GB1570387A - Colouring of textile materials - Google Patents

Description

(54) COLOURING OF TEXTILE MATERIALS (71) We, I.W.S. NOMINEE COM PANY LIMITED, a British Company, of Wool House, Carlton Gardens, London, S.W.1, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to the colouring of textile materials and more particularly to a method of producing novel dyeing and printing effects on textile materials such as fabrics and garments, preferably those comprising keratin fibres.

In the clothing trade, particularly the fashion clothing section, there is always a demand for new and unusual visual effects for instance, in garment construction, style and decoration.

We have now devised a method of producing a contrasting coloured effect for textile materials which is principally applicable to made-up garments but may also be used on textile piece goods.

We have now found in accordance with this invention, that by printing dye resist agents onto a fabric or garment comprising keratin fibres, fixing the agents thereafter, and overdyeing with at least one dye resisted by the printed area, contrasting colour effects may be produced.

A selected area of the fabric or garment is printed with an aqueous composition containing a dye resist agent and an amide or thioamide, the impregnated fabric, stored in the presence of moisture to fix the dye resist agent, and the fabric or garment thereafter dyed with at least one dye resisted by the printed area whereby the printed area retains a contrasting appearance against a coloured background.

The preferred conditions for fixation of the dye resist agent, more especially of a "reactive" agent on keratin fibres, are a pH value in the range 2 to 7 and a temperature of 10 to 60"C, in the presence of urea or thiourea. In some cases it may be desirable to wash the fabric after the storage step and, when a dye resist agent behaving like a blank reactive dye is used, the washing liquor is preferably as aqueous solution of a base or reducing agent.

The fabric or garment printed with the dye resist agent according to this invention is stored before subsequent dyeing, the invention thus also resides in the process of applying the resist agent by printing and moist storage, and in the resulting printed fabric.

Differential colouring of such fabrics can then be developed by subjecting them to a conventional dyeing process at a later date, with dyes appropriate to the resist agent applied.

In a preferred embodiment of the invention, the dye-resist agent is applied in admixture with a highly reactive dye to the fabric, i.e. as reactive as the resist agent where the latter is reactive. The dye, being highly reactive, fixes in situ with the dye resist, but on subsequent over-dyeing the dyed area will take up virtually none of the overdyed shade thus producing a two-coloured design on the fabric.

The local application of a dye resist agent in admixture with a reactive dye can give good results on subsequent overdyeing when the dye is fixed by other or conventional techniques, for example steaming or baking, instead of by the moist storage technique described above.

Accordingly a further aspect of the present invention provides a method of colouring a fabric or garment of keratinous fibres which comprises printing a selected area of the fabric or garment with a dye resist agent and a reactive dye, fixing the print, and thereafter dyeing the printed and fixed fabric or garment with at least one dye resisted by the printed area whereby the printed area retains a contrasting appearance against a coloured background.

In a further modification two or more different concentrations of dye resist agent may be printed, with or without highly reactive dyes in admixture. Thus a number of different shades and tones may be pro duced in any desired pattem.

It is to be understood that the term 'dye resist agent' as used herein is used in the sense, recognised in the dyeing field, of including substances which in some circumstances are dye attractants. For example, an agent which resists acid dyestuffs may well also be an attractant for basic dyestuffs and vice verso Thus the possibility of further effects is opened up by a suitable choice of the dyestuffs used in the overdyeing step.

In order to produce a garment which is washable in a domestic washing machine, we prefer to treat garments comprising keratin fibres with a shrink-resist resin following chlorination, to meet the desired standards of stability to washing.

Resin treatments, such as those described in our British Patents Nos. 1,074,731 and 1,174,822, and in Belgian Patent No. 789,701 are preferred. These treatments employ a polyamide/epichlorohydrin resin, such as "Hercosett 57" (Trade Mark -- Hercules), or a combined treatment with a polyamide/ epichlorohydrin resin and a cross-linkable acrylate polymer, such as SRevertex A272" (Trade Mark).

In a dye-resist treatment of textile fibres, the affinity of the fibres for dyes or for a particular class of dye, or the rate of dyeing is reduced. The fibre is made less accessible to the dye by the formation of a physical barrier, or the active chemical groups in the fibre, for example amine and thiol groups, are reduced in number by blocking or by reaction with a colourless or "blank" dye. In the case of keratin fibres, glyoxal-sodium bisulphite, which blocks guanidine end groups, or treatment with sulphonic acid or ammonium imidodisulphonic acid (Resilan Process) may bemused. Various tin compounds, such as stannous chloride may also be used.

