CA1272561A - Process for dyeing synthetic polyamide materials with fibre-reactive anthraquinone dyes - Google Patents
Process for dyeing synthetic polyamide materials with fibre-reactive anthraquinone dyesInfo
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- CA1272561A CA1272561A CA000494710A CA494710A CA1272561A CA 1272561 A CA1272561 A CA 1272561A CA 000494710 A CA000494710 A CA 000494710A CA 494710 A CA494710 A CA 494710A CA 1272561 A CA1272561 A CA 1272561A
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- 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
- D06P1/16—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 dispersed, e.g. acetate, dyestuffs
- D06P1/20—Anthraquinone dyes
-
- 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
- D06P3/24—Polyamides; Polyurethanes
- D06P3/248—Polyamides; Polyurethanes using reactive dyes
-
- 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
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/465—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an acryloyl group, a quaternised or non-quaternised aminoalkyl carbonyl group or a (—N)n—CO—A—O—X or (—N)n—CO—A—Hal group, wherein A is an alkylene or alkylidene group, X is hydrogen or an acyl radical of an organic or inorganic acid, Hal is a halogen atom, and n is 0 or 1
- C09B62/467—Anthracene dyes
-
- 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
- C09B67/0034—Mixtures of two or more pigments or dyes of the same type
- C09B67/0038—Mixtures of anthraquinones
-
- 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
- D06P3/24—Polyamides; Polyurethanes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Coloring (AREA)
Abstract
Process for dyeing synthetic polyamide materials with fibre-reactive anthraquinone dyes Abstract Process for preparing ozone-fast dyeings on synthetic polyamide fibre materials from aqueous liquor with anthraquinone dyes which comprises using at least one anthraquinone dye which contains one or two fibre-reactive groups and one or two sulfo groups.
The process according to the invention is suitable for dyeing synthetic polyamide materials producing with the monosulfoanthraquinone or disulfoanthraquinone dyes which contain one or two fibre-reactive groups level dye-ings having good fastness properties, in particular good ozone fastness.
The process according to the invention is suitable for dyeing synthetic polyamide materials producing with the monosulfoanthraquinone or disulfoanthraquinone dyes which contain one or two fibre-reactive groups level dye-ings having good fastness properties, in particular good ozone fastness.
Description
2S~L
1-15146/=/CG~ 1106 Process for dye;ng synthetic polyamide materials w;th f;bre-reactive anthraquinone dyes The present invention relates to a process for dyeing synthetic polyamide materials in ozone-fast shades with fibre-reactive sulfo-containing anthraquinone dyes.
It is repeatedly found that synthetic polyamide mate-rials dyed with anthraquinone dyes do not meet present-day demands on the ozone fastness of dyeings.
It is the object of the present ;nvent;on to prov;de a process for dyeing synthetic polyam;de materiaLs with anthraquinone dyes which produces dyeings of very good ozone fastness.
This object is achieved according to the invention w;th the process descr;bed here;nafter. The dye;ngs produced thereby meet the stated demands on ozone fastness.
The present invention accordingly provides a process for preparing ozone-fast dyeings on synthetic polyamide fibre materials from aqueous liquor with selected anthraquinone dyes which comprises using at least one anthraquinone dye which contains one or two fibre-reactive groups and one or two sulfo groups.
The process according to the invention produces dye-ings on synthetic polyamide fibre materials of very good ozone fastness.
Suitable anthraquinone dyes are ~elected anthraqu;n-one dyes hav;ng one or two fibre-reactive groups and one or two sulfo groups, for example the anthraqu;none dyes g;ven in the ~olour Index as react;ve blues.
~'~
:,, .,'', ., ~ r-~L~7~
In a preferred embodiment of the process according to the invention, a dye of the formula O NHAl --(S03H) 1-2 .~ \.. / \./ ~--A2 (1), ~ \t~! ---tX)1-2 _ 3 `
in which the ring L can be substituted by hydroxyl, halogen or sulfo, A1 is hydrogen, C1_g-alkyl~ C5_7-cYcloalkyl, phenyl or phenyl-C1_8-alkyl, A2 is hydrogen or halogen, such as chlorine or bromine, or is preferably a sulfo group, A3 is unsubstituted or C1_~-alkyl-, C1_4-alkoxy-, phenoxy-, c1_4-alkYlphenoxy~ or naphthoxy-substituted phenyl or ; phenyl-c1-g-alkyl~ and X is a fibre-reactive radical which is bonded either directly or via a bridge member, is used~
An alkyl radical A1 in the formula ~1) can be a straight-chain or branched alkyl radical, for example methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, iso-buty~, tert.-b~ty~, penty~, hexy~, hepty~ or octy~ D
A Cs_7-cycloalkyL radical Al can ~e for examp~e a~ u~s~stitute~ cyc~o~e~y~ ra~ica~ or a cyc~o~eY~y~
radical whlch is substituted by alkyl, such as methyl.
