AU619182B2 - Process for dyeing wool and other keratin fibres - Google Patents

Description

v 3 I i i i l~s~u u~ AU-AI-16214/88 ~ZIi~ PCT WORLD IILLE19UAOPY ONIZ N INTERATIONAL APPLICATION UBLISHED UNDER THE P T COOPERATION TR Y PCT) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 4 (11) International Publication Number: WO 88/ 07602 DO6P 3/14, D06M 13/46 Al A61K 7/13, D06P 3/16 (43) International Publication Date: 6 October 1988 (06.10.88) (21) Internatiorial Application Number: PCT/AU88/00086 (81) Designated States: AT (European patent), AU, r3E (European patent), CH (European patent), DE (Euro- (22) International Filing Date: 25 March 1988 (25.03.8,) pean patent), FR (European patent), GB (European patent), IT (European patent), JP, LU (European patent), NL (European patent), SE (European patent), (31) Priority Application Number: PI 1067 US.

(32) Priority Date: 25 March 1987 (25.03.87) Published (33) Priority Country: AU 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 (71) Applicant (for alt designated States except US): COM- of amendments.

MONWEALTH SCIENTIFIC AND INDUSTRIAL RESEARCH ORGANISATION [AU/AU]; Limestone Avenue Campbell, ACT 2601 (AU), (72) Inventor; and A. J.P. 1 DEC 1988 Inventor/Applicant (for US only) RIPPON, John, Anthony [GB/AU]; RMB 2500, Grossmans Road, Torquay, VIC 3228

AUSTRALIAN

(74) Agents: NOONAN, Gregory, J. et al.; Davies Collis- 2 NOV 1988 on, 1 Little Collins Street, Melbourne, VIC 3000 (AU).

PATENT

OFFICE

(54) Title: PROCESS FOR DYEING WOOL AND OTHER KERATIN FIBRES (57'1 Abstract A method of preparing keratin fibres for dyeing, printing or other treatments comprising contacting the fibres with a sodlution containing an amphoteric surfactant but substantially no dye, WO 88/07602 PCT/AU88/00086 1 "PROCESS FOR DYEING WOOL AND OTHER KERATIN FIBRES" The present invention relates to the application o6.dye to keratin fibres, and to products incorporating such fibres.

Wool and other keratinous fibres are usually dyed from acidic liquors that often contain various reagents, in addition to dyes. In conventional wool dyeing, the temperature of the dyebath is usually increased progressively to around 95-100'C, where it is maintained for a time, up to several hours, that depends on the particular dyes that are being applied. These dyeing procedures can consume large amounts of energy. Furthermore, a significant degree of fibre damage can be caused, particularly if the pH oZ the dyebath i5 far removed from the iso-electric region of wool (cr pH The object of the present invention is to enable wool to be dyed in fibre, yarn, fabric or garment form under milder conditions than are now commonly used.

The milder conditions may be shorter times and/or lover temperatures than those usually required in conventional practJcs to give good levelling, exhaustion and fastness properties. This results in benefits in terms of less fibre damage, less yellowing and savings in time and energy consumption, coWpared with traditional methods, A further objective of this invention is to produce dyeings that are less skittery than those produced by alternative procedures. (Note: "skittery" is a term used to denote an uneven distribution of dye along a fibre.) Anionic, cationic and amphoteric surfactants are used widely in the textile industry, as assistants for L

W

I

I i PCT/AU88/00086 0O 88/07602 dyeing wool and other fibres by exhaustion methods. It is well known that the rate of exhaustion of dyes onto wool is enhanced by addition of certain surfactants to acidic dye liquors (see, for example, Hine, R.J. and McPhee, J.R., Rapid Dyeing of Wool Without Damage, Dyer, 132, p.523 (1964). The compounds that are most commonly used for this purpose are nonionic or amphoteric in nature; their addition to acidic dye liquors gives improvements in the rate of exhaustion and penetration into the fibre of many dyes.

They also produce improvements in the appearance of the resultant dyeings, in terms of decreased skitteriness.

These effects are utilised in low temperature dyeing procedures, in which wool is dyed at temperatures below the boil (usually 75-90'C).

The present invention is based on the unexpected observation that aqueous pretreatment of keratin fibres, such as wool, with an amphoteric surfactant, preferably under alkaline conditions, prior to addition of dyes, increases the rate of exhaustion, rate of penetration and overall uniformity of dyes applied from acidic dyebaths.