It is currently preferred to employ as dye resist agents for the purposes of this invention reactive resist agents or colourless reactive "dyes", such as Sandospace R (Sandoz), or Paranyl B (Francolour). These compounds act as dye resist agents to anionic dyes but may increase affinity for cationic (basic) dyes.

Chemically representative of such agents are halogen-substituted di- or triazinyl compounds in which an aromatic group, e.g.

phenyl, substituted with one or more anionic groups, e.g. sulphonate or phosphate, is attached to the heterocyclic ring through an amino group. By way of example, Sandospace R is a blank reactive dye of heterocyclic structure, and is believed to have the formula which is disclosed in British Specification No. 1,410,552:

It has been found that Sandospace R is equally effective on untreated, chlorinated, acrylate polymer or polyamide/epichlorohydrin treated wool and application levels of 68% in the print paste are preferred, although slightly better results can be obtained with higher dosages, e.g. to 10% or more.

A chlorination aftertreatment does not dramatically affect the dye resist properties of Sandospace R-treated material, although the effect is reduced to some extent. This reduction may be overcome by applying higher dosages of Sandospace R.

Sandospace R treatment does not affect the exhaustion of polyamide/epichlorohydrin resins on to chlorinated wool. With the acrylate polymer process, in which the resin will probably be applied before Sandospace treatment, it appears that the resin system is unaffected.

In making the print paste for the dyeresist agent or dye-resist and dye, it is usual to add various conventional printing aids as well as the amide or thio-amide.

Thus, surfactants or wetting agents may he used and may be either anionic, non-ionic or cationic. Thickeners, levelling agents, antifoaming agents may all be used as is well understood in the printing art.

In addition, when using high (e.g. 68%) concentrations of dye-resist agents such as Sandospace R it is preferable to include about 2-3% of reducing agent, e.g. sodium sulphite in the print paste.

The acid amide or thio-amide may be e.g.

urea, thiourea, guanidine or their derivatives, but urea is preferred. The concentration of amide should be at least 10%, and preferably about 30% is employed.

Various reducing agents can be used for washing off the resist prints, and for the present purpose a reducing agent is a substance which is capable of breaking disulphide bonds in the keratin molecule bilt does not react chemically with constituents of the printing composition. Suitable reducing agents include alkali metal, ammonium and amine sulphites and bisulphites, for example, sodium bisulphite, sodium metabisulphite, and monoethanolamine bisulphite, certain quaternary phosphonium compounds, for example, tetrakis - (hydroxymethyl) - phosphonium chloride, sodium borohydride and thioglycollic acid. Various bases can be used which can comprise alkali metal or ammonium oxides and hydroxides, salts of strong bases and weak acids, tor example, sodium bicarbonate, water-soluble aliphatic amines, for example dimethylamine. The reducing agents or bases are employed in the form of aqueous solutions which contain preferably 0.1 to 2.0% by weight of the dissolved material based on the weight of the solution. Ammonia is the preferred agent to use in the after-treatment of the prints prior to over dyeing.

The dyeing of fabrics printed with dye resist agent by the process according to the invention can be performed by conventional techniques.

The amount of dye taken up from a dyebath by material treated with Sandospace R gradually increases as the amount of dye applied is increased. However, the amount required for over-dyeing will differ with individual dyes, depending upon their colour strength. With Lanasol Blue 3G, which has a high colour strength, application of up to 0.75% on the weight of wool (o.w.w.) is recommended. This is because with higher dosages, although there is a large difference in the actual amounts of dye taken up by the Sandospace R-treated material and by untreated material, the degree of contrast is reduced.

Generally, Sandospace R is effective with reactive, and selected acid milling 2:1 premetallised and chrome dyes, but with dyestuffs normally applied under strongly acid conditions (such as acid levelling and 1:1 premetallised types) then the effect is markedly reduced. With the chrome dyes, the Metachrome method produces the better results, followed by the normal method and finally the chrome mordant technique.

If a highly reactive dye is to be applied simultaneously with the resist agent it is preferred to use one of the 'Procion M' range (Trade Mark - ICI) as these react very quickly with wool.

