dyeing is carried out.

An attractive reddish-brown coloration is obtained.

EXAMPLE 16 15 g. of wool yarn are treated with solution l by immersion for 10 minutes at ambient temperature. After hydroextraction, the fabric is rinsed with a N/lO acetic acid solution and dyed by immersion in a dyestufi solution containing:

C.l. Reactive Yellow 6 0.2 g. glacial acetic acid 2 cc. water q.l. for 200 cc.

This dyeing takes place at ambient temperature for 40 minutes. After copious rinsing in water and hydroextraction, the boiling usual in wool dyeing is carried out.

An attractive yellow coloration is obtained.

EXAMPLE l7 l2 g. of wool fabric are treated with solution A by immersion for 10 minutes at ambient temperature. After hydroextraction, the fabric is rinsed with a N/lO sulfuric acid solution and dyed by immersion in a dyestuff solution containing:

C.l. Reactive Orange 2 0.2 g. glacial acetic acid 2 cc. water q.s. for 200 cc.

This dyeing takes place at ambient temperature for 40 minutes. After copious rinsing in water and hydroextraction, the boiling usual for wool dyeing is carried out.

An attractive bright orange coloration is obtained.

EXAMPLE 18 25 g. of wool yarn are treated with solution B by immersion at ambient temperature for 45 minutes. After hydroextraction, the yarns are rinsed with a N/l0 acetic acid solution and dyed by immersion in a dyestuff solution containing:

C.l. Reactive Red 4 0.2 g. glacial acetic acid 2 cc. water q.s. for 200 cc.

An attractive red coloration is obtained.

EXAMPLE l9 10 g. of wool fabric are treated with solution I by immersion at ambient temperature for 30 minutes. After hydroextraction, the wool fabric is rinsed with a N/lO acetic acid solution and dyed by immersion in a dyestuff solution containing:

C.l. Reactive Yellow 3 0.2 g. glacial acetic acid 2 cc. water q.s. for 200 cc.

This dyeing takes place at ambient temperature for 30 minutes. After copious rinsing in water and hydroextraction, the boiling usual for wool dyeing is carried out.

An attractive bright yellow coloration is obtained.

EXAMPLE 20 8 g. of wool fabric are treated with solution C by immersion at ambient temperature for 20 minutes. After hydroextraction, the wool fabric is rinsed in a N/ 10 sulfuric acid solution and dyed by immersion in a dyestuff solution containing:

C.l. Reactive Red 22 0.2 g. glacial acetic acid 2 cc. water q.s. for 200 cc.

An attractive red coloration is obtained.

EXAMPLE 21 Reactive Black CI. 0.2 g. glacial acetic acid 2 cc. anhydrous crystalline sodium sulfate 0.5 g. water q.s. for 200 cc.

This dyeing takes place at ambient temperature for 45 minutes. After copious rinsing in water and hydroextraction, the boiling usual for wool dyeing is carried out.

A deep black coloration is obtained.

EXAMPLE 22 l0 g. of wool fabric are treated with solution C by immersion at ambient temperature for 15 minutes. After hydroextraction, the fabric is rinsed with a N/lO acetic acid solution and dyed by immersion in a dyestuff solution containing:

C.l. Acid Green IZCI H3425) 0.2 g. glacial acetic acid 2 cc. water q.s. for 200 cc.

This dyeing takes place at ambient temperature for 30 minutes. After copious rinsing in water and hydroextraction, the boiling usual in wool dyeing is carried out.

An intense green coloration is obtained.

EXAMPLE 23 g. of wool fabric are treated with solution G by immersion at 40 C. for minutes. After hydroextraction. the wool fabric is rinsed in a N/ l 0 sulfuric acid solution and dyed by immersion in a dyestuff solution containing:

C.|. Acid Orange 62 0.2 g. glacial acetic acid 2 cc. water q.s. for 200 cc.

The dyeing takes place at a temperature of 45 C. for 15 minutes. After copious rinsing in water and hydroextraction, the boiling usual for wool dyeing is carried out.

An orange coloration is obtained.

EXAMPLE 24 C.l. Acid Black 43 (l569l) 0.2 g. glacial acetic acid 2 cc. water q.s. for 200 cc.

This dyeing takes place at a temperature of 40 C. for 15 minutes. After copious rinsing in water and hydroextraction, the boiling usual in wool dyeing is carried out.

An intense black coloration is obtained.

EXAMPLE 25 12 g. of wool fabric are treated with solution B by immersion at ambient temperature for minutes. After hydroextraction, the wool fabric is dyed by immersion in a dyestuft' solution containing:

E.l. Reactive Blue l C]. Reactive Yellow 7 glacial acetic acid 2 cc.

This dyeing takes place at ambient temperature for 40 minutes. After copious rinsing in water and hydroextraction. the boiling usual for wool dyeing is carried out.

An attractive green coloration is obtained.

EXAMPLE 26 10 g. of wool yarn are treated with solution A by immersion at ambient temperature for 20 minutes. After hydroextraction, the yarn is rinsed in a N/ 10 acetic acid solution and dyed by immersion in a dyestuff solution containing:

Procion Red 5 GS 02 g. C.l. Reactive Blue I 2 g.

Glaciai acetic acid 2 cc. crystalline anhydrous sodium sulfate 0.5 g. water q.s. for 200 cc.

