DE1444283A1 - Process for coloring animal hair products - Google Patents

Description

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Description of the patent application

PRECISION PROCESSES (TEXTILES) IBIITED, London, E.C.2., England

"concerning

Process for dyeing animal hair and animal hair products.

The present invention is concerned with the dyeing of normal wool as well as other types of normal animal Hair and products that consist entirely or partially of animal hair and in the form of loose fibers, card sliver, Tops, yarns and woven and knitted fabrics and garments.

Recently, dyes called reactive dyes and their application have emerged exceptional wet strength properties on textiles

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exhibit. These dyes contain various reactive ones Groups in the molecule. They all react via one or more such groups with reactive hydrogen atoms in the molecule of the textile to be dyed. Such dyes are widely used on cellulosic products. It could be shown that under certain conditions Can also be used on wool, silk and the polyamides. The dyes used on wool and silk are of the same type as those applied to cellulosic products while those applied to polyamides dyes are known not to be of this type.

As a rule, reactive dyes are not nouns dyes. Their ability to react is due to the presence η of an additional substance in the dye bath or back in the printing color. Cellulose fibers are treated with these dyes in an alkaline medium, whereby the temperature varies with the nature of the dye. That On the other hand, dyeing of wool has so far usually been carried out at elevated temperatures and in an acidic or neutral medium for a period of time which is detrimental to the properties of the dyed wool.

Recently, however, the proposal has been made to dye protein fibers in an alkaline medium at a temperature of not more than 50 ⁰ O with reactive dyes. Through this dyeing process, Ie-

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diglioh achieves a moderately satisfactory dyeing and also only weak color fastness, while the dyeing achieved on normal wool is so slight that it is not economically justifiable. Even in the case of the most reactive dyes, under conditions under which a satisfactory dyeing is achieved on cellulosic products, at best only so light dyeing is achieved on normal wool. If the dyeing according to the normal method for the application of dyes on wool, however, carried out using water-soluble reactive dyes, so only one un- Λ uniform coloring is achieved is not satisfactory for most purposes.

The object of the invention is therefore to provide an improved process for dyeing normal wool and to convey other kinds of normal animal hair and animal hair products ^ through the use of such animal fibers or products consisting partly of animal hair are colored with water-soluble, reactive dyes.

According to the invention a method for the dyeing of normal animal hair and products that contain or consist of normal animal hair posed. The same is to say, at least on selected areas of normal animal hair or products, which contain normal animal hair and prior to treatment with a solution of a peroxy compound

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and then subjected to the treatment with a water-soluble, sulfur-containing reducing agent described below, to apply an aqueous solution or printing ink preparation which is a water-soluble one. Contains reactive dye and an acid acceptor. This solution or preparation is kept at a temperature of not more than 60 ^° C. during its action on the hair.

The expression ⁿ peroxy compound ^w used here is to be understood as hydrogen peroxide, an oxide or a peroxide from which hydrogen peroxide is formed in acidic solution, as well as peracids, salts of peracids and salts from an anion in which a metal from group VII A of the periodic System of elements bound to oxygen is present in its highest valency level.

The present invention is based on the observation that normal wool and other types of normal animal Hair that has undergone (a) an oxidation treatment with a peroxy compound and (b) thereafter subjected to a reducing treatment with a water-soluble sulfur-containing reducing agent, a reactivity towards reactive dyes, as they are not in products that have not been treated in this way present.-This reactivity is of an exceptionally uniform character. · Are the products thus pretreated in an alkaline medium with reactive dyes

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"treated, the result is an extraordinarily uniform one Coloring and such a color print. The results obtained in this way are much more consistent than this was previously the pail for chlorinated wool. The dyes can be used at room temperature or at a slightly higher level Temperature for a short period of time sufficient for the treatment. That will color thus carried out under conditions that are not detrimental Have an effect on the pretreated wool. As the oxidation and reduction treatment to give a shrink resistance can be carried out on normal «· wool and wool products, the treatment is used to achieve a Shrink resistance and for dyeing or printing in one another carried out the following steps. It is clear that the successive implementation of the oxidation and Reduction treatment changes the chemical structure of wool or other animal hair in such a way that that thereby a substantially uniform distribution of readily reactive hydrogen atoms in the same is achieved.

These hydrogen atoms are then available to react with the reactive dyes.

The method according to the invention is of particular advantage for dyeing and printing textile products normal wool or products containing wool or products containing other normal animal hair, both

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for example for dyeing and printing products made from cashmere fibers. .