Table I shows the results of overdyeing with various dyes tested on wool material treated with Sandospace R.

TABLE I Effect of Dye Class

Dye Degree of Dye Class Exhaustion Contrast Reactive Drimalan Brilliant Blue F2RL ,, ,, Excellent Drimalan Brilliant Red F2BL Lanasol Blue 3R 91% Lanasol Blue G 79% Lanasol Scarlet 2R 62% Lanasol Red G 82% Lanasol Red B 88% Lanasol Red 5B 88% Lanasol Yellow 4G 84% Acid Levelling Lissamine Blue Moderate None Naphthaline Ink Scarlet 4R Good None Acid Milling Irganol Violet FLS Very good Excellent Carbolan Green SG " ,, 2:1 Irgalan Blue GL Very good Very good Premetallised Elbelan Bordeaux NGL ,, " Excellent Elbelan Navy NRD " ,, Very good Elbelan Orange N2R ,, r, Excellent TABLE I (Continued) Effect of Dye Class

Dye Degree of Dye Class Exhaustion Contrast 1::1 Neolan Red REG Moderate I Poor Premetallised Premetallised Chrome Eriochrome Red G-Normal Very good Very good -Metachrome Good Excellent -Mordant Very good Moderate Eriochrome Azurol B -Normal Good Moderate -Metachrome Moderate Very good -Mordant Very good Poor-Moderate Although Sandospace R-treated material possesses very good resist properties to acid dyes, it shows the reverse effect with basic dyes, i.e. the treated material dyes darker than the untreated.Therefore, when overdyeing Sandospace-printed material with à combination of acid and basic dyes, the unprinted areas take up the majority of the acid dyes, whilst the printed areas take up the majority of the basic dye. This, therefore, is an alternative method of producing prints which are paler than and/or of a different colour from that of the ground.

Since the preferred technique requires an overdyeing cycle, it is therefore generally applicable to undyed garments.

With untreated garments, the printing operation can be carried out before wet finishing or after the chlorination stage i.e.

just before the dyeing cycle. It is found however, that the latter route produces the better results in terms of print definition and dyeing levelness. Chlorination treatment is found to have only a slight effect upon the dye resist effect. When printing chlorinated garments a drying stage is required before the printing operation. With this routine, despite the fact that the dyeing cycle is carried out after printing, no skittery or frosty dyeing effects have been encountered with garments printed with 6.S8.0% Sandospace R.

With this technique, attractive three tone effects can be obtained by printing with two levels of Sandospace R.

The following are examples only of the practical application of this invention.

Example 1.

The following are two examples of typical print pastes for use in the process of this invention: Urea 30.0% 30.0% Galacto-mannan thickening agent (Indalca PA/1) 3.0% 3.0% Sodium phosphate seques tering agent (Calgon PT) 0.6% 0.6% Fatty acid amide non ionic printing assistant (Matexil PN-VP) 1.0% 1.0% Antifoaming agent 0.2% 0.2% Resist agent (Sandospace R) 4.0 , o 6.0% Reactive dye (Procion range) - 2.0% Sodium bisulphite 2.0% 2.0% Water to 100.0% 100.0% The words INDALCA, CALGON and MATEXIL are Trade Marks.

Because of a slight evolution of sulphur dioxide, which may occur, it is recommended that the printing operation be carried out in a well ventilated area.

Wool fabrics printed with these pastes, batched moist until the resist agent is fixed and washed off with dilute ammonia, can subsequently be dyed by conventional dyeing techniques to give two-tones coloured effects.

Example 2.

Samples of chlorinated wool fabric (3.5% o.w.w. Fichlor 60S at pH 3.5) were printed with pastes containing 6.0% Sandospace R/ 2.0% bisulphite and batched moist for 24 hours, after which they were washed off under alkaline conditions. They were then overdyed, along with an equal weight of unprinted material, using 2.0% (on the weight of untreated material) of the various reactive dyestuffs mentioned in Table I using a conventional Drimalan F dye cycle. The samples were finally treated with 2.5% (o.w.w.) Hercosett (Trade Mark) 57. An attractive toned effect was obtained on each printed sample.

Example 3.

Samples of chlorinated botany fabric were printed with the following paste composition.

