US3336097A

US3336097A - Sosna sosna

Info

Publication number: US3336097A
Authority: US
Publication date: 1967-08-15
Anticipated expiration: 1984-08-15

Description

United States. Patent PROCESS FOR THE COLORING OF NORMAL ANIMAL HAIR WITH WATER SOLUBLE RE- ACTIVE DYESTUFFS Eric Tom Fell, Ambergate, England, assignor to Precision Processes (Textiles) Ltd., Ambergate, England, a

corporation of Great Britain No Drawing. Filed July 16, 1965, Ser. No. 472,735

Claims priority, application Great Britain, July 20, 1961, 26,306/ 61 14 Claims. (Cl. 8-10) ABSTRACT OF THE DISCLOSURE A process for dyeing normal animal hair such as wool with reactive dyestuffs in which the material tobe dyed is first treated'with' a peroxygen compound such as permonosulfuric acid and then with'a reducing agent such as sodium sulphite, prior to treatment with the dyestuif.

This application is a continuation-in-part of application Ser. No. 210,577 filed July 17, 1962, and now abandoned. This invention relates to the coloration of normal wool and other kinds of normal animal hair and of materials consisting of or containing such materials in such forms as loose fibers, carded sliver, combed tops, yarns, and

woven and knitted fabrics and garments.

There have recently come into prominence dyestuffs known as reactive dyestuffs which when applied to textiles exhibit exceptional wetfastness properties. Reactive dyestuffs are dyes in which the chromophoric group is attached to a group capable of forming covalent bonds with hydroxyl, amino and/or sulphydryl groups, present in the textile fiber. Whilstthese dyestutfs contain diflerent reactive groups in. their molecules they all function by virtue of the reaction of one or more groups present in the dyestulf molecule with reactive hydrogen atoms present in the molecule of the textile material which is to be coloured. Whilst such dyestuffs have been very largely developed for use with cellulosic materials it has also been shown that under certain conditions they are capable of being applied to wool,- silk and .the polyamides. The dyestulfs used for wool and silk are of the same kinds as those used for the cellulosic materials, but those used for the polyamides are reported to be of a different kind.

The reactive dyestuflrs "are'fn'ot,.as a rule, substantive dyestuffs. Their reactivity depends upon the presence in the dyestuff bath or printing paste of an additional substance. When applied to cellulosic fibres dyeing has been carried out under alkaline conditions, the temperature varying with the nature of the dyestuff, but when applied to wool dyeing has hitherto usually been carried out under acid or neutral conditions at'elevated temperatures and for periods of time which are unfavourable to the properties of the dyed wool;

It has, however, recently been proposed to dye protein fibres with reactive dyestuffs under alkaline conditions at temperatures not exceeding 50 C. This dyeing method gives moderately satisfactory colour yields but poor solidity on chlorinated wool alone, whereas on normal wool the colour yield is so low as to be unacceptable commerother kinds of normal animal hair and of materials containing or consisting of such fibres with water-soluble reactive dyestuflfs.

According to the present invention there is provided a process for the coloration of normal animal hair and materials consisting of or containing normal animal hair which comprises applying to at least selected areas of normal animal hair or of normal animalhair-containing materials which have previously been subjected to a treatment with a solution of a peroxygen compound as hereinafter defined followed by a treatment with a water-soluble sulphur-containing reducing agent, an aqueous solution or printing composition containing a water-soluble form of a reactive dyestuif and an acid acceptor, said solution or composition being maintained at a temperature not exceeding 60 C. during contact with the hair.

. The expression peroxygen compound as used herein refers to hydrogen peroxide, oxides and peroxides which in acid solution give rise to hydrogen peroxide, peracids, including H 80 salts of peracids and salts containing a metal from Group VII-A of the Periodic Classification and oxygen in are anion, in which anion the metal is present in its state of maximum valence.

The present invention is based upon the observation that normal wool and other kinds of normal animal hair which have beenl subject to (a) an oxidation treatment treatment is necessery, the coloration is thus applied under conditions which do not exert any harmful eflect upon the pretreated wool. Since the oxidation and reduction treatments may be those utilized to impart shrink resistance to normal wool and woolen materials, treatment toimpart shrink resistance and dyeing or printing may be carried out as sequential operations. It is evident that the succes I group present in a cellulose molecule or of forming inv sive use of oxidation and reduction treatments modifies the chemical structure of the wool or other animal hair in such a way that a substantially uniform distribution of readily reactive hydrogen atoms is introduced thereinto: these hydrogen atoms are then available for reaction with the reactive dyestuffs.