The dye and acid acceptor can be dipped onto wool and other types of animal hair products be applied in a dyebath in which the dye and the acid acceptor are contained in the form of a solution are. This dye bath can also be any customary Contain textile auxiliaries, such as hardening or leveling auxiliaries, which are suitable for use in conjunction with reactive dyes. The dye and the acid acceptor can also be padded, or they can only be applied to certain areas of the Textile fabric made from protein fibers by means of a printing process be applied. In the case of such an application, the printing ink preparations may contain thickeners, which are essentially reactive dyes are neutral.

Reactive dyes which can be used are those which contain at least one water-solubilizing group and a group which are capable of forming a covalent bond with a hydroxyl group present in the cellulose molecule or with a similar group formed in situ. This is not intended to imply that there must be hydroxyl groups in wool products and other animal hair products as described above. What is the nature of the described

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No matter how handily introduced groups were, it could be found experimentally that they have properties similar to those found in cellulose Hydroxyl groups.

They Waseer solubilizing group on the dye molecule can be a carboxylic acid or a sulfonic acid group, or else an alkali metal of such a group as well as ammonia or an amine βein. In the dye molecule can optionally there are also several such groups.

The one capable of forming a covalent bond group can have a reactive halogen atom, such as for example in a mono- or di-chloro-sym-triazinyl, trichloropyrimidyl, Beta-halogenpropionyl-, beta-halogenethylsulfonyl-, Beta-halogenethylsulfamyl-, chloro-acetylamino- or beta-carbonomethylJ-beta-sulfatoethylsulfamylgruppej a reactive sulfate group, such as in a beta sulf atoäthylsulfonylgruppej a reactive hydroxyl or ester group, such as in a beta-hydroxyethylsulfonyl, Beta-alkylsulfcmyloxyalkylsulfonyl-, beta-j arylsulfoByloxyalkylsulfonyl- or a beta-acyloxy- j alkylsulfonyl group. This group can still be a be an ethylenically unsaturated group, such as an acryloxyamino- or vinylsulfonyl group, an alkyl phosphite group or a sulfonfluoride group. In the case of Sym-triazinyl and pyrimidyl groups instead of reactive ones Halogen atoms or atoms, other sub-

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there are substituents that can be dissociated by alkali, such as sulfonic acid. Negatively substituted thiocyanates Aryloxy and arylthio groups such as sulfophenoxy, sulfophenylthio, Nitrosulfophenoxy, disulfophenoxy and sulfonaphthoxy groups quaternary ammonium groups j single and multi-ring heterocyclic thio groups with 5 or 6 atoms in the heterocyclic ring, which are bonded to the thiol group via a carbon atom of the ringj dithiocarbamic acid groups the general formula

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in which R and R each optionally have the same Are alkyl, cycloalkyl, aryl or arylalkyl groups, or

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in which R and R together with the nitrogen atom form one Form 5- or 6-membered heterocyclic ring; or a group of. general 3? sleeves

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in which R and R may be identical to one another and are each a hydrogen atom or an alkyl, aryl or arylalkyl group.

The dyes used can belong to the series of Eitro, Azo, anthraquinone, or phthalocyanine compounds and optionally contain a complex bonded metal. An overview of the types of commercially available reactive dyes can be found in the

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Journal of the "Institut Textile de Prance", September 1960, on page 43 etc.

The peroxy compounds used in the pre-treatment process for normal wool and other normal animal hair products can be hydrogen peroxide, an inorganic or organic, water-soluble peracid such as peracetic acid or permonosulfuric acid, or a water soluble salt an inorganic or organic peracid, such as an alkali peracetate, permonosulfate, perborate, percarbonate or permanganate. Such compounds are usually used in a dilute, aqueous solution. Through the Concentration of the solutions and the working conditions prevailing during their application must not cause any significant degradation caused by the wool. The most favorable pH in each case varies with the particular peroxy compound used. In addition to the peroxy compound, surface-active substances can be used in the bathroom Means for uniform wetting and penetration of the products during the oxidation treatment worry, be present.

The sulfur-containing reducing agent can be an organic or inorganic compound. For example it can be a thiocarboxylic acid such as thioglycolic acid or thiopropionic acid. Conversely, it can also be water-soluble Be a salt of an oxidizable sulfur-containing acid, such as an alkali sulfite, bisulfite or hydrosulfite Amine salt of such an acid, such as monoethanolamine sulfite

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- ^{1 10} - H44283 ¹ ^ ² *

or a water-soluble salt as a thiocarboxylic acid.

