NZ216281A

NZ216281A - Dyeing natural or synthetic polyamide fibre materials

Info

Publication number: NZ216281A
Application number: NZ216281A
Authority: NZ
Inventors: Gerhard Back; Walter Mosimann
Original assignee: Ciba Geigy Ag
Priority date: 1985-05-24
Filing date: 1986-05-23
Publication date: 1990-04-26
Also published as: CA1273154A; ES555250A0; AU581316B2; EP0203890A1; AU5787186A; HK13894A; JPH0151593B2; JPS61275488A; EP0203890B1; KR860009083A; DE3668021D1; ES8706880A1; ZA863825B

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £16281 Patents Form No. 5 new zealand patents act 1953 complete specification "PROCESS FOR DYEING NATURAL OR SYNTHETIC POLYAMIDE FIBRE MATERIALS WITH MIXTURES OF DYES" —I/WE/ CIBA-GEIGY AG of Klybeckstrasse 141, 4002 Basle Switzerland, a Swiss Corporation hereby declare the invention, for which -£/-we pray that a patent may be granted to ree/us, and the method by which it is to be performed, to be particularly described in and by the following statement - 1 - (followed by page I A.) - 1Qr 21 1-15356/+ Process for dyeing natural or synthetic polyamide fibre materials with mixtures of dyes The present invention relates to a novel process for the non-skit-tery and level dyeing of natural and synthetic polyamide fibre materials from an aqueous liquor with mixtures of 1:1 metal complex dyes which contain sulfo groups and metal-free dyes which contain sulfo groups, in the presence of a source of fluoride ions such as an alkali metal or ammonium fluoride, an alkali metal or ammonium fluorosilicate, an alkali metal or ammonium fluoroborate, an alkali metal or ammonium fluorozirconate or an alkali metal or ammonium fluorosulfonate, and optionally in the presence of an assistant, in which process dyeing is carried out at a fibre-preserving pH value in the range from 3 to 7 with virtually complete exhaustion of the dyebath, and the dyeing so obtained has good allround fastness properties, in particular good fastness to wet processing and light. The invention further relates to the material dyed by the novel process and to a composition for carrying out said process. The disadvantage of the conventional methods of dyeing natural or synthetic polyamide fibre materials with 1:1 metal complex dyes or mixtures thereof with metal-free acid dyes is that these dyes or mixtures must be applied in the pH range from 1.9 to 2.8 in order to obtain level dyeings. In addition to the duration of dyeing, the pH of the dyebath is of decisive importance for dyeing natural and synthetic polyamide fibre materials, especially for dyeing wool, as these fibre materials, again in particular wool, are severely attacked both in the strongly acidic and in the strongly alkaline pH range. 216281 - 2 Surprisingly, there has now been found a novel process that does not have the shortcoming referred to above and which makes it possible to dye natural or synthetic polyamide materials, in simple manner, in the fibre-preserving pH range from 3 tu 7, preferably from 3 to 6 and, most preferably, from 3.5 to 5. Very particular preference is given to the pH range from 4 to 5. Accordingly, the present invention relates to a process for dyeing natural or synthetic polyamide fibre material from an aqueous liquor with mixtures of dyes, in the presence of an alkali metal salt or an ammonium salt and optionally in the presence of an assistant, which process comprises dyeing said fibre material with a mixture containing at least one 1:1 metal complex dye which contains sulfo groups and at least one metal-free dye which contains sulfo groups, in the presence of an alkali metal or ammonium fluoride, an alkali metal or ammonium fluorosilicate, an alkali metal or ammonium fluoroborate, an alkali metal or ammonium fluorozirconate or an alkali metal or ammonium fluorosulfonate, at a pH value in the range from 3 to 7. The eligible 1:1 metal complex dyes which contain sulfo groups are preferably monoazo or disazo dyes which contain a chromium ion as metal ion. It is also possible to use 1:1 metal complex azomethine dyes which preferably contain a chromium ion. The eligible metal-free dyes which contain sulfo groups are preferably acid to strongly acid dyes selected from the series of the monoazo or polyazo, anthraquinone, triphenylmethane or xanthene dyes that may contain the customary substituents of acid dyes. These sulfo-containing metal-free dyes may be substituted by fibre-reactive radicals. Depending on the desired depth of shade, the amounts in which the dye mixtures are added to the dyebaths may vary within wide limits. In general, amounts from 0.01 to 10 percent by weight, based on the goods to be dyed, of one or more dye mixtures are advantageous. 