This dyeing takes place at a temperature of 40 C. for 20 minutes. After copious rinsing in water and hydroextraction, the usual boiling for wool dyeing is carried out.

An attractive violet coloration is obtained.

EXAMPLE 27 sodium hypochloriie (22 C.) glacial acetic acid water q.s. for

I00 cc..

the pH of this solution being 2.7.

The treatment takes place for 15 minutes at ambient temperature. After this time, the wool is extracted from the solution and copiously rinsed in water or by means of a solution consisting of a mixture of 5 cc. of sodium bisulphite (solution at 35 B) and cc. ofwater.

The wool is thereafter hydroextracted and treated for 1 hour at ambient temperature in a solution containing:

polysulphydryl polymer resulting from the action of 1 grammol, of B-mercaptoethylamine per structural unit of the ethylene/maleic anhydride copolymer sold under the trade name Resine DX 840-l 1 0.500 g.

Nl-LOH (22 B.) 1 cc.

Water q.s. for 100 cc., the pH of this solution being 9.4.

The wool is then rinsed in water or in a very dilute acid solution, and then dried at moderate temperature.

The wool thus treated may be stored for any desired period of time. because this preservation has proved excellent.

At the time when it is desired to carry out the dyeing, the wool is immersed in a solution having the following composition:

reactive dyestutt' glacial acetic acid water q.s. for I00 cc.

EXAMPLE 28 5 g. of unbleached worsted wool are immersed in a solution containing:

Hydrogen peroxide 0.6 g. Na,HPO l g. Water q.s. for N30 cc.

the pH of this solution being 9.5.

The treatment takes place for 3 hours at a temperature of 50 C.

The wool is thereafter rinsed with water and immersed for 1 hour at ambient temperature in a solution having the following composition:

Polysulphydryl polymer resulting from the action of 1 grammol of B-mercaptoethylamine per structural unit of the maleic anhydride/styrene copolymer sold under the trade name Resine SMA 1000 A" Nl-LOH solution for a pH of 9.5

Water q.s. for 100 cc.

As indicated in the preceding example, after treatment with a weak acid solution, the dyeing is carried out, using a conventional reactive dyestufi or, for example, the dyestuff C.l. Reactive Red or that sold under the name Neolan Blue 2R (Acid Blue 154)." A good wool dye is obtained.

EXAMPLE 29 name Resine SMA 1000 A" 10 g. anhydrous Na PO, 13.5 g. anhydrous Na i-W 12.5 g.

The wool is thereafter rinsed and dyed as indicated in the preceding examples.

Equally good results are obtained.

EXAMPLE 30 g. of wool which has not previously undergone any bleaching treatment are dyed by the following procedure:

100 cc. of the above-described solution J is first prepared and it is then brought to a temperature of 50 C., whereafter the wool is immersed in this bath for 30 minutes.

When the wool has been withdrawn from the bath, it is found that the latter contains only about 75 percent of the SH which was initially present therein.

The wool is rinsed in water and then in an aqueous solution of 6 g. of acetic acid per liter of water.

A dyeing bath is prepared by dissolving in 250 cc. of water 0.30 g. of Bleu Cibacrone 3 GA and 2 g. of ammonium formate.

This bath is brought to 50 C. and the wool is introduced into it as previously indicated, whereafter the temperature is gradually raised to l00 C. in half an hour and maintained at this temperature for half an hour. lt is found that only about 3 percent of the initial dyestuff remains in the bath.

6 cc. of 40 percent acetic acid are added and the bath is boiled for about 30 minutes.

There are then added 5 cc. of ammonia (22 B.) and the heating is reduced in order to obtain a temperature of 80 C. in a period of about minutes.

By titrating the remaining solution, it is found that only about 5 percent of the dyestuff initially contained therein have remained.

Then the wool has been copiously rinsed with water, it is treated in a dilute solution of sulfonated fatty alcohols for a period of about 30 minutes at a temperature of 70 C.

The wool is then rinsed and dried, and then has an attractive blue coloration.

EXAMPLE 31 I0 g. of wool which has not previously undergone any bleaching treatment are dyed by the following procedure:

100 cc. of the above-described solution .l are prepared and this solution is brought to a temperature of 50 C., whereafter the wool is immersed in the said bath for 30 minutes.

When the wool has been withdrawn from the bath, it is found that the latter contains only 75 percent of the SH which was initially present therein.

A dyeing bath is prepared by dissolving in 250 cc. of water 0.30 cibacron Blue 3 GA and 2 g. of sodium formate.

This bath is brought to 50 C. and the wool is introduced as previously indicated, whereafter the temperature is gradually raised to C. for half an hour.

It is then found that there remain in the bath only about 3 percent of the initial dyestuff. 0.5 cc. of formic acid is added and the bath is boiled for about 30 minutes.

There are then added 5 cc. of ammonia (22'' B.) and the heating is reduced in order to obtain a temperature of 60 C. in a period of about 20 minutes.

On titrating the remaining solution, it is found that only about 5 percent of the dyestuff initially contained remains in the bath.

When the wool has been copiously rinsed in water, it is treated in a dilute solution of sulfonated fatty alcohols for a period of 30 minutes at a temperature of 80 C.

The wool is then rinsed and dried, and then has an attractive blue coloration.