Typical treatments are as follows

(a) treatment with aqueous permonosulfuric acid,

of a treatment with a SaI ζ of 8chwefligen acid anschließtϊ comparisons British Patent Specification No. 716

(b) Treatment with hydrogen peroxide, alkali perborates and percarbonates in the presence of a compound of copper, silver, winding or mercury, according to the British patent Ϊ3Ό. 614 966, who received treatment with a suitable reducing agent follows.

(c) treatment with an aqueous solution of an organic peracid such as performic acid or peracetic acid, the treatment with a suitable reducing agent follows.

(d) Treatment with hydrogen peroxide in neutral or weak alkaline medium, for example under the standard conditions for bleaching woolen fabrics, the treatment with a suitable reducing agent follows.

(e) treatment with aqueous potassium permanganate in the presence of sodium or potassium chloride, lightening the Coloring with a dilute, aqueous solution of a water-soluble one Bisulfite and further treatment with a separate bath of a suitable reducing agent.

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Preferably, the reduction treatment is carried out with a Hatriumeulfit- or -bisulfitlösung at a temperature of 20 to 65 ⁰ O.

Be after treatment with the reducing agent the products are preferably rinsed to remove excess reducing agent before the reactive dye is applied to the same.

It is clear that the oxidation treatment under conditions which may be sufficient to impart a certain resistance to the hull and at the same time prevent substantial degradation of the wool per se is not sufficient to impart the desired dyeing properties to the treated wool or other animal hair products. The oxidation treatment must be followed by a reduction treatment if the desired coloring properties are to be transferred to the treated product by fixing in an alkaline medium.

When carrying out the method according to the invention, either the wool or another animal hair product is used a solution or a printing ink is applied which is a water-soluble, reactive dye and a substance acting as an acid acceptor. According to the invention, any water-soluble, more reactive Dye used for dyeing cellulosic products with high wet strength when

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presence of an acid acceptor can be used.

The acid acceptor can be any alkaline substance useful for coloring cellulosic products with water-soluble, reactive dyes can be used can. These include soda ash, sodium and potassium carbonate, bicarbonate and silicate, as well as trisodium and Tripotassium phosphate.

The amount of acid acceptor present should be at least sufficient so that the entire amount during the reaction of the Dye fixation released acid is bound. In general, an amount of acid acceptor up to 3% by weight will be used aqueous dye bath and a corresponding amount used in the printing ink paste.

Leveling aids and organic solvents can also be added to the dyebath and the color printing pastes in which the dyes are readily soluble, and through which the dye absorption is facilitated, wherein the dyes do not preferentially react with the same under the process conditions * These additives are intended to have at least a low solubility in water, such as the aliphatic and arylaliphatic alcohols, for example n-butyl alcohol and the benzyl alcohol.

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Some of the reactive dyes react with wool essentially at room temperature. These are those which contain a dihalo-sym-triazinyl group or a beta-sulfatoethylsulfonyl group. The remaining, including those trichloro-pyrimidyl with monohalo symtriazinylgruppen and are placed preferably at a temperature used, which is higher than the room temperature, 60 ⁰ O but not exceeding. It has been found that dyes require a dichloro-sym-triazinyl a much shorter duration for the fixing on chemically modified wool than any other similar arbitrary and available type. It has been found that in the case of dyeing with dyes which require a much higher temperature than room temperature for fixing, the addition of water-soluble electrolytes such as sodium chloride and sodium sulfate facilitates fixing.

The process according to the invention has significant advantages over the processes previously used for dyeing normal wool and other products made from animal fibers with water-soluble, reactive dyes. Leveling can easily be achieved after a short period of time in a dyeing process carried out ^{at 20 to 30 ° C. in the cold.} Such dyeing gives better leveling than is possible in the case of chlorinated wool. With the method according to the invention, it is possible to obtain shiny, real pastel shades, such as

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UΆ4283 ^1Α ~ ^{24 298}

^ ie in the case of chlorinated wool because of the chlorine treatment resulting yellow color 'unattainable, so to speak are. The hand of the goods dyed according to the invention is also significantly better than in the case of chlorinated goods Wool. All dyeings and color prints obtained according to the invention are of excellent wash fastness.

