US3837802A

US3837802A - Process for dyeing

Info

Publication number: US3837802A
Application number: US00215403A
Authority: US
Inventors: Vuilleme J Guye; E Koller; A Litzler; H Liechti; B Milicevic; H Angliker
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1968-03-28
Filing date: 1972-01-04
Publication date: 1974-09-24
Anticipated expiration: 1991-09-24

Abstract

A process for dyeing wherein textile material is dyed or printed with a solution containing at least one fiber-reactive dyestuff in a solvent.

Description

- United States Patent [19'] Litzler et al.

[451 Sept. 24, 1974 PROCESS FOR DYEING [75] Inventors: Alfred Litzler, Itingen; Hans Wilhelm Liechti, Oberwill; I Jean-Frederic Guye-Vuilleme, Aigle; Eugen Johann Koller, Oberwil; Branimir Milicevic, Riehen; Hans-Joerg Angliker, Basel, all of Switzerland [73] Assignee: Ciba-Geigy AG, Basle, Switzerland [22] Filed: Jan. 4, 1972 21 Appl. No.: 215,403

Related US. Application Data [63] Continuation of Ser. No. 808,661, March 19, 1969,

abandoned.

[30] Foreign Application Priority Data Jan. 27, 1969 Switzerland 1200/69 Mar. 28, 1968 Switzerland 4626/68 [52] US. Cl. 8/173, 8/174 [51] Int. Cl D06p 1/38 [58] Field of Search 8/93, 172, 173, 163,54, 8/174 [56] References Cited UNITED STATES PATENTS 3,097,043 Mills 8/163 OTHER PUBLICATIONS W. AS. White, Amer. Dyestuff Reporter, 7-31-1967, pp. P591-P597.

Primary Examiner-Thomas J. Herbert, J r. Attorney, Agent, or FirmJoseph G. Kolodny; Edward McC. Roberts; Prabodh I. Almaula [57] ABSTRACT A process for dyeing wherein textile material is dyed or printed with a solution containing at least one fiberreactive dyestuff in a solvent.

10 Claims, No Drawings PROCESS FOR DYEING This is a continuation of application Ser. No. 808,661, filed Mar. 19, 1969, now abandoned.

It has been proposed to dye fibres containing amide groups, especially nylon fibres, with fibre-reactive disperse dyestuffs in an aqueousmedium, but this procedure has not become established in practice because in general the dyeing has to be carried out in two steps and the degree of colour fastness obtained is not particularly good.

This invention is based on the surprising observation that these disadvantages can be overcome when the dyeing is carried out in organic solvents.

Accordingly, this invention provides a process for dyeing textile material made from hydrophobic staple fibres or filaments containing polar groups, especially staple fibres or filaments containing nitrogen atoms or ester groups, wherein the textile material is dyed or printed batchwise or, preferably, continuously, with a solution containing at least one fibre-reactive dyestuff in a solvent or mixture of solvents that remains to a large extent inert towards the textile material, even at the temperature at which dyeing is carried out.

The term fibre-reactive dyestuff used in this specification has the conventional meaning and refers to a dyestuff that combines, for example, with acylatable groups present in the fibre to form a covalent chemical bond.

The dyeing process described herein is suitable for all natural and synthetic fibres containing nitrogen atoms and/or ester groups. Nitrogenous fibres are, for example, wool, synthetic polyamides, especially poly(hexamethyleneadipic acid amide) or nylon 66, poly(wcaprolactam) or nylon 6, poly(hexamethylene-sebacic acid amide) or nylon 610, and poly( 1 l-aminoundecanoic acid) or nylon 11, acrylic or acrylonitrile fibres, polyacrylonitrile fibres and copolymers of acrylonitrile and other vinyl compounds, for example, acrylic esters, acrylamides, vinylpyridine, vinyl chloride or vinylidene chloride, copolymers of dicyanoethylene and vinyl acetate, and also fibres made from acrylonitrile block copolymers, polyurethane fibres and basically modified polypropylene fibres.

