CA1273154A - Process for dyeing natural or synthetic polyamide fibre materials with mixtures of dyes - Google Patents
Process for dyeing natural or synthetic polyamide fibre materials with mixtures of dyesInfo
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- CA1273154A CA1273154A CA000509710A CA509710A CA1273154A CA 1273154 A CA1273154 A CA 1273154A CA 000509710 A CA000509710 A CA 000509710A CA 509710 A CA509710 A CA 509710A CA 1273154 A CA1273154 A CA 1273154A
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- Prior art keywords
- alkali metal
- ammonium
- dye
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/673—Inorganic compounds
- D06P1/67333—Salts or hydroxides
- D06P1/6735—Salts or hydroxides of alkaline or alkaline-earth metals with anions different from those provided for in D06P1/67341
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0041—Blends of pigments; Mixtured crystals; Solid solutions mixtures containing one azo dye
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/06—Material containing basic nitrogen containing amide groups using acid dyes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Coloring (AREA)
Abstract
Process for dyeing natural or synthetic polyamide fibre materials with mixtures of dyes Abstract of the Disclosure 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 fluoro-zirconate or an alkali metal or ammonium fluorosulfonate, at a pH
value in the range from 3 to 7.
The process of the invention is suitable for producing non-skittery and level dyeings of good fastness properties on synthetic polyamide material.
value in the range from 3 to 7.
The process of the invention is suitable for producing non-skittery and level dyeings of good fastness properties on synthetic polyamide material.
Description
~73~54 1-15356/+
Process fcr dyeing natural or synthetic polyamide fibre materials with mixtures of dye3 The present invention relates to a novel proces~ for the non-~kit-tery and level dyeing of natural and synthetic polyamide fibre material3 from an aqueou~ liquor with mixtures of l:1 metal complex dyes which contain sulfo groups and metal-free dyes which contsin sulfo groups, in the presence of a 60urce of fluoride ions such a3 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 fluoro6ulfonate, 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 cvmplete exhaustion of the dyebath, and the dyeing 80 obtained has good allround fastnes~
properties, in particular good fastness to wet processing and light.
The invention further relates to the material dyed by the novel proces~ and to a composition for carrying out said proce6s.
The disadvantage of the conventional methods of dyeing natural or synthetic polyamide fibre materials with 1:1 metal complex dyes or mlxtures thereof with metal-free acid dyes is that these dye~ or mixtures must be applied in the pH range from about 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 decislve importance for dyeing natural and synthetic polyamide fibre materials, especially for dyeing wool, a~ the3e fibre msterial3, again in particular wool, are severely attacked both in the 3trongly acidic and in the strongly alkaline pH range.
.~
~2731S4 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 to 7, preferably from 3 to 6 and, most preferably, from 3.5 to 5.
Accordingly, the present invention relates to a process for dyeing natural or synthetic polyamide flbre 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 comprlses dyeing said fibre material with a mixture contain-ing 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 dye~ 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 prefer-ably 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-reac-tive radicals.
Depending on the desired depth of shade, the amounts in which the dye mixtures are added to ths dyebaths may vary within wide limits.
In general, amounts from 0.01 to 10 percent by weight, based on the goodff to be dyed, of one or more dye mixtures are advantag~ous.
i~31~;4 It has long been known to dye natural or synthetic polyamide fibre materials wlth 1:1 metal complex dyes or mixtures thereof with metal-free ~yes in the presence of an alkali metal sulfate or alkali metal chloride, for example sodlum 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 NazSiF6, K2SiF6 or (NH4)2SiF6.
The alkali metal fluoroborate or ammonium fluoroborate employed in the process of ths invention is the alkali metal salt or ammonium salt of fluoroboric acid. It is preferred to use NaBF4, KBF4 or NH4BF4.
The alkali metal or ammonium fluorozircon~te smployed in the process of this invention is an alkali metal hexafluorozirconate or ~mmonium hexafluorozirconate, preferably Rz(ZrF6).
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 NaFSO3, KFSO3 or NH4FSO3.
~273154 Preferred embodim~nts 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 mixturs of sssistants, b) dyeing in the presence of an alkali metal fluorosilicate or ammonium fluorosilicate, preferably sodium or potassium fluoro-silicate 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 hexafluorozlrconate or ammonium fluorozirconate, preferably K2(ZrF6), e) dyeing in the presence of an alkali metal fluorosulfonate or ammonium fluorosulfonate, preferably KFSO3.
A particularly preferred embodiment of the process of thls invention comprises dyeing in the presence of an alkali metal fluoride or ammonium fluoride, an alkali metal fluorosilicate or ammonium fluorosillcate, 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 fluoro-borate, alkali metal or ammonium fluorozirconate or alkali metal or ammonium fluorosulfonate is added to the dyebaths may vary within wlde 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, i8 advantageous.
~2~315~
The asslstants which may be used in the process of this invention sre known per se and are prepared by known methods. Preferably, they are levelling a~sistants or mixtures of dlfferent levelling assist-ants. Suitable levelling assistants are anionic, cationic, nonionic and amphoteric compounds or mixtures 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 aclds, 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 ethars 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 acld alkylolamides. Typlcal 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 ( CH2-cH2-o~so3M
m (1) \( CH2-CH2-O~SO3M
wherein R i8 an alkyl or alkenyl radlcal of 12 to 22 carbon atoms, M
is hydrogen, an alkali metal or ammonium cation, and m and n ara integers, the sum of m ~ n being from 2 to 14; or compounds of the formula ~273154 ~ (CHz-CH2-O-~ H
R'- ~ P (2) ~ (CHz-CH2-~ ) H
A q wherein R' independently of R has the meaning of R, A ls an anion, Q
is an unsubstituted or substituted al~yl radical and p and q are integers, the ~um of p + q being from 2 to 50; or compounds of the formula OH
H-CH2- I-(CH2-CH2- ~ H
( H2)2 H-CH2- : (3) H ( H2)2 R"- I-(CH2-~H2-O-~yH
whereln 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 (l) and (2) or a mixture containing compounds of the formulae (1), (2) and (3).
It is particularly preferred to use a mixture of levelling a~sist-ants comprising 5 to 70 parts by weight of a compound of for-mula (1), 15 to 60 parts by weight of the compound of formula (2), and 5 to 60 part~ by welght 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.