The increased rate of penetration enables dyeings of excellent fastness properties and colour yield to be obtained at lower temperatures and/or in shorter times, compared with conventional practice. A feature of the present invention is that a differential dyeing effect is obtained when the pretreated wool is dyed in the same dyebath as untreated material. Treatment with an alkaline solution of an amphoteric surfactant, according to the method described herein, has also been found to SSUBSTITUTE SHEET WI 0O 88/07602 PCT/AU88/00086 -3provide an effective pretreatment for the application of dyes in the form of conventional print pastes to wool substrates. Thus, the surfactant/alkali treatement can be used instead of the chlorination procedures commonly employed in industry. Furthermore, it has' been found that the pretreatment can be applied to wool in the form of a paste containing the amphoteric surfactant, an alkali and thickening agent. The printed fabric is stored for a time between 1 min and 24 hr, precautions being taken to prevent the printed area from drying-out. After the chemicals have been washed from the fabric, the latter can be dyed immediately or dried and dyed later. When the fabric is dyed, a "tone-on-tone" effect is produced, with the printed regions dyed to a deeper shad than the base fabric.

The invention accordingly provides a method of preparing keratin fibres for dyeing, printing or other treatments comprising contacting the fibres with a4solution, preferably aqueous, containing an amphoteric surfactant but substantially no dye.

The invention also provides a method of applying dye to keratin fibres comprising pretreating the fibres by contacting them with,& solution, preferably aqueous, of an amphoteric surfactant, and thereafter applying dye to the pretreated fibres.

As extremely low concentrations of surfactant can improve dyeing properties of the fibres, there is no absolute lower limit for the amount of surfactant which WO 88/07602 PCT/AU88/0 0 086 WO 88/07602 -4needs to be used. However, for optimum results it is preferred that the weight of surfactant is at least equal to 0.1% of the weight of the fibre being treated.

An important feature of this invention is that the improvements in dyeing properties, obtained by pretreatment with an amphoteric sv, actant, are superior to the well-known effects described above, obtained by adding amphoteric or nonionic surfactants directly to acidic dye liquors.

The pretreatment can be applied, for example, by a long liquor method, or by padding or printing.

The dye can be applied by any suitable conventional technique, whether by way of simple dyeing or by way of printing.

I

W2 PCT/AU88/00 0 8 6 WO 88/07602 The amphoteric surfactants used for the purposes of the present invention may contain a variety of cationic and anionic groups. The preferred type of cationic groups are amine salt, quaternary nitrogen, pyridinium or substituted imidazoline groups and the anionic groups are carboxyl, sulphate ester or sulphonic acid moieties. The amphoteric reagents can contain more than one type of cationic and/or anionic group; they may also contain other types of groupings that are neutral in character, for example hydrocarbon or alkylene oxide chains.

Particularly useful are the following types of amphoteric surfactants: N-alkyl betaines and sulphobetaines of the type: R2 RiI I (CH 2 )nX-

R

3

R

I

R

2 and R 3 are alkyl groups; n Z 1; X- is either -COO- or -SO03 Alkyl-amide betaines and sulphobetaines of the type: R2 R1 CONH (CH 2 )n M (CH 2 m

X

R3 RI, R 2 and R 3 are alkyl groups; m 1; n 1 X- is either -CuO- or -s03 SSUSSTITUTE SHEET PCT/AU88/00086 wO 88/07602 -6- Amphoteric surfactants of the following type:

(CH

2 CH2 0 )m X 1 N- (CH2 CH2 0)n H

Y

R1 is an alkyl group, usually containing less than 22 Carbon atoms.

Im and n are usually between 1 and X is -COO-; -S0 3 or -OS0 3 Y is an amideqor other fatty acid derivative.

Amphoteric surfv"tants of the following type:

CH

2 N CH 2

C

2

H

4 0R 1 II I/ R C N+ X CH2Y R is a fatty acid radical.

R

1 is H, Na or CH 2

COQM.

ncc- c\ a"Non or X is OH, an aci" .A s- an anionic surface active sulphate or sulphonate.

.Y is COOM, CH 2 COOM or CHCH 2

SO

3

M

OH

M is Na, H or an organic base.

Amphoteric surfactants are often supplied in mixtures that also contain other types of surfactants, e.g.

nonionir, ca(ionic or anionic.

Cnmmercial products, containing amphoteric surfactants, that have been found to be effective include S the following: Albegal B (Ciba-Geigy), Abegal SET (Ciba- S -SUBS71TUTE

SHEET

PCT/AU88/00086 WO 88/07602 -7- Geigy), Avolan UL75 (Bayer), Avolan RE (Bayer), Keriolan A (CHT-Tabingen), Leveller NR (Holliday), Lyogen FN (Sandbz), Transferin KW (Dr. TH. Bohme), Uniperol SE (BASF) and Remol GES (Hoechst). However, other amphot ric reagents and products containing these reagents, particularly these used in the dyeing of wool or nylon, are also suitable for use according to the method described in the present invention.

The amount of surfactant required depends upon the percentage of the active constituent in the product; however, in general, this is in the range 0.1-20 g/1, when applied at a liquor ratio of 30:1.

As discussed above, the pretreatment is pref ab*y carried out under alkaline conditions. Although some improvements in dyeing rate are obtained when wool is pretreated with amphoteric surfactants from acidic liquors, optimum results are obtained only when the pretreatment is carried out at an alkaline pH value.

The most suitable pH values are in the range pH 7-11.