Examples of fibres containing ester groups are secondary acetate and triacetate fibres and fibres made from aromatic polyesters, for example, fibres made from terephthalic acid and ethylene glycol or 1,4-dimethylolcyclohexane, and copolymers of terephthalic and isophthalic acid and ethylene glycol.

When the nitrogenous fibres contain free amino groups they are capable of forming chemical bonds with the reactive dyestuffs used in accordance with the invention. When they do not contain reactive amino groups, the dyestuff is dispersed within the fibre as in the customary dyeing processes for disperse dyestuffs.

The dyestuffs to be used in accordance with the invention are preferably those of the well-known class of water-soluble or preferably water-insoluble fibrereactive disperse dyestuffs, for example, monoazo, disazo and polyazo dyestuffs, anthraquinone, perinone, quinophthalone, oxazine, nitroso, nitro, phthalocyanine, stilbene and methine dyestuffs, including styryl, azamethine, polymethine and azostyryl dyestuffs, and also metal-complex dyestuffs of the azo and formazan types.

Other types of suitable fibre-reactive dyestuff may also be used.

The dyestuffs to be used in accordance with the invention, which are preferably sparingly soluble or insoluble in water, contain in the molecule at least one fibrereactive group, for example s-triazinyl residues containing one or two chlorine or bromine atoms attached to the triazine ring, pyrimidyl residues containing one or two chlorine atoms or one or two arylsulphonyl or alkanesulphonyl groups attached to the pyrimidine ring, monoor bis(y-halogeno-B-hydroxypropyl) amino groups, B-halogeno-ethylsulphamyl residues, Bhalogeno-ethoxy groups, B-halogeno-ethylmercapto groups, 'y-halogeno-,Bhydroxypropy1sulphamy] residues, chloroacetylamino groups, vinylsulphonyl groups, 2,3-epoxypr0pyl groups, or other fibre-reactive residues which are preferably free from groups imparting solubility in water.

Suitable dyestuffs of the fibre-reactive disperse dyestuff series are indicated, for example, in British Pat. Nos. 822,500, 825,377, 833,396, 838,338, 821,963, 822,948, 856,899, 848,236, 840,903, 850,977, 862,269, 833,832, 836,671, 868,471, 856,898, 868,468, 855,715, 856,899, 879,263, 869,100, 877,250, 870,948, 895,424, 877,591, 901,434, 880,886, 917,873, 1,090,005 and 984,841, and also in US. Pat. No. 3,122,533 and French Pat. No. 1,276,443.

The following are given as examples of dyestuffs that can be used in accordance with the invention: 2-hydroxy-5-methyl-4-(4",6"-dichloro-s-triazinyl-2- amino)azobenzene, 2-chloro-4-ethanesulphonyl-4'-[N-B-hydroxyethyl-N- B-( 4 ,6 -dichloro-s-triazinyl-2-amino ethylamino]azobenzene,

4-(4' ,6 -dichloro-s-triazinyl-2-amino)-2- methylazobenzene, 2-hydroxy-5-methyl-4-(4' ,6 dibromo-s-triazinyl-2-amino) azobenzene, 2-hydroxy-5-methyl-4-(4"-chloro-6"-B- hydroxyethylamino-s-traizinyl-2-amino )azobenzene, 2-hydroxy-5-methyl-4 4 '-chloro6 -anilino-striazinyl-2-amino)-azobenzene,

2-hydroxy-5 -rnethyl-4 4 -chloro-6 -amino-striazinyl-2- amino)azobene, 2-chloro-4-ethanesulphonyl-4-[N-B-hydroxyethyl-N- B-( 4 '-chloro-6 'hydroxy-striazinylamino)ethylamino]azobenzene,

2-hydroxy-5 -methyl-4 4 '-bromo-6' N,N-di( B- hydroxyethyl)amino s-triazinyl-2-amino]azobenzene, 2-hydroxy-5-methyl-4-(4"-chloro-6"phenyl-striazinyl-2-amino) azobenzene,