~7:~i4 In the process of this invention it is preferred to use a mlxture of levelling assistantfi 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 from 20 to 50, also contalns an adduct of 50 to 100 moles of ethylene oxide with 1 mole of a Cls-C2~alkenyl alcohol.
It is also pre~erred to use a mix~ure 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 lQ.
It is further preferrsd to use a mixture of levelling assistants which contains compounds of formula (2), wherein the sum of p + q in formula (2) i9 30 to 40, and R' is a C1s-Cz2alkyl radical.
The amount in which the levelling assistant or mixture of levelling as~istants i5 added to the dyebaths can vary within wide limits; but in general an amount of 0.3 to 3 percent by ~eight, preferably of 1 or 2 percent by welght, based on the fibre material, of the levelling assistant or mixture thereof, i9 advantageous.
The dyebaths may contain, as further assistants, mineral acids such as sulfuric acid, sulfamic acid or phosphoric acid, or organic acid~, preferably lower aliphatic carboxylic acid3 such as formic acid, acetic acid or maleic acid. These acids are employed in particular for ad~u~ting the pH of the dyebath. It i8 preferred to ad~ust the pH of 3 to 7 with an organic acid, preferably with acetic acid or formic acid.
Dyeing i8 preferably carried out in the p~ 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 ~etal or ammonium fluoroborate, alkall :12'73~54 metal or ammonium fluorozirconate or alkali metal or ammonium fluoro~ulfonate, in particular an ammonium salt or alkali metal salt, for example am~onium sulfate, ammonium acetate or, prefer-sbly, 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 mixture3 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 dye~ employed in the process of thls invention are preferably those having good migration properties. The migrating power of these dyes r,hall 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 conditlons for determining the migrating power match those indicated in Example 1. Evaluation i8 made by spectrophoto-metric determination of the amount of dye present on the originally undyed wool in percent of ths 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 ~ed 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. Acld Green 3, 9 and 16; C.I. Acid Violet 9 and 36, C.I. Acid Brown 10, 11 and 248.
~2731~;4 In the process of this invention it i~ also posible to U58 mixtures of several dye mixtures as defined herein.
A preferred mlxture of dye mixtures as de~Eined herein is:
a) at least two 1:1 chromium complex azo o~ azomethine dyes and at least one sulfo-contalning 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 i8 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 r - ( or NRl) ~An (4) b ~--y~ _( S03Ml 1 -2 wherein -(CO) ~ and -(O- or -NRl) are linked to D and K ad~acent to the azo brldge, D i8 the radical of a diazo component of the benzene or naphthalene serie~, K i8 the radical of a coupling component of the benzene, naphthalene or heterocyclic series or of the acetoacet~rylide series, R1 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.
~273~54 In the process of this invention it is preferred to use sulfo-con-taining 1:1 chromium complex azo or azomethine dye~ of the for-mula (4), wherein D i9 a radical of the benzene or naphthalsne series which is unsub6tituted or substituted by halogen, C~-C4alkyl, C1-C4alkoxy, nitro or sulfamoyl, K is a phenyl, naphthyl, l-phenyl-3-methylpyrazol-5-one, acetoacetamide, preferably acetoacetanilide, or a quinoline radical, each unsubstituted or ~ubstituted by halogen, C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, sulfamoyl or hydroxy, R1 i9 hydrogen and M iB 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 aeries referred to above, which dyes may be substituted by e.g. C1-C4alkyl groups such as methyl, ethyl, propyl, isopropyl and butyl, or by C1-C4alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy and butoxy, or C1-C6acylamino groups such as acetylamino and propionylamino, benzoylamino, amino, C1-C4alkylamino, phenylamino, C1-C4alkoxy-carbonyl, nitro, scetyl, cyano, trifluoromethyl, halogen such as fluorine, chlorine and bromine, sulfamoyl, carbsmoyl, 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 German Offenlegungsschrift 29 13 102.
In the proces~ of this invention it is preferred to use mixtures of sulfo-containing 1:1 metal complex dyes and sulfo-containing metal-free dyes ln the weight ratio of 40:60 to 95:5.
The sulfo-containing dyes employad in the proces~ of this invention are either in the form of the free sulfonic acid or, preferably, of the salts thereof.
~2731~i4 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 dye~ employed in the proce~s of this invention are known per se and can be obtained by known methods.
The mixtures uf 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 i-~ carried out from an aqueous bath by the exhaust process, for example in the temperat~re range from 80 to 105C or 110C when using a wool protecting agent that splits off formaldehyde, prefer-ably in the range from 98 to 103C. 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.
~27:3154 The levelllng assistant and the alkali metal or ammonium fluoride, alkali metal or ammonium fluorosilicatP, alkali metal or ammonium fluoroborate, alkali metal or ammonium fluorozirconate or alkali metal or ammonium fluorosulfonate ls conveniently added to the aqueous dyebath and applied simultaneously with the dye. An alter-native procedure is to treat the goods to be dyed first wlth the levelling assistant and then to dye the good~, 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 asslstAnt and has a temperature of 30 to 70C. Then the dye mi~ture and the alkali metal or ammoni~m fluoride, alkali metal or ammonium fluoro-silicate, alkali metal or ammonium fluoroborate, alkali metal or ammonium fluorozirconate or alkali metsl or ammonium fluorosul-fonate is added and the temperature of th0 dyebath i8 raised at a rate of 0.75 to 3C per minute, optionally with a temperature stop during the heating up phase, in order to dye in the indicated temperature range from 80 to 105C, preferably for 30 to 120 min-utes. Finally, the bath is cooled and the dyed material i8 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 woolfpolyamide, wool/polyester, wool/cellulose or woollpolyacrylonitrile blends a~
well as silk. The fibre material may be in a very wide range of presenta~ion, 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.
~2731S4 A particularly preferred embodiment of the process of this lnvention comprises dyeing natural or synthetic polyamide fibre material, preferably wool, with at least one dye mixture as defined above, in the presence of sodlum fluoride, ammonium fluorosilicate or sodium fluorosilicate, preferably in two to three times the amount by 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 s~lfate, in the p~ range from 4 to 5.
The sulfo-containing metal-free dye~ used in the process of the present invention may contain one or more fibre-reactive groups. In the process of the invention it i5 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-react-ive 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 comprlses 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 proceas 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.