The pH value of the pretreatment liquor can be set by any convenient method, using organic or inorganic reagents, or mixtures of these. It is convenient, although not essential, to use a buffered system because this ensures that the maximum degree of repoducibility of the effect is obtained. A particularly useful treatment pH is in the range pH 8-8.5, because this provides the optimum improvement in dyeing rate whilst minimising the possibility of alkaline degradation of the fibre.

,l- O 8 2 PCT/AU88/000 8 6 WO 88/07602 -8- The treatment can be carried out at any temperature in the range 5-100°C. Temperatures that are particularly suitable are those commonly used for scouring wool, viz.

20-50°C. Although any treatment time from one minute to several hours can be used, times of 10-60 mins. are particularly suitable.

An especially advantageous application of the invention is to wool fibres. An advantage of the I process is that the treatment can be included in the normal sequence of wool processing. For example, as a pretreatment prior to the dyeing of loose stock, sliver, top, yarn, or fabric, the latter including fabric in the form of garments. The treatment can also be applied as part of the final stages of raw wool scouring. Application of the dye to a fabric can be in the form of a print paste, whereby to produce a print on the fabric. The method may comprise the further step of dyeing the printed fabric.

A further advantage of this invention is that the treated material can be dyed immediately, or dried and dyed at some later time, without any loss of the effect. The fibres may be pretreated as, e.g. raw scoured wool fibres or yarn, and incorporated into a fabric between said pretreatment and said application of dye to the fibres.

WO 88/07602 pCT/AU88/00086 -9- All classes of dyes used for the colouration of keratin fibres may be used; e.g. acid levelling,.

acid milling, 1:1 premetallised, 1:2 premetallised, chrome, reactive and vat dyes.

The keratin fibres that can be treated will normally be new or reprocessed wool from sheep. This can include wool that has been modified, for example, by a shrink-resist or otier treatment. The keratin fibres may, however, also be derived from the following sources: alpaca, angora, cashmere, mohair, vicuna, guanaco, rabbit, camel, llama or human hair; or blends of t:.ese fibres with the wool from sheep. The material may consist wholly of keratinous fibres, or of blends with synthetic fibrous and filamentary material, or with natural or regenerated cellulosic fibres.

~f WO 88/07602 PcT/AU88/00086 In the case of human hair, the pretreatment is preferably carried out under neutral or'slightly alkaline conditions, at room temperature. It may be applied either after shampooing, or as part of a shampooing procedure. In either case, the amphoteric surfactant is advantageously left in contact with the hair for 5-60 min, before rinsing. The pretreated hair is then dyed with a suitable formulation used for colouration. The advantage of the pretreatment is an improvement in the penetration of the hair dye and hence better colour yield and fastness to shampooing, compared with untreated hair.

The invention is illustrated by the following examples.

EXAMPTL 1 Samples of a pure wool, woven worsted fabric were treated, at a liquor:goods ratio of 28:1, for 2 hours at with solutions of Albegal B (1 set to various pH values l)y means of "Universal" buffer (A Textbook of Quantitative Inorganic Analysis, A.I. Vogel, Longmans, Green and Co. (1951), y. 872). The samples were rinsed with water and then dyed, at 40'C and a liquor ratio of 28:1,. with .I.

Acid Red 18 (t1 ovw). The dyebaths were buffered to pH with sodium acetate and acetic acid. Dyebath exhaustions were measured spectrophotometrically. The rates of exhaustion, expressed in terms of time to 50% exhaustion and the dyebath exhaustion after 120 sin. (E 1 2 0 are shown in Table 1. Also shown, for comparison, are the values for the above parameters, obtained for wool fabrics treated with the buffer solutionrn only.

SUBSTIUTE

SHEET

VVIo 88/07602 PCr/AU88/00086 -11- TABLE I Buffer Albegal B Buffer Only pH of pretreatment liquor T (min) E 120 T4 (min) E 120 (1) 4 170 40 200 37 120 50 200 6 62 78 195 32 7 43 95 160 42 8 43 96 195 9 40 94 150 44 38 93 160 31 Untreated fabric T4 200 min E120 The fabrics pretreated with Albegal B were superior, in terms of higher colour yield and lower skitteriness, compared with those pretreated with the buffer alone. The improvements were most marked for the samples pretreated at pH values of 7 and above.

EXAMPLE 2 Samples of a pure wool woven worsted fabric were treated for various times at 40" or 50'C and a liquor:goods ratio of 28:1, with an aqueous liquor of the following composition: Albegal B product oww), disodium hydrogen phosphate (1.6 g/1) and sodium dihydrogen phosphate (0.1 The pH value of the liquor varied from 8.2 to during the course of the treatment, The samples were rinsed with water and dyed, as described in Example 1. The dye exhausted more rapidly onto the treated fabrics compared with untreated wool, as shown by the values for the times to SUBSTITUTE SHEET WO 8807602PCT/AU88/0 00 86 -12exhaustion and the dye liquor exhaustions after 120 min CE12o) in Table 2.