2 1 62 - 3 - It has long been known to dye natural or synthetic polyamide fibre materials with 1:1 metal complex dyes or mixtures thereof with metal-free dyes in the presence of an alkali metal sulfate or alkali metal chloride, for example sodium sulfate and sodium chloride, and optionally of an assistant. Surprisingly, the use of an alkali metal or ammonium fluoride, of an alkali metal or ammonium fluorosilicate, of an alkali metal or ammonium fluoroborate, of an alkali metal or ammonium fluorozirconate or of an alkali metal or ammonium fluoro-sulfonate, optionally in the presence of an assistant, makes it possible to dye these materials in a fibre-preserving pH range to give level dyeings with good penetration of the dye. In the process of this invention, it is preferred to use sodium or potassium fluoride as alkali metal fluoride. The alkali metal fluorosilicate or ammonium fluorosilicate employed in the process of this invention is the alkali metal salt or ammonium salt of hexafluorosilicic acid. It is preferred to use Na2SiF6, K2SiF6 or (NHu)2SiF6. The alkali metal fluoroborate or ammonium fluoroborate employed in the process of the invention is the alkali metal salt or ammonium salt of fluoroboric acid. It is preferred to use NaBFu, KBFi» or nhi»bfi». The alkali metal or ammonium fluorozirconate employed in the process of this invention is an alkali metal hexafluorozirconate or ammonium hexafluorozirconate, preferably K2(ZrFe). The alkali metal or ammonium fluorosulfonate employed in the process of this invention is an alkali metal salt or an ammonium salt of fluorosulfonic acid, and is preferably NaFSC>3, KFSO3 or NHi»FS03. 2 1 62 - 4 - Preferred embodiments of the process of this invention comprise: a) dyeing in the presence of an alkali metal fluoride or ammonium fluoride, preferably sodium or potassium fluoride or ammonium fluoride, optionally in the presence of an assistant or of a mixture of assistants, b) dyeing in the presence of an alkali metal fluorosilicate or ammonium fluorosilicate, preferably sodium or potassium fluorosilicate or ammonium fluorosilicate, c) dyeing in the presence of an alkali metal fluoroborate or ammonium fluoroborate, d) dyeing in the presence of an alkali metal hexafluorozirconate or ammonium fluorozirconate, preferably KziZrF^), e) dyeing in the presence of an alkali metal fluorosulfonate or ammonium fluorosulfonate, preferably KFSO3- A particularly preferred embodiment of the process of this invention comprises dyeing in the presence of an alkali metal fluoride or ammonium fluoride, an alkali metal fluorosilicate or ammonium fluorosilicate, or of an alkali metal fluoroborate or ammonium fluoroborate. The amount in which the alkali metal or ammonium fluoride, alkali metal or ammonium fluorosilicate, alkali metal or ammonium fluoroborate, alkali metal or ammonium fluorozirconate or alkali metal or ammonium fluorosulfonate is added to the dyebaths may vary within wide limits. In general, half to four times the amount by weight, preferably one to three times the amount by weight and, most preferably, two to three times the amount by weight, of alkali metal or ammonium fluoride, alkali metal or ammonium fluorosilicate, of alkali metal or ammonium fluoroborate, alkali metal or ammonium fluorozirconate or alkali metal or ammonium fluorosulfonate, based on the amount by weight of dye, is advantageous. 2 1628 1 - 5 - The assistants which may be used in the process of this invention are known per se and are prepared by known methods. Preferably, they are levelling assistants or mixtures of different levelling assistants. Suitable levelling assistants are anionic, cationic, nonionic and amphoteric compounds or fixtures thereof. Examples of suitable anionic compounds are: substituted naphthalene-sulfonic acids, sulfonic acid hemiesters of ethoxylates, salts of alkanesulfonic acids of longer chain length, salts of alkylaryl-sulfonic acids, in particular dodecylbenzenesulfonic acids> fatty acid amide sulfonic acids, and sulfuric acid hemiesters of fatty amine polyglycol ethers. Representative examples of cationic compounds are: polyglycol ethers of fatty amines, polyglycol ethers of fatty acid amide-amines, and quaternary ammonium compounds. Typical examples of nonionic compounds are: polyglycol ethers of fatty alcohols, of alkylphenols, of resinic acids, and of fatty acid alkylolamides. Typical examples of amphoteric compounds are: reaction products of ethoxylated fatty amines and hydroxyethane-sulfonic acids, reaction products of phenol and styrene, and polyethylene glycol di-fatty acid esters. It is preferred to use levelling assistant compositions containing compounds of the formula a ch2-ch2-ch—s03m r-< " (1) (ch2-ck2-cH—so3m n wherein R is an alkyl or alkenyl radical of 