GB2041010A

GB2041010A - Improvements in and Relating to the Dyeing and Printing of Keratinous Material

Info

Publication number: GB2041010A
Application number: GB8000543A
Authority: GB
Original assignee: Aziende Colori Nazionali Affini ACNA SpA; ACNA Chimica Organica SpA
Current assignee: Aziende Colori Nazionali Affini ACNA SpA; ACNA Chimica Organica SpA
Priority date: 1979-01-12
Filing date: 1980-01-08
Publication date: 1980-09-03
Also published as: FR2446348B1; GB2041010B; ES487628A0; IT7919230A0; DE3000422A1; FR2446348A1; ES8100380A1; IT1110980B

Abstract

In the dyeing or printing of keratinous fibres, especially wool, by the pad-steam process, using an aqueous dye solution or paste, there is incorporated a ternary dye-carrier composition which enhances the dye- fixing speed, the carrier comprising a first compound of the formula <IMAGE> in which X and Y, which may be the same or different, are primary, secondary or tertiary amino, or C1-8 alkoxyl or aryl, whilst Z is oxygen, sulphur or -NH, a second compound selected from ethylene glycol, diethylene glycol, propylene glycol, glycerol, polyglycols, thiodiglycol, cyclohexanol, benzyl alcohol, tertiary butanol and cyclohexanone, and a third compound being a sodium or potassium salt which is a reducing agent selected from the sulphite, bisulphite, metabisulphite, hydrosulphite and thiosulphate.

Description

SPECIFICATION Improvements in and Relating to the Dyeing and Printing of Keratinous Materials The present invention relates to the continuous dyeing, Vigourous printing and printing of keratinous fibrous material, in any form, according to the general scheme of the so-called 'Pad-Steam' system which basically involves a foularding and subsequent steaming operation.

There are known processes for the continuous dyeing of keratinous fibres, consisting in impregnating by foularding the material to be dyed, for instance of a combed wool silver, with a dye bath containing the wool dye, a soaking agent, a thickener, an acid or acid-generating substance and material for boosting the dye-fixing speed such as, for instance, lauryl-diethanolamide and benzyl alcohol, and, finally, in fixing the dye by vaporizing suitabiy at 1000 to 1 200C in a continuous vaporizer or in an autoclave, for times that may vary from twenty minutes, for light shades, up to 1 20 minutes, for dark shades or for mordant dyestuffs.

However, such continuous dyeing methods for keratinous fibres are not in general use because of the low fixing speed of the dyestuffs on the keratinous base, this involving severe limitations with regard to the range of dyes usable for the purpose, in particular of mordant dyestuffs, and leading to low hourly production rates, as well as restricting the possibility of attaining full shades.

Various attempts have been made to reduce the vaporization times, which also involved considerable losses of energy, as well as restricting output, with a view to rendering the continuous dyeing system more advantageous.

Thus, in U.S. Patent No. 2,552,404 there is described a dyeing process essentially characterized by the use of an "acid-shock" treatment, according to which the impregnated material, soaked with a solution of an acid wool dye is, after squeezing, passed through a boiling bath containing an aqueous solution of a mineral or organic acid such as sulphuric acid, formic or oxalic acid, of an acidity corresponding to that of an aqueous solution containing not more than 30 g of sulphuric acid per litre of water.

In this way it is possible to fix the dye in times amounting to two to ten minutes. However, this method has not achieved success, inasmuch as it shows, to a more or less serious degree, the following drawbacks:- the dyeings that were achieved were to a various extent "mottled"; there occurs a bleeding of the dye in the acid dyeing bath; it is not possible to use mordant dyestuffs.

In British Patent No. 1,103,736 a dyeing and printing method for keratinous fibres is described, which consists in treating the fibres with an aqueous solution or paste containing from 30% to 35% by weight of urea together with a wool dye, vaporizing the material in order to cause swelling of the fibres and the fixing of the dye onto the swollen fibres, and, finally, subjecting the material to washing in order to remove the urea.