EXAMPLE 32 After having been pretreated with a polysulphydryl polymer solution under the same conditions as are described in example 30, the wool is left in the polymer bath, to which formic acid is added until a pH of about 6 to 7 is obtained.

There is then added to the solution 0.3 g. of Cibracon Blue 3 GA in highly concentrated solution.

The wool is then dyed under the same conditions as described in example 1.

Equally good results are obtained, the wool having a blue shade of particularly interesting brightness and brilliance.

By way of comparison, if the 10 g. of wool employed in the two preceding examples are treated by a conventional dyeing method with reactive dyestufi, for example in accordance with the instruction contained in the brochure published by ClBA of Basle (Switzerland) under the reference 3050/59 and entitled Colorants Cibacrone et Cibacrolaine sur laine," it is found that in the final treatment with a weak alkali (ammonia) added to the dyeing bath, only 5 percent of the dyestuff employed is removed in the case of the process of the invention, while in the case of the conventional process about 9.5 is removed.

In the conventional processes, the dyeing bath is heated to 50 C., this bath containing the necessary adjuvants, namely:

Neovadine AN or AL (Ethylene oxide condensate of a fatty acid; nonionic) acetic acid to give the solution a pH of 4 to 5 sodium sulfate which serves to slow down the development of the dye.

The temperature of the bath is raised in 20 minutes from 50 to 80 C., whereafter treatment is carried out at this temperature for about 30 minutes. At this instant, the bath must be almost entirely exhausted.

It is then brought to boiling point in the space of 10 minutes and in accordance with the depth of the shade desired, and treatment is carried out at boiling point for 30 to 60 minutes.

At the end of the dyeing, the heating is interrupted and from 1.5 percent to 4 percent of 25 percent ammonia are gradually added to the exhausted bath. Treatment is thus carried out for 15 to 20 minutes while the bath cools. The pH at the end of the operation is about 8.

After this time, the wool is removed and hot-rinsed and then cold-rinsed.

EXAMPLE 33 I0 g. of wool fabric are treated with solution K by immersion at ambient temperature for 20 minutes. After hydroextraction, the fabric is dyed by immersion is a dyestuff solution containing:

C.l. Reactive Red 2 0.2 g. glacial acetic acid 2 cc.

water q.s. for 200 cc.

EXAMPLE 34 10 g. of wool yarn are treated with solution K by immersion at ambient temperature for 30 minutes. After hydroextraction, the fabric is rinsed with a N/lO acetic acid solution and dyed by immersion in a dyestuff solution containing:

C.l. Reactive Blue I 0.2 g. glacial acetic acid 2 cc.

water q.s. for I cc.

This dyeing takes place at ambient temperature for 30 minutes. After copious rinsing in water and hydroextraction, the boiling usual in wool dyeing is carried out. An attractive blue coloration is obtained.

EXAMPLE 35 g. of wool fabric is treated with solution K by immersion at ambient temperature for 20 minutes. After hydroextraction, the fabric is rinsed with a N/lO acetic acid solution and dyed by immersion in a dyestuff solution containing:

C1. Reactive Red 12 (Abacron Brilliant Red 8) 0.2 g. glacial acetic acid 2 cc.

water q.s. for 200 cc.

This dyeing takes place at ambient temperature for 30 minutes. After copious rinsing in water and hydroextraction, the boiling usual for the dyeing of wool is carried out.

An attractive dark pink coloration is obtained.

EXAMPLE 36 C.I. Acid Green l2 (13425) 0.2 g. glacial acetic acid 2 cc. water q.s. for 200 cc.

This dyeing takes place at ambient temperature for 30 minutes. After copious rinsing in water and hydroextraction, the boiling usual for dyeing wool is carried out.

An intense green coloration is obtained.

EXAMPLE 37 ll) g. of wool fabric are treated with solution X by immersion at ambient temperature for 20 minutes. After hydroextraction, the fabric is dyed by immersion in a dyestuff solution containing:

C.l. Reactive Blue l7 0.2 g. glacial acetic acid 2 cc.

water 200 cc.

This dyeing takes place at ambient temperature for 30 minutes. After copious rinsing with water and hydroextraction, the usual boiling for the dyeing of wool is carried out.

An attractive blue coloration is obtained.

.6 EXAMPLE 38 4 g. of wool yarn are treated with solution L by immersion at a temperature of 50 C. for 30 minutes.

After hydroextraction and rinsing with an 0.6 percent acetic acid solution, this wool is dyed by immersion in a dyestuff solution containing:

C.l. Reactive Red 2 (H2 g. glacial acetic acid 2 cc. water (1.5. for 200 cc.

This dyeing takes place at a temperature of 50 C. for l hour. There is then added to this dyeing bath, and at the same temperature, an ammoniacal solution to produce a pH or 7. After contact for 15 minutes, the yarn is rinsed with water.

The boiling usual for the treatment of wool thus dyed is then effected by means of a sulfated fatty alcohol solution in a concentration of about l percent.

After rinsing, an attractive dark red coloration is obtained, which is superior to that which could be obtained under the same conditions, but without the pretreatment of the wool with solution L.

EXAMPLE 39 4 g. of wool yarn are treated with solution M by immersion at a temperature of 50 C. for 30 minutes.

C.]. Reactive Red 2 0.12 g. glacial acetic acid 2 cc.

water q.s. for 200 cc.