A pheny~ radical A1 in the formuia (1) can be a phenyl radical which can be substituted by C1_4-alkyl, c1_4-aLkoxy or haLogen and can be further substituted by a su~fo group and a fibre-reactive radical; the phenyl radi-cal is preferably substituted by a sulfo group and a fibre-reactive radica~.
,~ .
:`:
Phenyl-c1-8-alkyl radicals A1 and A3 ;n the formula (1), independently of each other, can each be for example a benzyl, phenethyl, phenylbutyl or phenyl-sec.-butyl radical which ;s preferably substituted by a sulfo group and at least one fibre-reactive radical.
A phenyl radical A3 in the formula (1) can be a phenyl radical which is substituted by C1_4-alkyl, in parti-cular methyl, C1_4-alkoxy, in particular methoxy, phenoxy, C1-c4-alkylphenoxy~ such as methylphenoxy or naphthoxy and which can be further substituted by a sulfo group and preferably one or two fibre-reactive radicals.
F;bre-reactive radicals X are to be understood as meaning radiGals which are capable of reacting ~ith the hydroxyl groups of cellulose, with the amino, carboxyl, hydroxyl and ~hioL groups of ~ool and silk, or with the amino and, where relevant, carboxyl groups of synthetic polyamides to form covalent chemical bonds.
X is preferably a fibre-reactive radical of the aliphatic, aromatic or heterocyclic series which is bonded to the radical A1 and/or A3 either directly or via a bridge member.
X is preferably bonded to the radical A1 and/or A3 either directly or v;a an amino group which can be monoalky-lated, for example via -NH-, -N(CH3)-, -N(C2Hs)- or -N~C3H7)-, or via a br;d9e member conta;ning an amino group.
A fibre-react;ve radical X in the formula (1) can be for example one of the following aliphatic or aromatic radi-cals:
vinylsulfonyl~ ~-chloroethylsulfonyl, ~-sulfatoethyl-sulfonyl, ~-acetoxy-ethylsulfonyl, phosphonooxyethylsulfonyl, ~thiosulfatoethylsulfonyl, N-methyl-N-~-sulfatoethyl-sulfonyl)-amino, acryloyl, monochloroacryloyl~ dichloro-acryloyl or trichloroacryloyl such as -CO-CCl=CH2, -CO-CH=CH-Cl, -CO-CCl=CH-CH3; monobromo3cryloyl~ dibromo-acryloyl or tribromoacryloyl such as -CO-CBr=CH2, -CO-CH=CH-Br, -CO~CBr-CH-CH3i and also -CO-CCl=CH-COOH, -CO-CH=CCl-COOH, ~7~ria~
-- 4 ~
-CO-CBr=CH-COOH, -CO-C~=CBr-COOH; -CO-CCl=CCl-COOH, -CO-CBr=
CBr-COOH; precursors of the acryloyl radical and of the derivatives of the acryloyl radical, such as ~-chloropropionyl, ~-bromopropionyl, 3-phenylsulfonylpropionyl, 3-methylsulfonyl-propionyl, 3-chloro-3-phenylsulfonylpropionyl, 2,3-dichloro-prop;onyl, 2,~-d;bromoprop;onyl; and also 2-fluoro-2-chloro-3,3-d;fluorocyclobutane-1-carbonyl, 2,2,3,3-tetrafluorocyclo-butane-1-carbonyl or -1-sulfonyl, ~-(2,2,3,3-tetrafluorocyclo-but-1-yl)-acryloyl,~- or ~-alkylsulfonylacryloyl orarylsulfonyl-acryloyl groups such as ~- or ~-methylsulfonylacryloyl, propiolyl~ chloroacetyl, bromoacetyl, 4-(~-chloroethyl-sulfonyl)-butyryl, 4-vinylsulfonyl-butyryl, 5-(~-chlorethyl-sulfonyl)-valeryl, 5-vinylsulfonyl-valeryl, 6~ chloroethyl-sulfonyl)-caproyl, 6-vinylsulfonyl-caproyl; and also 4-fluoro-3-nitrobenzoyl, 4-fluoro-3-n;trophenylsulfonyl, 4-fluoro-3-methylsulfonylbenzoyl, 4-fluoro-3-cyanobenzoyl,
1-15146/=/CG~ 1106 Process for dye;ng synthetic polyamide materials w;th f;bre-reactive anthraquinone dyes The present invention relates to a process for dyeing synthetic polyamide materials in ozone-fast shades with fibre-reactive sulfo-containing anthraquinone dyes.
