GB2207152A

GB2207152A - Production of multicolour effects on polyamide fibre material

Info

Publication number: GB2207152A
Application number: GB08817056A
Authority: GB
Inventors: Hans-Peter Stakelbeck
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1987-07-22
Filing date: 1988-07-18
Publication date: 1989-01-25
Also published as: JPS6440684A; IT1224857B; GB8817056D0; IT8848200A0; BE1001682A3; FR2618461A1

Abstract

A process for dyeing natural and/or synthetic polyamide fibre material comprises:- a) applying at least one reactive dye having a K'-value of 8 or less together with a colourless fibre-reactive resist agent (e.g. an halo-heterocyclic or aliphatic sulfonyl compound) having a K'-value of more than 8, to an area of the material, or to some of the fibres from which the material is woven prior to step b); and optionally fixing the dye and agent; b) applying a further dye (e.g. an acid, basic, disperse or metal-complex dye) to the whole material whereby the further dye is fixed to the remainder of the material. n

Description

DYEING PROCESSES WITH REACTIVE DYES The present invention relates to a process for the production of multi-colour effects on polyamide material which are resistant to boiling.

According to the invention there is provided a process for dyeing natural and/or synthetic polyamide fibre material comprising a) applying at least one reactive dye having a K'-value of 8 or less together with a colourless fibre reactive resisting agent having a K'-value of more than 8 to an area of the material; and optionally fixing the dye and agent; (hereinafter defined as Step a); b) applying a further dye to the whole material whereby the further dye is fixed to the remainder of the material (hereinafter defined as Step b).

The K' pH6-value represents the combinability value of an anionic dye experimentally assessed at pH6 in the presence of cationic compound; this value is usually employed to indicate the combination capacity of anionic dyes (See GB Patent 1,489,456; GB Published Patent Application 2,102,454; Otten H.G. Bayer Farbenrevue 21.32 (1972); and Beckmann W. Hoffman F. and Otten H.G. Melliand Textilber. 6 pages 641-646 [1973]). The K'-value is a specific dyestuff characteristic which provides a practical indication of the behaviour in dyeing of an anionic dye in relation with its combination capacity.

The K'pH6-value of the anionic dyes may be assessed according to the following test method with reference to a standard anionic dye whose K'pH6-value is known; Nylon yarn (Du Pont, type 846) is introduced at a goods to liquor ratio of 1:40 in a dyebath at 400C and pH6. This dyebath contains demineralized water, a standard anionic dye and the dye to be tested in an amount corresponding for each dye respectively to the amount sufficient to obtain a standard dyeing of 1/3 S.I. (Standard Intensity), 2 g/l sodium dihydrogen phosphate, 0.3 g/l disodiumhydrogen phosphate, and 2 X, by weight of the substrate, of tallow fatty amino-propylene-amine ethoxylated with an average of 100-120 mols of ethylene oxide.

The dyebath is then heated from 40 to 1000C at a rate of 1OC/min. The dye concentration in the dyebath is determined spectrophotometrically every 5 min (or 2.5 min when the dye builds up quickly) and calculated with a computer. The K'pH6-value of the dye to be tested is then calculated according to the method indicated by Atherton E. Downey D.A. and Peters R.H. in J.S.D.C. 74.242(1958).

The natural and synthetic polyamide material may be selected from wool, silk, the various commercial types of nylon, and the so-called "differential polyamides. The fibre material may be present in various states of processing, e.g. in the form of fleece, yarn, flocks, tops, wovens, knit fabrics, felts, plush fabrics or carpets.

Step a) of the process according to the invention is a dyeing process, which may be carried out by continuous or discontinuous methods. Such continuous methods include impregnation, (e.g.

padding), spraying, pouring or printing. It is when the material is in the form of individual fibres, that these fibres may be dyed by discontinuous methods such as exhaust dyeing, after which the dyed and treated fibres are woven with untreated fibres before the application of Step b). Depending on the method chosen, the resisting agent and the reactive dye can be applied to the fibre material from a long or a short dyebath, as a foam or printing paste.