The process of the invention is of particular advantage in the dyeing and printing of piece goods comprising or consisting of normal wool or of other normal animal hairs, for example, cashmere goods.

The dyestuff and acid acceptor may be applied to wool and other kinds of animal hair by immersion in a dyebath containing the dyestutf and acid acceptor in solution, which dye-bath may also contain any conventional textile auxiliaries such as wetting and levelling agents suitable for use with reactive dyestuffs. The dyestuff and acid acceptor may also be applied by a padding technique or may be applied to selected areas only of the protein fibre containing textile material by a printing technique. For such applications the printing compositions may include thickeners which are substantially inert towards the reactive dyestuffs.

The reactive dyestufis which may be used are those which contain at least one water-solubilizing group in the dyestuff molecule as well as a group which is capable of forming a covalent link by reaction with an hydroxyl situ a group which will react in this way. This does not means that hydroxyl groups are necessarily present in wool and other animal hairs which have been subject to treatment in the manner described: whatever the nature of the groups introduced by the treatment it has been experimentally established that they behave in a manner analogous to the hyd-roxyl groups present in cellulose.

The water-solubilizing group present in the dyestuif molecule may be a carboxylic acid or sulphonic acid group or a salt of such group with an alkali metal, ammonia or an amine. One or more such groups may be present in the dyestufli molecule.

The group which is capable of forming a covalent link may be a group containing a reactive halogen atom such as that present in a monoor di-chloro-sym-triazinyl, a trichloropyrimidyl, a beta-halogenpropionyl, a beta halogenoethylsulphonyl, a beta-halogenoethylsulphamyl, a chloro-acetylamino or a beta-(chloromethyl)beta-sulph'atoethylsulphamyl group; a reactive sulphate group such as that present in a beta-sulphatoethyls-ulphonyl group; a reactive hydroxyl or esterified hydroxyl group such as that present in a beta-'hydroxyethylsulphonyl, a beta-alkylsulphonyloxyalkylsulphonyl, a beta-'arylsulphonyloxyalkylsulphonyl or a beta-acyloxyalkylsulphonyl group: an ethylenically unsaturated group such as an acryloxyamino or vinylsulphonyl group; an alkyl phosphite group or a sulphonfluoride group. In the case of the symtriazinyl and pyrimidyl groups in place of a reactive halogen atom or atoms there may be present other substituents which are dissociable in therpresence of alkalies' such as sulphonic acid; thiocyanate; negatively substituted aryloxy and arylthio groups such as sulphophenoxy, sulphophenylthio, nitrosulphophenoxy, disulphophenoxy and sulphonaphthoxy groups; quaternary ammonium groups: heterocyclic and fused heterocyclic thiol groups having five or six atoms in theheterocyclic ring which are linked through a carbon atom of the heterocycle to the thiol group; dithiocarbamic acid groups having the general formula -S-( J-NR R in which R and R are like or unlike and each is an alkyl, cycloalkyl, aryl or aralkyl group or R and R taken together with the nitrogen atom form a heterocyclic ring having five or six atoms in the ring; or a group having the general formula NR3 sc R4 in which R and R are like or unlike and each is a hydrogen atom or an alkyl, aryl or aralkyl group.

The dyestuifs used may belong to such classes as the nitro, azo, anthraquinone or phthalocyanine series and may be free from metal or contain .metal complexed therein. An account of the commercially available kinds of reactive dyestuffs will be found in the Journal of the Institut Textile de France, September 1960, at pp. 43 et seq.

The peroxygen compounds used in the first part of the pretreatment process of the normal wool or other kind of normal animal hair may be hydrogen peroxide, an inorganic or organic peracid which is soluble in water such as peracetic or permonosulphuric acid or a water-soluble salt of an inorganic or organic peracid' such as an alkali metal peracetate, permonosulphate, perborate, percarbonate or permanganate. Such compounds are usually used in dilute aqueous solution: the concentration and conditions of application should avoid substantial degradation of the wool. The most favourable pH varies with the particular peroxygen compound employed. Surface acting agents which assist in securing uniform wetting and penetration of the goods being subject to the oxidizing treatment may be present in the bath containing the peroxygen compound.