This dyeing takes place at a temperature of 50 C. for l hour. An ammoniacal solution is thereafter added to this dyeing bath, at the same temperature, until a pH of 7 is obtained. After contact for 15 minutes, the yarn is rinsed with water.

The usual boiling is thereafter effected by treatment of the wool thus dyed with a sulfated fatty alcohol in a concentration of about 1 percent.

After rinsing, there is obtained an attractive red coloration which is superior to that obtained under the same conditions on a wool not treated with the polymer of solution M.

EXAMPLE 40 C.l. Reactive Red 0. l 2 g. glacial acetic acid 2 cc.

water q.s. for 200 cc.

This dyeing takes place at a temperature of 50 C. for 1 hour. An ammoniacal solution is thereafter added to this dyeing bath, at the same temperature, until a pH of 7 is obtained. After contact for 15 minutes, the yarn is rinsed with water. The usual boiling is thereafter carried out by treatment with the wool thus dyed with a sulfated fatty alcohol solution in a concentration of about 1 percent.

After rinsing, a red coloration is obtained which is much deeper than that which would be obtained under the same conditions on a wool not treated with the polymer of solution P EXAMPLE 4l 4 g. of wool yarn are treated with solution S by immersion at a temperature of 50 C. for 30 minutes.

After hydroextraction and rinsing with an 0.6 percent acetic acid solution. this wool is dyed by immersion in a dyestuff solution containing:

Cl. Reactive Red 2 012 g glaclal acetic acid 2 cc water q... for 2110 on This dyeing takes place at a temperature of 50 C. for 1 hour. An ammoniacal solution is thereafter added to this dyeing bath, at the same temperature, until a pH of 7 is obtained. The usual boiling is thereafter effected by treatment of the wool thus dyed with a sulfated fatty alcohol in a concentration ofabout 1 percent.

After rinsing, an intense red coloration is obtained. which is superior to that which would be obtained under the same conditions on a wool not treated with the polymer of solution 8.

Water-soluble polysulphydryl polymers are known in the keratin fiber treating art to be polymers which have a plurality of chemically bonded SH groups which react with the SS bonds in the keratin fiber. These polymers are broadly described in French Pat. No. 1,349,140 which became a patent Dec. 9, 1963. The corresponding US. application Ser. No. 267,851, filed Mar. 25, 1963 was abandoned in favor of Ser, No. 520,075 filed Jan. 12,1966 now abandoned and Ser. No. 633,394 filed Apr. 25, 1967, now U.S. Pat. No. 3,484,417.

The water-soluble polysulphydryl polymers of formula 1 were specifically disclosed in French Pat. No. 1,349,140, and in the US. Pat. applications Ser. No. 267,851 now abandoned, Ser. No. 520,075 now abandoned and Ser. No. 633,394, now U.S. Pat. No. 3,484,417.

The water-soluble polysulphydryl polymers of formula 11 were described in French applications 978,830 filed June 19, 1964 and 2,338 filed Jan. 18, 1965 and the corresponding U.S. applications Ser. No. 463,890 filed June 14, 1965 now abandoned, and Ser. No. 795,717 filed .Ian. 31, I969.

The water-soluble polysulphydryl polymers of formula 111 were described in French applications 978,832 filed June 19, 1964 and 2,339 filed Jan. 18, 1965 and the corresponding U.S. Pat. No. 3,472.820.

U.S. application Ser. No. 360,730, filed Apr. 17, 1964, discloses the use of other water soluble polysulphydryl polymers having the formula:

in which R is an alkylene group having two to four carbon atoms, R" and R' are H or phenyl, R is H, and n is 1-25 which have a molecular weight ofless than about 6,000.

The water-soluble polysulphydryl polymers that are used in the improved dye process of this invention can be any water soluble polymer that has a plurality of sulphydryl groups that remain bound to the polymer in solution. The SH groups on the polymer reacts with the SS bond in the keratin fiber and remain there to form a reaction cite for an aqueous reactive dye solution because the polymer attached to the SH groups prevent the SH groups from ionizing and to remain in contact with the keratin fiber without washing off as a monomer mercapto compound or an ionizable SH containing salt compound would wash offin an aqueous solution.

Water-soluble polysulphydryl polymers differ from polymer salts that have ionizable sulphydryl groups, such as those disclosed in U.S. Pat. No. 3,247,067, because the ionizable sulphydryl groups disassociate from the polymer salt and the polymers are not sulphydryl polymers in solution.

The method of bonding the SH group to the polymer to keep it from ionizing has no bearing on the reaction between the SH groups on the polymer and the disulfide bond in the keratin fiber. Any known chemical reactions can be used to form these polymers, including the preferred reaction between anhydride groups on the polymer and mercaptoammes.

The present invention does not reside in the use of any specific water soluble polysulphydryl polymer but in the discovery that the reaction product of this type of polymer and the keratin fiber can be directly dyed with a reactive dye or a metalliferous dye. In view ofthe prior art knowledge that reactive dyes do not directly dye keratinic fibers even in the presence of keratin reducing agents this discovery was unexpected.