TABLEL2 Pretreatment L~ .C Pretreatment Temp. 508C Pretraitment Tine-~- (min) T% 1 (min) E120 (min) Ta 1 (min) 1120 (min) 0 200 35 200 75 so 70 48 92 44 89 40 96 36 97 32 99 32 9 120 28 100 28 100 After rinsing and drying, it was apparent that the pretreated, dyed fabrics had a hiqjher crlour yield and were less skittery than the untreated, dyed samples.

it is vell know In the Prior art that addition of amphoterie or nonionic surfactants to dyebaths increases the rate of uptake of dyes by wool. However, the improvements in dyeing rate obtained by treatments carried out according to the present invention are greater than thoot obtaij!'md by addition of surfactant to the dyebath. This is il, itrated by the following example.

Saw-les of the wool fabric were treated, at a liquor:goods ratio of 28:1, for 30 min at 400C in an aqueous solution of Albegal B (24 product oww). The solution was buffered to PH 8-8.2 as described in Example 2. The samples were rinsed and then the treated samplest and also untreated

A,

I

I

II

II

Ii 14

I)

IL

PCT/AU88/00086 WO 88/07602 -13controls, were dyed as described in Example 1. Surfactants were added to the dyebaths as indicated in Table 3, which also shows the rates of exhaustion of the liquors (expressed in terms of Tb),.

Ti (an) Surfactant added to dyobath Untreated Fabric pretreated fabric with Albegal B None 200 49 ow Nonionic 126 48 ow 110 oww 169 oww Albegal B 113 56 ow 108 54 ow 100 58 A nonylphenol/ethylene oxide condensate, containing an average of 8 moles of ethylene oxide per mole of nonylphenol.

^itAMPLa This example illustrates that improvements in the rate of uptake of dyes by wool, produced by the amphoteric surfactant/alkali treatments of the present invention, are also obtained when the wool is dyed at Also demonstrated is the superiority of the new pretreatments compared with the effects of adding a surfactant to the dye liquor, according to the previously known methods for dyeing wool at low temperatures (see, for example, the work of Hine and McPhee described in, Dyer, p.523 (1964).

U, WO 88/07602 -14- Samples of the~ wool fabric were treated with an aqueouz solution of Albegal B, as described in Example 3.

The samples were rinsed and then dyed with Danasol Blue 3G (Ciba-Geigy) oww),. from liquors set at pH 4.5 with a sodium acetate/acetic acid buffer. Where indicated in Table 4, the dyobaths also contained the nonionic surfactant, Liasapol TN450 (ICI). The temperature of the dyebath was held at 401C for 10 Min and then increased to 906C over a period of 60 min, where it was held for a further 40 mi~i. The samples were removed from the liquor, rinsed and dried, T4, (min) ISurfactan~t added to dyebath I Untreated 11 Fabric pretreated fabric with Albegal B None Lispl48 29 ow Lispl37 27 The dyeing. on the pretreated fabrics (column II) were of better colour yield and of less skittery appearance than the control samples (column 1).

A sample of the wool fabric was treated fo~r 30 min with Albegal B, as described in Example 1. The fabric was rinved, dried and then stored for one week before re-wetting and dyeing# as described in Example 1. The value for Tih p.- WO 88/0 17602 PCT/AU88/000 86 obtain ed fQ,r the pretreated and dried fabric was identical to the value obtained for a sample pretreated in a similar manner with Albegal B, but dyed immediately without intermediate drying. Furthermore, the quality of the dyeing on the pretreated fabric was equal to that'on a fabric dyed immediately after the pretreatment. Thu., intermediate drying and storage are not detrimental to the beneficial effects of the treatment.

Samples of the wool fabric were tr:eated, at a liquor:goods ratio of 28:1, for 2 hours at 40*C with solutions containing Compound (1.7 g/J1).

(CH

2

CH

2

O)

7 S0 3

I

H

3 7

C

1 8

(CH

2 C11 2 0) 7 H (I) The solutions were adjusted to pH 8 with sodium carbonate or Ammonium hydroxide. During the course of the treatments, the ]Jquors were maintained at pH 8 by further additio~ns of the above alkaline reagents. The samples were rinsed and dyed, as described in Example 1.

Treatment liquor h(i)E2W additlva Alkali Alkal. Alkali Alkali Only Corspound I Only Compound I Sodium Carbonate 190 32 32 96 Amuonium Hydroxide 180 40 32 93 Untreated 200 WO 8807602PCT/AU88/00 0 86 -16- The values kor Th and E 12 0 in Table 5 show that the surf actant-pretreated samples' were superior, with respect to dyeing rate and final exhaustion, compared with untreated or alkali-treated wool.' Samples of the wool fabric were treata4f at a liquor ratio of 28:1 for 30 min at 404C, in solutions containing 5 9/1 of the various proprietary compounds listedi in Table 6. The solutions were set to pH 8 with the phosphate buffer mixture described in Example 2. The samples were rinsed and dyed as described in Example 1.

