AU626818B2 - Enzymatic treatment of wool - Google Patents

Abstract

The invention relates to a process for the production of wool and animal hairs with a low-in felt or felt-free finish, with a soft woolly handle and special shrink-resistance and strength. In this process, the wool is treated with a protease and is then treated at a temperature of between room temperature and 140 DEG C.

Description

OPI DATE 23/05/89 AOJP DATE 29/06/89 APPLN. ID 27101 88

PCT

PCT NUMBER PCT/EP88/00971 INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT 'r)OPERATION TREATY (PCT) (51) International Patent Classification 4 ll ern na bli: n er: WO 89/ 03909 D06M 16/00 A l er'0ltnaliblica on I 5 May 1989 (05.05.89) (21) International Application Number: PCT/EP88/00971 (22) International Filing Date: 27 October 1988 (27.10.88) (31) Priority Application Number: 4214/87 (32) Priority Date: (33) Priority Country: 28 October 1987 (28.10.87)

CH

(74) Agent: D'HAEMER, Jan; Sandoz AG, Patentabteilung, CH-4002 Basle (CH).

(81) Designated States: AT (European patent), AU, BE (European patent), BR, CH (European patent), DE (European patent), DK, Fl, FR (European patent), GB (European patent), IT (European patent), JP, KR, LU (European patent), NL (European patent), NO, SE (European patent), US.

Published With international search report.

Before the expiration of the time limit for amending the claims and to be republished in the event of the receipt of amendments.

(71) Applicant (for all designated States except US): SCHO- ELLER HARDTURM AG [CH/CH]; Hardturmstrasse 122, CH-8005 Zurich (CH).

(72) Inventors; and Inventors/Applicants (for US only) CIAMPI, Luigi [IT/ CH]; Tifrkheimerstrasse 5, CH-4055 Basle (CH).

FORSTER, Otto [CH/CH]; Im Sydefadeli 41, CH- 8037 Zurich HAEFELY, Hans, Rudolf [CH/ CH]; Kempfhofweg 10, CH-8037 Zurich (CH).

KNAUSEDER, Franz [AT/AT]; Oberndorf 306, A- 6322 Kirchbiehl (AT).

(54) Title: ENZYMATIC TREATMENT OF WOOL (57) Abstract The invention relates to a process for the production of wool and animal hairs with a low-in felt or felt-free finish, with a soft woolly handle and special shrink-resistance and strength. In this process, the wool is treated with a protease and is then treated at a temperature of between room temperature and 140°C.

WO 89/03909 1 PCT/EP88/00971 ENZYMATIC TREATMENT OF WOOL The present invention relates to a process for the production of wool and animal hairs with a low-in-felt or felt-free finish and to the wool or animal hairs so obtained.

To obtain felt-free wool has been a problem for many years and many methods including enzymatic treatments have been proposed to solve this problem. A review of such methods has been published by E.P. Frieser in Textil-Praxis, 18 (1963, 03), pages 236-240 and he refers back to articles by W.R. Middlebrook and H. Phillips in J. Soc.Dyers and Colorists, 57 (1941), pages 137-144 and A.N. Davidson and R. Preston in J. Text.

Inst. 47 (1956), pages 685-707 (also described in Belgian Patent No. 536 819). Although not always as explicitly stated as in European Patent Application 134 267, the object of these enzymatic treatments was to achieve a complete descaling of the wool, i.e. that the outer surface of the fibres is totally removed and the character of the fibres changed in such a way that the natural aspect of the wool is lost.

The object of the present invention is to produce wool and animal hairs which keep their natural aspect and still have scales, but are low-in- -felt or felt-free. This object is achieved by an enzymatic treatment which, in contrast to the known treatments, is superficial and short but effective to obtain a product that can be washed without negative consequences in ordinary household washing machines. A reliable method to differentiate this product from natural wool is the IWS Test Method 31, published by the International Wool Secretariate. Whereas the untreated fibres start to felt at the latest after 3 cycles of the described 7 A washes, the enzymatically treated wool according to the invention can stand at least 5 of these cycles without felting.

i -2- Another method to determine whether the wool fibres can be called felt-free is the weil known Cubex-Test according to IWS Test Method 185, in which the shrinkage properties of wool are determined by treatment for one hour in cube form in a standardised washing appliance.