If the material is present in the form of yarn or flocks, Step a) of the process according to the invention is preferably carried out by exhaust dyeing . After the yarn or the flock has been dyed with the reactive dye and the resisting agent, it is then woven with fibres that have not been treated according to Step a) before it is over-dyed. For example, dyed yarns may be mixed with untreated yarns by twisting, and then either over-dyed as a yarn, or tufted, woven or knitted and finally over-dyed as a ready-made piece. Fibre flocks, after mixing with untreated material, may be spun, twisted, and either tufted, woven or knitted and then over-dyed as a ready-made piece.

Fixing of the reactive dye and -the resisting agent preferably take place at elevated temperature. Fixing preferably takes place in a moist atmosphere, for example with saturated steam for 2 to 10 minutes.

In Step a) preferably the reactive dye and the resisting agent are applied locally to the woven, tufted or knitted fibre material by impregnation or printing.

Suitable colourless, fibre-reactive resisting agents for the dyeing process according to the invention are preferably selected from heterocyclic compounds containing 1 or 2 reactive halogen atoms (preferably containing a halogenated triazinyl group) and aliphatic compounds containing sulphonyl groups and having at least one double bond or a halide group.

Preferred heterocyclic compounds include compounds of formula I

in which Hal is F, C1 or Br,

X is a group of one of the formulae a) to m)

Z is Hal or Z1; Y is hydrogen, F or C1; Z1 is an amino group unsubstituted or substituted by one or two C1-4alkyl groups; or C1-6alkoxy; n is 0, 1, 2 or 3; and R is an alkyl group with 1 to 4 carbon atoms, and the -SO3 H and -COOH groups of the groups of formula a) to m) are preferably not bonded to the aromatic nuclei in an ortho-position to the oxygen or imino bridge member, and the aromatic nuclei may be substituted by 1 to 3 groups selected from halogen atoms, nitro-, cyano- or C1-4alkyl groups. Although the carboxy and sulpho groups 5 are represented in their free acid form, they may also be in salt form.

Preferred aliphatic compounds as fibre resisting agents include compounds of any one of formulae II to XVI R S02-CH2-CH2-O-SO3H (II) R1-SO2-CH=CH2 (III) R1-SO2-NH-CH2-CH2-O-SO3H (IV) R1-SO2-NH-CH2-CH2-C1 (V)

X-CO-CH=CH-CH2-Ha1' (VII) X-CO-CH2-Ha1' (VIII) X-CO-CH2-CH2-Ha1' (IX)

X-CO-CH=CH2 (XI)

X-CO-CH=CH-Ha1' (XIV)

in which R1 is a phenyl radical, unsubstituted or substituted by 1 to 3 groups selected from halogen, Alkyl and C1-4alkoxy; (preferably C1 and CH3); and Hal' is Cl or Br and X is as defined above.

Preferably the resisting agent contains at least one carboxy or sulpho group.

More preferably the colourless, fibre-reactive resisting agents are of formula I'

wherein R2' is a group of formula -N= or =C-Cl; Ra is C1~6alkoxy or a chlorine atom; Za is an alkali metal or -NH40 ; and m is 1 or 2.

The fibre-reactive resisting agents to be used according to the invention may be used in various quantities, depending on the application conditions or the desired colouring effect. In an exhaust process, 0.5 - 3 % of the fibre-reactive resisting agent is used, calculated on the dry goods. In an impregnation or printing process, the liquor or paste may contain up to about 30 g/kg of the fibrereactive resisting agent (100 % active substance), more preferably 1 to 20 g/kg, most preferably 2 to 15 g/kg (based on the liquor or paste).