The sulphur-containing reducing agent may be organic or inorganic in nature. It may, for example, be a thiolcarboxylic acid such as thioglycollic acid or a thiolpropionic acid. Alternatively, it may be a water-soluble salt of an oxidizable sulphur-containing acid, such as an alkali metal sulphite, bisulphite or hydrosulphite, an amine salt of such an acid such as monoethanolamine sulphite or a water-soluble salt of a thiolcarboxylic acid.

Typical treatments are the following:

(a) Treatment with aqueous permonosulphuric acid followed by treatment with a salt of sulphurous acid: see British patent specification No. 716,806.

(b) Treatment with hydrogen peroxide, alkali metal perborates and percarbonates in the presence of a compound of copper, silver, nickel or mercury (see British patent specification No. 614,966) followed by treatment with a suitable reducing agent.

(c) Treatment with an aqueous solution of an organic peracid such as performic or peracetic acid followed by treatment with a suitable reducing agent.

(d) Treatment with hydrogen peroxide under neutral or mildly alkaline conditions, e.g. under standard bleaching conditions for woolen fabrics, followed by treatment with a suitable reducing agent.

(e) Treatment with aqueous potassium permanganate in the presence of sodium or potassium chloride, clearing the staining with a dilute aqueous solution of a watersoluble bisulphite and then further treating with a separate bath of a suitable reducing agent.

The preferred reducing treatments are with sodium sulphite or bisulphite solution at temperatures of 20- 65 C.

After the treatment with the reducing agent the treated goods are preferably rinsed to remove excess reducing agent prior to applying the reactive dyestuif thereto.

It should be clearly understood that the use of an oxidation treatment under conditions which may or may not suffice to impart a degree of shrink-resistance whilst avoiding substantial degradation of the wool is insufiicient per se to impart the desired level dyeing characteristics to the treated wool or other animal hair. A reduction treatment must follow the oxidizing treatment if the desired level dyeing properties under alkaline conditions of fixation are to be imparted to the material undergoing treatment.

In carrying out the process of the invention the wool or other animal hair has applied thereto either a solution of or a paste comprising a water-soluble reactive dyestuif and a substance which acts as an acid acceptor. Any water-soluble reactive dyestufif which may be used to produce dyeings of high wet fastness upon cellulosic materials in the presence of an acid acceptor may be used in the process of the present invention.

The acid acceptor employed may be any of those which may be used as alkaline substances in the coloration of cellulosic materials with water-soluble reactive dyestuifs. These include soda ash, sodium and potassium carbonates, bicarbonates and silicates and trisodium and tripotassium phosphates.

With respect to the amount of acid acceptor present this should be at least suflicient to combine with any acid liberated by the reaction or reactions which lead to dyestufl? fixation. As a general rule amounts up to 3% of the weight of the aqueous dyebath are employed with corresponding proportions in the printing pastes.

In addition there may be added to the dyebaths and printing pastes levelling agents and organic solvents in which the dyestuffs are readily soluble and which assist the uptake but with which the dyestuffs do not preferentially react under the conditions of use, and which are at least moderately soluble in water, such as the aliphatic and araliphatic alcohols, e.g. n-butyl and benzyl alcohols.

Some of the reactive dyestuffs will react with wool at substantially room temperatures: these are those containing a dihalo-sym-triazinyl group or a beta-sulphatoethylsulphonyl group. The remainder, including those containing monohalo-sym-triazinyl and trichloro-pyrimidyl groups, are preferably applied at temperatures higher than room temperature but no exceeding 60 C. Those dyestuffs containing a dichloro-sym-triazinyl group have been found to require a much shorter period for fixation with chemically modified wool than any other available type. In the case of dyeings with those dyestuffs which require temperatures substantially above room temperature for fixation it has been found that the addition of water-soluble electrolytes such as sodium chloride and sodium sulphate will assist fixation.

The process of the present invention has marked advantages over the available processes for the dyeing of normal wool and other animal hair fibres using watersoluble reactive dyestuffs. Level dyeings may be readily obtained in a cold dyeing process (2030 C.) in a short time; such dyeings are much more level than those obtainable using chlorinated wool. The present process enables bright fast pastel shades to be obtained: these are almost unobtainable with chlorinated wool owing to the yellowing resulting from chlorination. The handle of the treated goods obtained by the present process is also markedly better than that obtainable with chlorinated wool. All dyeings and prints produced by this process are of excellent fastness to washing.