In this test the wool should have an area shrinkage of 10 after a Cubex test lasting at least one hour. By area shrinkage is understood the sum of the shrinkage in length and of the shrinkage in width. This corresponds to about 15-20 machine washes at high speed in a domestic washing machine without shrinkage or without significant alteration to the surface and shape.

Furthermore, the yarn strength of the treated wool should, compared with untreated wool, be lost by less than 15% Rkm and the elongation should deteriorate by less than The invention, therefore, relates to a process for the production of wool, or protein-containing animal hair, 20 which have a finish which is low in felt or felt-free and which retains its natural scales, defined by a) an area shrinkage (sum of the shrinkage in length and the shrinkage in width) of 10% after a Cubex 25 test of at least one hour or after 5 cycles 7 A according to IWS TM 31, b) a loss of yarn strength, compared with untreated wool or hair, of less than 15% Rkm; and c) an elongation which deteriorates by less than which process comprises bringing the wool or the hair into contact with a protease and subsequently subjecting 0C E 920527,dbda 124,27 101.res,2 U C-, 2a the wool or hair thus contacted to thermal treatment by means of high frequency radiation, the thermal treatment being carried out at a tempsrature of between room temperature (20 0 C) and 1400C.

By protease is understood any protein-splitting enzyme.

Suitable proteases are enzymes recovered from bacteria, for example esperase, pronase 4 00000* 0 9 0000 000000 6 00 9 000 00 0 @0 0@ 000000 0 0000 0* 00 0 000000 0 0

OSOOOO

0 00 0 *0 00 0 00 00 0

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911121,dbdatO94,27101.res,3 WO 89/03909 PCT/EP88/00971 3 E, protease P, subtilysin, thermolysin, as well as enzymes from animal or plant origin, for example trypsin, pepsin, pancreatin or bromelain.

Mixtures of various enzymes can also be used. These proteases are available commercially. Preferred proteases for the process according to the invention are the animal and vegetable enzymes, especially bromelain.

The effectiveness of the enzyme employed can be increased by adding specific activators such as cystein, dithioerythrol, dithiothreitol or mercaptoethanol. Further additives, such as salts which are known for stabilising enzymes, can also be used, e.g. calcium or zinc chloride.

These salts are employed in a quantity which corresponds to the enzyme.

Treatment of the wool or hair with a protease may take place in a long or short bath. Treatment is preferably effected by means of impregnation from a short bath, for examnle by padding, spraying, coating or printing.

The protease may be applied from an aqueous medium or from organic solvent, or also as a paste or foam. The liquor-to-goods ratio is conveniently in the range 1:0.7 to 1:10, preferably 1:1 to 1:5 if treatment is continuous, and in the range 1:10 to 1:40 if treatment is from a long bath.

Application of the protease is preferably effected at a temperature between room temperature and 60°C. The treatment liquor or paste is preferably set at a pH value between 4 and 9, especially 5-7, using a commercial buffer.

The protease is conveniently used in a quantity of 0.1 to 5 calculated on the dry weight of the wool. When applied by means of impregnation, the protease is used in a quantity of 0.1 to 2 corresponding to an enzyme activity of 400 to 1500 CDU/mg. Preferably a quantity of 0.5 to 1 is used. When applied from a long bath, the protease is used in a quantity of 1 to 5 again calculated on the dry weight of the wool.

Directly after the enzymatic treatment, the wool or hair is either left i _J c

I,

WO 89/03909 PCT/EP88/00971 -4to dwell and/or undergoes thermal treatment. The dwelling period may last from a short interim period to several hours, with partial or complete drying of the goods. Depending on the temperature, the thermal treatment may take place for a few minutes up to several hours, optionally until the wool is dry. Saturated steam, super-heated steam, hot air or high frequency (HF) waves may be used for the thermal treatment. When steaming with saturated steam for example, the wool or hair is advantageously left to dwell for between 10 and 30 minutes. In the HF drier, the wool or hair is conveniently treated at about 100-1020C between 10 minutes and 1 hour.

The conditions for the dwelling period or the thermal treatment are chosen such that the wool obtained has the desired properties, and preferably such that the enzyme is simultaneously disactivated at the end of the treatment. Any enzyme that is still active can also be disactivated by known methods after treatment.

The wool or hair is then washed and dried, and further processed.

The process according to the invention may be used both for wool and for other protein-containing animal hairs. The fibre material may exist in various stages of processing, e.g. in the form of flocks, tops and roving, yarn, knitted goods, woven goods, non-wovens or felts. The wool may be used for the process according to the invention in the raw or pre-treated state.