Compound T4~ (min) E 120 (1) None 200 29 Albegal SET (Ciba-C*Igy) 124 49 Lyogen FN (Sandoz) 54 81 Avolan UL75 (Bayer) 74 66 Laveller MR (Holliday) 57 al Xeriolan A (CHT TLbingen) 70 71 Transferiu KW (Th lahme) 45 84 Avolan RE (layer) al66 Resol C18 (Hoechst) 60 78 Uniparol- SE (BASF) 35 92 Table 6 indicate. that the pretreatment increased the rate of exhaustion of the dyes, and also inc~eased the equilibrium exhaustion obtained for a dyeing time of 120 min. In all cases the dycings were more level and less skittery than similar dyeings on untreated fabric.

WO 88/07602 PCT/AU88/00086 WO 88/07602 -17- EXAMPLE 8 A sample of the wool fabric was treated, at a liquor ratio of 28:1, for 30 min at 40'C with a solution of Albegal B oww). The solution was set to pH 8 with the phosphate buffer mixture described in Example 2. The sample was rinsed and then dyed at pH 4.5 and 70*C with Lanasol Red 6G (Ciba-Geigy) (1 oww). A level dyeing of good penetration was obtained. The dye liquor was completely exhausted within 20 min, compared with only 36% exhaustion for an untreated sample.

EXAMPLE 9 Samples of the wool fabric were treated for 60 min at 40'C, as described in Example 8, and then rinsed with water. The treated fabrics, and also untreated ramples, were dyed with the dyes indicated in Table 7 by the following method. The bath was set at pH 4,5 with a sodium acetate/acetic acid buffer and the dyeing commenced at After 20 min at 40*C, the temperature of the dye liquor was increased to 80*C over a peri&o of 70 min. The dyebath was maintained at 80*C for 30 ain and then the samples were rinsed and dried in the usual manner.

SUBSTITUTE SHEET 1 -1 WO 88/07602 pIA8/0 8 -18-E f S03 Wash Test Crocking Fastness* Dye Shade Change Cotton Stain Dry Wet Unt. Pro-tr. Unt. Pro-er. Unt. Pre-tr. Tint. Pro-er.

Acidol Red H3R 4 4-5 4-5 5 4-5 4-5 3.4 3.4 Carbolan Blue BS 4-5 4-5 4-5 5 5 5 4-.5 Lanasol Red 6C 5 5 5 5 4-5 5 4-5 *Measured by AAVC TM 8-1981 The pre-triitied samples were evenly dyed and were less skittery than the untreated controls. Furthermore, as shown in Table 7, the dyeings on the pretreated wool were of good fastness to washing and rubbing.

ZXNRLZ-12 A sample of wool fabric was treated at a liquor ratio of 28:1, for 30 min at 409C and pH 8-8.2, with the suiphobetaine, N-hexadecyl N-dimethyl-3 -amino-l -propane suiphonic acid oww). The sample ias rinsed and dyed at pH 4.5 and 40*C with C.1. Acid Red 13 ow), by the method described in Example The values for Th and 2 1 2 0 of 70 min and 68%, respectively, show that the pretreatment inc.reased 7ooth dyeing rate and final exhaustion, compared with untreated wool (tha. values for untreated wool were 200 min and 40%, respectively).

WO 88/07602 WO 8807602PCr/AU88/00086 -19- A sample of wool f abric was treated with a solution containing 5 g/l of either an alkyl betaine (Compound II) or an alkylamido propyl dimethylaxnine betaine (Compound III).

The treatment conditions were as described in Example The samples were then dyed, also by the method described in Example

CH

3 R N- a 2 C00- R CONH(CH 2 3 NL C21 2 C00 Cit 3 COI4PUND II CO1MNhD III In both cases, R is predominantly C 1 2 /C1 4 MiA

F

I

T4 (win) 1120 M% Comnpound 11 83 62 Compound 111 57 s0 Untreated 200 The results in Table 8 show that alkyl betaines and alkcyl amido be~aines can be used, according to the present invention, to improve the dyeing properties of wool, SUBSTITUTE

SHEET

i:i I WO 88/07602 PCT/AU88/00 08 6 Samples of the vool fabric were treated, at a liquor ratio of 28:1 for 30 min at 40*C, in solutions containing 5 g/l of the compounds listed in Table 9. The solutions were set to pH 8 with the phosphate butfer described in Example 2. The samples wer* rinsed and dyed as described in Example 1.

