GB2055905A

GB2055905A - Multicoloured and reserve dyeing process

Info

Publication number: GB2055905A
Application number: GB8020754A
Authority: GB
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1979-06-29
Filing date: 1980-06-25
Publication date: 1981-03-11
Also published as: FR2460364A1; IT8049049A0; DE3023223A1

Abstract

A process for dyeing a textile substrate in a single step with specked reserve or multicoloured effects in which an oil-in-water dispersion containing a thickening agent and at least one water-soluble or organic solvent-soluble dyestuff is applied to the substrate, the organic phase of the dispersion comprising an organic solvent selected from polyglycol ethers, higher alcohols, carboxylic acid esters, ketones, nitriles arid saturated cyclic hydrocarbons and mixtures thereof and being uniformly distributed through the aqueous phase in form of droplets from 0.2 to 2 mm diameter, the density of the organic phase differing by 0.01 to 0.2 g/cm<3> from that of the aqueous phase, and the substrate being subsequently treated to effect fixation of the dyestuff, and the oil-in-water dispersions used for this process.

Description

SPECIFICATION Improvements in or relating to organic compounds The present invention relates to a process for dyeing a textile substrate to produce in one step reserve and/or multicolored effects.

The use of dyeing preparations comprising two mutually immiscible liquid phases for dyeing textile substrates is known. Such 2-phase systemsmay be finely divided water-in-oil (w/o) emulsions or oil-in-water (o/w) emulsions, containing an emulsifying agent and usually a thickening agent.

The o/w emulsion type is used for pigment printing, the pigment dyes being dispersed in either the organic or the aqueous phase. With the known o/w emulsions, the substrate is either dyed in a single shade or with tone-in-tone effects in a single step or printed with multicolored effects in a process requiring at least two successive applications of a printing emulsion.

It has now been found that it is possible to dye a textile substrate in a single step with speckled reserve and/or multicolored effects by using an o/w dyeing dispersion comprising organic solvent droplets of visible size uniformly distributed through the aqueous phase.

Accordingly, the present invention provides a process for dyeing a textile substrate in a single step with speckled reserve or multicolored effects, comprising applying to the substrate an oil-inwater dispersion containing a thickening agent and at least one water-soluble or organic solventsoluble dyestuff, the organic phase of the dispersion comprising an organic solvent immiscible or slightly miscible with water and selected from (C1 4)alkylene oxide polyglycol ethers, higher alcohols, carboxylic acid esters, ketones, nitriles and saturated cyclic hydrocarbons and mixtures thereof and being in form of droplets from 0.2 to 2 mm diameter which are uniformly distributed through the aqueous phase, the density of the organic phase differing by 0.01 to 0.2 g/cm3 from that of the aqueous phase, and subsequently treating the dyed substrate to effect fixation of the dyestuff.

The invention also provides oil-in-water dispersions containing a thickening agent and at least one water-soluble or organic solvent-soluble dyestuff, as described above.

The amount of organic phase in the dispersion depends essentially on the desired effect on the substrate.. Generally, the organic phase is up to 10%, preferably 2 to 5% by weight of the aqueous phase. The organic droplets have preferably a diameter from 1 to 2 mm.

The choice of the organic solvent is essentially determined by the density difference with the aqueous phase. Preferably, the density of the organic phase differs by 0.01 to 0.1 g/cm3 from that of the aqueous phase.

Suitable polyglycol ethers are the addition products of a (C,~4)alkylene oxide, for example ethylene oxide or propylene oxide, and a polyglycol, e.g. ethylene glycol, propylene glycol, 2,3-butylene glycol, 1,3-butylene glycol and the like. Preferred poiyglycoi ethers are the addition products of propylene oxide to propylene glycol having a molecular weight from 1,000 to 2,500, preferably from 1,700 to 2,000, or the addition products of ethylene oxide and propylene oxide to propylene glycol, more preferably those resulting from the addition of 20 to 40 mols propylene oxide and 2 to 10, preferably 5 to 8 mols ethylene oxide to 1 mol propylene glycol, such polyglycol ethers having a molecular weight from 1,200 to 3,000.The latter type of polyglycol ethers are commercially available under the Registered Trade Mark PLURONICS (BASF, Ludwigshafen, W. Germany).