In order to attain certain effects and/or to optimise the effect of the protease, it may be convenient to carry out special pre-treatments prior to the enzymatic treatment. Suitable pre-treatments for wool or hair may be for example oxidative treatments, e.g. with hydrogen peroxide, optionally in the presence of a stabiliser, with potassium permanganate, Caro's acid, chlorine or chlorine-containing compounds such as chlorine gas, hypochlorites or organic chlorine carriers, or with ozone, reducing pre-treatments, e.g. with hydrosulphite, a sulphoxylate or sulphide, alkaline treatments, pre-treatments with acids, solvents or enzymes such as lipases, catalases, oxydases or peroxydases, or physical treatments, WO 89/03909 PCT/EP88/00971 for example with various forms of radiation such as HF waves or cold discharges. These pre-treatments are known and are used in part to modify the wool.

After the pre-treatment, the wool or hair is rinsed and dried.

In a preferred feature of the process according to the invention, the wool or hair is chlorinated by oxidation and then treated with a protease.

The oxidative chlorination of the wool or hair is preferably carried out using active chlorine, e.g. in the form of chlorine gas in water or in the form of sodium hypochlorite with hydrochloric acid. This pretreatment may be carried out by known methods. The wool or hair preferably undergoes mild chlorination. The wool or hair is preferably chlorinated with a quantity of 0,1 to 2 of active chlorine, calculated on the dry weight of the wool or hair. This treatment advantageously takes place at a pH of 2-3 for 1 to 10 seconds. Chlorination is preferably effected at a temperature of between 10 and 30 0

C.

After the pre-treatment, in order to attain the desired enzymatic effect, i.t is advantageous for the wool or hair to be free from residual pre- -treatment agents and to have a pH in a neutral range.

After chlorination, the fibre material is treated so as to be free from residual chlorine, and is subsequently or simultaneously neutralised. The chlorine present on the fibre or in the fibre is removed by treatment with a reducing agent, for example sodium bisulphite, sodium sulphite etc. Neutralisation is advantageously carried out with an alkaline compound, for example an alkali metal carbonate.

Depending on the chosen conditions of the process, with or without pre-treatment, the scaly layer of the wool or hair is partly or only slightly changed or activated. As a result of the enzyme treatment, 1' -4- WO 89/03909 PCT/EP88/00971 6 woolor hair is obtained which has reduced felt behaviour and does not provoke problems during further processing (spinning, bleaching, dyeing) and during usage and washing of the articles made therefrom. The wool which is treated in accordance with the invention has a soft and, which is particularly advantageous, natural woolly handle. When it is chlorinated as tops and is then treated enzymatically as mentioned above, an especially soft wool or hair is produced. The dyeing behaviour of the wool or hair which is treated according to the invention and the fastness properties of the dyed wool or hair are also not adversely affected, on the contrary they are considerably improved.

The following examples illustrate the invention. All percentages are by weight and all temperatures are given in Centigrades.

EXAMPLE 1 Wool tops are padded at 400 with an aqueous liquor which is buffered to pH 6.0 and contains 0.5 esperase [Bac. lich., obtainable from Novo (Denmark)] calculated on the dry weight of the tops, and then squeezed out to a pick-up of 50 The impregnated tops are subsequently left to dwell for 15 minutes in saturated steam at 1020. After this treatment, the tops are washed out and then dried.

A soft wool which is low in felt and which can be spun with little waste is obtained.

EXAMPLE 2 The process of example 1 is repeated, whereby after padding and squeezing

I:

i: i.

WO 89/03909 PCT/EP8/00971 -7 out, the tops are first of all left for an interim period and then treated for 30 minutes in a HF drier at 100-1020.

EXAMPLE 3 Wool tops aze firstly padded for 3 seconds at a temperature of 10-200 on a split padder for tops with chlorine water containing 0.4 active chlorine. The wool is subsequently rinsed, then treated for 45 seconds with liquor containing 4 g/l sodium carbonate and 1 g/l sodium bisulphite, and washed twice.

After drying, the chlorinated tops undergo enzymatic treatment in accordance with example 1 or 2.

EXAMPLE 4 Wool tops are treated for 60 minutes at 30° with a bath containing, per litre, 15 ml of hydrogen peroxide 40 by volume and 3 ml of a commercial silicate-free hydrogen peroxide stabiliser, set at a pH of 5.5 6.0. The liquor-to-goods ratio is 1:20. The tops are then rinsed and subsequently treated enzymatically according to the process of example 1.