12 to 22 carbon atoms, M is hydrogen, an alkali metal or ammonium cation, and m and n are integers, the sum of m + n being from 2 to 14; or compounds of the formula 2 1628 1 6 © (ch2-ch2-0-3 h P R'- (2) e (ch2-ch2-o—j—h q a wherein R' independently of R has the meaning of R, A is an anion, Q is an unsubstituted or substituted alkyl radical and p and q are integers, the sun of p + q being from 2 to 50; or compounds of the formula wherein R" independently of R has the meaning of R and x and y are integers, the sum of x + y being from 80 to 140; or a mixture containing compounds of the formulae (1) and (2) or a mixture containing compounds of the formulae (1), (2) and (3). It is particularly preferred to use a mixture of levelling assistants comprising 5 to 70 parts by weight of a compound of formula (1), 15 to 60 parts by weight of the compound of formula (2), and 5 to 60 parts by weight of the compound of formula (3), based on 100 parts by weight of said mixture, wherein R, R' and R" in formulae (1), (2) and (3) are independently an alkyl or alkenyl radical of 16 to 22 carbon atoms. It is advantageous to use a compound of formula (2), wherein A and Q are derived from a quaternising agent selected from the group consisting of chloroacetamide, ethylene chlorohydrin, ethylene bromohydrin, epichlorohydrin, epibromohydrin or, preferably, dimethyl sulfate. r"—n—( ch2—chj—0—)—h y (3) - 7 - 21628 1 In the process of this invention it is preferred to use a mixture of levelling assistants which, in addition to comprising the compounds of the formulae (1), (2) and (3), wherein the sum of p + q in formula (2) is preferably fros 20 to 50, also contains an adduct of 60 to 100 moles of ethylene oxide with 1 mole of a Cis~C2oalkenyl alcohol. It is also preferred to use a mixture of levelling assistants which contains the compounds of the formulae (1) and (2), wherein the sum of p + q in formula (2) is 4 to 10. It is further preferred to use a mixture of levelling assistants which contains compounds of formula (2), wherein the sum of p + q in formula (2) is 30 to 40, and R" is a Cis-Czaalkyl radical. The amount in which the levelling assistant or mixture of levelling assistants is added to the dyebaths can vary within wide limits; but in general an amount of 0.3 to 3 percent by weight, preferably of 1 or 2 percent by weight, based on the fibre material, of the levelling assistant or mixture thereof, is advantageous. The dyebaths may contain, as further assistants, mineral acids such as sulfuric acid, sulfamic acid or phosphoric acid, or organic acids, preferably lower aliphatic carboxylic acids such as formic acid, acetic acid or maleic acid. These acids are employed in particular for adjusting the pH of the dyebath. It is preferred to adjust the pH of 3 to 7 with an organic acid, preferably with acetic acid or formic acid. Dyeing is preferably carried out in the pH range from 3 to 6, preferably from 3.5 to 5 and, most preferably, from 4 to 5. The dyebath may contain, as further assistants, a salt other than an alkali metal or ammonium fluoride, alkali metal or ammonium fluorosilicate, alkali metal or ammonium fluoroborate, alkali - 8 - 7 1628 1 metal or ammonium fluorozirconate or alkali metal or ammonium fluorosulfonate, in particular an ammonium salt or alkali metal salt, for example ammonium sulfate, ammonium acetate or, preferably, sodium acetate or sodium sulfate. It is preferred to use 0.1 to 10 percent by weight of ammonium salt or alkali metal salt, based on the fibre material. The dye mixtures employed in the proces of this invention are preferably mixtures that contain at least one 1:1 chromium complex azo or azomethine dye containing 1 to 3, preferably 1 or 2, sulfo groups, and at least one metal-free dye containing 1 or 2 sulfo groups. The sulfo-containing metal-free dyes employed in the process of this invention are preferably those having good migration properties. The migrating power of these dyes shall correspond to those of the 1:1 chromium complex azo or azomethine dyes. A range from 25 to 50 % has proved advantageous as a good migrating power (dyeing at pH 4 to 5 and measured as difference in strength)- The migrating power is determined on wool by treating a sample which has been dyed to 1/1 standard depth of shade, together with an undyed sample of the same weight, in a blank bath. The treatment conditions for determining the migrating power match those indicated in Example 1. Evaluation is made by spectrophotometry determination of the amount of dye present on the originally undyed wool in percent of the originally dyed wool. Examples of metal-free sulfo-containing dyes are C.I. Acid Blue 1, 7, 13, 23, 40, 40:1, 43, 45, 47, 72, 147, 258 and 277; C.I. Acid Red 1, 5, 37, 42, 52, 57 and 361; C.I. Acid Yellow 10, 17, 25, 27, 99 and 219; C.I. Acid Orange 1, 3 and 156; C.I. Acid Green 3, 9 and 16; C.I. Acid Violet 9 and 36; C.I. Acid Brown 10, II and 248. 