~27~1S~
The invention further relates to a composition for carrying out the process of the invention. The compositioD 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 dye, and 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 i9 prepared by mixing a sulfo-containing 1:1 chromium complex dye and at least one sulfo-con-taining 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.
~2~3~
Example 1: 800 parts of worsted spun yarn are pretreated for 15 mlnutes at 50C in a dyebath containing, in 20,000 part3 of water of 50C, 64 parts of godium sulfate, 24 parts of (NH4)zSiF6 and 12 parts of a levelling assistant consisting of:
24 parts of the anionic compound of formula (CH2-CH2-0-~--S03NH4 R2_ ~ m ~CH2-CH2-0 ~ S03NH4 R2 - C16-C1ghydrocarbon radical; m + n ~ 7;
24 parts of the quaternary compound of formula ~ (CHz-CH2-0-t--H
R3- ~ P p ~ q = 34, 1 (CHz-CH2- ~ H
CH30-SOz-0 R3 - Czo-Cz2hydrocarbon 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
Process fcr dyeing natural or synthetic polyamide fibre materials with mixtures of dye3 The present invention relates to a novel proces~ for the non-~kit-tery and level dyeing of natural and synthetic polyamide fibre material3 from an aqueou~ liquor with mixtures of l:1 metal complex dyes which contain sulfo groups and metal-free dyes which contsin sulfo groups, in the presence of a 60urce of fluoride ions such a3 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 fluoro6ulfonate, 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 cvmplete exhaustion of the dyebath, and the dyeing 80 obtained has good allround fastnes~
properties, in particular good fastness to wet processing and light.
The invention further relates to the material dyed by the novel proces~ and to a composition for carrying out said proce6s.
The disadvantage of the conventional methods of dyeing natural or synthetic polyamide fibre materials with 1:1 metal complex dyes or mlxtures thereof with metal-free acid dyes is that these dye~ or mixtures must be applied in the pH range from about 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 decislve importance for dyeing natural and synthetic polyamide fibre materials, especially for dyeing wool, a~ the3e fibre msterial3, again in particular wool, are severely attacked both in the 3trongly acidic and in the strongly alkaline pH range.
.~
~2731S4 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 to 7, preferably from 3 to 6 and, most preferably, from 3.5 to 5.
Accordingly, the present invention relates to a process for dyeing natural or synthetic polyamide flbre 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 comprlses dyeing said fibre material with a mixture contain-ing 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 dye~ 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 prefer-ably 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-reac-tive radicals.
Depending on the desired depth of shade, the amounts in which the dye mixtures are added to ths dyebaths may vary within wide limits.
In general, amounts from 0.01 to 10 percent by weight, based on the goodff to be dyed, of one or more dye mixtures are advantag~ous.
i~31~;4 It has long been known to dye natural or synthetic polyamide fibre materials wlth 1:1 metal complex dyes or mixtures thereof with metal-free ~yes in the presence of an alkali metal sulfate or alkali metal chloride, for example sodlum 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 NazSiF6, K2SiF6 or (NH4)2SiF6.
The alkali metal fluoroborate or ammonium fluoroborate employed in the process of ths invention is the alkali metal salt or ammonium salt of fluoroboric acid. It is preferred to use NaBF4, KBF4 or NH4BF4.
The alkali metal or ammonium fluorozircon~te smployed in the process of this invention is an alkali metal hexafluorozirconate or ~mmonium hexafluorozirconate, preferably Rz(ZrF6).
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 NaFSO3, KFSO3 or NH4FSO3.
~273154 Preferred embodim~nts 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 mixturs of sssistants, b) dyeing in the presence of an alkali metal fluorosilicate or ammonium fluorosilicate, preferably sodium or potassium fluoro-silicate 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 hexafluorozlrconate or ammonium fluorozirconate, preferably K2(ZrF6), e) dyeing in the presence of an alkali metal fluorosulfonate or ammonium fluorosulfonate, preferably KFSO3.
A particularly preferred embodiment of the process of thls invention comprises dyeing in the presence of an alkali metal fluoride or ammonium fluoride, an alkali metal fluorosilicate or ammonium fluorosillcate, 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 fluoro-borate, alkali metal or ammonium fluorozirconate or alkali metal or ammonium fluorosulfonate is added to the dyebaths may vary within wlde 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, i8 advantageous.
~2~315~
The asslstants which may be used in the process of this invention sre known per se and are prepared by known methods. Preferably, they are levelling a~sistants or mixtures of dlfferent levelling assist-ants. Suitable levelling assistants are anionic, cationic, nonionic and amphoteric compounds or mixtures 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 aclds, 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 ethars 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 acld alkylolamides. Typlcal 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 ( CH2-cH2-o~so3M
m (1) \( CH2-CH2-O~SO3M
wherein R i8 an alkyl or alkenyl radlcal of 12 to 22 carbon atoms, M
is hydrogen, an alkali metal or ammonium cation, and m and n ara integers, the sum of m ~ n being from 2 to 14; or compounds of the formula ~273154 ~ (CHz-CH2-O-~ H
R'- ~ P (2) ~ (CHz-CH2-~ ) H
A q wherein R' independently of R has the meaning of R, A ls an anion, Q
is an unsubstituted or substituted al~yl radical and p and q are integers, the ~um of p + q being from 2 to 50; or compounds of the formula OH
H-CH2- I-(CH2-CH2- ~ H
( H2)2 H-CH2- : (3) H ( H2)2 R"- I-(CH2-~H2-O-~yH
whereln 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 (l) and (2) or a mixture containing compounds of the formulae (1), (2) and (3).
It is particularly preferred to use a mixture of levelling a~sist-ants comprising 5 to 70 parts by weight of a compound of for-mula (1), 15 to 60 parts by weight of the compound of formula (2), and 5 to 60 part~ by welght 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.
~7:~i4 In the process of this invention it is preferred to use a mlxture of levelling assistantfi 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 from 20 to 50, also contalns an adduct of 50 to 100 moles of ethylene oxide with 1 mole of a Cls-C2~alkenyl alcohol.
It is also pre~erred to use a mix~ure 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 lQ.