However, this method also has not yet found commercial application, because of the great quantities of urea consumed and because of the difficulties that must be overcome in order to avoid the 'frosting effect' (the so-called 'grey veil') and 'mottling'.

Moreover, with this method, with the exception of the use of reactive dyes, it is not possible to obtain deep shades, because the degree of fixing is too low and moreover, mordant dyestuffs, which as is well known lead to dyes with a full and deep shade, cannot be applied.

It has now, surprisingly, been found that it is possible to carry out the dyeing or printing of keratinous fibres and in particular of wool, by a process which affords dyeings and printings free from 'frosting' and 'mottling' effects, and with a high degree of fixing of the dyes for all classes of wool dyes used, including mordant dyes, and which process entails only short vaporizing times.

The invention consists in a process of dyeing or printing keratinous fibres which comprises impregnating the fibres with an aqueous dye solution or paste containing a water-soluble dyestuff for the fibre, a first compound of the formula:

wherein X and Y, which may be the same or different are primary secondary or tertiary amino, Cis alkoxyl or aryl whilst Z is oxygen, sulphur or -NH, a second compound selected from ethylene glycol, diethylene glycol, propylene glycol, glycerol, polyglycols, thiodiglycol, cyclohexanol, benzyl alcohol, tertiary butanol and cyclohexanone, and a sodium or potassium salt which is a reducing agent selected from the sulphite, bisulphite, metabisulphite, hydrosulphite (dithionite) and thiosulphate, the impregnated fibre being subject to vaporization with moist steam at 98-11 1 SOC, preferably at 98- 1060C.

The vaporization may be carried out in a pressurized closed autoclave, or in a continuous vaporizer, under atmospheric or superatmospheric pressure.

It will be understood that, in addition to the aforesaid first and second compound and salt which, together constitute a ternary carrier for the dyestuff, other additives may be incorporated for their various purposes, such as conventional additives for improving the impregnation of the fibres and for hindering dye migration.

Further, it will be understood that the aforesaid first and second compound and salt may be incorporated separately into the aqueous dye solution or paste with which the fibres are to be dyed, although it is in general more convenient and is preferred to premix the three materials to constitute a ternary carrier mixture.

Desirably the concentration of the first compound in the aqueous dye solution or paste is 620% by weight, that of the second compound 1.57.5% by weight, and that of the (reducing) salt 0.53% by weight. Their mutual proportions preferably correspond to a ternary carrier composition constituted by, for 100 parts by weight of the composition, 60-80 parts of the first compound, 1 5-30 parts of the second compound and 5-12 parts of the salt. The above-indicated desirable concentrations correspond to the incorporation of 1025% by weight of such ternary carrier into the aqueous dye solution or paste.

Preferred carrier compositions are prepared using urea or thiourea with ethylene glycol or tertiary butyl alcohol and with a metabisulphite or thiosulphate, in ratios as indicated above.

A particularly advantageous form of the invention involves the use of a carrier of the following composition (in parts by weight): 780 parts Urea 1 60 parts Ethylene glycol 60 parts Sodium metabisulphite This carrier mixture, added at a ratio 100--250 g/kg of aqueous dye solution used as impregnating bath, also containing dyes, thickeners and conventional additives suitable for improving the penetration and distribution of the dye in the fibre, allows a sufficient swelling of the fibre to be achieved for achieving a good penetration of the dye during vaporization, and in a short time.

Particularly suitable dyes belong to the series of acid dyes, pre-metallized at 1:1 and 1:2 (sulphonated or not) and to the mordant dye series.

The process of the invention is particularly convenient when applied using the Vigoureux printing method, for obtaining special 'melange' effects, free of streaking defects which are on the contrary met with in yarns obtained from mixtures of white and dyed yarns.

The present invention will be illustrated further without however limiting its wider scope, by the following examples in which the indicated parts are by weight.