Suitable reactive dyes which are used together with the fibrereactive resisting agent include all those reactive dyes which contain at least one fibre-reactive group and have an affinity for polyamide t a K'-value of 8 or less. Such dyes are known from the Colour Index and may be selected from the azo (monoazo, polyazo and metal-azo), anthraquinone, formazan, triphenyldioxazine, nitro and phthalocyanine series.

Apart from .he reactive dye and the fibre-reactive resisting agent a dye bath or printing paste used in Step a) of a process according to the invention may contain further dyeing assistants, for example a levelling agent, a hydrotropic agent, e.g. urea, a dispersing agent or a thickener. The dyebath or printing paste is advantageously set at a pH of 6-7. For impregnation or printing, the dyebath or printing paste is preferably applied at room temperature.

In the exhaust process, dyeing is preferably effected at a temperature between room temperature and 980C, advantageously at a goods to liquor ratio of 1:10 to 1:40, the pH of the dyebath being adjusted to pH 4 to 5.5 towards the end of dyeing so as to allow the bath to be completely exhausted. This reduction in pH may take place by adding an acid or an acid donor or by using a salt, such as ammonium sulphate to release acid.

Step b) of a process according to the invention may take place continuously or discontinuously. For example, the dyed fibre material may be over-dyed by an exhaust process at between 400 and 980C, advantageously at a goods to liquor ratio of 1:10 to 1:40. The dye bath is preferably initially set at a neutral/slightly alkaline pH value, and then a controlled pH reduction takes place to a final slightly acidic range at the end of dyeing. This may be effected by adding a suitable acid or by using an acid donor, for example as described in DOS 3,417,780.

Step b) may also be effected continuously, for example by the pad-steam, pad-roll or pad-batch process. The fibre material is impregnated with the dye liquor, preferably padded or poured, after which the dye is then fixed. The ratio of the amount of goods to liquor applied is preferably 1:0.7 to 1:10. Fixing preferably takes place between room temperature and 1O00C, whereby the duration of fixing depends on the chosen temperature conditions.

Dyes which are suitable for use in Step b) belong to the class of acid dyes, metal complex dyes and disperse dyes. If the fibre material contains "differential" polyamide or basic-modified synthetic polyamide, basic dyes may also be employed, optionally together with the disperse dyes. It is preferable to use acid dyes and/or 1:2-metal complex dyes having at least 1, preferably 2 sulpho groups in Step b). Disperse dyes are only used if special effects are to be obtained in combination with acid dyes or metal complex dyes, since they can also dye treated fibres.

In addition to the dyestuffs, the dyebath or printing paste used in Step b), may also contain further dyeing assistants, such as a levelling agent, a dispersing agent, a thickener, or a carrier.

After the completion of Step b), the fibre material is dried, after optionally rinsing.

The dyeings or prints obtained according to the invention, which are brilliant, are fast to washing and to light, and in addition have good resistance to boiling. These properties lead to very good reproducibility of the effects and high flexibility in the choice of Step b) method. In addition, depending on the conditions chosen, very great variability in colouring effects may be produced, which is especially pleasing to the eye.

The invention will now be illustrated by the following Examples in which all parts are by weight or by volume, all percentages are by weight; and all temperatures are given in OC, unless indicated to the contrary.

EXAMPLE 1 A polyamide-6 woven fabric is printed with 3 pastes, the pH of each being 6, and contain the following components in 1000 parts: 30 parts of a commercial resisting agent based on a sulphonated phenyltriazine according to Example 1 of DE-OS 2828030; 15 parts of a thickener based on locust bean ether; 100 parts of urea 5 parts of a commercial amphoteric levelling agent; 3 parts of C.I. Reactive Yellow 69 for paste 1; 5 parts of C.I. Reactive Red 100 for paste 2; and 3.7 parts of C.I. Reative Blue 209 for paste 3; the balance being water.

The printed woven fabric is then steamed for 5 minutes at 1020 and then over-dyed in a vat for 60 minutes at 980 in the following aqueous bath at a goods to liquor ratio of 1:20.