The closest known related art is U.S. Pat. No. 3,340,000 which dyes keratinic fibers with reactive dyes in the presence of a reducing agent such as ammonium thioglycolate, pyrogenic colloidal silica and a hydrogen bond breaker, such as a mixture of lithium bromide and sodium chloride. This reference specially discloses the known fact that keratinous materials cannot be dyed directly with reactive dyes even after the keratin had been reduced to fonn reactive sulfhydryl groups and that the reduced keratinic fibers can only be dyed when a hydrogen bond breaker is added to the dye composition.

In some unknown manner, we found that by pretreating keratin fibers with a polysulphydryl polymer one can directly dye the keratin with a reactive dye without using pyrogenic colloidal silica and a hydrogen bond breaker.

The preferred polysulphydryl polymers are those that have lateral side chains which have a terminal SH group, in which said side chain are bonded to a linear polymer chain by an amide bond. lllustrative examples of the preferred water soluble SH polymers include the following:

I S H u---un-cn cn ctruii,- n-cnca H 000011, (2001i 60011 +0 NH on-i 7 (income (G i)! i zls N(CHI)2 (11) 01111 OCH;

HCH;+--CH-KFJHCH,-(iiI-CHCH H 0N 60011 30 (IN 00011 (:30

NH NH 7 l t 2): ($112M NH N\ I o E E SH E em-en CH-()H-CH-CHr-CH-?H -H 000cm coon :0 OCH; 000B 30 NH NH 5 :)t

CH(IJH(IJHCH H The term keratinic fibers is used in a broad sense to cover 5 any fiber that contains a keratinic material which has the keratinic disulfide bonds that will react with the sulphydryl or SH groups on the water soluble polymer. illustrative examples of keratinic fibers that can be treated with reactive dyes are wool, human hair, fur and these fibers may be in any form, such as textiles, threads, natural. etc. without effecting the reactions between the polysulphydryl polymer, the keratin and the reactive dye.

in the examples the formula of reactive dyes of examples 2, 5, 7, 9, l3, l4 and [7 to 19 are disclosed in the collection of Czechoslovak Chemical Communications V25, Oct. 1960,

page 2783-2798 as being respectively:

Examp1e2 (I) NH2 SOQH ll l N 0 NH- NHI W-NH R,

Ri=H This reference and American Dyestuff Reporter, Oct. 29, W62, pages til to 88 discloses other illustrative reactive dyes that may be used in the process ofthis invention.

Further in accordance with this invention the polysulfhydryl polymers are characterized by the fact that they comprise an anhydride homopolymer onto which at least one aminothioi compound has been condensed.

In accordance with the invention, the homopolymer may be polymaleic anhydride, polyitaconic anhydride, polyacrylic anhydride, a polyacrylic-methacrylic anhydride mixture of a methacrylic polymer, but this list is not to be considered exhaustive.

Aminothiols having the following formula may be used to sulfhydrylize the homopolymers according to the invention:

HSR--NHR' In this formula:

R designates either an alkylene radical having preferably from two to four carbon atoms, which may be substituted by lower alkyls which may have up to four carbon atoms. by a carboxyl radical, or by a carbalkoxy group, and

R designates a hydrogen atom or a lower alkyl such as Cl-l or C H Among the amino-thiols corresponding to the foregoing formula, the following may be cited by way ofexample:

B-mercaptoethylamine,

cysteine, and

ethylcysteinate.

Mercapto-amide amines responding to the following formula may also be used to polysulfhydrylize the homopolymers:

in this formula:

R, represents H or COOH q is a whole number between one and five inclusive,

q is equal to zero or one,

p is equal to zero or one.

Among the mercapto-amide amines responding to this last formula are those obtained from the esters of thioglycolic acid, thiolactic acid, or B-mercaptoproprionic acid. and diamines such as ethylene diamine, hexamethylene diamine, and N-hydroxyethyl ethylene diamine.

in accordance with the invention it is also possible to condense amines which have no SH groups on the anhydride homopolymers at the same time that the mercapto-amines are condensed thereon.

in this way the proportionate number of SH groups in the polysulfhydryl homopolymers may be reduced, while introducing into the formula of the polymer groups which permit it to impart particular qualities to the hair.

For example, alkylamines responding to the following formula may be condensed on the homopolymer at the same time as the mercapto-amines:

In this formula:

R represents a hydrogen atom or a lower alkyl, R represents either a hydrogen atom or a lower alkyl or a radical having the formula in which r and r are identical or different lower alkyls, or may be part of a heterocycle such as that of morpholine or piperidine,

m is a whole number equal to zero or four.

Among the compounds responding to the above formula are: butylamine, N,N-dicthylpmpylene diamine and N. ([3- amino-ethyl i-morpholine, but this list is not exhaustive.

When partial sulthydryl homopoiymers are being prepared in accordance with the invention it is possible to vary the pro- 5 portions of mercapto-amine and no-sulfl'iydryl diamine on the homopolymer within broad limits ranging for example from l to 99 percent, but preferably from 20 to 80 percent of mer capto'amine in proportion to the nonsulfhydryl amine.

The polysulfhydryl homopolymcrs have certain advantages over those polysulfhydryi polymers heretofore known when used in either the cosmetic or the industrial textile field.

In the first place those homopolymers which are formed by polymerizing an anhydride are capable of combining with a substantially larger number of SH groups than the polysulfhydryI polymers heretofore known, which were made from resins which were copolymers of an anhydride and another monomer which did not combine with SH groups.