Urea 30.0% Galacta-mannan thickening agent (Indalca PA/1) 3.0% Sodium phosphate sequestering agent (Calgon PT) 0.6% Fatty acid amide non-ionic wet ting agent (Matexil PN-VP) 1.0% Anti-foaming agent 0.2% Resist Agent (Sandospace R powder) 6.0% Sodium sulphite (anhydrous) 3.0% Water to 100.0% The printed samples were then maintained in a wet condition, by covering with impermeable sheeting, for 24 hours and then washed off in dilute ammonia solution.

Samples of printed and unprinted material were then overdyed, in the same dyebath, using various reactive dyestuffs. Conventional dyeing techniques were employed, as follows: Liquor ratio 50:1 Dyebath pH 5.5 Bath additions: Ammonium sulphate 4% o.w.w.

Levelling agent (Albegal B or Drimalan F) 1% o.w.w.

Sodium sulphate (anhy drous) 10% o.w.w.

The word ALBEGAL is a Trade Mark.

The goods were agitated in a bath containing the above auxiliaries for 10 mins. at 40"C, after which 1.5% (on weight of unresisted material) of predissolved dye was added and the treatment continued for a further 10 mins. The temperature was then raised to 70"C at 130C/min, held at this value for 10 mins, and then raised to the boil at 10C/min. After boiling for 45 minutes, the bath was cooled to 800 C, sufficient dilute ammonia added to give a pH of 8.5, and treatment was continued for a further 10 min.

The dyestuffs employed were selected from the Lanasol and Drimalan F range, and, in all cases, extremely good contrasts between printed and unprinted material were obtained.

Example 4.

Samples of chlorinated botany fabric were printed with the following paste composition.

Urea 30.0% Sodium alginate thickening (Manutex F) 6.0% Sodium phosphate sequestering agent (Calgon OT) 0.6% Fatty acid amide non-ionic wet ting agent (Matexil PN-VP) 1.0% Anti-foaming agent 0.2% Resist Agent (Sandospace R powder) 3.5% Procion MX dyestuff 4.0% Sodium sulphite (anhydrous) 2.4% Water to 100.0% The word MANUTEX is a Trade Mark.

The printed samples were batched in the moist condition for 24 hours and then washed off in dilute ammonia.

Samples of printed and unprinted material were then overdyed in the same dyebath using various reactive dyes. The dyeing technique and dyestuffs used were as in Example 3.

In all cases, the effect of the overdyeing shade on the original shade of the Procion M printed fabric was greatly reduced by the presence of the resist agent in the print.

WHAT WE CLAIM IS: 1. A method of colouring a fabric or garment comprising keratin fibres, which comprises printing a selected area of the fabric or garment with an aqueous composition containing a dye resist agent and an amide or thioamide, the impregnated fabric is stored in the presence of moisture to fix the dye resist agent, and thereafter dyeing the printed and fixed fabric or garment with at least one dye resisted by the printed area whereby the printed area retains a contrasting appearance against a coloured background.

2. A method according to claim 1, wherein the fabric or garment is stored at a pH of 2 to 7 and a temperature of 10 to 60"C.

3. A method according to claim 2, wherein the printed fabric or garment is washed with an aqueous solution of a base or reducing agent after storage.

4. A method according to any of claims 1 to 3, wherein the printed and stored fabric or garment is dyed with a reactive, acid milling, 2:1 premetallised or chrome dye.

5. A method according to any of claims 1 to 4, wherein the resist agent is colourless reactive dye.

6. A method according to any of claims 1 to 4, wherein the printing composition additionally contains a coloured reactive dye.

7. A method according to claim 6, wherein the printing composition additionally contains a coloured reactive dye as reactive as the resist agent with the fibres of the fabric or garment.