Comercial Ti 2 1 2 0 Compound Nam (min) (1) Triothanolanine salt of 86 63 N-lauryl -myristyl-paminopropionic acid Sodium salt of 57 67 N- lauryl-myristyl-Aaninopropionic acid N-R-0-amnobutyric acid Armeen Z 57 79 (Akzo Chemicals Ltd) OH, conc. 68 [227 (Miraz ol Chemical Co) r+ 1 Miranol HK1 I C 11

H

23

C-NQI

2

CH

2

N(C

2

H

4 0H) (CH 2 CCJ)OH' con. 22 97 Chemical Co) irawol OM.SI C1 7

H

33

C-NI

2

CH

2

N(C

2 W0H) (CH2COO)]OI coac. 79 64 (Mirnol Cheical Co) Note: R is coco fatty acid The results in Table 9 show that pretreatment with the various anphoteric surfactantG increased the dyeing rate and equilibrium exhaustion.

I SUBSTITUTE SHEET .I i PCT/ ,,U88/00086 WO 88/07602 -21- EXAMPLE 13 A sample of a pure wool, woven fabric was treated at a liquor ratio of 28:1, with an aqueous solution of Albegal B (2 g/l) for 30 min at 40*C. The solution was buffered to nH 8-8.2 as described in Example 2. After rinsing and drying, a design was printed onto the fabric with a paste of the following composition: urea thiodiglycol Indalca PA-3 (Cesalpinia) 2% Carbolan Blue BS (ICI) 83% water The printed fabric was dried, steamed for 30 min at 100'C and washed-off for 15 min at 40"C in an aqueous solution of Aerosol OT (Cyanamid) (5 g/l) and 0.880 ammonium hydroxide (5 dried and pressed. The print on the pretreated fabric was deeper and of less skittery appearance, compared with a print on untreated wool.

EXAMPLE 14 A sample of 2/28's worsted yarn was treated, at a liquor ratio of 15:1, for 30 min at 40C with an aqueous solution of Albegal B oww). The solution was buffered to pH 8-8.2, as described in Example 2. The yarn was rinsed several times with water and dried.

A fabric was knitted, consisting of alternate stripes (2 cm wide) of pretreated and untreated (scoured only) yarn. The fabric was dyed with Lanasol Red 6G, SUBSTITUTE SHEET

S(

I l II I m WO 88/0762 PCT/AU88/00 0 8 6 WO 88/07602 -22accordi.g to the method described in Example 8. A differentia? dyeing effect was obtained, with the portions of the fabric constructed from the pretreated yarn being more deeply dyed than the parts knitted from untreated yarn.

EXAMPLE A design was printed onto a pure wool fabric with a paste of the following composition: 2% Albegal B 0.2% Sodium carbonate Solvitosegum OFA (Avebe) 92.8% water.

The fabric was covered with polythene, to prevent the printed area from drying out, and stored for 60 min at room temperature. The fabric was wvshed-off in warm water containing acetic acid (1 g/1) and then dyed with Acidol Brilliant Blue M5G oww) at pH 4.5. The dyebath was heated from 40'C to 85"C at 1'C/min and held at the latter temperature for 30 min. The sample was rinsed and dried.

The printed design was dyed more deeply than the remainder of the fabric a "tone-on-tone" effect).

BSTITUTE SHET SUBSTITUTE SHEET

"I

Claims (16)

1. A method of applying dye to keratin fibres comprising pretreating the fibres by contacting them with an alkaline solution of an amphoteric surfactant, and thereafter applying dye to the pretreated fibres.

2. A method according to claim 1 wherein said alkaline solution has a pH in the range 7 to 11.

3. A method according to claim 1 wherein said elkaline solution has a pH in the range 8 to 15 4. A method according to any preceding <laim wherein the surfactant is present in the. amount of at least 0.1% w/w with respect to the fibres. A method according to any preceding claim wherein said pretreatment is carried out at a temperature in the range 5 to 100°C.

6. A method according to claim 5 wherein said pretreatment is carried out at a temperature in the range 20 to

7. A method according to any preceding claim wherein said pretreatment is carried out for a period in the range 10 to 60 mins.