1 628 1 - 9 - In the process of this invention it is also posible to use mixtures of several dye mixtures as defined herein. A preferred mixture of dye mixtures as defined herein is: a) at least two 1:1 chromium complex azo or azomethine dyes and at least one sulfo-containing metal-free dye; and b) at least three 1:1 chromium complex azo or azomethine dyes and at least one sulfo-containing metal-free dye; or c) for trichromatic dyeing, at least three 1:1 chromium complex azo or azomethine dyes selected from dyes that give yellow or orange, red and blue dyeings, and at least one metal-free dye selected fromm dyes that give yellow or orange and/or red and/or blue dyeings. By trichromatic dyeing is meant the additive blending of suitably chosen dyes that give yellow or orange, red and blue dyeings with which any desired shade of the visible colour spectrum can be matched by suitable choice of the quantity ratios of the dyes. 1:1 Chromium complex azo or azomethine dyes employed in the process of this invention are, in particular, those of the formula (0 or NRi) (co) 0-1 I N=Y—& An (4) -(S03M) 1-2 wherein -(CCs)q_^0— and -(0- or -NRi) are linked to D and K adjacent to the azo bridge, D is the radical of a diazo component of the benzene or naphthalene series, K is the radical of a coupling component of the benzene, naphthalene or heterocyclic series or of the acetoacetarylide series, Ri is hydrogen or an unsubstituted or substituted alkyl or phenyl radical, M is a cation and An is an anion, and Y is a nitrogen atom or the -CH- group. 216281 10 In the process of this invention it is preferred to use sulfo-con-taining 1:1 chromium complex azo or azomethine dyes of the formula (4), wherein D is a radical of the benzene or naphthalene series which is unsubstituted or substituted by halogen, Cj-Cualkyl, Cj-Cualkoxy, nitro or sulfamoyl, R is a phenyl, napntnyi, i-pnenyl-3-methylpyrazol-5-one, acetoacetamide, preferably acetoacetanilide, or a quinoline radical, each unsubstituted or substituted by halogen, Ci-Cualkyl, Ci-C^alkoxy, Cj-Cbalkanoylamino, sulfamoyl or hydroxy, Ri is hydrogen and M is an alkali metal cation. Y in formula (4) is preferably a nitrogen atom. The sulfo-containing metal-free dyes employed in the process of this invention are preferably those of the dyestuff series referred to above, which dyes may be substituted by e.g. Ci-Cualkyl groups such as methyl, ethyl, propyl, isopropyl and butyl, or by Ci-Citalkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy and butoxy, or Ci-Csacylamino groups such as acetylamino and propionylamino, benzoylamino, amino, Ci-Cualkylamino, phenylamino, Ci-Cualkoxy-carbonyl, nitro, acetyl, cyano, trifluoromethyl, halogen such as fluorine, chlorine and bromine, sulfamoyl, carbamoyl, ureido, hydroxy, carboxy and sulfomethyl. The sulfo-containing metal-free dyes may also be substituted by one or more fibre-reactive radicals. Examples of suitable fibre-reactive radicals are those listed in USA 4228363. In the process of this invention it is preferred to use mixtures of sulfo-containing 1:1 metal complex dyes and sulfo-containing metal-free dyes in the weight ratio of 40:60 to 95:5. The sulfo-containing dyes employed in the process of this invention are either in the form of the free sulfonic acid or, preferably, of the salts thereof. 216281 - li - Examples of suitable salts are alkali metal, alkaline earth metal or ammonium salts, or the salts of an organic amine. Representative examples are the sodium, lithium, potassium or ammonium salts or the salt of triethanolamine. The sulfo-containing 1:1 metal complex dyes and the sulfo-containing metal-free dyes employed in the process of this invention are known per se and can be obtained by known methods. The mixtures of dyes used in the process of the invention may be prepared by mixing the individual dyes. Mixing is carried out in suitable mills, e.g. ball or pin mills, as well as in kneaders or mixers. Further, the mixtures can also be prepared by spray drying aqueous dye mixtures. In addition to containing the dye and the aforementioned assistants, the dyebaths may contain further conventional auxiliaries, for example wool protecting agents, wetting agents and antifoams. The liquor to goods ratio may be chosen within a wide range from 1:6 to 1:80, preferably from 1:10 to 1:30. Dyeing is carried out from an aqueous bath by the exhaust process, for example in the temperature range from 80° to 105°C or 110°C when using a wool protecting agent that splits off formaldehyde, preferably in the range