It is further preferrsd to use a mixture of levelling assistants which contains compounds of formula (2), wherein the sum of p + q in formula (2) i9 30 to 40, and R' is a C1s-Cz2alkyl radical.
The amount in which the levelling assistant or mixture of levelling as~istants i5 added to the dyebaths can vary within wide limits; but in general an amount of 0.3 to 3 percent by ~eight, preferably of 1 or 2 percent by welght, based on the fibre material, of the levelling assistant or mixture thereof, i9 advantageous.
The dyebaths may contain, as further assistants, mineral acids such as sulfuric acid, sulfamic acid or phosphoric acid, or organic acid~, preferably lower aliphatic carboxylic acid3 such as formic acid, acetic acid or maleic acid. These acids are employed in particular for ad~u~ting the pH of the dyebath. It i8 preferred to ad~ust the pH of 3 to 7 with an organic acid, preferably with acetic acid or formic acid.
Dyeing i8 preferably carried out in the p~ 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 ~etal or ammonium fluoroborate, alkall :12'73~54 metal or ammonium fluorozirconate or alkali metal or ammonium fluoro~ulfonate, in particular an ammonium salt or alkali metal salt, for example am~onium sulfate, ammonium acetate or, prefer-sbly, 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 mixture3 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 dye~ employed in the process of thls invention are preferably those having good migration properties. The migrating power of these dyes r,hall 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 conditlons for determining the migrating power match those indicated in Example 1. Evaluation i8 made by spectrophoto-metric determination of the amount of dye present on the originally undyed wool in percent of ths 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 ~ed 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. Acld Green 3, 9 and 16; C.I. Acid Violet 9 and 36, C.I. Acid Brown 10, 11 and 248.
~2731~;4 In the process of this invention it i~ also posible to U58 mixtures of several dye mixtures as defined herein.
A preferred mlxture of dye mixtures as de~Eined herein is:
a) at least two 1:1 chromium complex azo o~ azomethine dyes and at least one sulfo-contalning 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 i8 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 r - ( or NRl) ~An (4) b ~--y~ _( S03Ml 1 -2 wherein -(CO) ~ and -(O- or -NRl) are linked to D and K ad~acent to the azo brldge, D i8 the radical of a diazo component of the benzene or naphthalene serie~, K i8 the radical of a coupling component of the benzene, naphthalene or heterocyclic series or of the acetoacet~rylide series, R1 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.
~273~54 In the process of this invention it is preferred to use sulfo-con-taining 1:1 chromium complex azo or azomethine dye~ of the for-mula (4), wherein D i9 a radical of the benzene or naphthalsne series which is unsub6tituted or substituted by halogen, C~-C4alkyl, C1-C4alkoxy, nitro or sulfamoyl, K is a phenyl, naphthyl, l-phenyl-3-methylpyrazol-5-one, acetoacetamide, preferably acetoacetanilide, or a quinoline radical, each unsubstituted or ~ubstituted by halogen, C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, sulfamoyl or hydroxy, R1 i9 hydrogen and M iB 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 aeries referred to above, which dyes may be substituted by e.g. C1-C4alkyl groups such as methyl, ethyl, propyl, isopropyl and butyl, or by C1-C4alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy and butoxy, or C1-C6acylamino groups such as acetylamino and propionylamino, benzoylamino, amino, C1-C4alkylamino, phenylamino, C1-C4alkoxy-carbonyl, nitro, scetyl, cyano, trifluoromethyl, halogen such as fluorine, chlorine and bromine, sulfamoyl, carbsmoyl, 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 German Offenlegungsschrift 29 13 102.
In the proces~ of this invention it is preferred to use mixtures of sulfo-containing 1:1 metal complex dyes and sulfo-containing metal-free dyes ln the weight ratio of 40:60 to 95:5.
The sulfo-containing dyes employad in the proces~ of this invention are either in the form of the free sulfonic acid or, preferably, of the salts thereof.
~2731~i4 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 dye~ employed in the proce~s of this invention are known per se and can be obtained by known methods.
The mixtures uf 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 i-~ carried out from an aqueous bath by the exhaust process, for example in the temperat~re range from 80 to 105C or 110C when using a wool protecting agent that splits off formaldehyde, prefer-ably in the range from 98 to 103C. 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.
~27:3154 The levelllng assistant and the alkali metal or ammonium fluoride, alkali metal or ammonium fluorosilicatP, alkali metal or ammonium fluoroborate, alkali metal or ammonium fluorozirconate or alkali metal or ammonium fluorosulfonate ls conveniently added to the aqueous dyebath and applied simultaneously with the dye. An alter-native procedure is to treat the goods to be dyed first wlth the levelling assistant and then to dye the good~, 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 asslstAnt and has a temperature of 30 to 70C. Then the dye mi~ture and the alkali metal or ammoni~m fluoride, alkali metal or ammonium fluoro-silicate, alkali metal or ammonium fluoroborate, alkali metal or ammonium fluorozirconate or alkali metsl or ammonium fluorosul-fonate is added and the temperature of th0 dyebath i8 raised at a rate of 0.75 to 3C per minute, optionally with a temperature stop during the heating up phase, in order to dye in the indicated temperature range from 80 to 105C, preferably for 30 to 120 min-utes. Finally, the bath is cooled and the dyed material i8 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 woolfpolyamide, wool/polyester, wool/cellulose or woollpolyacrylonitrile blends a~
well as silk. The fibre material may be in a very wide range of presenta~ion, 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.
~2731S4 A particularly preferred embodiment of the process of this lnvention comprises dyeing natural or synthetic polyamide fibre material, preferably wool, with at least one dye mixture as defined above, in the presence of sodlum fluoride, ammonium fluorosilicate or sodium fluorosilicate, preferably in two to three times the amount by 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 s~lfate, in the p~ range from 4 to 5.
The sulfo-containing metal-free dye~ used in the process of the present invention may contain one or more fibre-reactive groups. In the process of the invention it i5 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-react-ive 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 comprlses 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 proceas 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.
~27~1S~
The invention further relates to a composition for carrying out the process of the invention. The compositioD 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 dye, and 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 i9 prepared by mixing a sulfo-containing 1:1 chromium complex dye and at least one sulfo-con-taining 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.