The actual structures of a number of reactive dyestuifs are given in the series of patents published on the subject by Imperial Chemical Industries and others, for example, British Patent Nos. 838,340, 838,338, 838,335, 838,311, 837,035, 836,248, 832,400, 826,405, 805,562, 803,473, 785,222, 785,120, 784,221. Also structures for reactive dyestuffs are contained in the publication Collection of Czechoslovakian Chemical Communications, vol. 25, No. 10, dated October 1960.

The following examples illustrate the nature of the invention.

Example 1 A piece of wool fabric was treated with permonosulphuric acid and subsequently with .a solution of a salt of sulphurous acid in accordance with British Patent No. 716,806 using the following conditions:

A bath was prepared from 3,000 parts of water, 20 parts of a solution of permonosulphuric acid and 1 part of a commercial non-ionic wetting agent. 100 parts of wool fabric were treated in this bath for 1 hour and then treated for a further 30 minutes in a bath made from 3,000 parts Water and 20 parts sodium sulphite crystals. Both baths were at substantially 20 C.

The fabric was rinsed and then dyed as follows:

A dye bath was prepared at 25 C. by dissolving 6 grams of Remazol Brilliant Violet 5R, CI Reactive Violet 5 (Colour Index, 2nd edition, Additions and Amendments #14, January 1962, p. 61) and 30 grams of sodium carbonate in 3,000 parts of water. The fabric, already wet out, was dyed in this solution for 10 minutes Whilst maintaining the temperature at 25 C. throughout. This was followed by rinsing with cold water so as to remove any surplus dyestutf. The resulting dyeing was fast to washing without the necessity of any steam or heat treatment to fix the dyestuff onto the wool fibre.

Example 2 A piece of wool fabric which had been prepared for dyeing, as described in the foregoing example, was treated in selected areas with dye solution in a manner to simulate the operation of screen printing as carried out commercially upon textiles.

The solution was made from:

100 parts of water 1' part of .Remazol Brilliant Blue R, CI Reactive Blue v r 19 (Colour Index, 2nd edition, Additions and Amendments 14, January 1962, p. 61) 1 part of sodium carbonate The cloth treated in this manner was allowed to stand for 30 minutes and then rinsed.

The treated areas of the fabric was quite fast to normal Washing without any further steam or heat treatment.

Example 3 W001 top was prepared for dyeing as described in Example 1. The solution for dyeing was made from:

parts of water 1 part of Remazol Black B, CI Reactive Black 5 (Colour Index, 2nd edit-ion, Additions and Amendments #14, January 1962, p. 62)

3 parts of sodium carbonate 5 parts of commercial benzyl alcohol, 60% grade.

The wool top was immersed in this solution at 25 C. for 2 minutes, lightly mangled and then allowed to lie for 3 minutes. After this period most of the surplus dye liquor was removed from the wool by re-mangling and then by rinsing.

The resultant dyeing was fast to washing without the necessity of any steam or heat treatment to fix the dyestuff onto the Wool fibre.

Example 4 W001 fabrics, each 30 parts, were treated separately by means of two known shrink resist processes:

(a) The treatment with permonosulphuric acid and sodium sulp-hite solution described in Example 1;

(b) According to Example 1 of British patent specification No. 614,966 which describes a treatment of woolen materials with small amounts of metallic salts, followed by alkaline hydrogen peroxide solutions and subsequently a treatment with sodium bisulphite solution together with sulphuric acid.

Dyebaths were prepared from:

2 parts of Procion Red G, CI Reactive Red 5 (Colour Index, 2nd edition, Additions and Amendments #7, April, 1960, p. 16)

10 parts soda ash 1000 parts of water.

Wool fabrics respectively prepared as described under (a) and b) were dyed separately in these baths for 10 minutes at 25 C. and rinsed well.

The dyeings so produced were fast to Washing.

ExampleS A dye bath was made from:

20 parts of trisodium phosphate 20 parts of common salt 2 parts of Procion Orange Brown HGS, CI Reactive Brown 1 (Colour Index, 2nd edition, Additions and Amendments #7, April 1960, p. 18)

1000 parts of Water.

30 parts of all-wool material were prepared by treatment with permonosulphuric acid and sodium sulphite as in Example 1, and then dyed in this bath for 10 minutes at 50 C. followed by rinsing with water.