from 98° to 103°C. The dyeing time is normally from 30 to 120 minutes. Special apparatus is not required for carrying out the process of the invention. The conventional dyeing machines, e.g. for flocks, tops, hank yarn, packages, piece goods and carpets, may be used. 2 1 62 8 - 12 - The levelling assistant and the alkali metal or ammonium fluoride, alkali metal or ammonium fluorosilicate, alkali metal or ammonium fluoroborate, alkali metal or ammonium fluorozirconate or alkali metal or ammonium fluorosulfonate is conveniently added to the aqueous dyebath and applied simultaneously with the dye. An alternative procedure is to treat the goods to be dyed first with the levelling assistant and then to dye the goods, in the same bath, after addition of the dye and of the alkali metal or ammonium fluoride, alkali metal or ammonium fluorosilicate, alkali metal or ammonium fluoroborate, alkali metal or ammonium fluorozirconate or alkali metal or ammonium fluorosulfonate. It is preferred to put the fibre material into a bath which contains acid and the assistant and has a temperature of 30° to 70°C. Then the dye mixture and the alkali metal or ammonium fluoride, alkali metal or ammonium fluorosilicate, alkali metal or ammonium fluoroborate, alkali metal or ammonium fluorozirconate or alkali metal or ammonium fluorosulfonate is added and the temperature of the dyebath is raised at a rate of 0.75 to 3°C per minute, optionally with a temperature stop during the heating up phase, in order to dye in the indicated temperature range from 80° to 105°C, preferably for 30 to 120 minutes. Finally, the bath is cooled and the dyed material is rinsed and dried in conventional manner. Natural polyamide fibre material that may be dyed by the process of this invention is, in particular, wool and also wool/polyamide, wool/polyester, wool/cellulose or wool/polyacrylonitrile blends as well as silk. The fibre material may be in a very wide range of presentation, for example as loose material, tops, yarn and piece goods or carpets. Synthetic polyamide material that may be dyed by the process of this invention comprises all known synthetic polyamides. The fibre material may be in a very wide range of presentation, for example as loose material, tops, yarn and piece goods or carpets. 2 1 62^1 - 13 - A particularly preferred embodiment of the process of this invention comprises dyeing natural or synthetic polyamide fibre material, preferably wool, with at least one dye mixture as defined above, in the presence of sodium fluoride, ammonium fluorosilicate or sodium fluorosilicate, preferably in two to fhree tises the smcunt bv weight, based on the amount by weight of 1:1 chromium complex dye, and optionally in the presence of a levelling assistant comprising compounds of the formula (2) or a mixture of compounds of the formulae (1) and (2) or (1), (2) and (3), and in the presence of sodium acetate, ammonium acetate or sodium sulfate, in the pH range from 4 to 5. The sulfo-containing metal-free dyes used in the process of the present invention may contain one or more fibre-reactive groups. In the process of the invention it is preferred to use those mixtures of 1:1 metal complex dyes as defined herein, wherein the metal—free dyes are either all reactive dyes or are all devoid of fibre-reactive groups. It is most preferred to use sulfo-containing metal-free dyes that do not contain fibre-reactive groups. A very particularly preferred embodiment of the invention comprises the use of dye mixtures consisting of those metal-containing and metal-free dyes which give dyeings of the same shade, i.e. for example the use of a mixture of at least one sulfo-containing 1:1 metal complex dye and at least one sulfo-containing metal-free dye, each of which dyes in a blue shade. Compared with the known processes for dyeing natural or synthetic polyamide fibre material, the process of this invention has the following advantages in addition to those already mentioned above. The material dyed under the dyeing conditions has better allround fastness properties, in particular better wetfastness properties. A further essential advantage is that the dyes are taken up almost completely onto the fibre. When dyeing is complete, the dyebaths are almost completely exhausted. 