Other suitable organic solvents for the organic phases are those which are insoluble or slightly soluble in water, for example: higher alcohols: e.g. pentanol carboxylates: e.g. propyl, butyl or benzyl acetic acid esters, dodecyl phthalate nitriles: e.g. 3-(benzyloxy)propionitrile saturated cyclic hydrocarbons: e.g.

cyclohexane, methyl-cyclohexane Mixtures of any of the above organic solvents or mixtures of such a solvent with a solvent which is more soluble in water, e,g. a carboxylic acid ester such as ethyl or isopropyl acetate or a ketone such as 2-butanone, may also be used. Preferred mixtures are those comprising at least one carboxylic acid ester such as benzyl acetate and a nitrile, more preferably those comprising a mixture of higher alcohols, carboxylic acid esters, ketones and/or nitriles (components having a good dissolving power for the dyestuffs soluble in an organic medium) together with a saturated cyclic hydrocarbon (components for adjusting the density of the organic phase).The choice and proportion of each component depend on the desired final density of the organic phase, the solubility of the dyestuff in the resulting organic phase and the immiscibility of the organic phase with the aqueous medium. Preferably, the solvent mixture is immiscible with the aqueous phase.

Particularly preferred solvent mixtures are those comprising benzyl acetate, cyclohexane and methylcyclohexane, preferably in a weight ratio from 1.5:0.3:1 to 2.5:1.2:1.5.

Preferred organic solvents are (C,~4)alkylene oxide polyglycol ethers, particularly the above mentioned preferred polyglycol ethers.

Although any textile substrate may be dyed according to the process of the invention, with the proviso that the substrate must be dyeable with at least one water-soluble dyestuff or a dyestuff soluble in the indicated organic phase, preferred textile substrates are those comprising natural or synthetic polyamide, e.g. wool, nylon 6, 6.6 etc.... and blends thereof. The substrate may be in any conventional form, e.g. woven or knitted goods, yarn, carpets, non-wovens, tops. The process of the invention is particularly suitable for dyeing flat form textile substrates, preferably carpets. In another preferred embodiment, carpet yarn is knitted and then dyed according to the invention. Subsequently, the dyed yarn is unknitted and used for the fabrication of carpets.

With the o/w dispersions of the invention, various speckled effects may be obtained on the substrate, depending on the number and type of dyestuffs used. In the case where several dyestuffs are used, an o/w dispersion may be obtained containing droplets of different colours corresponding to each dyestuff respectively. If each organic solution of a dyestuff is added separately to the aqueous phase, surprisingly, little or no colour mixing takes place under these conditions. In some cases, a partial mixing of the dyestuffs present in the organic phase may be desirable to obtain a larger range of colours. On application to the substrate of an o/w dispersion containing one or more dyestuffs in the organic phase, speckled spots of one or more colours are obtained.These effects may result on a ground dyed substrate when the aqueous phase of the dispersion contains one or more dyestuffs, or on a white ground when the aqueous phase is free of dyestuff. By contrast, a substrate speckled with white spots on a dyed ground may be obtained when the applied o/w dispersion contains only one or more water-soluble dyestuffs in the aqueous phase and no dyestuff in the organic phase.

According to the process of the invention, dyestuffs belonging to various classes may be employed, depending on the substrate to be dyed, with the proviso that the dyestuff has to be soluble in the aqueous or organic phase. Pigments and disperse dyestuffs which are soluble in the specified organic solvents are included in the classes of dyestuffs suitable for the process of the invention. Such dyestuffs are known from the Color Index. Preferred dyestuffs are those classified in the Color Index under "Solvent Dyes".

When the substrate comprises natural or synthetic polyamides, preferred dyestuffs for the aqueous phase are anionic dyestuffs, more preferably acid dyestuffs. Such dyestuffs are known from the Color Index. Among the acid dyestuffs, some are more readily soluble in the organic phase than in the aqueous phase and may be used in the organic phase.

The concentration of the dyestuffs in the aqueous and organic phases depends on various factors, particularly on the desired depth of shade.

The organic phase may contain up to 1 SOg/liter of dyestuff, this upper range depending on the solubility of the dyestuff in the organic phase.

Preferably, the organic phase contains up to 1 00g/liter of dyestuff. The concentration of the dyestuff in the aqueous phase may generally be up to 75 g/liter.