0.155 % C.I. Acid Orange 127 0.025 % C.I. Acid Red 299 0.155 % C.I. Acid Blue 113; and 2 % of a commercial cationic levelling agent based on a polyethoxylated fatty amine.

(All percentages are based on the dry weight of the goods). The dye bath also contains a commercial acid donor (Example 1 of DE-OS 3,417,780), so that the bath has a pH of 8 at the beginning of dyeing and a pH of 5 at the end.

The woven fabric obtained is then dried. Boil-resistant, brilliant yellow, red, blue prints are obtained on a grey background EXAMPLE 2 A polyamide 6 yarn is dyed by the exhaust process with an aqueous bath of the following composition: 0.5 % C.I. Reactive Yellow 69 0.3 % C.I. Reactive Blue 209 3 % of the resisting agent of Example 1, and 2 x of a commercial cationic levelling agent based on a polyethoxylated fatty amine.

The bath is set at pH 6-7 by the addition of mono/disodium phosphate. The goods to liquor ratio is 1:20. After dyeing for 30 minutes at 960, the pH of the dyebath is adjusted to 4-5 by adding the acid donor as described in Example 1, and dyeing is continued for a further 30 minutes at 960. The yarn is subsequently spun, with untreated PA-6 yarn, twisted and over-dyed with the acid dyes, as described in Example 1. A brilliant green resisted yarn, mixed with grey yarn, is obtained.

EXAMPLE 3 A polyamide-6 woven fabric is printed as described in Example 1, is treated with saturated steam for 5 minutes at 1020 and then padded with a 2nd bath, which contains the following components per 1000 parts: 0.31 parts of C.I. Acid Orange 127 0.05 parts of C.I. Acid Red 299 0.31 parts of C.I. Acid Blue 113 2 parts of a commercial cationic levelling agent from Example 2, 3 parts of a commercial wetting agent based on an ethoxylated alkylphenol; and 4 parts of the commercial thickener of Example 1; with the balance being water.

The bath is at pH 6. The liquor pick-up is 500 %. The woven fabric is then treated with saturated steam for 5 minutes. A clear yellow, red-, blue print on a grey background is obtained.

EXAMPLE 4 A polyamide 6.6 fabric is printed with a paste containing the following components in 1000 parts: 60.0 parts of a commercially available resisting agent (20 actives) based on a sulphonated phenyltriazine according to Example 1 of DOS 2,828,030; 15.0 parts of the thickener of Example 1, 100.0 parts of urea 5.00 parts of a commercially available amphoteric levelling agent 50.00 parts of NaCl 10.00 parts of the sodium saLt of trichloroacetic acid 5.00 parts of 10 % sulphuric acid 2.4 parts of C.I. Reactive Yellow 69; and 3.2 parts of C.I. Reactive Red 100; the balance being water.

The fabric is then steamed at 1020 for 15 minutes and is then overdyed for 60 minutes at 980 in a bath having a goods to liquor ratio of 1:15 containing: 0.08 % C.I. Acid Orange 127 0.20 x C.I. Acid Blue 113 and 2.0 X of a commercially available cationic levelling agent based on a polyethoxylated fatty amine.

The percentages are based on the dry weight of the material being dyed. The dyeing liquor contains a sufficient amount of a commercially available acid donor so that the pH at the beginning of the dyeing process is 8 and at the end the pH is 5.

The resulting fabric is then dried. A boil resistant brilliant red printing on a blue background results.

EXAMPLE 5 A polyamide 6 fabric is printed with a paste containing the following component in 1000 parts: 90 parts of the resisting agent of Example 1; 100 parts of urea 5 parts of a commercially available amphoteric levelling agent 50 parts of NaCl 14 parts of the sodium salt of trichloroacetic acid 0.24 parts of C.I. Reactive Yellow 69 0.14 parts of C.I. Reactive Red 100 and 0.18 parts of C.I. Reactive Blue 209.