EXAMPLE 6 Wool tops are treated for 5 hours at 450 with a bath containing, per litre, 15 ml of hydrogen peroxide 40 by volume and 4 g/l of sodium pyrophosphate, set at a pH of 7.5 8.5. The liquor-to-goods ratio is 1:20. The wool is subsequently rinsed and then treated enzymatically as described in example 1.

EXAMPLE 7 WO 89/03909 PCT/EP88/00971 8- Wool tops are treated for 60 minutes at 200 with a bath containing 6 peroxymonosulphuric acid (Caro's acid). The liquor-to-goods ratio is 1:20. 2 sulphuric acid is subsequently added to the bath, and the wool is treated further with this bath for 30 minutes at 260. Then, 12 sodium sulphite is added to the bath, and the wool is further treated for minutes at 301.

After rinsing, the wool is treated enzymatically according to example 1.

EXAMPLE 8 Wool tops are padded at 30° with liquor containing, per litre, 25 ml of hydrogen peroxide 40 by volume and 25 g/1 of potassium persulphate, set at a pH o" 7. The pick-up is 60 After leaving at room teperature for hours, the wool is washed out and subsequently treated enzymatically as described in example 1 or 2.

EXAMPLE 9 Wool tops are treated for 6 hours at 40° with a bath containing 0.5 of a commercial peroxidase and 0.25 mol/l hydrogen peroxide. The liquor-to- -goods ratio is 1:25. The wool is subsequently rinsed and then treated with the esperase as in example 1 or 2.

EXAMPLE Wool tops are treated for 6 hours at 400 with a bath containing 0.5 of a commercial lipase. The liquor-to-goods ratio is 1:20. The wool is subsequently rinsed and then treated with the esperase as in example 1 or 2.

I WO 89/039 09 PCT/EP88/00971 -9- EXAMPLE 11 Wool tops are padded to a pick-up of 50 with liquor containing 0.2 of a commercial katalase and 40 ml/l of hydrogen peroxide 40 by volume.

The impregnated wool is subsequently left for 6 hours at room temperature and then rinsed.

The pre-treated wool is then treated with the esperase as in example 1 or 2.

A protease such as pancreatin can be used in examples 1 to 11 instead of the esperase. A wool with a soft woolly handle and shrink-resistant properties is obtained.

EXAMPLES 12 and 13 Examples 1 and 2 are repeated using, instead of 0.5 of esperase, 0.5 of bromelain.

Wool with a soft woolly handle and shrink resistant properties is obtained.

Examples 3 to 11 can be repeated using an appropriate amount of bromelain instead of esperase. Wool with a soft woolly handle or shrink resistant properties is obtained.

Example 14 Example 1 is repeated using, instead of esperase, 1 of bromelain which is applied from a long bath with a liquor-to-goods ratio of 1:20. The treatment continues for 4-6 hours at 500. After rinsing, the wool tops are dried and show a soft woolly handle and good shrink resistance WO 89/03909 PCT/EP88/00971 10 properties.

Example Wool tops are pretreated as in Example 3 and after washing, further processed to finished goods. These finished goods can now be treated as in Example 14 and show excellent properties.

Claims (8)

1. A process for the production of wool, or protein- containing animal hair, which have a finish which is low in felt or felt-free and which retains its natural scales, defined by a) an area shrinkage (sum of the shrinkage in length and the shrinkage in width) of 10 after a Cubex test of at least one hour or after 5 cycles 7 A according to IWS TM 31, b) a loss of yarn strength, compared with untreated wool or hair, of less than 15% Rkm; and c) an elongation which deteriorates by less than *eo which process comprises bringing the wool or the hair into contact with a protease and subsequently subjecting 20 the wool or hair thus contacted to thermal treatment by means of high frequency radiation, the thermal treatment being carried out at a temperature of between room temperature (20°C) and 140 0 C. 25 2. A process according to claim 1, characterized in i that the protease is permitted to dwell on the hair.

3. A process according to claim 1 or claim 2, characterised in that the protease used is esperase, pronase E, protease P, subtilysin, thermolysin, trypsin, pepsin, pancreatin or bromelain.