Further dyeings were carried out in a similar manner replacing the Procion Orange Brown HGS in turn by Cibacron Scarlet 4GP, CI Reactive Red 16 (Colour Index, 2nd edition, Additions and Amendments #14, January 1962, p. 60), Reactone Brilliant Yellow SGL, CI Reactive Yellow 11 (Colour Index, 2nd edition, Addi tions and Amendments #13, October 1961, p. 42), and Drimarene Violet ZRL, CI Reactive Violet 3 (Colour Index, 2nd edition, Additions and Amendments #13, October 1961, p. 43).

In all cases satisfactory dyeings were obtained of good fastness without the necessity for steam or heat treatment to obtain fixation of the dyestuff.

7 Example 6 30 parts of wool fabric were prepared by treatment with permonosulphuric acid and sodium sulphite as described in Example 1. A dye bath was made from:

20 parts Procion Brilliant Red 2B, CI Reactive Red 1 (Colour Index, 2nd edition, Additions and Amendments #7, April 1960, p. 16)

20 parts soda ash 1000 parts water.

The prepared wool fabric was passed into this bath for 30 seconds at 25 C., extracted and rinsed well. The resultant dyeing was fast to washing without the necessity for steam or heat treatment for col-our fixation.

Dyeings of similar fastness were obtained by separately using:

Procion Blue 368, CI Reactive Blue 1 (Colour Index, 2nd edition, Additions and Amendments #7, April 1960, p. 17)

Procion Brilliant Orange 2RS, CI Reactive Orange 4 (Colour Index, 2nd edition, Additions and Amendments #11, April 1961, p. 31)

Procion Yellow RS Procion Yellow 4R8 Procion Red Brown 4RS Procion Rubine BS, CI Reactive Red 6 (Colour Index, 2nd edition, Additions and Amendments #7, April 1960, p. 17)

Example7 Wool was treated according to the process described in the Textile Research Journal, 1960, page 358, using potassium permanganate and common salt followed by a solution of sodium bisulphite.

A fresh bath was prepared at 60 C. from:

1000 parts of water 6 parts of sodium sulphite crystals.

The wool was treated in this bath for 30 minutes and then rinsed.

30 parts of wool were then dyed at 25 C. for 30 minutes in a bath containing:

2 parts of Procion Red GS, CI Reactive Red '5 (Colour Index, 2nd edition, Additions and Amendments #7, April 1960, p. 17)

10 parts of soda ash 1000 parts of water.

The resultant dyeing was fast to washing.

Example 8 30 parts each of wool top and cashmere fibre were prepared for dyeing by treatment with permonosulphuric acid and sodium sulphite as described in Example 1.

Each was then dyed in a bath made from:

1000 parts of water 1 part of Procion Brilliant Orange 2R, CI Reactive Orange 4 (Colour Index, 2nd edition, Additions and Amendments #11, April 1961, p. 31)

1 part of non-ionic wetting agent obtained by condensing octylphenol with ethylene oxide.

After 10 minutes dyeing at 25 C., 30 parts of common salt were added and dyeing continued for a further minutes when 6 parts of soda ash was added. After a further 30 minutes dyeing the dye-bath was dropped and the goods rinsed.

A satisfactory shade was obtained with good wash fastness on each material.

8 Example 9 30 parts of wool fabric were treated for 60 minutes in the following bath at 20 C.:

1000 parts of water 4 parts of peracetic acid (40% strength) 1 part of the commercial non-ionic wetting agent used inExample 8.

A fresh bath was prepared at 60 C. from:

1000 parts of water 6 parts of sodium sulphite crystals.

The wool was treated in this bath for 30 minutes and then rinsed.

It was next dyed at 25 C. for 15 minutes in a bath made from:

1000 parts of water 2 parts of Procion Brilliant Red 2BS, CI Reactive Red 1 (Colour Index, 2nd edition, Additions and Amendments #7, April 1960, p. 16)

10 parts of soda ash.

After dyeing the wool was rinsed and a satisfactory shade obtained of good wet fastness.

Example 10 parts of wool were subjected to a bleaching treatment for 6 hours at 45 C. in 3,000 parts of a hath made from 3-volume hydrogen peroxide adjusted to pH 8.5 by means of sodium pyrophosphate.

The resulting bleached wool was given a treatment at 60 C. for 30 minutes in a bath made up from 3,000 parts of water and 15 parts of anhydrous sodium sulphite.

After being rinsed the wool was then dyed as described in Example 4.