~2~3~
Example 1: 800 parts of worsted spun yarn are pretreated for 15 mlnutes at 50C in a dyebath containing, in 20,000 part3 of water of 50C, 64 parts of godium sulfate, 24 parts of (NH4)zSiF6 and 12 parts of a levelling assistant consisting of:
24 parts of the anionic compound of formula (CH2-CH2-0-~--S03NH4 R2_ ~ m ~CH2-CH2-0 ~ S03NH4 R2 - C16-C1ghydrocarbon radical; m + n ~ 7;
24 parts of the quaternary compound of formula ~ (CHz-CH2-0-t--H
R3- ~ P p ~ q = 34, 1 (CHz-CH2- ~ H
CH30-SOz-0 R3 - Czo-Cz2hydrocarbon 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 c~3 S~3H ~ H0 ~ N=N-C-C0-NH~
N~z 1~'731~;4 2.4 part~ of the 1:1 chromium complex of the dye of formula N ~ CH3 OH HO/
il i SO3H \,~
0.6 part of the 1:1 chromium complex of the dye of formula H3~ 1~ HO
N----N~
0.65 part of the 1:1 chromlum complex of the dye of formula / OH IOH ~03H
HO3s-~ /.-N-N t ~~ .
2.2 parts of the dye of formula ~ N=~ --N=N--~ ~--OCN3 S~3H
12~31~i~
2.4 parts of the dye of formula CH3~ H /-~ 2 N~2 t~ N=N-~
.=.
and 1.2 parts of the dye of formula ~ ~2 i~ il il ~i-so3H
1~1 bH---~ NH--CO--CH2CH3 the dyebath is kept for 10 minutes at 50C and then heated to 98C
at a rate of 0.8C/mlnute. The pH is 4.6 at the commencement of dyeing. After a dyeing time of 90 minutes at 98C, the dyebath is cooled to 50C and drained off. The brown wool yarn i8 rinsed first for 10 minutes at 505 and thsn for 10 minutes at room temperature and dried in conv2ntional manner. The medium brown dyeing 80 obtained has excellent levelness and good fastness properties.
Exam~le 2: 100 parts of wool fabric are pretreated for 15 minutes at 40C in a dyebath containing, in 2000 parts of water of 40C, 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 i8 4.3.
After addition of a solution of 1.9 parts of sodium fluoride and 0.695 part of the dye of formula ~2731S4 0.59 part of the dye of form~la ~ ~:=X \SO3Na i1 c~3 0.26 part of the dye of formula C~ D~ ~SO3Na 0.31 part of the dye of formula ~ r ~ Sl03Na NaO3S- f ~ N-i~
~273i5~
0.28 part of the dye of formula C~;
~
NaO3S~ -N=N--~ ~ \Cl C`H3 0.28 part of the dye of formula H3C\ c(C6Hll) ~2 N~2 t~ N=N-.
~ / H0 SO3Na and 0.27 part of the dye of formula R ~H2 /SO 3 Na i1 i1 iH~ CH3 ~SO2NHCH2CH20H
the dyebath i8 kept for a further lQ minutes at 40C and then heated to 70C at a rate of 1Clmin. After a dyeing time of 20 minutes at 70C, the dyebath i5 heated to 100C and dyeing is carried out for 90 minutes at thls temperature. The dyebath i8 then cooled to 60C
and drained off. The brown wool fabric is rinsed first for 5 minutes at 50C and then for 5 minute~ at room temperature and drled in conventional manner. The dyeing has excellent levelness and good fastness propertie~.
Example 3: 100 par~s of wool fabric are pretreated for 10 minutes at 40C in a dyebath containing, in 1000 parts of water of 40C, 8 part~ of sodium sulfate, 1.5 parts of the levelling assistant employed in Example l and 2 parts of 85 % formic acid. The pH of the bath i3 3.8. After addition of a solution containing 1.2 parts of the dye of formula ~. O
C~ ~ / NaO3S/ ~ \SO3Na 0.28 part of the dye of formula R ~H2 /SO 3 Na !~ ,i!, ,'!, ~! ~CH3 d ~H--~ ~-CH3 \SO2NHCH2CH20H
and 1.6 parts of K2(ZrF6), the tyebath is kept for a further 10 minutes at 40C and then heated to 100C at a rate of 0.8C/min. After a dyeing time of 90 minutes at 100C, the dyebath i9 cooled to 60C 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 NazSiF6 instead of 1.6 parts of K2(~rF6).
~Z~31~;~
Example 4: lO0 parts of wool fabric are pretreated for lS minutes at 40C in a dyebath containing, in 1500 parts of water of 40C, 8 parts of sodium sulfate, 1.5 parts of the levelling assistant of the following compo~itio~:
14.6 parts of the anionic compound of formula ( CH2-cH2-o~so3NHl~
R2-N/ m ~(CH2-CH2-O ~ SO3NH4 Rz ~ hydrocarbon radical of tallow amine, m + n = 8;
21 parts of the quaternary compound of formula ~ (CHz-CH2-O-~--N
R3-l ~ P p + q = 34, / (CHz~CH2~0-~-q-H
CH30-SOz-O
R3 ~ C20-C22hydrocarbon radical;
7 parts of the adduct of oleyl alcohol with 80 moles of sthylene oxide; and 7 part~ of the compound of formula ClaH3 7 - ~ - CH2-CH2-~-CHz -CH2-~(CH2CH20)yH
( H2CH20x H ~Hz CH2-CIH-OH
~H-OH ~-\
i~ \. 1~ ~i1 ~-~ x + y ~ c. 100, and 49.7 parts of water, based on 100 parts of levelling assistant ~ixture;
and 1.5 parts of 85 % formic acid. The pH of the bath is 4.5. After additlon of a ~olution containing 1.94 parts of NaF, 1.66 parts of the dye of formula ~Z~315~
NaO3S /~r~\
\.=./ \.= \SO3Na C~ C~3 and 1.5 parts of the dye of formula H~ ~NCOCH3 NaO3S ~ SO3Na the dyebath is kept for a further 10 minutes at 40C and then heated to 100C at a rate of 0.8C/min. After a dyeing time of 90 minutes at 100C, the dyebath i8 cooled to 50C and drained off. The red wool fabric is rinsed and dried in conventional manner. The deep red dyeing 80 obtained has excellent levelness and good fastness properties .