4. A process according to any one of claims 1 to 3, characterised in that the wool or hair is contacted with the protease, allowed to dwell for a short time, and then treated thermally for at least 10 minutes. I Z c 920527,dbda.124,27101.res,11 \oxF._ )1 -12- A process according to claims 1 to 4, characterised in that the protease is used in a quantity of 0.1 to calculated on the dry weight of the wool or hair.

6. A process according to any one of claims 1 to characterised in that the wool or hair is initially subjected to pretreatment.

7. A process according to claim 6, characterised in that the pretreatment is oxidation or reduction.

8. Wool or animal hair which is treated according to any one of claims 1 to 7.

9. Enzymatically treated, resin free wool or animal hair with substantially unchanged scaly layer having the following properties: a) an area shrinkage (sum of the shrinkage in length 20 and the shrinkage in width) of 10% after a Cubex test of at least one hour or after 5 cycles 7 A according to IWS TM 31, .i b) a loss of yarn strength, compared with untreated 25 wool or hair, of less than 15% Rkm; and c) an elongation which deteriorates by less than A process for the production of wool, or protein- containing animal hair, which have a finish which is low in felt or felt-free and which retains its natural scales substantially as hereinbefore described with reference to the Examples. DATED this 27th day of May, 1992 Schoeller Hardturm AG By Its Patent Attorneys DAVIES COLLISON CAVE ,dbda 24,10.res,12 P1 .920527,dbdatl124,27101.res,12 c cc I: 1 w c .f E v i INTERNATIONAL SEARCH REPORT Internatlonal Application No PCT/EP 88/00971 I. CLASSIFICATION OF SUBJECT MATTER (If several classification symbols apply, Indicate all) According to International Patent Classification (IPC) or to both National Classification and IPC IPC 4 D 06 M 16/00 II. FIELDS SEARCHED Minimum Documentation Searched 7 Classification System I Classification Symbols IPC 4 D 06 M Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included In the Fields Searched III. DOCUMENTS CONSIDERED TO BE RELEVANTO Category Citation of Document, "I with indication, where appropriate, of the relevant passages 2 Relevant to Claim No. is X Journal of the Textile Institute, 1,2,4-7 Proceedings, volume 47, 1956, A.N. Davidson et al.: "Shrink- resisting wool:'some novel features and the description of a new process", pages 685-707 see page 687, no. 3; page 691, paragraph II end X Journal of the Society of Dyers and 1,2,4-7 Colorists, volume 57, 1941, W.R. Middlebrook et al.: "The application of enzymes to the production of shrinkage-resistant wool and mixture fabrics", pages

137-144 see the whole article X Textil-Praxis, volume 18, no. 3, March 1,2,4-7 1963, E.P. Frieser: "Das Filzfreiaus- rUsten von Wolle", pages 236-237 SSpecial categories of cited documents: 10 later document published after the International filing date document defnning the general state of the art which is not pority date and not In conflict with the application but considered to be of particular relevance "cited to understand the principle or theory underlying the cnsiderd to bI of particular rlvane nvention earlier document but published on or after the international document of particular relevance; the claimed invention filing date cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive step which is cited to establish the publication date of another document of particular relevance; the claimed invention citation or other special rpason.(as specified) cannot be considered to Involve an inventive step when the document referring to.an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the international filing date but in the art. later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this Iernational Search Report 13th February 1989 MAR 1989 International Searching Authority Snator i cr EUROPEAN PATENT OFFICE jrm PCTIISA20 second heet) (Janu ryD 1 i'rm PCT/ISA/210 (second sheet) (January 1945) m International Application No. PCT/EP 88/00971 III, DOCUMENTS CONSIDERED TO BE RELEVANT (CONTINUED FROM THE SECOND SHEET) Category Citation of Oocument, witm indicationl, where appropriate, of the relevant passages Relevant to Claim No see pages 236-237, left-hand column EP, A, 0134267 (KURASHIKI BOSEKI K.K.) March 1985 see claims; page 3, line 16 -page 7, line BE, A, 536819 (WIRA) 13 February 1959Q see claims 1-7 1,12, 4-7 Form PCT ISA:210 (extra sheat) (January 1945) L FI: I I~ .~CL" ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. EP 8800971 SA 25203 This annex lists the, patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP file on 24/02/89 The European Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Patent document Publication Patent family Publication cited in search report date member(s) date EP-A- 0134267 20-03-85 BE-A- 536819 Smo details about this anne :see Official Journal of the European Patent Office, No. 82 w For more details about this annex see Official Journal of the European Patent Office, No. 12/82