The printed fabric is then steamed for 15 minutes at 1020 and then overdyed in a bath containing, in 1000 parts, the following components: 0.31 parts of C.I. Acid Orange 127 0.05 parts of C.I. Acid Red 299 0.31 parts of C.I. Acid Blue 113 2.00 parts of a commercially available cationic levelling agent based on a polyethoxylated fatty amine 3.00 parts of a commercially available wetting agent based on an ethoxylated alkyl phenol and 4.00 parts of the thickener of Example 1.

The bath is at pH 6 and the liquor pick-up is 500 %. The fabric is then treated with steam for 5 minutes.

A beige print on a grey background results.

EXAMPLE 6 Example 4 is repeated using for overdyeing additionally 0.1 % of C.I. Basic Blue 120. A violet print on a blue background results.

Claims

CLAIMS:

1. A process for dyeing natural and/or synthetic polyamide fibre material comprising a) applying at least one reactive dye having a K'-value of 8 or less together with a colourless fibre reactive resisting agent having a K'-value of more than 8 to an area of the material; and optionally fixing the dye and agent; (hereinafter defined as step a); b) applying a further dye to the whole material whereby the further dye is fixed to the remainder of the material (hereinafter defined as step b).

2. A process according to Claim 1, in which the colourless fibre reactive resisting agent is selected from heterocyclic compounds containing 1 or 2 reactive halogen atoms and aliphatic compounds containing sulphonyl group and having at least one double bond or a halide group.

3. A process according to Claim 2, in which the fibre reactive resisting agent contains at least one carboxy or one sulpho group.

4. A process according to Claim 2, in which the fibre reactive resisting agent is selected from compounds of formula I

in which Hal is F, Cl or Br,

X is a group of one of the formulae a) to m)

Z is Hal or Z1; Y is hydrogen, F or Cl; Z1 is an amino group unsubstituted or substituted by one or two C1-4alkyl groups; or C1~6alkoxy; n is 0, 1, 2 or 3; and R is an alkyl group with 1 to 4 carbon atoms, the aromatic nuclei may be substituted by 1 to 3 groups selected from halogen atoms, nitro-, cyano- or Alkyl groups; or compounds of formula II to XVI R1-SO2-CH2-CH2-O-SO3H (II) R1-SO2-CH=CH2 (III) R1-SO2-NH-CH2-CH2-O-SO3H (IV) R1-SO2-NH-CH2-CH2-Cl (V)

X-CO-CH=CH-CH2-Hal' (VII) X-CO-CH2-Hal' (VIII) X-CO-CH2-CH2-Hal' (IX)

X-CO-CH=CH2 (XI)

X-CO-CH=CH-Hal' (XIV)

in which R1 is a phenyl radical, unsubstituted or substituted by 1 to 3 groups selected from halogen? C14alkyl and C1-4alkoxy; Hal' is Cl or Br and X is as defined above.

5. A process according to Claim 1, in which the resisting agent is a compound formula I'

wherein R2' is a group of formula -N= or =C-Cl; Ra is C1-6alkoxy or a chlorine atom; Za is an alkali metal or -NH4+ ; and m is 1 or 2.

6. A process according to any one of the preceding claims in which the reactive dyes of Step a) are selected from the azo series, anthraquinone series, forazan series, triphenyldioxane series, nitro series and phthalocyanine series.

7. A process according to any one of the preceding claims in which Step a) is a printing or impregnation process.

8. A process according to any one of the preceding claims, in which the dyes used in Step b) are selected from acid dyes, metal complex dyes, dispersed dyes or basic dyes.

9. A process according to any one of the preceding claims in which Step b) is an exhaust dyeing process.

10. A process according to Claim 9, in which the dyebath of Step b) contains additionally one or more dyeing assistants selected from levelling agents, dispersing agent thickeners and carriers.

11. A process according to Claim 1 substantially as herein described with reference to any one of Examples 1 to 6.