Example 1 6 parts of Yellow Stenolana S5B (C.l. Acid Yellow, sulphonated premetallized dye 1:2) were dissolved in hot water and to this solution were added 1 50 parts of preferred urea-ethylene glycolsodium metabisulphite carrier composition indicated above, 20 parts of lauryl diethanolamide, 5 parts of an anionic soaking agent (Madeol BDS) ("Madeol" is a Registered Trade Mark) and 3 parts of a thickener based on carob meal and acetic acid, bringing the pH to 5.

The whole mixture was then made up to 1,000 parts with water.

A combed wool sliver was soaked with this solution at 300C, with a 100% squeezing effect. Two samples of the combed sliver so impregnated were subjected to vaporizing, one in a star vaporizer at 1040C for 2 minutes, and the other in a continuous vaporizer at 980C for 5 minutes.

In both cases there was obtained, in good yield, a yellow shade of medium depth and of excellent general fastnesses corresponding to those that are obtained on material dyed in a traditional way.

Without the above-indicated carrier, and employing the same vaporizing times, the yield was heavily reduced.

Example 2 20 parts of Bordo Stenolana SB (C.l. Acid Violet 90, prematallized dye 1:2 sulphonate) were dissolved in hot water and there were then added 200 parts of the carrier indicated in Example 1, and also the same additives as in Example 1, followed by water to 1 ,000 parts.

Wool staple was impregnated at 250C with a squeezing effect of 110%; of this impregnated staple two parts were taken of which the one was vaporized in a star vaporizer at 1020C for 5 minutes while the other was vaporized in a continuous vaporizer at 980C for 10 minutes.

In both cases the dye was fixed with a high yield onto the fibre, giving it a Bordeau shade of excellent general fastnesses, fully corresponding to those of conventional dyeings.

Operating in the same way but using staple wool fabric, there were obtained analogous results.

Example 3 30 parts of Black Stenolana SR (C.l. Acid Black 194, pre-metallized dye 1:2 sulphonate) were dissolved in hot water and the printing paste was prepared as described in Example 2.

Some combed wool sliver was then printed with a 75% hiding according to the Vigoureux method, after which vaporization was effected at 980C in a continuous vaporizer (Model ILMA T/CF) for a period of 1 5 minutes. On the sliver there thus formed a Vigoureux printing which, during washing in a backwashing machine, did not discharge any dye and which displayed excellent general fastness.

When operating at 1060--1080C in a closed vaporizer, the dye-fixing times are reduced to about 7 minutes.

In order to obtain the same result when not using the indicated carrier, the fixing time for the dye at the above indicated temperatures ranged from 60 to 90 minutes.

Example 4 20 parts of Bordo Stenolana SB (C.I. Acid Violet 90, premetallized dye 1:2 sulphate) were dissolved in hot water and there were then added 200 parts of the ternary complex as used in Examples 1 and 2, 10 parts of lauryl diethanolamide, 5 parts of anionic steeping agent (Madeol BDS), and 3 parts of a thickener based on carob meal.

The whole mixture was then made up to 1,000 parts with water, and the procedure of Example 2, was followed, giving results analogous to those of that Example.

Example 5 20 parts of Bordo Stenolana SB (C.l. Acid Violet 90, premetallized dye 1:2 sulphate) were dissolved in hot water and there were then added 200 parts of the ternary carrier as used in Examples 1 and 2, 10 parts of lauryl diethanolamide, 5 parts of an anionic steeping agent (Madeol BDS), 500 parts of a thickening paste based on a carob meal prepared at an 8% concentration, and 20 parts of ammonium sulphate. The whole mixture was then made up to 1,000 parts with water.

An unchlorinated wool cloth was printed with the paste thus prepared and vaporization was then effected in an autoclave at 104"C for 5 minutes.

On the material there formed a regular printing of a Bordeau tinge of excellent overall fastness characteristics. When operating as above indicated, but using a chlorinated woolen cloth, the vaporizing times in the autoclave, at 1040C, reduce to 2 minutes.