2 1 62% - 14 - The invention further relates to a composition for carrying out the process of the invention. The composition is a solid mixture containing at least one sulfo-containing 1:1 metal complex dye, in particular a 1:1 chromium complex dye, and at least one sulfo-containing metal-free aye, ana an alkali metal or ammonium fluoride, alkali metal or ammonium fluorosilicate, alkali metal or ammonium fluoroborate, alkali metal or ammonium fluorozirconate or alkali metal or ammonium fluorosulfonate. The composition of this invention is prepared by mixing a sulfo-containing 1:1 chromium complex dye and at least one sulfo-containing metal-free dye with an alkali metal or ammonium fluoride, alkali metal or ammonium fluorosilicate, alkali metal or ammonium fluoroborate, alkali metal or ammonium fluorozirconate or alkali metal or ammonium fluorosulfonate. Mixing is carried out, for example, in suitable mills, e.g. ball or pin mills, as well as in kneaders or mixers. Preferred compositions contain sodium or ammonium fluoride or sodium or ammonium fluorosilicate, in addition to the dye mixture. The solid mixtures can be used for dyeing natural or synthetic polyamide fibre materials. The same preferences apply to the solid mixtures as to the process. The invention is illustrated by the following Examples, in which parts and percentages are by weight. The relationship of parts by weight to parts by volume is the same as that of the gram to the cubic centimetre. The indicated amounts of dye refer to commercially available dye. O -* n - 15 - Example 1: 800 parts of worsted spun yarn are pretreated for 15 minutes at 50°C in a dyebath containing, in 20,000 parts of water at 50°C, 64 parts of sodium sulfate, 24 parts of (NHi,)2SiF6 and 12 parts of a levelling assistant consisting of: 24 parts of the anionic compound of formula (chz-chj-o—)—s03nhu r2-< ( ch 2 -ck 2-0—3 s03nhi» n R2 « Ci6-Cighydrocarbon radical; m + n * 7; 24 parts of the quaternary compound of formula © (ch2-ch2-0-3—h R3"isf P p + q - 34, ( ch2-ch2-0—j h ch3 q ch30-s02-0e R3 * C2o~C22hydrocarbon radical; 5 parts of ammonium chloride 3 parts of oxalic acid and 44 parts of water, based on 100 parts of levelling assistant. After addition of a solution of 2.2 parts of the 1:1 chromium complex of the dye of formula Ho|3 N=N-C-C0-NH—^ N6Z £ '6 S£p ftgp 2 1 628 1 - 16 - 2.4 parts of the 1:1 chromium complex of the dye of formula =N- ? \ I II I •« • • Io3h f)H T~? /x/* T u i -ch] 0.6 part of the 1:1 chromium complex of the dye of formula ho 3 f f HO. \ K „ / \ j i ii rN=N~\ /* • • • • SS • I y \ I i so3h 0.65 part of the 1:1 chromium complex of the dye of formula ^OH <j)H |03H • s* • • • / \ ^ / \ ^ . . ^ f 2.2 parts of the dye of formula /0CH3 n=n—^ n=n—^ och3 s63h 628 1 - 17 - 2.4 parts of the dye of formula CH3-$— ( H )* I "fL I II \ / V ho-< )• ss03h and 1.2 parts of the dye of formula | J., S \ \ s \ cn u • • • •— SOiH I II II I 3 • • • • ^ / \ / \ / • • •' $ 1H—^ nh-CO-CH2CH3 the dyebath is kept for 10 minutes at 50°C and then heated to 98°C at a rate of 0.8°C/minute. The pH is 4.6 at the commencement of dyeing. After a dyeing time of 90 minutes at 98°C, the dyebath is cooled to 50°C and drained off. The brown wool yarn is rinsed first for 10 minutes at 50°C and then for 10 minutes at room temperature and dried in conventional manner. The medium brown dyeing so obtained has excellent levelness and good fastness properties. Example 2: 100 parts of wool fabric are pretreated for 15 minutes at 40°C in a dyebath containing, in 2000 parts of water of 40°C, 8 parts of sodium sulfate, 1.2 parts of the levelling assistant employed in Example 1 and 1.5 parts of 85 % formic acid. The pH of the bath is 4.3. After addition of a solution of 1.9 parts of sodium fluoride and 0.695 part of the dye of formula * - 18 - Na03S. ? ? I r—0. \ rs=CH' s f *\ /* —• i •=• V-=H NSO,> cfi3 0.59 part of the dye of formula rT^ N'aO 3 S ' y v ! 8 >i \0jNa V Cf(, k 0.26 part of the dye of formula per f ^ \ 1 „ / \ / ^ . jj-S—M-J j; | cf Na03S/ N«^ NS03Na 6CH3 0.31 part of the dye of formula r -Cr- t f 03Na Na03S—' ' M=n-^ v S / » \ y 1 I! I ss\s' 628 1 - 19 0.28 part of the dye of formula HO :s—( so?Na Na03S—' N=N—' T •=• *=N CI Cn3 0.28 part of the dye of formula H3C, ^c(C6Hh) i ii \ / • • •=• V H0-< )• XS03Na and 0.27 part of the dye of formula f I ?ra2 S~\ y'\ s'% /s°3Na • 9 • I II II I /CH3 s j„~r\ \o2nhch2ch2oh the dyebath is kept for a further 10 minutes at 40°C and then heated to 70°C at a rate of l°C/min. After a dyeing time of 20 minutes at 70°C, the dyebath is heated to 100°C and dyeing is carried out for 90 minutes at this temperature. The dyebath is then cooled to 60°C and drained off. The brown wool fabric is rinsed first for 5 minutes at 50°C and then for 5 minutes at room temperature and dried in conventional manner. The dyeing has excellent levelness and good fastness properties. 