Example 5: 100 parts of wool fabric are pretreated for 15 mlnutes at 40C in a dyebath containing, in 2000 parts of water of 40C, 8 part3 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 i~ 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 C~, ~0 NaO3S~ -N=N-~
c~3 ~3i5~
and 0.695 part of the dye of formula ~ 50 1.56 parts of a solid mixture Consisting of:
0.69 part of Na~, 0.59 part of the dye of formula ~r--I
and 0.28 part of the dye of formula H3C c(C6Hl1) ~; 2 N~2 T ,, N ~,_,/
SO3Na and 1.63 parts of a solid mixture consisting of 0.79 part of NaF, 0.26 part of the dye of formula ~'73~54 l - Clr - f C~ ~- NaO3S ~ SO3Na 0.31 part of the dye of formula ~--IcL---1 j;O3Na NaO 3 S~ N t il ._.~
and 0.27 part of the dye of formula R ~H2 /SO3Na il i 1~ ~H--.~ ~.--CH3 \SO2NHCH2CHzOH
The dyebath is kept for a further 10 minutes at 40C and then heated to 70C at a rate of 1C/min. After a dyeing tim2 of 20 mlnutes at 70C, the dyebath iS heated to lOO~C and tyeing is carried out for 90 mlnutes at this temperature. The dyebath i8 then cooled to 60C
and drained off. The brown wool fabric ~s rinsed first for 5 minutes at 50C and then for 5 minutes at room temperature and dried in conventlonal manner. The dyeing has excellent levelness and good fastne~3s properties.
N~z 1~'731~;4 2.4 part~ of the 1:1 chromium complex of the dye of formula N ~ CH3 OH HO/
il i SO3H \,~
0.6 part of the 1:1 chromium complex of the dye of formula H3~ 1~ HO
N----N~
0.65 part of the 1:1 chromlum complex of the dye of formula / OH IOH ~03H
HO3s-~ /.-N-N t ~~ .
2.2 parts of the dye of formula ~ N=~ --N=N--~ ~--OCN3 S~3H
12~31~i~
2.4 parts of the dye of formula CH3~ H /-~ 2 N~2 t~ N=N-~
.=.
and 1.2 parts of the dye of formula ~ ~2 i~ il il ~i-so3H
1~1 bH---~ NH--CO--CH2CH3 the dyebath is kept for 10 minutes at 50C and then heated to 98C
at a rate of 0.8C/mlnute. The pH is 4.6 at the commencement of dyeing. After a dyeing time of 90 minutes at 98C, the dyebath is cooled to 50C and drained off. The brown wool yarn i8 rinsed first for 10 minutes at 505 and thsn for 10 minutes at room temperature and dried in conv2ntional manner. The medium brown dyeing 80 obtained has excellent levelness and good fastness properties.
Exam~le 2: 100 parts of wool fabric are pretreated for 15 minutes at 40C in a dyebath containing, in 2000 parts of water of 40C, 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 i8 4.3.
After addition of a solution of 1.9 parts of sodium fluoride and 0.695 part of the dye of formula ~2731S4 0.59 part of the dye of form~la ~ ~:=X \SO3Na i1 c~3 0.26 part of the dye of formula C~ D~ ~SO3Na 0.31 part of the dye of formula ~ r ~ Sl03Na NaO3S- f ~ N-i~
~273i5~
0.28 part of the dye of formula C~;
~
NaO3S~ -N=N--~ ~ \Cl C`H3 0.28 part of the dye of formula H3C\ c(C6Hll) ~2 N~2 t~ N=N-.
~ / H0 SO3Na and 0.27 part of the dye of formula R ~H2 /SO 3 Na i1 i1 iH~ CH3 ~SO2NHCH2CH20H
the dyebath i8 kept for a further lQ minutes at 40C and then heated to 70C at a rate of 1Clmin. After a dyeing time of 20 minutes at 70C, the dyebath i5 heated to 100C and dyeing is carried out for 90 minutes at thls temperature. The dyebath i8 then cooled to 60C
and drained off. The brown wool fabric is rinsed first for 5 minutes at 50C and then for 5 minute~ at room temperature and drled in conventional manner. The dyeing has excellent levelness and good fastness propertie~.
Example 3: 100 par~s of wool fabric are pretreated for 10 minutes at 40C in a dyebath containing, in 1000 parts of water of 40C, 8 part~ of sodium sulfate, 1.5 parts of the levelling assistant employed in Example l and 2 parts of 85 % formic acid. The pH of the bath i3 3.8. After addition of a solution containing 1.2 parts of the dye of formula ~. O
C~ ~ / NaO3S/ ~ \SO3Na 0.28 part of the dye of formula R ~H2 /SO 3 Na !~ ,i!, ,'!, ~! ~CH3 d ~H--~ ~-CH3 \SO2NHCH2CH20H
and 1.6 parts of K2(ZrF6), the tyebath is kept for a further 10 minutes at 40C and then heated to 100C at a rate of 0.8C/min. After a dyeing time of 90 minutes at 100C, the dyebath i9 cooled to 60C 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 NazSiF6 instead of 1.6 parts of K2(~rF6).
~Z~31~;~
Example 4: lO0 parts of wool fabric are pretreated for lS minutes at 40C in a dyebath containing, in 1500 parts of water of 40C, 8 parts of sodium sulfate, 1.5 parts of the levelling assistant of the following compo~itio~:
14.6 parts of the anionic compound of formula ( CH2-cH2-o~so3NHl~
R2-N/ m ~(CH2-CH2-O ~ SO3NH4 Rz ~ hydrocarbon radical of tallow amine, m + n = 8;
21 parts of the quaternary compound of formula ~ (CHz-CH2-O-~--N
R3-l ~ P p + q = 34, / (CHz~CH2~0-~-q-H
CH30-SOz-O
R3 ~ C20-C22hydrocarbon radical;
7 parts of the adduct of oleyl alcohol with 80 moles of sthylene oxide; and 7 part~ of the compound of formula ClaH3 7 - ~ - CH2-CH2-~-CHz -CH2-~(CH2CH20)yH
( H2CH20x H ~Hz CH2-CIH-OH
~H-OH ~-\
i~ \. 1~ ~i1 ~-~ x + y ~ c. 100, and 49.7 parts of water, based on 100 parts of levelling assistant ~ixture;
and 1.5 parts of 85 % formic acid. The pH of the bath is 4.5. After additlon of a ~olution containing 1.94 parts of NaF, 1.66 parts of the dye of formula ~Z~315~
NaO3S /~r~\
\.=./ \.= \SO3Na C~ C~3 and 1.5 parts of the dye of formula H~ ~NCOCH3 NaO3S ~ SO3Na the dyebath is kept for a further 10 minutes at 40C and then heated to 100C at a rate of 0.8C/min. After a dyeing time of 90 minutes at 100C, the dyebath i8 cooled to 50C and drained off. The red wool fabric is rinsed and dried in conventional manner. The deep red dyeing 80 obtained has excellent levelness and good fastness properties .