Equally well suited for the treatment described in the foregoing Examples are the following sulphonated premetallized 1:2 dyes: Biu Stenolana C.l. Acid Blue 1 93 Rosso Stenolana SR C.l. Acid Red 362 Bruno Stenolana SG C.l. Acid Brown 402 Bruno Stenolana SRF C.l. Acid Brown 403 Example 6 20 parts of solid 'Blu follone' SBL (C.l. Acid Blue 80, sulphonated acid dye) were dissolved in hot water and there were then added with 180 parts of the ternary carrier as used in Examples 1 and 2, 20 parts of lauryl diethanolamide, 5 parts of an anionic steeping agent (Madeol BDS) and 3 parts of a thickening agent based on sodium alginate.

The whole mixture was then made up to 1 ,000 parts, with water.

A woolen cloth was foularded with the resulting dye solution under a squeezing effect of 120%.

This was then followed by vaporization for 5 minutes at 1020C. There was obtained a deep blue tinge with very high general fastness characteristics and with a colour fixing degree of 98%.

With the same advantage there may be substituted any of the following sulphonated acid dyes: Giallo follone solido 4G C.l. Acid Yellow 79 Giallo follone solido R C.l. Acid Yellow 42 Rosso follone solido R C.l. Acid Red 114 Rosso follone solido 3B C.l. Acid Red 131 Violetto follone solido R C.l. Acid Violet 103 Verde follone solido BVA C.1. Acid Green 84 Blu follone solido GRA C.l. Acid Blue 120 Blu follone solido 5RA C.l. Acid Blue 113 Nero Novamina STR C.l. Acid Black 126 Example 7 30 parts of Bruno Diacromo MRH (C.l. Mordant Brown 33) were dissolved in hot water together with 220 parts of a ternary carrier mixture composed of: Urea 680 parts Ethylene glycol 270 parts Sodium bisulphite 50 parts To the 220 parts of carrier there had previously been added 30 parts of chromium fluoride. To the whole mixture there were further added 20 parts of lauryl diethanolamide, 5 parts of an anionic steeping agent (Madeol BDS) and 3 parts of a thickening agent based on carob meal. The whole was then made up with water to 1,000 parts.

With the resulting paste, at 250C, a combed wool sliver was impregnated with a squeezing effect of 110%. The sliver was then divided into two parts, one of which was subjected to vaporization at 980C for 1 5 minutes, while the second part was vaporized for 10 minutes at 1040C.

The sliver was thereby dyed in a uniform, deep brown shade displaying fastness characteristics corresponding to C.l. Mordant Brown 33 dyed in the traditional way.

In a similar way there were obtained dyeings of excellent characteristics, by substituting the dye of this Example with each of the following mordant dyes: Giallo Diacromo BN C.l. Mordant Yellow 3 Arancio Diacromo R C.l. Mordant Orange 3:1 Rosso Diacromo 3B C.l. Mordant Red 26 Rosso Diacromo G C.l. Mordant Red 19 Blu Cielo Diacromo BN C.l. Mordant Blue 1 Blu Diacromo B C.l. Mordant Blue 1 7 Blue Diacromo BL C.l. Mordant Blue 7 Bruno Diacromo KE C.l. Mordant Brown 1 5 Grigio Diacromo BLC C.l. Mordant Black 81 Nero Diacromo PSS C.l. Mordant Black 11 Nero Diacromo AS/D C.l. Mordant Black 1 Nero Diacromo R C.l. Mordant Black 15 Example 8 20 parts of Giallo Stenolana GL (C.l. Acid Yellow 140, premetallized 1:2 dye) were dissolved in hot water and there were then added 200 parts of the ternary complex as used in Examples 1 and 2.

The procedure of Example 2 was then followed, when the wool staple was dyed to a deep yellow shade of excellent general fastness characteristics altogether corresponding to the characteristics that are obtained with this dye on material dyed in the traditional way.