8. A method according to any preceding claim wherein said Ssolution is an aqueous solution. 9t0411,GJNDAT.039,I(214op,23 r I t~ .i I~ ./FCrI Al TO i00 rflOd Wu 88/0u7602 -24- r U Avo JZ A method according to any preceding claim wherein said amphoteric surfactant contains cationic groups selected from the set comprising amine salt, quaternary nitrogen, pyridinium and substituted imidazoline groups, and further contains anionic groups selected from the set comprising carboxyl, sulphate ester and sulphonic acid moiety groups. A'method according to any one of claims 1 to 9 wherein said amphoteric surfactant is selected from the set comprising:- N alkyl betaines and sulphobetaines of the type:- R2 R (CH 2 )nX- R3 KI Ri, R 2 and R3 are alkyl groups; n a 1; X- is etther -COO- or -SO alkyl amide betaines and sulphobetaines of the type; R2 1 CON (C (CH2)n (C 2 X R3 RI, R 2 and R3 are alkyl groups a k 1; n 1 X is either -COO- or -SOc surfactants of the type:- (CH2 02 O)n X Ri N- (CH 2 C2 O)n H Y Ri is an alkyl group, usually containing less than 22 carbon atoms. m and n are usually between 1 and X_ is -COO'; -S03o; or -oso 3 Y is an amide or other fatty acid derivative, SUBSTfl)TE SHEET VUVoo WO 88/07602 PCT/AU88/00086 and surfactants of the type:- CH 2 N CH 2 C 2 H 4 0R 1 R-C- -N X- CH 2 Y R is a fatty acid radical. RI is H, Na or CH 2 COOM. X is OH, an acid saan anionic surface active sulphate or suiphonate. Y is COOM, CH 2 COOM or CHCH 2 SO3M OH M is Na, H or an organic base. IZ-. A method according to any preceding claim wherein the fibres are wool fibres. A method according to arny preceding claim wherein the fibres are in a fabric. A. 3 A method according to claim 19 wherein the dye is applied to the pretreated fibres of the fabric in the form of a print paste, whereby to produce a print on the fabric. 13 t A method according to claimit further comprising 4 dyeing the printed fabric. S rII IE A method according to any one of claims 1 tojtE wherein the wool fibres are pretreated while raw scoured fibres or while in a yarn. It. A method according to any preceding claim wherein the fibres are incorporated into a fabric between said pretreatment and said application of dye to the fibres. fr- -26-

17. A method of preparing keratin fibres for dyeing, printing or other treatments comprising contacting the fibres with an alkaline solution containing an amphoteric surfactant but substantially no dye.

18. A method according to claim 17 wherein said alkaline solution has a pH in the range 7 to 11.

19. A method according to claim 18 wherein said alkaline solution ha a pH in the range 8 to

20. A method according to any one of claims 17 to 19 wherein the surfactant is present in the amount of at least 0,1% w/w with respect to the fibres.

21. A method according to any one of claims 17 to carried out at a temperature in the range 5 to 100"C.

22. A .ethod according to claim 21, carried out at a temperature in the range 20 to 50 0 C.

23. A method according to any one of claims 17 to 22, carried out for a period in the range 10 to i mins.

24. A mefhod according to any one of claims 17 to 23 wherein said solution isI an aqueous solution. 0 A m .hod according to any one of claims 17 to 24 Wherein said amphoteric surfactant contains cationic groups selected from the set comp.'ising amine salt, quaternary nitrogen, pyridinium and substituted imidazoline groups, and further contains anionic groups selected from the set comprising carboxyl, sulphate ester and sulphonic acid moiety groups.