4-amino-4 4 'chloro-6' '-phenyl-s-triazinyl-2- amino)azobenzene,

l-[4-(4 ,6 '-dichloro-s-triazinyl-2-amino )ani1ino]- anthraquinone,

1- 4 chloro-6 -phenoxy-s-triazinyl-2-amino)anilino anthraquinone, 4-(4",6"-dichloro-s-triazinyl-2-amino)-2,4- dinitrodiphenylamine,

4 4' -chloro-6' -methoxy-s-triazinyl-2amino )2,4- dinitrodiphenylamine,

2-hydroxy-s-methyl-4 '-(4 ,6 -dichloropyrimidinyl-2- amin0)-azobenzene,

1 ,4-bis('y-chloro-B-hydroxypropy1)aminoanthraquinone, 4-B-chloroethylsulphonylphenylazo-4-B-hydroxyethylaminonaphthalene,

3 4 4-B-chloroethylsulphonyl-2-methyl-5-N-ethyl-N-B- alcohols, for example, methanol, ethanol, n-propanol hydroxyethylaminoazobenzene, and isopropanol, ketones, for example, acetone, ethers 2-chloro-4-Bchloroethylsulphonyl-2'-methyl-5-di(B- and acetals, for example, dioxan, tetrahydrofuran, hydroxyethyl) aminoazobenzene, I glycerolformaldehyde and glycolformaldehyde, and l-methylamino-4-B-chloroethylaminoanthraquinone, 5 also acetonitrile and pyridine, diacetone alcohol and l,4'-(4",6"-dichloro-s-triazinyl-2-amino)phenylazo-Z- higher-boiling glycol derivatives, for example, ethylene naphthol, glycol monomethyl ether, ethylene glycol monoethyl 1-amino-2-B-bromoethoxy-4-hydroxyanthraquinone, ether, ethylene glycol monobutyl ether and diethylene 1-amino-4-hydroxy-2,B-(B-chloroethoxy)ethoxyanglycol monomethyl ether, diethylene glycol monoethyl thraquinone, l ether, thiodiglycol, polyethylene glycols, provided they 1-amino-2,,8-(B-bromoethoxyanthraquinone, are liquid at room temperature, ethylene carbonate, 2-cyano-4-methylsulphonyl-2'-'y-chlorocrotonylaminoy-butyrolactone and especially the group of active sol- 4'-bis(B-hydroxyethyl)aminoazobenzene, vents miscible with water which boil at a temperature l,B-hydroxyethylamino-4B-(B',B'- above 120 C, for example, N,N-dimethylformamide, dibromoacryl)aminoethylamino-S,8-dihydroxyanl5 N,N-dimethylacetamide, bis-(dimethylamido)- thraquinone, methane phosphate, tris-(dimethylarnido)-phosphate, and also the dyestuffs of the following formulae obtain- N-methylpyrrolidone, l,5-dimethylpyrrolidone, able in accordance with British Pat. No. 984,841: N,N-dimethylmethoxyacetamide, N,N,N,N-

tetramethylurea, tetramethylenesulphone (sulpholan), 3-methylsulpholan and dimethylsulphoxide.

ll T There are three preferred sub-groups in the series of hydrophilic solvents, namely 1) those suitable for disoH2-NH-co-oH o1 solving linear synthetic polymers or polycondensates capable of being spun, for example, acrylonitrile poly- Y mers, (2) those miscible with water in all proportions,

0 NH-C Hr and (3) solvents free from hydroxyl groups.

NH Specially preferred are mixtures of chlorinated aliz phatic hydrocarbons and up to 50 percent of a hydro- H @A CH3 1 philic solvent, especially an amide of a low-molecular OH NH CO CH 01 weight fatty acid, for example, dimethylacetamide or dimethylformamide.

I The process of the invention is preferably carried out NH-Q-CHE without the addition of dispersing agents with the advantage that the dyed textile material is more easily and A specially preferred use for the process in accordance cleaned. The addition of surfactants to the dyeing or with the invention is the dyeing of filament fabrics. padding liquor is optional.