The invention is illustrated in more detail by the following examples.

example 1

A piece of woolen fabric was treated with permonosulfuric acid and then with a solution of a sulfite according to British patent specification No _e 716 806 while observing the following reaction conditions: A bath of 3000 parts of water, 20 parts of a 10bigen solution of permonosulfuric acid and 1 part was treated a commercially available, non-ionic IT wetting agent. In this bath, 100 parts of woolen fabric were treated for one hour, which were then treated for a further 30 minutes in a bath of 3000 parts of water and 20 parts of crystalline sodium sulfite. The two bathrooms had a temperature of generally 2O ⁰ C. The fabric was rinsed and then dyed as follows: A dye bath at 25 ° was prepared by dissolving 6 g of “Remazol” Brilliant Violet 5R and 30 g of sodium carbonate in 3000 parts of water. The fabric was fully

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come * soaked state for 10 minutes dyed in this solution, the temperature was kept ^{at 25 0 C all the time.} It was then rinsed off with cold water so that excess dye could be separated off. The dyeing formed in this way was very fast to washing and did not require any hite or steam treatment to fix the dye on the wool fiber.

Example 2

A piece of woolen fabric prepared for dyeing as in the previous example was turned into selected areas treated in such a way with a dye solution as ^ ies economically on Textiles is carried out when printing on canvas. The solution was made from:

100 parts of water,

1 part "Remazol" Brilliant Blue R

1 part sodium carbonate

The cloth treated in this way was left in the solution for 30 minutes and then rinsed off.

The colored areas of the fabric showed a high Fastness to normal washing without the need for heat or steam treatment.

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Example 3

Woolen tops were prepared for dyeing as in Example 1. The dye solution consisted of: 100 parts of water
1 part "Remazol" Black B 3 parts sodium carbonate 5 parts commercial benzyl alcohol with a purity of $ 60.

The woolen sliver was ^{immersed in this solution for two minutes at 25 °} C., then lightly ironed and then left to lie for three minutes. Most of the excess dye solution was then removed from the wool by mangling again and then rinsing.

The dyeing obtained in this way was very fast to washing without it being necessary for the dye to be fixed to apply heat or steam treatment to the wool fiber.

Example 4

There were 30 parts of wool fabric according to two known, a shrink-proof procedure, treated separately:

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(a) Treatment with permonosulfuric acid and sodium sulfite solution as in example 1

(b) Treatment of the wool products with a small amount of metal salt as in Example 1, according to the British Patent No. 614 966, followed by a treatment with an alkaline hydrogen peroxide solution and then a treatment with sodium bisulfite solution and sulfuric acid followed.

The dye baths were made up

2 parts Procion Red G-10 [bearing soda ash
1000 parts of water

Woolen fabrics produced according to (a) and (b) were separately ^{dyed for 10 minutes at 25 °} C. in these baths and then rinsed well.

The dyeings obtained were very fast to washing. |

Example 5

A dye bath was made out

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20 parts trisodium phosphate 20 parts table salt *

2 parts Prooion Orange Brown HGS 1000 parts water

As 30 parts of a woolen product entirely pretreated with permonosulphuric acid and Katriumsulfit and then stained for 10 minutes at 50 ⁰ C in this bath and then rinsed with water in Example. 1

Further staining were carried out in the same way, but using Procion Orange Brown HGS Cibacron Scarlet 4GP, or »was replaced by Reactone Brilliant Yellow 5Gl, or by Drimarene Violet ZRl.

In all cases, the coloration was satisfactory achieved, which had good color fastness without the need for a heat or for fixing the dye Use steam treatment.

Example 6

30 parts of woolen fabric were obtained by treatment with permonosulfuric acid and sodium sulfite as in Example 1 pretreated. A dye bath was made from:

20 parts Procion Brilliant Red 2B 30 parts soda ash 1000 parts of water

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The wool fabric pretreated in this way was placed in this bath at 25 ⁰ O for 30 seconds, then removed and rinsed well. The coloration obtained was very fast to washing. Fixing the dye required no or steam treatment.

Dyeings of the same fastness were obtained by using:

Procion Blue

Procion Brilliant Orange 2RS

Procion Yellow RS

Prooion Yellow 4RS

Frooion Red Brown 4RS

Frocion Rubine BS

Example 7

According to that in "Textile Research Journal", page In the method described in 358, wool was treated using potassium permanganate and common salt, on what treatment with a sodium bisulfite solution connected.

At 6O ⁰ C a fresh bath was made from:

10000 parts of water

6 parts of crystalline sodium sulfite.

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

Then 30 parts of wool were dyed for 30 minutes at 25 ⁰ C in a bath that was made out

2 parts Procion Red GS

10 parts of soda ash

1000 parts of water consisted. The dyeing obtained was very fast to washing.