This property enables homopolymcrs according to the invention to exhibit a much higher reactivity toward keratinic substances.

Moreover, treatments utilizing homopolymers of the invention are more consistent and homogenous in their effects than treatments utilizing those polysulthydryl polymers. In effect, during the polymerization of the copolymers, the proportions of the two monomers comprised by the copolymers varies from one molecule to the next and the products obtained may therefore differ in two ways. to wit. first according to the lengths of their chains, and second according to the proportion between the two monomers making up the copolymers.

On the other hand, the homopolymers of the invention all have the same chemical structure, the only possible difference between one molecule and another being a difference in the lengths of their chains.

lt foltows that the homopolymers are more easily reproduced and consequently produce more consistent results when they are applied to keratinic fibers.

In general these homopolymers and methods of making them are described in greater detail in application Ser. No.

565,37", filed July I5, 1966 now abandoned.

Solution T Pollysulfhydryl homopolymer which responds to the formu- Cl I-CH err-oa O OH ('30 O OH (5D in 11m 311: (EH9 1 CH: ill (:0 6H2 Ammonia solution at 22 B. 4,5 cc. Water, q.s.p. I00 cc.

Solution U Pollysulfhydryl homopolymer which responds to the formu- CHgC-CHr /C C'OOH CH2 (160K OH;

r m r 111 CH; zOs

H2 HCl 15H cz Hs crHr n Polysulfhydryl homopolymer which responds to the formula CH1 CH1 -CHr-(I3H CHCH-CH OH- 00011 ('10 coon (13o 1 11i 1711i CH2 (Club): (EH-1 N HCl l SH CgHs CgHs 1| Ammonia solution at 22 B. 2 cc. Water, q.s.p. lOO cc.

EXAMPLE 42 4 g. of wool yarn is treated with solution T by immersion therein at the ambient temperature for minutes. After drying, the yarn is rinsed with an N/lO acetic acid solution and dyed by immersion in a dyeing solution containing:

Cibacron Blue 3 GA 0. l 2 g.

Glacial acetic acid 2 cc.

Water, q.s.p. 200 cc.

The dyeing takes place at a temperature of 80 C. over a period of 60 minutes. The yarn is rinsed lavishly with water and scoured at 50 C. for minutes in 2 percent ammonia solution. It is again rinsed and boiled as usual when dyeing wool.

The result is a blue color.

EXAMPLE 43 4 g. of wool yarn is treated with solution T by immersion therein at room temperature, for 15 minutes. After drying, the yarn is rinsed with an N/lO acetic acid solution and dyed by immersion in a dyeing solution containing:

Procion Red H5 (H2 g. Glacial acetic acid 2 cc. Water. q.s.p. 200 cc.

The wool is dyed at 80 C. over a period of 60 minutes. It is then rinsed lavishly with water and scoured at 50 C. for 20 minutes in a 2 percent ammonia solution. It is again rinsed and boiled as usual when dyeing wool.

The result is a beautiful red color.

EXAMPLE 44 4 g. of woolen yarn is treated with solution U by immersing it therein at the ambient temperature for [5 minutes. After 26 drying the yarn is rinsed with an N/l0 acetic acid solution and dyed by immersing it in a dyeing solution containing:

('Ibauun Blue K (IA 0 )2 g (il-iual acetic acid 2 ct Water. q s p 10!] cc The dyeing takes place at a temperature of C. over a period of 60 minutes. The wool is lavishly rinsed with water and scoured at 50 C. for 20 minutes in a 2 percent ammonia solution. It is again rinsed and boiled as usual when dyeing wool.

The result is a beautiful blue color.

EXAMPLE 45 4 g. of woolen yarn is treated with solution U by immersing it at the ambient temperature for l5 minutes. After drying, it is rinsed with an N/l0 acetic acid solution and dyed by immersing it in a dyeing solution comprising:

Cihacron Red rown RP 0 I} g. Glacial acetic acid 2 cc Water. qsp. 200 L1 The dyeing takes place at a temperature of I00?- C. over a period of 60 minutes. The wool is rinsed lavishly with water and scoured at 50 C. for 20 minutes in 2 percent ammonia solution. It is again rinsed and boiled as is usual when dyeing wool.

The result is a reddish brown color.

EXAMPLE 46 4 g. of woolen yarn is treated with solution V by immersing it therein. at a temperature of 50 C. for 30 minutes. After drying, it is rinsed with an N/lO acetic acid solution and dyed by immersion in a dyeing solution containing:

Procion Red 5 BS H I2 Glacial acetic acld 2 cc Water, q.s.p. 200 cc.

The dyeing takes place at a temperature of 50 C. over a period of 60 minutes. The wool is rinsed lavishly with water and then scoured at 50 C. for 60 minutes in a 2 percent ammonia solution. It is again rinsed and boiled as usual when dyeing wool.

A beautiful red color results.

EXAMPLE 47 4 g. of woolen yarn is treated with solution V by immersion therein at a temperature of 50 C. for 30 minutes. After drying. it is rinsed with a solution of NH 0 acetic acid and dyed by immersion in a dyeing solution'containing:

Cihacron Scarlet RP 0.!2 g. Glacial acetic acid 1 cc. Water. q.s.p. 200 cc.