Suitable solvents which have [0 be substantially inert Important surfactants are particularly those of the towards the staple fibres Ol' filaments at the temfollowing classes of non-ionic mpound; perature, that is to say, must not dissolve the staple a, ethers f l h d nd f x le, fibres filaments, for example, hydrophobic polyoxalkylated fatty alcohols, polyoxalkylated polyvents which are immiscible or only slightly miscible 1 l xalk l t d m rea mn and aliphatic amines, with water, for example, eyclohexanol, benzyl alcohol, l lk l ik l and alkyinaphthols, esters, for example, ethyl acetate, propyl acetate, butyl l lk l d alkylarylmemaptans and l l acetate, ethers, for example, diisopropylether or dimines p y oxide, ketones, for p y t ylb. fatty acid esters of ethylene glycols and polyethyl ketone, acetophenone 0r cyclohexanone, yd a ene glycols, fatty acid esters of propylene glycol and bons, for example, benzene, xylene or toluene and habutylene glycol, fatty acid esters of glycerol or polyglylogenated hydrocarbons, for example, Carbon te acerols and of pentaerythritol, and also of sugar alcochloride, chloroform, methylene chloride, tl'lClllOfOfithhols, for example, sorbitol, sorbitans and saccharose. ylene, perchloroethylene, trichloroethane, tetrachloroc. N-hydroxyalkyl-carboxylic acid amides, polyoxalkethane, dibromoethylene or chlorobenzene. ylated carboxylic acid amides and sulphonamides.

Hydrophilic solvents miscible with water are a spe- It is advantageous to use, for example, surfactants of cially preferred class of solvents, for example, aliphatic the following groups: the addition products obtained from 8 mols of ethylene oxide and 1 mol of para-tert.- octylphenol; from or 6 mols of ethylene oxide and castor oil; from mols of ethylene oxide and the alcohol C H OH; also the addition products of ethylene oxide with di-[a-phenylethyll-phenols, polyethylene oxide-tert.-dodecylthioethers or polyaminepolyglycol ethers, or the addition products obtained from 15 or 30 mols of ethylene oxide and 1 mol of the amine C H NH or C H ,NH

In the batchwise exhaustion method of dyeing, the textile material to be dyed may be in the form of loose material, a web, yarn, a knitted fabric or a woven fabric. Dyeing may be carried out in various types of apparatus, for example, pack-dyeing machines, cheesedyeing machines, jigs, winch becks, and so forth, depending on the nature of the material to be dyed.

The dyeing plant may be open to the ambient atmosphere (for example, via a reflux condenser) or it may be of the closed, for example, pressurized, type, and dyeing may be carried out under atmospheric pressure or superatmospheric pressure.

When the material has been dyed to the required depth of shade, it is removed from the dyebath and the solvent still adhering to it is removed either by a steam or hot-air treatment.

The dyeing process is however preferably carried out in a continuous manner, the textile material dyed in this way being mainly woven fabrics and carpets of all kinds; some kinds of knitted material can also be dyed continuously. The material is impregnated or printed, especially padded, and is then subjected to a heat treatment to fix the dyestuff on the fibre, preferably by a dry heat treatment at a temperature below the softening point of the fibre.

Impregnation on apadding mangle may be carried out either at room temperature or at an elevated temperature. After the passage through the dyestuff solution, the material is squeezed as required to a liquor uptake of about 50 to 130 percent referred to the dry weight of the material.

On leaving the padding mangle or printing machine, the impregnated or printed material may be dried if necessary; for example, it may be dried in a stream of air heated, for example to to 90 C, the treatment being of short duration, or it may be freed of most of the dyestuff solution still adhering to it by other means, for example, by centrifuging, or it may be subjected to fixation or thermofixation as it is. Fixation is carried out at a temperature above 100 C, preferably at a temperature of at least 170 to 240 C. On no account should the fixation temperature be as high as the softening temperature of the fibre.