As mentioned above, the aqueous phase contains a thickening agent in order to stabilize the dispersion and to hinder the coalescence of the organic droplets. Any natural, chemically modified or synthetic thickening agent used in the textile industry, is suitable. Preferred thickening agents are those which may be at least partially flocculated by the addition of a lower aliphatic carboxylic acid, preferably formic acid. As examples of such thickening agents may be given the alginates and their derivatives and guar derivatives which are at least partially flocculated by the addition of formic acid. Such thickening agents are known and commercially available. The amount of thickening agent present in the aqueous phase is from 0.1 to 10%, preferably from 1 to 8% by weight.

Depending on the water-soluble dyestuff the aqueous phase may contain further dyeing assistants such as a buffer, an acid, a levelling agent, a surface active agent having no or low emulsifying properties. Preferably, the aqueous phase contains an amine salt, preferably guanidine hydrochloride. Such a salt is used in order to hinder the bleeding of dyestuff present in the organic phase into the aqueous phase. The amount of amine salt in the aqueous phase is conveniently from 1 to 10 g/liter, preferably from 1 to 5 g/liter.

The o/w dispersions of the invention may be applied on the substrate according to known methods, depending on the nature of the substrate. In the case where the substrate comprises natural or synthetic polyamide, the application of the o/w dispersion thereon is preferably carried out by padding, impregnation, dipping or screen printing, more preferably by padding or impregnation.

After dyeing, the substrate is treated for fixation in known manner depending on the nature of the substrate, e.g. by treatment with saturated or superheated steam or with hot air, or by storage at a temperature from room temperature to 400C.

Subsequently, the substrate is washed and dried.

The o/w dispersions of the invention may be prepared according to known methods, e.g. as described in Example 1 or 9 below. When several dyestuffs are used for the organic phase, it is convenient to add separately each organic solution of the dyestuff to the stirred aqueous phase which already contains an at least partially flocculated thickening agent and optionally a dyestuff and further additives, particularly an organic ammonium salt. Preferred o/w dispersions are those comprising at least one dyestuff dissolved in the aqueous phase, preferably an acid dyestuff, and at least one dyestuff dissolved in the organic phase.

The dyeing process of the invention displays all the advantages of a one step process, particularly when the substrate is a carpet. The process is easy to carry out and requires no special machines although the resulting multicolored effects on the substrate may comprise a large choice of various colours and spots having a diameter below 5 mm (microspace dyeing). Such small spots cannot be obtained by the conventional carpet dyeing techniques in a single step.

The following Examples further serve to illustrate the invention. In the Examples all parts are by weight and all temperatures are in degrees Centigrade unless otherwise stated.

EXAMPLE 1 60 parts of a commercially available alginate, 40 parts of sodium chloride and 10 parts of formic acid are introduced with stirring in 400 parts of water. This thickened mixture is adjusted with water, after addition of 0.2 parts of guanidine hydrochloride, to a volume of 1000 parts. To this mixture the following solutions are successively added with continuous stirring: a) a solution of 1.6 parts of C.l. Solvent Yellow 83 in 20 parts of benzyl acetate, b) a solution of 0.8 parts of C.l. Solvent Red 91 in 10 parts of benzyl acetate; and c) a solution of 0.8 parts of C.l. Solvent Black 45 in 10 parts of benzyl acetate.

The resulting aqueous dispersion contains yellow, red and black oil droplets of about 1 mm, the droplets being uniformly distributed through the emulsion.

A knitted polyamide substrate is padded with the resulting oil-in-water dispersion to a pick-up of 120% and then treated for 4 minutes with saturated steam at 1200 C. After the washing with warm water at 600C and drying, the knitted goods are unknitted. A yarn dyed with statistically distributed yellow, red and black spots having notable fastnesses is obtained. This dyed yarn is further used for the fabrication of carpets.

EXAMPLE 2 By following the procedure of Example 1, an oilin-water dispersion containing, per 1000 parts: 2.0 parts of C.l. Acid Yellow 19 dissolved in the aqueous phase 1.6 parts of C.l. Solvent Yellow 83 in 20 parts of a mixture containing 32.0 parts of benzyl acetate and 8.0 parts of 3-(benzyloxy)propionitrile, 0.8 parts of C.l. Acid Red 399 in 10 parts of a mixture of benzyl acetate and 3-(benzyloxy)propionitrile as specified above, 0.8 parts of C.l. Acid Blue 296 in 10 parts of the same solvent mixture, and 500 parts of a 12% alginate thickening containing 40 parts of sodium chloride and 10 parts of formic acid (see Example 1 ) is prepared. The oil droplets are uniformly distributed through the dispersion and have a size of about 1 mm.