Example 8

As in Example 1, each 30 parts of woolen tops were made and cashmere fibers by treatment with permonosulfuric acid and sodium sulfite prepared for dyeing. After that, each fabric was dyed in a bath consisting of:

1000 parts of water
1 part of Procion Brilliant Orange 2R 1 part of a non-ionic wetting agent, which had been obtained by condensation of octylphenol 'with ethylene oxide.

After a Pärben for 10 minutes at 25 ⁰ C, 30 parts of common salt was added and dyeing continued for a further 5 minutes, with 6 parts of soda ash were added. After further dyeing for 30 minutes, the colored product was removed from the bath, drained and then rinsed.

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A satisfactory shade of color was obtained for each product obtained with very good fastness properties against washing.

Example 9

30 parts of a woolen fabric were ^{treated for 60 minutes at 20 0} O in a bath of the following composition »

1000 parts of water

4 parts peracetic acid (40 $ ig)

1 part of the commercially available non-ionic curing agent used in Example 8.

At 60 ⁰ O a fresh bath was off

1000 parts of water

6 parts of crystalline sodium sulfite prepared.

The woolen fabric was treated in this bath for 30 minutes and then rinsed. Then it was at 25 Ο colored for 15 minutes in a bath consisting of »

1000 parts of water

2 parts of Procion Brilliant Red 2BS and 10 parts of soda ash. "*

After the dyeing, the wool was rinsed off. It was a satisfactory shade with good wet strength properties obtain.

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Example 10

There were subjected to 100 parts of wool for 6 hours' at 45 ⁰ O a bleaching treatment in 3000 parts of a bath containing 3 parts by volume hydrogen peroxide and had a pH of 8.5 by addition of sodium pyrophosphate.

The bleached wool obtained was ^{treated for 30 minutes at 60 0} O in a bath which had been prepared from 3000 parts of water and 15 parts of anhydrous sodium sulfite.

After unwinding, the wool was as in Example 4 colored.

Example 11

A solution was made from:

10 parts of Procion Brilliant Red 8BS 30 parts of sodium carbonate 2 parts of Calsolene Oil HS and 1000 parts of water.

As in Example 1, a "Botany Slubbing ¹¹ " pattern was pretreated with permonosulfuric acid and sodium sulfite and then placed in the above solution.

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Contained amount that was equal to their own weight.
impregnated wool was left for 5 minutes at 20 ° 0 and then rinsed with cold water to separate unfixed dye. The wool swatch was then dried.

A strong red coloration was obtained, which was resistant to washing and tumbling.

In the above example, the sodium carbonate was replaced by an equal amount by weight of trisodium phosphate. Da- ^ Similar results were obtained for.

By replacing Procion Brilliant Red 8BS with an equal amount by weight of Procion Black HNS, a
dark gray color obtained.

Claims

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Claims (10)

- 24 - η 444283 "iA '^ 298 P__a. ^ T je ntanspriiclie 1. A method for dyeing animal hair and animal hair products with Reakti ^ f arbstof f en, characterized in that the hair is treated with a solution of a peroxy compound and then with a water-soluble, sulfur-containing reducing agent, whereupon an aqueous alkaline dye solution or allowed to act color printing preparation containing a water-soluble reactive dye and an acid acceptor, wherein the solution or composition is maintained during its exposure time to the hair at a temperature that does not exceed the 60 G ^0. 2. The method according to claim 1, characterized in that the treatment with the preparation containing the reactive dye is carried out ^{at 10 to 50 0 O.} 3. The method according to claim 1 or 2, characterized β e "τ e η η ζ cich η et that a water-soluble peracid or a water-soluble salt of a peracid is used as the peroxy compound. 4. The method according to claim 3, characterized that permonosulfuric acid is used as a water-soluble peracid » 9 0 9 8 2 2/1151 - ²⁵ - UU 283 ^u ~ ²⁴ 5. The method according to claim 3> thereby g e - k e η η ζ e ic h not that one is called a water-soluble salt an alkali salt of pernonosulphuric acid ends. 6. The method according to claim 3, characterized in that a water-soluble, organic peroxide used. 7. The method according to claim 6, characterized in that peressific acid is used. 0. The method according to claim 1 or 2, dad u r c h characterized that r.ian as a peroxy compound Hydrogen peroxide is used. 9. The method according to claim 1 to 8, characterized characterized that as water soluble, sulfur-containing reducing agent an alkali sulfite, bisulfite or hydrosulfite used 10. The method according to claim 1 "to 9, characterized marked that one is normal animal Dyes hair, normal wool or normal cashmere fibers. 9 0 9 8 2 2/1 1 S 1