Thermofixation may be carried out, for example, by steaming in saturated or unsaturated steam, or preferably by a dry heat treatment, for example, contact heat, a treatment with high-frequency alternating current, or infra-red radiation.

The optimum fixation conditions without damage to the fibre can be determined by a simple preliminary trial.

Fixation can also be carried out by a so-called coldbatching process in which the padded and squeezed fabric is batched up at room temperature without intermediate drying, wrapped in a plastic cover if necessary, and then left for some time, for example, for 24 hours, at room temperature. The fabric is finally unwrapped and freed from solvent by drying.

The following Examples illustrate the invention. Unless otherwise stated, the parts and percentages are by weight.

EXAMPLE 1 A nylon 66 filament fabric (anorak fabric) is padded cold with a solution of 10 parts of the dyestuff of the formula in 1,000 parts of dimethylacetamide, squeezed to a liquor uptake of 30 percent referred to the dry weight of the fabric, dried at 40 to 50 C in a stream of warm air and then thermofixed for one minute at 200 C in a thermofixation unit (dry air). A level, brilliant yellow dyeing is obtained in which a large proportion of dyestuff is chemically bound.

EXAMPLE 2 Padding is carried out in the manner described in Example 1, but using a mixture of 900 parts of perchloroethylene and 100 parts of dimethylacetamide as solvent. The fabric is then squeezed to a liquor uptake of 42 percent referred to the dry weight of the material. A brilliant yellow dyeing is obtained.

EXAMPLE 3 The same brilliant and level dyeing as that described in Example 2 is obtained by padding in the manner described in that Example and then fixing the dyestuff by steaming for 3 minutes at 100 C in a pad-steam unit. The proportion of chemically bound dyestuff in the dyeing is smaller than that present in the dyeing obtained by the process described in Example 2.

Example 4 EXAMPLE 5 A nylon 66 fabric is padded cold with a solution of 10 parts of the dyestuff of the formula N N CIH al lNagmg in 1,000 parts of a mixture comprising percent of perchloroethylcne and 10 percent of dimethylacetamide, squeezed to a liquor uptake of 42 percent referred to the dry weight of the material, dried at 40 to 50 C in a stream of warm air and then thermofixed for 1 minute at 200 C. A level, brilliant yellow dyeing is obtained in which a large proportion of dyestuff is chemically bound.

EXAMPLE 6 The procedure described in Example 5 is followed,

but using 20 parts of the dyestuff of the formula .A level, orange dyeing containing a high proportion of chemically bound dyestuff is obtained.

EXAMPLE 7 The procedure described in Example 5 is followed,

but using 20 parts of the dyestuff of the formula dissolved in dimethylacetamide without the addition of solvent and the fabric is squeezed to a liquor uptake of 30 percent. A level, orange dyeing containing a high proportion of chemically bound dyestuff is obtained.

I EXAMPLE 8 Dyeing is carried out in the manner described in Example 7, but using mixture of 90 percent of perchloroethylene and 10 percent of dimethylacetamide as solvent. The padded fabric is squeezed to a liquor uptake of 42 percent. A level, orange dyeing containing a high proportion of chemically bound dyestuff is obtained.

EXAMPLE 9 Dyeing is carried out in the manner described in Example 8, but using the dyestuff of the formula l zHs obtained by acylation with chloroacetyl chloride. A level, red dyeing containing a larger portion of chemically bound dyestuff is obtained.

EXAMPLE l0 Dyeing is carried out in the manner described in Example 9, but using as substratum a polyester fabric (Terylene twill). The padded material is squeezed to a liquor uptake of 43 percent referred to the dry weight of the material, and thermofixed for 1 minute at 210 C. A level, brilliant red dyeing fast to boiling is obtained.