2 1 62 - 20 - Example 3: 100 parts of wool fabric are pretreated for 10 minutes at 40°C in a dyebath containing, in 1000 parts of water of 40°C, 8 parts of sodium sulfate, 1.5 parts of the levelling assistant employed in Example 1 and 2 parts of 85 % formic acid. The pH of the bath is 3.8. After addition of a solution containing 1.2 parts of the dye of formula rt—! / \ I „ ^ \ ^ i r I s i ci Na03s/ ^ SS03Na OCH3 0.28 part of the dye of formula If T h2 S\ /\ • m • I II II I \y\y\y /CH3 i L-r> \ \ so2nhch2ch2oh and 1.6 parts of K2(ZrFs), the dyebath is kept for a further 10 minutes at 40°C and then heated to 100°C at a rate of 0.8°C/min. After a dyeing time of 90 minutes at 100°C, the dyebath is cooled to 60°C and drained off. The blue wool fabric is rinsed and dried in conventional manner. The medium blue dyeing has excellent levelness and good fastness properties. A comparably good result is obtained by using 1.8 parts of Na2SiF6 instead of 1.6 parts of K2(ZrF6). 2 1628 1 - 21 - Example 4: 100 parts of wool fabric are pretreated for 15 minutes at 40°C in a dyebath containing, in 1500 parts of water of 40°C, 8 parts of sodium sulfate, 1.5 parts of the levelling assistant of the following composition: 14.6 parts of the anionic compound of formula (ch2-ch2-0—}—s03nh<. r2-< ( ch2-ch3-oh sojnhu n R2 " hydrocarbon radical of tallow amine, m + n = 8; 21 parts of the quaternary compound of formula ©/(ch2-ch2-ch h R3-1i P p + q = 34, (ch2—ch2-0—}—h ch3 q ch3o-so2-o0 R3 * C2o~C22hydrocarbon radical; 7 parts of the adduct of oleyl alcohol with 80 moles of ethylene oxide; and 7 parts of the compound of formula c18h37—n—ch2—ch2—n—ch2—ch2—^s(ch2ch20)yh ;ch2ch2o> h ch2 ch2-ch-oh !T H-°H - • ' • I I! x + y «* c. 100, and 49.7 parts of water, based on 100 parts of levelling assistant mixture; and 1.5 parts of 85 % formic acid. The pH of the bath is 4.5. After addition of a solution containing 1.94 parts of NaF, 1.66 parts of the dye of formula 2 162 81 - 22 - <r * NaO)Ss — < )"i-< N"=< ;•=• y=K S03Na Cl CH3 and 1-5 parts of the dye of formula H<j> |HCOCH3 \=/ ! » ! Na03S/ \o3Sa the dyebath is kept for a further 10 minutes at 40°C and then heated to 100°C at a rate of 0-8°C/min. After a dyeing time of 90 minutes at 100°C, the dyebath is cooled to 50°C and drained off. The red wool fabric is rinsed and dried in conventional manner. The deep red dyeing so obtained has excellent levelness and good fastness properties. Example 5; 100 parts of wool fabric are pretreated for 15 minutes at 40°C in a dyebath containing, in 2000 parts of water of 40°C, 8 parts of sodium sulfate, 1.2 parts of the levelling assistant mixture employed-in Example 1 and 1.5 parts of 85 % formic acid. The pH of the bath is 4.3. To this dyebath are then added 1.4 parts of a solid mixture consisting of: 0.425 part of NaF, 0.28 part of the dye of formula HOv . V_ so3Na Na03S—^ N=N— * f N,=V •=• C erf, " C1 13 m - 23 - and 0.695 part of the dye of formula I o N'a03S \* \ • i I m+s-y H' V ^ I cti «=s \ _ / V. "S03Na 02 1.56 parts of a solid mixture consisting of: 0.69 part of NaF, 0.59 part of the dye of formula rr—? - /-% NaO i S • • • Na°3\ ^ \ ^ f \ _ / . •-*=*- •=. I II ii \ cfi. =?? S03Na and 0.28 part of the dye of formula H3Cv .c(CeHn) I II \ / • • •=• s •' HO-< > NS03Na and 1.63 parts of a solid mixture consisting of 0.79 part of NaF, 0.26 part of the dye of formula </div>

Claims

<div class="application article clearfix printTableText" id="claims"> i 62 - 24 - H' ? y s.-A=k-' \' \ i » ' » ] cf Na03S/ X*^ SS03Na 6ch3 0.31 part of the dye of formula (j) Or (j) ^03Na Na°3S~•( )-4=n-/ Y N •=• • • « and 0.27 part of the dye of formula ft f Hz S03Na ^ N / \ / / • • • • I 11 lj I % /\ /*\ / ,ch3 ># • •' / h iih—^ ch3 nso2nhch2ch2oh The dyebath is kept for a further 10 minutes at 40°C and then heated to 70°C at a rate of l°C/min. After a dyeing time of 20 minutes at 70°C, the dyebath is heated to 100°C and dyeing is carried out for 90 minutes at this temperature. The dyebath is then cooled to 60°C and drained off. The brown wool fabric is rinsed first for 5 minutes at 50°C and then for 5 minutes at room temperature and dried in conventional manner. The dyeing has excellent levelness and good fastness properties. -25- 21628i WHAT WE CLAIM IS: 1. A process for dyeing natural or synthetic polyamide fibre material from an aqueous liquor with mixtures of dyes, in the presence of an alkali metal salt or an ammonium salt and optionally in the presence of a levelling assistant or a mixture of levelling assistants, which process comprises dyeing said fibre material with a mixture containing at least 1:1 metal complex dye which contains sulfo groups and at least one metal-free dye which contains sulfo groups, in the presence of an alkali metal or ammonium flouride, an alkali metal or ammonium fluorosilicate, an alkali metal or ammonium fluoroborate, an alkali metal or ammonium fluorozirconate or an alkali metal or ammonium fluorosulfonate, at a pH value in the range from 3 to 7. 