Knitted goods of polyamide 66 carpet yarn are padded with this dispersion and aftertreated as described in Example 1. A dyed yarn with statistically distributed yellow, red and blue spots having notable fastnesses is obtained.

EXAMPLE 3 By following the procedure of Example 1, an oilin-water dispersion containing, per 1000 parts: 1.6 parts of C.l. Solvent Yellow 83 in 20 parts of a mixture containing 17.64 parts of benzyl acetate 1 5.96 parts of dodecyl phthalate and 8.4 parts of 3-(benzyloxy)-propionitrile 0.16 parts of C.l. Acid Red 399 in 2 parts of the same three-component mixture 1.6 parts of C.l. Acid Blue 296 in 20 parts of the same solvent mixture, and 500 parts of a 8% alginate thickening containing 50 parts of sodium chloride and 10 parts of concentrated formic acid (as in Example 1) is prepared.

Knitted goods of polyamide 66 carpet yarn are padded with this dispersion and aftertreated as described in Example 1. A dyed yarn with statistically distributed yellow, red, and blue (and some green) spots having very good fastnesses is obtained.

EXAMPLE 4 By following the procedure of Example 1 , an oilin-water dispersion containing, per 1000 parts: 0.8 parts of C.l. Solvent Yellow 83 in 10 parts of a mixture containing 24 parts of benzyl acetate, and 6 parts of 3-(benzyloxy)-propionitrile 0.8 parts of C.l. Solvent Brown 28 in 10 parts of the same solvent mixture 0.8 parts of C.l. Acid Blue 296 in 10 parts of the same solvent mixture, and 500 parts of a 3% commercially available thickening (Meyprogum PAT, Meyhall Chemical A.G., Switzerland, or Kelzan, Kelco Co., USA, New Jersey) containing 40 parts of sodium chloride and 2 parts of concentrated formic acid is prepared.

Knitted goods of polyamide carpet yarn are padded with this dispersion and aftertreated as described in Example 1. A dyed yarn with statistically distributed yellow, brown and blue spots having notable fastnesses is obtained.

EXAMPLE 5 By following the procedure of Example 1, an oilin-water dispersion containing, per 1000 parts: 3 parts of C.l. Acid Yellow 19 dissolved in the aqueous phase 3 parts of C.l. Solvent Brown 28 in a mixture containing 23.5 parts of benzyl acetate 1 2.5 parts of cyclohexane, and 14 parts of methyl-cyclohexane and 400 parts of the alginate thickening of Example 1 is prepared.

Knitted goods of polyamide 66 carpet yarn are padded with the dispersion and aftertreated as described in Example 1. A yellow dyed yarn with statistically distributed brown spots having notable fastnesses is obtained.

EXAMPLE 6 By following the procedure of Example 1, an oilin-water dispersion containing, per 1000 parts: 1 part of C.l. Acid Orange 127 dissolved in the aqueous phase 2 parts of C.l. Acid Orange 147 dissolved in the aqueous phase 1 part of C.l. Acid Yellow 19 dissolved in the aqueous phase 1 part of C.l. Solvent Brown 28 in parts of a mixture containing 14 parts of benzyl acetate 7.5 parts of cyclohexane, and 8.5 parts of methyl-cyclohexane and 400 parts of the thickening of Example 1 is prepared.

A cut pile polyamide 66 carpet is impregnated with this composition to a pick-up of 250%.

Subsequently, the impregnated carpet is rolled up on a roll, packed in a plastic sheet and rotated slowly for 1 2 hours at room temperature. The carpet is then washed and dried.

A natural brown dyed carpet with statistically distributed spots of various brown shades is obtained.

EXAMPLE 7 Wool tops are padded with an oil-in-water dispersion containing, per 1000 parts: 5 parts of C.l. Solvent Black 45 in a mixture containing 23.5 parts of benzyl acetate 12.5 parts of cyclohexane, and 14 parts of methyl-cyclohexane and 500 parts of the thickening of Example 4 to a pick-up of 120%.

The substrate is then treated with steam for 20 minutes at 1020, washed and dried. Black spots which are statistically distributed on the substrate are obtained.

EXAMPLE 8 A polyamide 6.6 velvet carpet is wetted out with an aqueous solution containing-5 g/l of a commercially available non-ionic, alkylene oxide addition product. The pick-up is 100%.