The dyeing is carried out at a temperature of 50 C. for 60 minutes. The yarn is rinsed lavishly with water and scoured at 50 C. for 60 minutes in a 2 percent ammonia solution. It is again rinsed and boiled as is usual when dyeing wool.

A scarlet red color results.

EXAMPLE 48 4 g. of woolen yarn is treated with solution W by immersion therein at a temperature of 50 C for 30 minutes. After drying. the yarn is rinsed with an M10 acetic acid solution and dyed by immersion in a dyeing solution containing:

("ihacron Olive RP (LIZ g. Glacial acetic acid 2 cc. Water. qsp. 200 cc.

The dyeing is carried out at a temperature of I00 C. over a period of 20 minutes. The wool is then rinsed lavishly with water and then scoured for 60 minutes in a 2 percent ammonia solution.

It is again rinsed and boiled as is usual when dyeing wool.

A beautiful olive green color results.

lclaim:

l. A process for dyeing keratinic fibers comprising treating said fibers with an aqueous solution of a water soluble polysulfhydryl polymer selected from the group consisting of l. a polysulfhydryl polymer consisting essentially of recurring structural units having the formula wherein R is selected from the group consisting of alkylene having two to four carbon atoms and alkylene having two to four carbon atoms carrying a substituent selected from the group consisting of lower alkyl having one to four carbon atoms, carboxy and carbalkox y wherein the alkoxy moiety has one to six carbon atoms, R is selected from the group consisting of hydrogen and lower alkyl having one to sit carbon atoms, R and R each independently represent a member selected from the group consisting of hydrogen, lower alkyl having one to six carbon atoms, phenyl and lower alkoxy having one to six carbon atoms and R is selected from the group consisting of hydrogen, OCOCH COOCH and C N;

2. a polysulfhydryl polymer consisting essentially of recurring structural units having the formula wherein R is selected from the group consisting of hydrogen and lower alkyl having one to six carbon atoms and hydroxyl lower alkyl having one to six carbon atoms, R is selected from the group consisting of hydrogen and methyl, q is an integer of two to six inclusive, p is zero or one; R and R each independently represent a member selected from the group consisting of hydrogen, lower alkyl having one to six carbon atoms, phenyl and lower alkoxy having one to six carbon atoms and R represents a member selected from the group consisting of hydrogen, OCOCH C()OCH and C N;

3. a polysulfltydryl polymer consisting essentially of recurring structural units having the formula [in it. 0:; i=0 .0 into i=0] ing one to six carbon atoms, R, represents a member selected from the group consisting of hydrogen, -OCOCH COOCH and C N. O is L in J,

wherein R represents a member selected from the group consisting of hydrogen and methyl, R represents a member selected from the group consisting of hydrogen and carbox y, q is an integer of one to live inclusive, 1; is zero or one and p is zero or one. ti Q is wherein R represents a member selected from the group consisting of hydrogen and lower alkyl having one to six carbon atoms, R represents a member selected from the group consisting of hydrogen, lower alkyl having one to six carbon atoms and wherein r and r each independently represent lower alkyl having one to six carbon atoms or form with the nitrogen atom to which they are attached a member selected from the group consisting of morpholinyl and piperidinyl, and m is an integer ofone to four inclusive;

4. a polysulfhydryl homopolymer of a homopolymer selected from the group consisting of po|y(maleic anhydride), poly(itaconic anhydride), poly(acrylic anhydride), poly(acrylic methacrylic anhydride) and polylmethacrylic anhydride) having condensed on the anhydride function thereof a member selected from the group consisting of a. an amino thiol having the formula HSRNHR' wherein R is selected from the group consisting of alkylene having two to four carbon atoms and alkylene having two to four carbon atoms carrying a substituent selected from the group consisting of lower alkyl having one to four carbon atoms, carboxyl and carbalkoxy and R represents a member selected from the group consisting of hydrogen and lower alkyl having one to six carbon atoms; and b. a mercapto-arnide amine having the formula wherein R represents a member selected from the group consisting of hydrogen, CH C H and CH CH -0H, R represents a member selected from the group consisting of hydrogen and COOH, q is an integer of one to live inclusive, q is zero or one and p is zero or one, said water-soluble polysult'hydryl polymer being present in amounts of about 0. l-l0 percent by weight of said aqueous solution and applying to said treated fibers a dye composition comprising a member selected from the group consisting of reactive dye and metallized monoazo acid dye to color said fibers,

2. The process of claim 1 wherein said water-soluble polysulthydryl polymer is present in amounts of about 0.5-2.0 percent by weight ofsaid aqueous solution.

3. The process of claim 1 wherein the aqueous solution of said water-soluble polysulfhydryl polymer has a pH of about.

4. The process of claim I wherein said keratinic fiber is wool and said wool is contacted with the aqueous solution of said water-soluble polysulfhydryl polymer for a period of about -60 minutes at a temperature ranging from about l5-30 C.

5. The process of claim 4 which includes contacting said wool, after treatment with the aqueous solution of water-soluble polysulthydryl polymer and before contact with said dye composition, with an aqueous acidic solution to insolubilize said polysulfhydryl polymer.

6 The process of claim I wherein said water-soluble polysulfhydryl polymer has the structural formula in l) and wherein R, and R are both hydrogen. and R is selected from the group consisting of OCOCH COOCH and C N.