26. A method according to any one of claims 17 to 910411,GJNDAT.039,16214.p,26 27 wherein the fibres are wool f ibres.

27. A method according to any one of claims 17 to 26 wherein the wool fibres are in a fabric. DATED this 9th day of A~pril 1991 s. S OOOQ S SSSSSO 0 S. 0 S. S* SS S 0 OSS S S Commonwealth Scientific Organisation By its Patent Attorneys DAVIES COLLISON and industrial Research 0 OSS*SS S OS.. 0S 5S 0 5.9. 0 OOOS 00 0 5* SS 0 *SOSSO S S 91041 I.GJNDAT.039,16214.cop,27 &--jaw-c .Lv61 afld less skittery than similar dyeings on untreated fabric. It ~-il 4 .1 INTERNATIONAL SEARCH REPORTI International Application NoPCT/AU88/00086 1. CLASSIFICATION OF SU1BJECT MATTER (it several classlfcllon symbols apply. Indicate all) According to International Patent Classification (IPC ot to bolth National Classification and IPC Int. C1. 4 D06P 3/14, D06M 13/40, A61K 7/13, D06P 3/16 It, FIELDS SEARCHED Minimum Documentation Searched Clasuification System Classificatlon Symbols IPC j A61K 7/13, D06P 3/14, D06P 3/16, D06P 5/22, D06P 5/00, D06P 3/06, D06M 13/46 Documnation Saarched other than Minimum Documentation to the Extent that such Documients are Included In the Fields SearchedI AU:IPC as above Ill. DOCUMENTS CONSIDERED TO BE RELEVANT' Caaqo~y j Citation of Document, 11 with Indication, where appropriate, of the relevant passages 13 Rtelevant to( C im No. is Y AU, A, 32643/78 (CIBA GEIGY 2 August 1979 1 (1-12) (02.08.79) See page 15 lines 10-20 X, Y AU, B, 66438/74 (484180) (GAF Corporation) (18-21) 11 September 1975 (11.09.75) (26-27) Y US, A, 3619106 k"'Oreal) 9 November 1971 (09.11.71) (1-12) X, Y AU, B, 32642/78 (514734) (CIBA GEIGY 2 August 1979 (02.08.79) 5, 12) Y GB, A, 1444426 (SANDOZ LTD) 28 July 1976 (28.07.16) (1-12) Y AU, B, 49923/79 (535617) (COMMONWEALTH SCIENTIFIC 11) AND INDUSTRIAL RESEARCH ORGANISATION AND and 13) IWS NOMINEE COMPANY LTD) 1 May 1980 (01.05.80) Y US, A, 4293543 (SOCIETE NATIONALE ELF AQUITAINE) (18-27) 6 October 1981 (06.10.81) Y DE, A, 2520700 (WELLA 18 November 1976 (18) (18.11,76) (continued.. Special categories of cited documents, 10 later document published atear the International filing date document defining the general state of the art which Is not or Priority date and not In. conict wit h the application but conaidered to be ot particular relevance tited to understand the principle or theory undertying the lla doumet bt pulised n o afer te iteratinal Invention 0E eiirdcmn u ulse o ratrteItraint X* document of particular relevance; the claimed invention filng atecannot be considtered~ novel or cannot be considered to document which may throw doubts on priority claim(s) or Involve an Inventive, atop which Is cited to establish the publication data of another oueto.atclrrivne h lie neto Citation or other special reason as specilled) dcn t f consiurred ivi nentv e staied whventhen O0" document referring to an oral disclosure, use, exhibition or document Is combined with one or more other such docu- other means mnents, such combination being obvious to a person skilled document Published Prior to the International filing date but In the art, later than the ,riority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search Dnle of Mailing of, t, Is International Search Report 18.07.88 (yo7t 1~~9g. e International Searching Authority, Signature o1 Authorized Officer AUSTRALIAN PATENT OFFICE J.P. PULVIRENTI I~j Form PCTIISA/2iO 40icond sheet) (January 1905) ia~ I 4 International ADPllcatlon No. PCT/AU88/0 0086 ~1 Ill. DOCUMENTS CONSIDERED TO BE RELEVJANT (CONTINUED FROM THE SECOND SHEET) Category citation of Document. with indication, WIere appropriate. or the relevant passages Relevant to Claim No AU, A, 69181/87 (CIBA GEIGY 27 August 1987 (2 Patents Abstracts of Japan, C-70, page 27, JP, A, 54-140739 (SHISEIDO 11 January. 1979 US, A, 4425132 (L'OREAL) 10 January 1984'(10.01.84) US, A, 4615709 (IPPOSHA OIL INDUSTRIES' CO. LTD. JAPAN) 7 October 1986 (07.10.86) AU, B, 21426/83 (552316) (BRISTOL-MYERS COMPANY) 14 June 1984 (14.06.84) AU, B, 15303/76 (498883) (L'OREAL) 26 January 1978 (26.01.78) (18-22) (18) (1, (18) (18) Fotm PCTfiSA12IO (*%itsa shoot) (January ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL APPLICATION NO. PCT/AU 88/00086 This Annex lists the known publication level patent family members relating to the patent documents cited in the above-mentioned international search report. The Australian Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Patent Document Cited in Search Patent Family Members Report AU 32643/78 DE 2802304 FR 2393876 JP 53094671 LU 76634 AU 664.174 BR 7402654 CA 1038766 CH 601473 DE 2416018 FR 2224445 GB 1470712 IT 1010925 JP 50051984 NL 7404799 US 4132657 BE 813502 US 4138371 CA 1073309 DE 2643795 FR 2363627 NL 7612899 BR 7606808 DE 2643794 FR 2347342 NL 7612898 BE 661515 DE 1469791 LU 45729 US 3619106 NL 6503668 DE 1518077 DE 1794377 NL 6507939 US 3549602 BE 665026 AU 32642/78 BE 863190 CA 1146570 CH 645231 DE 2802305 ES 466255 FR 2393875 GB 1562062 JP 53094395 LU 76633 NL 7800545 US 4343620 US 4615837 ZA 7800402 BE 806372 CH 15473/72 DE 2352465 ES 419821 FR 2203907 GB 1444426 IT 1008582 NL 7314403 AU 49923/79 CH 631312 DE 2927909 FR 2431002 GB 2025471 IT 1122578 JP 55036381 NL 7905491 PL 217049 US 4455147 DE 3037497 FR 2466492 GB 2062016 IT 1133801 ANNEX/CONTnU 23/kk/83/J. ANNEX TOD THE INTENATIONAL SEARCH R~EPORT ON INTERNATIONAL APPLICATIONNO. PCT/AU 88/0086 (CONI'INUED) Patent Doc-irnnt Cited in Search Patent Family Memnbers Report US 42935.43 FR 2491080 AU 69181/87 EP 235088 J3P 62205050 ZA 8701324 BE 875342 CA 1142856 CH 642255 DE 2913755 FR 2421607 GB 2018302 IT 1117647 JP 55006571 US 4425132 JP 60134080 US 4615709 AU 21426/83 BE 898397 BR 8306691, CA 1201067 CH 655654 DE 3341053 DK 5614/83 ES 527728 ES 8503506 FI 834430 FR 2536993 GB 8332591 GB 2132464 GB 2132642 JP 59144712 NL 8304157 NO 834454 NZ 206182 PT 77787 SE 8306730 ZA 8308098 END OF ANNEX 23/kk/83/2