Example 5: 100 parts of wool fabric are pretreated for 15 mlnutes at 40C in a dyebath containing, in 2000 parts of water of 40C, 8 part3 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 i~ 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 C~, ~0 NaO3S~ -N=N-~
c~3 ~3i5~
and 0.695 part of the dye of formula ~ 50 1.56 parts of a solid mixture Consisting of:
0.69 part of Na~, 0.59 part of the dye of formula ~r--I
and 0.28 part of the dye of formula H3C c(C6Hl1) ~; 2 N~2 T ,, N ~,_,/
SO3Na and 1.63 parts of a solid mixture consisting of 0.79 part of NaF, 0.26 part of the dye of formula ~'73~54 l - Clr - f C~ ~- NaO3S ~ SO3Na 0.31 part of the dye of formula ~--IcL---1 j;O3Na NaO 3 S~ N t il ._.~
and 0.27 part of the dye of formula R ~H2 /SO3Na il i 1~ ~H--.~ ~.--CH3 \SO2NHCH2CHzOH
The dyebath is kept for a further 10 minutes at 40C and then heated to 70C at a rate of 1C/min. After a dyeing tim2 of 20 mlnutes at 70C, the dyebath iS heated to lOO~C and tyeing is carried out for 90 mlnutes at this temperature. The dyebath i8 then cooled to 60C
and drained off. The brown wool fabric ~s rinsed first for 5 minutes at 50C and then for 5 minutes at room temperature and dried in conventlonal manner. The dyeing has excellent levelness and good fastne~3s properties.
Claims (25)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
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 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 a compound chosen from the group consisting of alkali metal fluoride, ammonium fluoride, alkali metal fluorosilicate, ammonium fluorosilicate, alkali metal fluoroborate, ammonium fluoroborate, alkali metal fluorozirconate, ammonium fluorozirconate, alkali metal fluorosulfonate and 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 fluoride or potassium fluoride.
3. A process according to claim 1, which comprises using half to four times the amount by weight of a compound chosen from the group consisting of alkali metal fluoride, ammonium fluoride, alkali metal fluorosilicate, ammonium fluorosilicate, alkali metal fluoroborate, ammonium fluoroborate, alkali metal fluorozirconate, ammonium fluorozirconate, alkali metal fluorosulfonate and ammonium fluorosulfonate, based on the amount by weight of dye employed.
4. A process according to claim 1, wherein the pH range of 3 to 7 is adjusted with an organic acid, and which optionally comprises using, in addition to a compound chosen from the group consisting of alkali metal fluoride, ammonium fluoride, alkali metal fluorosilicate, ammonium fluorosilicate, alkali metal fluoroborate, ammonium fluoroborate, alkali metal fluorozirconate, ammonium fluorozirconate, alkali metal fluorosulfonate and ammonium fluorosulfonate another ammonium or alkali metal salt.
5. A process according to claim 1 wherein dyeing is carried out in a pH range from 3 to 6.
6 A process according to claim 1, wherein dyeing is carried out in the presence of a leveling assistant or a mixture of levelling assistants.
7. A process according to claim 6, which comprises using 0.3 to 3 percent by weight based on the fibre material, of levelling assistant or levelling assistant mixture.
26a 21489-6944
26a 21489-6944
8. A process according to claim 1, which comprises using a dye mixture that contains at least one 1:1 chromium complex azo or azomethine dye containing 1 to 3 sulfo groups and at least one metal-free dye containing 1 or 2 sulfo groups.
9. A process according to claim 8 for trichromatic dyeing, which comprises using a, mixture of 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 from dyes that give yellow or orange and/or red and/or blue dyeings.
10. A process according to claim 8, wherein the 1:1 chromium complex azo or azomethine dyes correspond to formula (4) wherein -(CO)O-1-O and -(O- or -NR1) are linked to D and K
adjacent to the azo bridge, D is a radical of the benzene or naphthalene series which is unsubstituted or substituted by halogen C1-C4alkyl, C1-C4alkoxy, nitro or sulfamoyl, K is a phenyl, naphthyl, 1-phenyl-3-methylpyrazol-5-one, acetoacetamide or quinoline radical, each unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, sulfamoyl or hydroxy, R1 is hydrogen, M is an alkali metal cation, and An is an anion, and Y is a nitrogen atom or the -CH- group.
adjacent to the azo bridge, D is a radical of the benzene or naphthalene series which is unsubstituted or substituted by halogen C1-C4alkyl, C1-C4alkoxy, nitro or sulfamoyl, K is a phenyl, naphthyl, 1-phenyl-3-methylpyrazol-5-one, acetoacetamide or quinoline radical, each unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, sulfamoyl or hydroxy, R1 is hydrogen, M is an alkali metal cation, and An is an anion, and Y is a nitrogen atom or the -CH- group.
11. 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 weight ratio of 40:60 to 95:5.
12. A process according to claim 8, wherein the metal-free sulfo-containing dyes are those of the monoazo, polyazo, anthraquinone, xanthene or triphenylmethane series.
13. A process according to claim 1, wherein the fibre material is synthetic polyamide material, silk or wool.
14. A process according to claim 13, wherein the fibre material is wool.
15. A composition comprising at least one 1:1 metal complex dye which contains sulfo group, at least one metal-free sulfo-containing dye and half to four times the amount by weight of a compound chosen from the group consisting of alkali metal fluo-ride, ammonium fluoride, alkali metal fluorosilicate, ammonium fluorosilicate, alkali metal fluoroborate, ammonium fluoroborate, alkali metal fluorozirconate, ammonium fluorozirconate, alkali metal fluorosulfonate and ammonium fluorosulfonate, based on the amount by weight of dye employed.