7. The process of claim 1 wherein said water-soluble polysulfhydryl polymer has the structural formula in (l) and wherein R is hydrogen. R is methyl and R is COOCH,.

8. The process of claim 1 wherein said water-soluble polysulfhydryl polymer has the structural formula in (2) and wherein R and R are both hydrogen, and R is selected from the group consisting ofOCOCH C N and COOCl-l 9. The process of claim I wherein said water-solulole polysulfhydryl polymer has the structural formula in (2) and wherein R is hydrogen, R is methyl and R is COOCH,.

10. The process of claim I wherein said water-soluble polysulfhydryl polymer is the polysulfhydryl homo-polymer in (4) and wherein the aminothiol condensed on the anhydride function of said homopolymer is selected from the group consisting of B-mercapto ethylamine. cysteine and ethylcysteinate.

ll. The process of claim I wherein said water-soluble polysulfhydryl polymer is the polysullhydryl homopolymer in (4) and wherein a portion of anhydride functions thereof are condensed with an alkyl amine having the formula wherein R is selected from the group consisting of hydrogen and lower alkyl having one to six carbon atoms and R is selected from the group consisting of hydrogen, loser alkyl having one to six carbon atoms and wherein r and r are each independently lower alkyl having one to six carbon atoms or together with the nitrogen atom to which they are attached form a member selected from the group consisting of morpholinyl and piperidinyl and m is an integer ofzero to four inclusive.

I l i I

Claims

2. a polysulfhydryl polymer consisting essentially of recurring structural units having the formula
2. The process of claim 1 wherein said water-soluble polysulfhydryl polymer is present in amounts of about 0.5-2.0 percent by weight of said aqueous solution.
3. The process of claim 1 wherein the aqueous solution of said water-soluble polysulfhydryl polymer has a pH of about 7-10.
3. a polysulfhydryl polymer consisting essentially of recurring structural units having the formula
4. a polysulfhydryl homopolymer of a homopolymer selected from the group consisting of poly(maleic anhydride), poly(itaconic anhydride), poly(acrylic anhydride), poly(acrylic methacrylic anhydride) and poly(methacrylic anhydride) having condensed on the anhydride function thereof a member selected from the group consisting of a. an amino thiol having the formula HS-R-NH-R'' wherein R is selected from the group consisting of alkylene having two to four carbon atoms and alkylene having two to four carbon atoms carrying a substituent selected from the group consisting of lower alkyl having one to four carbon atoms, carboxyl and carbalkoxy and R'' represents a member selected from the group consisting of hydrogen and lower alkyl having one to six carbon atoms; and b. a mercapto-amide amine having the formula wherein R1 represents a member selected from the group consisting of hydrogen, -CH3, -C2H5 and -CH2-CH2-OH, R2 represents a member selected from the group consisting of hydrogen and -COOH, q is an integer of one to five inclusive, q'' is zero or one and p is zero or one, said water-soluble polysulfhydryl polymer being present in amounts of about 0.1-10 percent by weight of said aqueous solution and applying to said treated fibers a dye composition comprising a member selected from the group consisting of reactive dye and metallized monoazo acid dye to color Said fibers.
4. The process of claim 1 wherein said keratinic fiber is wool and said wool is contacted with the aqueous solution of said water-soluble polysulfhydryl polymer for a period of about 5-60 minutes at a temperature ranging from about 15*-30* C.
5. The process of claim 4 which includes contacting said wool, after treatment with the aqueous solution of water-soluble polysulfhydryl polymer and before contact with said dye composition, with an aqueous acidic solution to insolubilize said polysulfhydryl polymer.
6. The process of claim 1 wherein said water-soluble polysulfhydryl polymer has the structural formula in (1) and wherein R2 and R3 are both hydrogen, and R4 is selected from the group consisting of -OCOCH3, -COOCH3 and -C N.
7. The process of claim 1 wherein said water-soluble polysulfhydryl polymer has the structural formula in (1) and wherein R2 is hydrogen, R3 is methyl and R4 is -COOCH3.
8. The process of claim 1 wherein said water-soluble polysulfhydryl polymer has the structural formula in (2) and wherein R7 and R8 are both hydrogen, and R9 is selected from the group consisting of -OCOCH3, -C N and -COOCH3.
9. The process of claim 1 wherein said water-soluble polysulfhydryl polymer has the structural formula in (2) and wherein R7 is hydrogen, R8 is methyl and R9 is -COOCH3.
10. The process of claim 1 wherein said water-soluble polysulfhydryl polymer is the polysulfhydryl homo-polymer in (4) and wherein the aminothiol condensed on the anhydride function of said homopolymer is selected from the group consisting of Beta -mercapto ethylamine, cysteine and ethylcysteinate.
11. The process of claim 1 wherein said water-soluble polysulfhydryl polymer is the polysulfhydryl homopolymer in (4) and wherein a portion of anhydride functions thereof are condensed with an alkyl amine having the formula wherein R3 is selected from the group consisting of hydrogen and lower alkyl having one to six carbon atoms and R4 is selected from the group consisting of hydrogen, lower alkyl having one to six carbon atoms and wherein r and r'' are each independently lower alkyl having one to six carbon atoms or together with the nitrogen atom to which they are attached form a member selected from the group consisting of morpholinyl and piperidinyl and m is an integer of zero to four inclusive.