2. A process according to claim 1, wherein dyeing is carried out in the presence of sodium flouride or potassium flouride. 3. A process according to claim 1, which comprises using half to four times the amount by weight of alkali metal or ammonium flouride, alkali metal or ammonium fluorosilicate, alkali metal or ammonium fluoroborate, alkali metal or ammonium fluorozirconate or alkali metal or ammonium fluorosulfonate, based on the amount by weight of dye employed. I 216281 -26- 4. A process according to claim 1, wherein the pH is adjusted into the range of from 3 to 7 with an organic acic and which process optionally comprises using, in addition to an alkali metal or ammonium fluoride, alkali metal oc ammonium fluorosilicate, alkali metal or ammonium fluoroborate, alkali metal or ammonium fluorozirconate or alkali metal or ammonium fluorosulfonate, another ammonium or alkali metal salt. 5. A process according to any one of claims 1 to 4, wherein eyeing is carried out in a pH range from 3 to 6. 6. A process according to claim 1, which comprises using 0.3 to 3 percent by weight, based on the fibre material, of levelling assistant or levelling assistant mixture. 7. A process according to claim 1, which comprises using a dye mixture that contains at least one 1:1 chromium complex azo or azomethine eve containing 1 to 3 sulfo groups and at least one metal-free dye containing 1 or 2 sulfo groups. 8. A process according to claim 7 for trichromatic dyeing, which comprises using a mixture of at least three 1:1 chromium complex azo or azomethine dyes selected from eves that give yellow or orange and/or red ana/or blue dyeings, and at least one metal-free dve I 21B281 — S / dyes that cive yellow or orange anc/or red anc/or blue dveincs. 9. A process according to claim 7, wherein the 1:1 chromium complex azo or azomethine eves correspond to formula 0 or .YRx) (co) 0-1 | -S=Y-4i © "(SOjH) An" 1-2 (4) wherein -(C0}q_]_-0- and -(0 or NR^)- are linked to D and K adjacent to the azo brides, D is a radical of benzene or naphthalene which is unsubstituted or substituted by halogen, -Chalky! , C]_-C^al!<oxy, nitro or sulfamoyl, K is a benzene, naphthylene, l-phenyl-3-methylpyrazol-5-one, acetoacetamide or quinoline radical, each unsubstituted or substituted by halogen, C^-C^alky!, Ci-C4alkoxy, C2~C4alkanoylamino, sulfamoyl or hydroxy, Rj_ is hydrogen, M is an alkali metal cation, and An is an anion, and '£ is a nitrogen atom or the group =CH~. 10. A process according to claim 1, which comprises using mixtures of sulfo-containing 1:1 metal complex dyes and sulfo-containing metal-free dyes in the veight^sfiaifcc^of 4 0:60 to 95:5. -28- 216231 11. A process according to claim 7, wherein the metal-free sulfo-containing dyes are those of the monoazo, polvazo, anthraquinone, xanthene or tr ipnenylmet'nane series. 12. A process according to claim 1, wherein the fibre material is synthetic polyamide material, silk or wool. 13. A process accor-ding to claim 12, wherein the fib-re material is wool. 14. A polyamide fibre dyeing composition for dyeing natural and synthetic polyamide fibre material at a pH value in the range of from 3 to 7, comprising at least 1:1 metal complex dye, at least one metal-free sulfo-containing dye and an alkali metal or ammonium fluoride, an alkali metal or ammonium fluorosilicate, and alkali metal or ammonium fluoroborate, an alkali metal or ammonium fluorozirconate or an alkali metal or ammonium fluorosulfonate. 15. A process according to claim 3, wherein the amount by weight of said fluoride, fluorosilicate, fluoroborate, fluorozirconate or fluorosulfonate is one to three times the amount by weight of dye employed. 15. A process according to claim 15, wherein the amount by weight of said fluoride, fluorosilicate, fluoroborate, fluorozirconate or fluorosulfonate is two to^feh-ree times /£> o\, tne amount bv weicht of ave emplovea. Z9- ■^\ :/ , ^\\ I oH * Z- 9 MAR S990 17. A process according to claim 4, wherein said organic acid is formic acid or acetic acid. 18. A process according to claim 4, wherein said another ammonium or alkali metal salt is an alkali metal acetate or alkali metal sulfate. 19. A process according to claim 18, wherein said salt is sodium acetate or sodium sulfate. 20. A process according to claim 5, wherein said pH range is 3.5 to 5. 21- A process according to claim 20, wherein said pH range is 4 to 5. 22. A process according to claim 6, wherein said percent by weight of levelling assistant or levelling assistant mixture is 1 to 2 percent. 23. A process according to claim 7, wherein said 1:1 chromium complex dye contains 1 or 2 sulfo groups. 24 - A process according to claim 14, wherein said 1:1 metal complex dye is a 1:1 chromium dye. CIBA-GEIGY AG by their attorneys Baldwin Son & Carey </div>