16. A process according to claim 3, wherein the amount by weight of a compound chosen from the group consisting of alkali metal fluoride, ammonium fluoride, alkali metal fluorosilicate, ammonium fluorosilicate, alkali metal fluoroborate, ammonium fluoroborate, alkali metal fluorozirconate, ammonium fluorozirconate, alkali metal fluorosulfonate and ammonium fluorosulfonate is from one to three times the amount by weight of dye employed.
17. A process according to claim 3, wherein the amount by weight of a compound chosen from the group consisting of alkali metal fluoride, ammonium fluoride, alkali metal fluorosilicate, ammonium fluorosilicate, alkali metal fluoroborate, ammonium fluoroborate, alkali metal fluorozirconate, ammonium fluorozirconate, alkali metal fluorosulfonate and ammonium fluorosulfonate is from two to three times the amount by weight of dye employed.
18. A process according to claim 4, wherein the organic acid is formic acid or acetic acid.
19. A process according to claim 4, wherein another ammonium or alkali metal salt is alkali metal acetate or alkali metal sulfate.
20. A process according to claim 19, wherein the alkali metal salt is sodium acetate or sodium sulfate.
21. A process according to claim 5, wherein the pH range is from 3.5 to 5.
22. A process according to claim 21, wherein the pH range is from 4 to 5.
23. A process according to claim 7, wherein the amount of levelling assistant, or mixture of levelling assistants, is 1 to 2 percent by weight, based on the fibre material.
24. A process according to claim 8, wherein the chromium complex azo or azomethine dye contains 1 to 2 sulfo groups.
25. A composition according to claim 15, wherein the 1:1 metal complex dye is a 1:1 chromium complex dye.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH2219/85-2 | 1985-05-24 | ||
| CH221985 | 1985-05-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1273154A true CA1273154A (en) | 1990-08-28 |
Family
ID=4228637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000509710A Expired - Lifetime CA1273154A (en) | 1985-05-24 | 1986-05-22 | Process for dyeing natural or synthetic polyamide fibre materials with mixtures of dyes |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0203890B1 (en) |
| JP (1) | JPS61275488A (en) |
| KR (1) | KR860009083A (en) |
| AU (1) | AU581316B2 (en) |
| CA (1) | CA1273154A (en) |
| DE (1) | DE3668021D1 (en) |
| ES (1) | ES8706880A1 (en) |
| HK (1) | HK13894A (en) |
| NZ (1) | NZ216281A (en) |
| ZA (1) | ZA863825B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4818248A (en) * | 1986-10-10 | 1989-04-04 | Ciba-Geigy Corporation | Process for dyeing natural or synthetic polyamide fibre materials with 1:1 metal complex dyes in presence of alkali metal fluordsilicate or amindnlum silicate |
| FR2611737B1 (en) * | 1987-03-04 | 1993-07-23 | Sandoz Sa | MIXTURES OF ANIONIC DYES FOR WOOL DYEING |
| JP4724391B2 (en) * | 2004-07-26 | 2011-07-13 | 純三郎 情野 | Bright blue-green dyeing method |
| EP2483472B1 (en) * | 2009-09-28 | 2014-05-07 | Huntsman Advanced Materials (Switzerland) GmbH | Dyeing auxiliary |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1544433A1 (en) * | 1963-12-04 | 1969-03-20 | Crompton & Knowles Corp | Process for preparing a 1: 1 azo dye-chromium complex |
| US3630662A (en) * | 1966-09-19 | 1971-12-28 | Celanese Corp | Process of dyeing shaped condensation polymer material in heated two-phase dye liquid |
| US3592584A (en) * | 1968-01-23 | 1971-07-13 | Du Pont | Dyeing continuous filament nylon with 1:1 premetallized dyes and mixtures thereof with dye assistants |
| US3990842A (en) * | 1975-05-15 | 1976-11-09 | Pennwalt Corporation | Ammonium silicofluoride assisted dyeing |
| DE3363011D1 (en) * | 1982-03-12 | 1986-05-22 | Ciba Geigy Ag | Process for dyeing fibrous material from natural polyamides |
| US4563192A (en) * | 1983-09-19 | 1986-01-07 | Ciba-Geigy Corporation | Process for dyeing fibre material made of synthetic polyamides with anionic dyes and an auxiliary mixture |
| EP0163608B1 (en) * | 1984-05-30 | 1988-09-07 | Ciba-Geigy Ag | Process for dyeing natural or synthetic polyamide fibrous material with 1:1 metallic complex dyes |
-
1986
- 1986-05-20 EP EP86810218A patent/EP0203890B1/en not_active Expired - Lifetime
- 1986-05-20 DE DE8686810218T patent/DE3668021D1/en not_active Expired - Lifetime
- 1986-05-22 CA CA000509710A patent/CA1273154A/en not_active Expired - Lifetime
- 1986-05-22 ZA ZA863825A patent/ZA863825B/en unknown
- 1986-05-23 JP JP61117665A patent/JPS61275488A/en active Granted
- 1986-05-23 KR KR1019860004042A patent/KR860009083A/en not_active Application Discontinuation
- 1986-05-23 ES ES555250A patent/ES8706880A1/en not_active Expired
- 1986-05-23 AU AU57871/86A patent/AU581316B2/en not_active Ceased
- 1986-05-23 NZ NZ216281A patent/NZ216281A/en unknown
-
1994
- 1994-02-24 HK HK138/94A patent/HK13894A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ES555250A0 (en) | 1987-07-16 |
| ES8706880A1 (en) | 1987-07-16 |
| HK13894A (en) | 1994-03-04 |
| KR860009083A (en) | 1986-12-20 |
| ZA863825B (en) | 1987-01-28 |
| DE3668021D1 (en) | 1990-02-08 |
| JPS61275488A (en) | 1986-12-05 |
| EP0203890A1 (en) | 1986-12-03 |
| JPH0151593B2 (en) | 1989-11-06 |
| NZ216281A (en) | 1990-04-26 |
| AU581316B2 (en) | 1989-02-16 |
| EP0203890B1 (en) | 1990-01-03 |
| AU5787186A (en) | 1986-11-27 |
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