Subsequently, an oil-in-water dispersion containing, per 1000 parts: 3 parts of C.l. Acid Yellow 19 dissolved in the aqueous phase, 3 parts of C.l. Solvent Black 45 in a mixture containing 23.5 parts of benzyl acetate 12.5 parts of cyclohexane, and 14 parts of methyl-cyclohexane and 200 parts of the thickening of Example 4 is poured on the pile side of the pretreated carpet to a pick-up of 500%. After a treatment with saturated steam for 10 minutes to effect fixation, the carpet is washed and dried. A yellow dyed carpet comprising black spots distributed on the pile tops is obtained.

EXAMPLE 9 60 parts of a commercially available alginate, 40 parts of sodium chloride and 10 parts of formic acid are introduced with stirring in 400 parts of water. This thickened mixture is adjusted with water, after addition of 0.2 parts of guanidine hydrochloride, to a volume of 1000 parts. To this mixture the following solutions are successively added with continuous stirring: a) a solution of 1.6 parts of C.l. Solvent Yellow 83 in 20 parts of the addition product of propylene-glycol with propylene oxide (MW = 1780); b) a solution of 0.8 parts of Cl. Solvent Red 91 in 10 parts of the same addition product; and c) a solution of 0.8 parts of C.l. Solvent Black 45 in 10 parts of the same addition product.

The resulting dispersion contains yellow, red and black oil droplets of about 1 mm which are uniformly distributed.

A knitted polyamide substrate is padded with the resulting oil-in-water dispersion to a pick-up of 120% and then treated for 4 minutes with saturated steam at 1020C. After the washing with warm water at 600C and drying, yarn with statistically distributed yellow, red and black spots with notable fastnesses is obtained.

EXAMPLE 10 By following the procedures of Example 2 to 8 but replacing the indicated solvent mixture by an addition product of propylene glycol with propylene oxide having a molecular weight of 1800 or 1890 or by an addition product of propylene glycol with ethylene oxide and propylene oxide (MW 2111 or 2165), the same good results are obtained.

EXAMPLE 11 A plain loop pile carpet of polyamide 6.6 with a base of polypropylene is padded with an oil-inwater dispersion fo a pick-up of 500%. The dispersion contains the following components per 1000 parts: 3 parts of C.l. Acid Yellow 19 dissolved in the aqueous phase 2 parts of C.l. Solvent Black 45 in 40 parts of a propylene glycol/propylene oxide addition product having a molecular weight of 1780 2 parts of Cl. Solvent Red 91 in 40 parts of the same addition product 2 parts of guanidine hydrochloride 1 part of a commercially available non ionic surface active agent based on an addition product of ethylene oxide on a higher alkylphenol 1 part of a commercially available anionic surface active agent based on a naphthalene sulphonic acid/formaldehyde condensation product 2 parts of a commercially available phosphate buffer (pH5), and 5 parts of a chemically modified thickener based on a derivative of locust bean gum flour (commercially available).

Subsequently, the carpet is treated for 10 minutes with saturated steam at 1 020C and then washed and dried. A yellow dyed carpet with statistically distributed red and black spots having good fastnesses is obtained.

EXAMPLE 12 By following the procedure of Example 11, but using an oil-in-water dispersion containing, per 1000 parts: 4 parts of C.l. Solvent yellow 63 in 50 parts of the propylene glycol/propylene oxide addition product of Example 11 2 parts of C.l. Solvent Brown 28 in 50 parts of the same addition product 2 parts of C.l. Acid Red 399 in 50 parts of the same addition product 2 parts of a commercially available anionic surface active agent based on a higher sodium alkylsulphonate, and 4 parts of the thickener of Example 11 and buffered to pH 6, a carpet statistically speckled with yellow, brown and red is obtained.

Claims

1. A process for dyeing a textile substrate in a single step with speckled reserve or multicolored effects, comprising applying to the substrate an oil-in-water dispersion containing a thickening agent and at least one water-soluble or organic solvent-soluble dyestuff, the organic phase of the dispersion comprising an organic solvent immiscible or slightly miscible with water and selected from (C,~4)aikylene oxide polyglycol ethers, higher alcohols, carboxylic acid esters, ketones, nitrides and saturated cyclic hydrocarbons and mixtgures thereof and being in form of droplets from 0.2 to 2 mm diameter which are uniformly distributed through the aqueous phase, the density of the organic phase differing by 0.01 to 0.2 g/cm3 from that of the aqueous phase, and subsequently treating the dyed substrate to effect fixation of the dyestuff.