8. A method of colouring a fabric or gar ment comprising keratinous fibres which com

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (11)

**WARNING** start of CLMS field may overlap end of DESC **. a conventional Drimalan F dye cycle. The samples were finally treated with 2.5% (o.w.w.) Hercosett (Trade Mark) 57. An attractive toned effect was obtained on each printed sample. Example 3. Samples of chlorinated botany fabric were printed with the following paste composition. Urea 30.0% Galacta-mannan thickening agent (Indalca PA/1) 3.0% Sodium phosphate sequestering agent (Calgon PT) 0.6% Fatty acid amide non-ionic wet ting agent (Matexil PN-VP) 1.0% Anti-foaming agent 0.2% Resist Agent (Sandospace R powder) 6.0% Sodium sulphite (anhydrous) 3.0% Water to 100.0% The printed samples were then maintained in a wet condition, by covering with impermeable sheeting, for 24 hours and then washed off in dilute ammonia solution. Samples of printed and unprinted material were then overdyed, in the same dyebath, using various reactive dyestuffs. Conventional dyeing techniques were employed, as follows: Liquor ratio 50:1 Dyebath pH 5.5 Bath additions: Ammonium sulphate 4% o.w.w. Levelling agent (Albegal B or Drimalan F) 1% o.w.w. Sodium sulphate (anhy drous) 10% o.w.w. The word ALBEGAL is a Trade Mark. The goods were agitated in a bath containing the above auxiliaries for 10 mins. at 40"C, after which 1.5% (on weight of unresisted material) of predissolved dye was added and the treatment continued for a further 10 mins. The temperature was then raised to 70"C at 130C/min, held at this value for 10 mins, and then raised to the boil at 10C/min. After boiling for 45 minutes, the bath was cooled to 800 C, sufficient dilute ammonia added to give a pH of 8.5, and treatment was continued for a further 10 min. The dyestuffs employed were selected from the Lanasol and Drimalan F range, and, in all cases, extremely good contrasts between printed and unprinted material were obtained. Example 4. Samples of chlorinated botany fabric were printed with the following paste composition. Urea 30.0% Sodium alginate thickening (Manutex F) 6.0% Sodium phosphate sequestering agent (Calgon OT) 0.6% Fatty acid amide non-ionic wet ting agent (Matexil PN-VP) 1.0% Anti-foaming agent 0.2% Resist Agent (Sandospace R powder) 3.5% Procion MX dyestuff 4.0% Sodium sulphite (anhydrous) 2.4% Water to 100.0% The word MANUTEX is a Trade Mark. The printed samples were batched in the moist condition for 24 hours and then washed off in dilute ammonia. Samples of printed and unprinted material were then overdyed in the same dyebath using various reactive dyes. The dyeing technique and dyestuffs used were as in Example 3. In all cases, the effect of the overdyeing shade on the original shade of the Procion M printed fabric was greatly reduced by the presence of the resist agent in the print. WHAT WE CLAIM IS:

1. A method of colouring a fabric or garment comprising keratin fibres, which comprises printing a selected area of the fabric or garment with an aqueous composition containing a dye resist agent and an amide or thioamide, the impregnated fabric is stored in the presence of moisture to fix the dye resist agent, and thereafter dyeing the printed and fixed fabric or garment with at least one dye resisted by the printed area whereby the printed area retains a contrasting appearance against a coloured background.

2. A method according to claim 1, wherein the fabric or garment is stored at a pH of 2 to 7 and a temperature of 10 to 60"C.

3. A method according to claim 2, wherein the printed fabric or garment is washed with an aqueous solution of a base or reducing agent after storage.

4. A method according to any of claims 1 to 3, wherein the printed and stored fabric or garment is dyed with a reactive, acid milling, 2:1 premetallised or chrome dye.

5. A method according to any of claims 1 to 4, wherein the resist agent is colourless reactive dye.

6. A method according to any of claims 1 to 4, wherein the printing composition additionally contains a coloured reactive dye.

7. A method according to claim 6, wherein the printing composition additionally contains a coloured reactive dye as reactive as the resist agent with the fibres of the fabric or garment.

8. A method of colouring a fabric or gar ment comprising keratinous fibres which com

prises printing a selected area of the fabric or garment with a dye resist agent and a reactive dye, fixing the print, and thereafter dyeing the fabric or garment with at least one dye resisted by the printed area whereby the printed area retains a contrasting appear ance against a coloured background.

9. A method according to claim 1 sub stantially as described with reference to the Examples herein.

10. A fabric or garment coloured by a method according to any preceding claim.

11. A fabric or garment comprising keratin fibres for overdyeing in accordance with a method according to any of claims 1 to 7 and 9, which has been printed with an aqueous composition containing a dye resist agent and an amide or thioamide and stored in the presence of moisture whereby the resist agent is fixed on the fabric or garment.