Example 11 A solution was made up containing:

10 parts of Procion Brilliant Red 8B8, CI Reactive Red 11 (Colour Index, 2nd edition, Additions and Amendments #7, April 1960, p. 17)

30 parts of sodium carbonate 2 parts of Calsolene Oil HS in 1000 parts of water.

A sample of Botany Slubbing pretreated with permonosulphuric acid and sodium sulphite by the method described in Example 1 was passed through this solution and immediately through a pair of squeeze rollers so that on emerging from the rollers the wool contained an amount of the solution equal to its own weight. The impregnated wool was allowed to stand at 20 C. for 5 minutes and was then washed in cold water to remove unfixed dye and dried.

A strong red dyeing, fast to washing and milling was produced.

In the above example the sodium carbonate was replaced by an equal weight of tri-sodium phosphate. A similar result was obtained.

By replacing the Procion Brilliant Red 885 by an equal weight of Procion Black HNS, a dark grey dyeing is obtained.

In the following examples using dye stuffs of the Procion type, the wool employed was Sir James Hill dry combed tops (13 g./m.) which had been treated with 2.1% permonosulphuric acid (o.w.w.) as described in British Patent No. 716,806; corresponding to United States Patent No. 2,739,034. The wool is thereafter treated with a solution containing 100 parts of sodium sulfite crystals, 30 parts of sodium bicarbonate and 1000 parts of water in accordance with the procedure of Example 14 of the aforesaid British patent. In Examples 1217, the wool was passed through a small bath containing 10 g./l. reactive dyestuffs, 20 g./l. Tergitol TMN non-ionic wetting agent and 20 g./1. sodium carbonate. The wool then passed through a nip which gave 100% pick-up of dye liquor and was then batched in a can for 1 hour at 25 C. and

finally scoured, rinsed and dried.

The wool was dyed bright yellow.

- Example 13 Reactive dye used had the structure:

N or SOaNa OH NHN N: N or NaSOa SO3Na The wool was dyed bright red.

Example 14 Reactive dye used had the structure:

SOsNa N 01 OaNfi H NH- -NH N soaNa N or The wool was dyed brilliant blue.

' Example 15 v Reactive dye used had the structure:

I NH- Nasca 1 N 01 Q o 0 OH S03 N or i The wool was dyed bright yellow. Example 16 Reactive dye used had the structure:

The wool was dyed bright orange.

In the following Examples 17-21 the wool was passed through a small bath containing 10 g./l. dyestufi, 20 g./l. Tergitol TMN, 20 g./l. sodium carbonate and 10 g./l. sodium chloride. The wool was passed through a nip which gave 100% pick-up of dye liquor and was then batched at 45 C. for two hours, scoured and dried.

Example 17 Reactive dye used had the structure:

SOaNa. N NaSO3 N=NN=N -NH 01 S u 3N a SO Na The wool was dyed a bright orange brown.

1 0 Example 18 The reactive dye used had the structure:

SOaNa OH .Ac-NHN=N N S O 3N8 NaSOa NH NH The wool was dyed bright scarlet.

Example 19 The reactive dye used had the structure:

I Nil N Nasmmr- NH@ N N so Na G1 The Wool was dyed Bordeaux.

Example 20 Te reactive dye used had the structure:

NaSOs O..( 3u..0 i

N02 I N N H NH:

The wool was dyed grey.

Example 21 SO Na V N=N NH NH:

NHA0 N SOaNa Cl The Wool was dyed brilliant golden yellow.

Example 22 Scoured wool tops which had not been pretreated with permonosulphuric acid according to British Patent No.

716,806 were submitted to the procedure described in The structure of the dyestufi' used was:

SOaNa The wool was dyed bright red.

1 l Example 24 The structure of the dyestuff used was:

NaSOa NaSo;

Class Reactive Group Source Procion Dichlorotriazine- Imperial Chemical Industries. Cibacroue.-- Monochlorotriazine Ciba. Reactone Dichloropyrimidiuc--- Geigy. Drimare11e Trichloropyrimidine Sandoz. Remazol Sulphuric ether of p-hydroxy- Hoechst.

ethylsulionc. I claim:

1. A process for the coloration of normal animal hair which comprises the steps of treating a textile form of normal animal hair with (a) a solution of a peroxygen compound, (b) a solution of a water-soluble sulphurcontaining reducing agent and finally '(c) applying to at least selected areas a dyestuif composition comprising water, a water-soluble form of a reactive dyestufi and an acid acceptor, said composition being maintained at a temperature not exceeding 60 C. during contact With said animal hair.