2. A process according to Claim 1, wherein the organic solvent is an (C,~4)alkylene oxide polyglycol ether.

3. A process according to Claim 2, wherein the (C,~4)alkyiene oxide polyglycol ether is an addition product of propylene oxide to propylene glycol having a molecular weight from 1,000 to 2,500.

4. A process according to Claim 2, wherein the (C,~4)alkylene oxide polyglycol ether is an addition product of 20 to 40 mols propylene oxide and 2 to 10 mols ethylene oxide to 1 mol propylene glycol.

5. A process according to Claim 1, wherein the organic solvent is selected from pentanol, propyl acetate, butyl acetate, benzyl acetate, dodecyl phthalate 3-(benzyloxy)propionitrile, cyclohexane, methylcyclohexane and mixtures thereof.

6. A process according to Claim 5, wherein the organic solvent is a mixture comprising benzyl acetate, cyclohexane and methylcyclohexane in a weight ratio from 1.5:0.8:1 to 2.5 :1.2 :1.5.

7. A process according to any one of the preceding Claims, wherein the organic phase is up to 10% by weight of the aqueous phase.

8. A process according to any one of the preceding Claims, wherein the organic droplets have a diameter from 1 to 2 mm.

9. A process according to any one of the preceding Claims, wherein the density of the organic phase differs by 0.01 to 0.1 g/cm3 from that of the aqueous phase.

10. A process according to any one of the preceding Claims, wherein the oil-in-water dispersion contains one or more dyestuffs dissolved in the aqueous phase and one or more dyestuffs dissolved in the organic phase.

11. A process according to any one of the preceding Claims, wherein the aqueous phase contains a thickening agent at least partially flocculated by the addition of a lower aliphatic carboxylic acid.

1 2. A process according to any one of the preceding Claims, wherein the aqueous phase contains an amine salt.

13. A process according to Claim 12, wherein the amine salt is guanidine hydrochloride.

1 4. A process according to any one of the preceding Claims, wherein the textile substrate comprises natural or synthetic polyamide or blends thereof, the water-soluble dyestuffs being anionic dyestuffs.

1 5. A process for dyeing a textile substrate substantially as hereinbefore described with reference to any one of Examples 1 to 12.

1 6. An oil-in-water dispersion containing a thickening agent and at least one water-soluble or organic solvent-soluble dyestuff, the organic phase of the dispersion comprising an organic solvent immiscible or slightly miscible with water and selected from (C,~4)alkylene oxide polyglycol ethers, higher alcohols, carboxylic acid esters, ketones, nitriles and saturated cyclic hydrocarbons and mixtures thereof and being in form of droplets from 0.2 to 2 mm diameter which are uniformly distributed through the aqueous phase, the density of the organic phase differing by 0.01 to 0.2 g/cm3 from that of the aqueous phase.

1 7. An oil-in-water dispersion according to Claim 16, in which the organic solvent is an (C,~4)alkylene oxide polyglycol ether.

1 8. An oil-in-water dispersion according to Claim 16, in which the organic solvent is selected from pentanol, propyl acetate, butyl acetate, benzyl acetate, dodecyl phthalate, 3-(benzyloxy)propionitrile, cyclohexane, methylcyclohexane and mixtures thereof.

1 9. An oil-in-water dispersion according to any one of Claims 1 6-1 8, in which the organic phase is up to 10% by weight of the aqueous phase.

20. An oil-in-water dispersion according to any one of Claims 1 6-1 9, containing one or more dyestuffs dissolved in the aqueous phase and one or more dyestuffs dissolved in the organic phase.

21. An oil-in-water dispersion according to any one of Claims 1 6-20, containing a thickening agent at least partially flocculated by the addition of a lower aliphatic carboxylic acid.

22. An oil-in-water dispersion according to any one of Claims 16-21, in which the aqueous phase contains an amine salt.

23. An oil-in-water dispersion according to Claim 22, in which the amine salt is guan'idine hydrochloride.

24. An oil-in-water dispersion according to any one of Claims 16-23, containing one or more anionic dyestuffs.

25. An oil-in-water dispersion substantially as hereinbefore described with reference to any one of Examples 1 to 12.

26. A textile substrate whenever dyed by a process according to any one of Claims 1 to 1 5.