EXAMPLE ll Dyeing is carried out in the manner described in Example 5, but using the dyestuff of the formula on or We claim:

1. A process for dyeing textile material made from polyamide, polyester, or polyacrylonitrile fibers which consists essentially of applying to said textile material a substantially anhydrous solution containing at least one fiber-reactive dyestuff in a solvent or mixture of solvents which are substantially inert to the textile material at the temperature of the application andlwhich is additionally selected from the group consisting of cyclohexanol, benzyl alcohol, ethyl acetate, propyl acetate, butyl acetate, diisopropylether, diphenyl oxide, methylethylketone, acetophenone, cyclohexanone, benzene, toluene, xylene, carbon tetrachloride, clhloroform, methylene chloride, trichloroethylene, perchloroethylene, tetrachloroethane, dibromoethylene, chlorobenzene, methanol, ethanol, n-propanol, isopropanol, acetone, dioxan, tetrahydrofuran, glycerolformaldehyde, glycolformaldehyde, acetonitrile, pyridine, diacetone alcohol, ethylene glycol [monoethyllmonomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, thiodiglycol, ethylene carbonate, y-butyrolactone, N,N-dimethylformamide, N,N- dimethylacetamide, bis-(dimethylamido)-methane phosphate, tris-( dimethylamido )-phosphate, N- methylpyrrolidone, 1,5-dimethylpyrrolidone, N,N- dimethylmethoxy-acetamide, N,N,N,N- tetramethylurea, tetramethylenesulphone, 3-

methylsulpholan and dimethylsolphoxide, drying the textile material, and thereafter heating the textile material to fix the dyestuff thereon by reaction between the fiber-reactive dyestuff and the fibers to form a covalent bond.

2. A process according to claim 1 in which the solvent used is miscible with water in all proportions.

3. A process according to claim 1 in which the solvent is N,N-dimethylacetamide or N,N-dimethylformamide.

4. A process according to claim 1 in which the solvent used is N-methylpyrrolidone.

5. A process according to claim 1 in which the solvent used is tetramethylenesulphone, or 3- methylsulpholan.

6. A process according to claim 1 in which ethylene carbonate or butyrolactone is the solvent,

7. A process according to claim 1 in which there is incorporated in the dyeing solution a non-ionic surfactant.

8. A process according to claim 1 in which the fiberreactive dyestuff contains a heterocyclic residue selected from s-triazinyl containing one or two halogen atoms, said halogen atoms being selected from chlorine or bromine, or pyrimidyl containing one or two chlorine atoms or phenylsulphonyl or methylsulphonyl groups.

9. A process according to claim 1 in which the fiberreactive dyestuff contains an aliphatic acyl group selected from y-chlorocrotonylamino, a,B-dibromocrotonylamino, B,/3-dibromoacrylamino, a-chloroacrylamino, a,B-bromoacrylamino, monochloroacetyl and monochloroacetylamino.

10. A process according to claim 1 in which the fabric is dried by evaporation prior to fixation of the dyestuff.

Claims

2. A process according to claim 1 in which the solvent used is miscible with water in all proportions.
3. A process according to claim 1 in which the solvent is N,N-dimethylacetamide or N,N-dimethylformamide.
4. A process according to claim 1 in which the solvent used is N-methylpyrrolidone.
5. A process according to claim 1 in which the solvent used is tetramethylenesulphone, or 3-methylsulpholan.
6. A process according to claim 1 in which ethylene carbonate or butyrolactone is the solvent.
7. A process according to claim 1 in which there is incorporated in the dyeing solution a non-ionic surfactant.
8. A process according to claim 1 in which the fiber-reactive dyestuff contains a heterocyclic rEsidue selected from s-triazinyl containing one or two halogen atoms, said halogen atoms being selected from chlorine or bromine, or pyrimidyl containing one or two chlorine atoms or phenylsulphonyl or methylsulphonyl groups.
9. A process according to claim 1 in which the fiber-reactive dyestuff contains an aliphatic acyl group selected from gamma -chlorocrotonylamino, Alpha , Beta -dibromocrotonylamino, Beta , Beta ''-dibromoacrylamino, Alpha -chloroacrylamino, Alpha , Beta -bromoacrylamino, monochloroacetyl and monochloroacetylamino.
10. A process according to claim 1 in which the fabric is dried by evaporation prior to fixation of the dyestuff.