Equally suitable for the procedure of this Example are the following pre-metallized 1:2 dyes: Arancio Stenolana R C.l. Acid Orange 139 Rosso Stenolana GL C.l. Acid Red 272 Grigio Stenolana MB C.l. Acid Black 184 Bruno Stenolana M3R (No C.l.) Blu Stenolana M2R (No C.l.) Nero Stenolana MN C.i. Acid Black 183 Example 9 20 parts of Rosso Stenamina GRE (C.l. Acid Red 183, sulphonated premetallized 1:1 dye) were dissolved in hot water and there were then added 200 parts of the ternary carrier used in Examples 1 and 2, with the same additives as those of Example 2.

The procedure of Example 2, was followed, to give on the combed wool sliver a red shade of medium depth, having excellent general fastness characteristics, corresponding to those of the-same dye applied on wool in the traditional way.

For the procedure of this Example, the following sulphonated premetallized 1:1 dyes are equally suitable: Giallo Stenamina R C.l. Acid Yellow 99 Arancio Stenamina GRE C.l. Acid Orange 74 Rosa Stenamina BA C.l. Acid Red 186 Bordo Stenamina R C.l. Acid Red 179 Blu Stenamina ZG C.l. Acid Blue 158:2 Verde Stenamina BL C.l. Acid Green 12 Bruno Stenamina 2G (No C.l.) Nero Stenamina B C.l. Acid Black 52

Claims

1. A process for the dyeing or printing of keratinous fibres, in which the fibres are impregnated with an aqueous solution or paste containing a water-soluble dyestuff having an affinity for the fibre, a first compound of the formula:

where X, Y and Z are as hereinbefore defined, a second compound selected from ethylene glycol, diethylene glycol, propylene glycol, glycerol, polyglycols, thiodiglycol, cyclohexanol, benzyl alcohol, tertiary butanol and cyclohexanone, and a sodium or potassium salt which is a reducing agent selected from the sulphite, bisulphite, metabisulphite, hydrosulphite and thiosulphate, the impregnated fibre being subjected to vaporization with moist steam at 98-11 500.

2. A process according to claim 1 in which the vaporization is effected at 98--1060C.

3. A process according to claim 1 or 2 in which the aqueous dye solution or paste contains by weight 620% of the first compound, 1.57.5% of the second compound, and 0.53% of the reducing salt.

4. A process according to claim 1, 2 or 3 in which the first and second compounds and reducing salt are added to the aqueous dye solution or paste as a pre-mixed carrier composition.

5. A process according to claim 4 in which said composition contains, for 100 parts of the recited components, 60-80 parts of said first compound, 15-30 parts of said second compound and 5-12 parts of said reducing salt.

6. A process according to claim 4 or 5 in which the carrier composition is incorporated in the aqueous dye solution or paste in an amount of 1 0-25% by weight.

7. A process according to any foregoing claim in which said first compound urea or thiourea, said second compound is ethylene glycol or tertiary butyl alcohol, and said salt is a metabisulphite or thiosulphate.

8. A process according to claim 4, 5 or 6 in which the carrier composition contains, by weight: 780 parts of urea 1 80 parts of ethylene glycol 60 parts of sodium metabisulphate

9. A process according to any preceding claim, in which the dye used is a sulphonated or non sulphonated-premetallized 1:1, premetallized 1:2, acid, or mordant dyestuff.

1 0. A process according to any preceding claim in which the fibre being dyed comprises wool.

11. A process according to any of the preceding claims in which the aqueous dye solution or paste is used for the impregnation of combed fibre by the Vigoureux method.

12. A process according to any of claims 1-10 in which the vapourization is effected in an autoclave.

13. A process according to any of claims 1-10 in which the vapourization is effected in a countinuous vapourizer.

14. A process according to claim 7 or 8 in which the dye used is a mordant dye and the carrier composition is premixed with a suitable trivalent chromium salt.

1 5. A carrier composition suitable for use in a dyeing process according to claim 1 which comprises, for 100 parts by weight of the recited components, 60-60 parts of said first compound, 1 5-30 parts of said second compound and 5-1 2 parts of said reducing salt.

16. A composition according to claim 15, in which said first and second compounds and said salt are as set out in claim 7 or 8.

17. Articles made of keratinous fibre, dyed or printed by a process according to any of claims 114.