2. The process of claim 1 in which said composition is maintained at a temperature within the range of 10 to 50 C. during contact with said animal hair.

3. A process for the coloration of normal animal hair which comprises the steps of separately treating a textile form of normal animal hair with (a) an aqueous solution containing a water-soluble peroxygen compound and (b) an aqueous solution of a water-soluble sulphur-containing reducing agent whereby a substantially uniform distribution of reactive hydrogen atoms is introduced into said animal hair, and thereafter treating the resulting modified animal hair in at least selected areas with a composition containing water, a water-soluble form of a reactive dyestuff and an acid acceptor, said composition being maintained at a temperature not exceeding 60 C. during contact with said animal hair, whereby substantially uniform coloration of said selected areas by said reactive dyestuff is obtained.

4. The process of claim 3 in which said composition is maintained at a temperature within the range of to 50 C. during contact with said animal hair,

5. A process for dyeing normal wool which comprises successively treating a textile form of normal wool in (a) an aqueous bath containing a water-soluble peroxygen compound and (b) an aqueous bath containing a watersoluble sulphur-containing reducing agent whereby a substantially uniform distribution of reactive hydrogen atoms is introduced into said wool, and thereafter (0) dyeing the resulting modified wool in a dye-bath comprising an aqueous solution of a water-soluble form of a reactive dyestuif containing at least sufiicient acid acceptor to combine with any acid liberated during fixation of said reactive dyestuif on the wool, said dye bath being maintained at a temperature not exceeding 60 C. during said dyeing.

6. The process of claim 5 in which the temperature of said dye bath is maintained within the range of 10 to 50 C.

7. A process for printing wool which comprises treating a textile form of normal wool in (a) an aqueous bath containing a water-soluble peroxygen compound and (b) an aqueous bath containing a water-soluble sulphur-containing reducing agent whereby a substantially uniform distribution of reactive hydrogen atoms is introduced into said wool, and thereafter (c) printing the resulting modified wool by applying to at least selected areas thereof a dyestuff printing paste comprising water, a water-soluble form of a reactive dyestuff, at least sufiicient of an acid acceptor to combine with any acid liberated during fixation of said dyestuif, and a textile printing paste thickener, said printing paste being maintained at a temperature not exceeding 60 C. during contact with said wool.

8. A process for dyeing normal cashmere which comprises successively treating a textile form of normal cashmere in (a) an aqueous bath containing a water-soluble peroxygen compound and (b) an aqueous bath containing a water-soluble sulphur-containing reducing agent whereby a substantially uniform distribution of reactive hydrogen atoms is introduced into said cashmere, and thereafter (c) dyeing the resulting modified cashmere in a dye bath comprising an aqueous solution of a water-soluble form of a reactive dyestuff containing at least suflicient acid acceptor to combine with any acid liberated during fixation of said reactive dyestuff on the cashmere said dye bath being maintained at a temperature not exceeding 60 C. during said dyeing.

9. The process of claim 8 in which the temperature of said dye bath is maintained within the range of 10 to 50 C.

10. A textile form of animal hair which has been colored by the process of claim 1.

11. A textile form of animal hair which has been colored by the process of claim 3.

12. A textile form of wool which has been dyed by the process of claim 5.

13. A textile form of wool which has been printed by the process of claim 7.

14. Cashmere which has been dyed by the process of claim 8.

No references cited.

NORMAN G. TORCHIN, Primary Examiner.

T. I, HERBERT, Assistant Examiner,

Claims

1. A PROCESS FOR THE COLORATION OF NORMAL ANIMAL HAIR WHICH COMPRISES THE STEPS OF TREATING A TEXTILE FORM OF NORMAL ANIMAL HAIR WITH (A) A SOLUTION OF A PEROXYGEN COMPOUND, (B) A SOLUTION OF WATER-SOLUBLE SULPHURCONTAINING REDUCING AGENT AND FINALLY (C) APPLYING TO AT LEAST SELECTED AREAS A DYESTUFF COMPOSITION COMPRISING WATER, A WATER-SOLUBLE FORM OF A REACTIVE DYESTUFF AND AN ACID ACCEPTOR, SAID COMPOSITION BEING MAINTAINED AT A TEMPERATURE NOT EXCEEDING 60*C. DURING CONTACT WITH SAID ANIMAL HAIR.