It is repeatedly found that synthetic polyamide mate-rials dyed with anthraquinone dyes do not meet present-day demands on the ozone fastness of dyeings.
It is the object of the present ;nvent;on to prov;de a process for dyeing synthetic polyam;de materiaLs with anthraquinone dyes which produces dyeings of very good ozone fastness.
This object is achieved according to the invention w;th the process descr;bed here;nafter. The dye;ngs produced thereby meet the stated demands on ozone fastness.
The present invention accordingly provides a process for preparing ozone-fast dyeings on synthetic polyamide fibre materials from aqueous liquor with selected anthraquinone dyes which comprises using at least one anthraquinone dye which contains one or two fibre-reactive groups and one or two sulfo groups.
The process according to the invention produces dye-ings on synthetic polyamide fibre materials of very good ozone fastness.
Suitable anthraquinone dyes are ~elected anthraqu;n-one dyes hav;ng one or two fibre-reactive groups and one or two sulfo groups, for example the anthraqu;none dyes g;ven in the ~olour Index as react;ve blues.
~'~
:,, .,'', ., ~ r-~L~7~
In a preferred embodiment of the process according to the invention, a dye of the formula O NHAl --(S03H) 1-2 .~ \.. / \./ ~--A2 (1), ~ \t~! ---tX)1-2 _ 3 `
in which the ring L can be substituted by hydroxyl, halogen or sulfo, A1 is hydrogen, C1_g-alkyl~ C5_7-cYcloalkyl, phenyl or phenyl-C1_8-alkyl, A2 is hydrogen or halogen, such as chlorine or bromine, or is preferably a sulfo group, A3 is unsubstituted or C1_~-alkyl-, C1_4-alkoxy-, phenoxy-, c1_4-alkYlphenoxy~ or naphthoxy-substituted phenyl or ; phenyl-c1-g-alkyl~ and X is a fibre-reactive radical which is bonded either directly or via a bridge member, is used~
An alkyl radical A1 in the formula ~1) can be a straight-chain or branched alkyl radical, for example methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, iso-buty~, tert.-b~ty~, penty~, hexy~, hepty~ or octy~ D
A Cs_7-cycloalkyL radical Al can ~e for examp~e a~ u~s~stitute~ cyc~o~e~y~ ra~ica~ or a cyc~o~eY~y~
radical whlch is substituted by alkyl, such as methyl.
A pheny~ radical A1 in the formuia (1) can be a phenyl radical which can be substituted by C1_4-alkyl, c1_4-aLkoxy or haLogen and can be further substituted by a su~fo group and a fibre-reactive radical; the phenyl radi-cal is preferably substituted by a sulfo group and a fibre-reactive radica~.
,~ .
:`:
Phenyl-c1-8-alkyl radicals A1 and A3 ;n the formula (1), independently of each other, can each be for example a benzyl, phenethyl, phenylbutyl or phenyl-sec.-butyl radical which ;s preferably substituted by a sulfo group and at least one fibre-reactive radical.
A phenyl radical A3 in the formula (1) can be a phenyl radical which is substituted by C1_4-alkyl, in parti-cular methyl, C1_4-alkoxy, in particular methoxy, phenoxy, C1-c4-alkylphenoxy~ such as methylphenoxy or naphthoxy and which can be further substituted by a sulfo group and preferably one or two fibre-reactive radicals.
F;bre-reactive radicals X are to be understood as meaning radiGals which are capable of reacting ~ith the hydroxyl groups of cellulose, with the amino, carboxyl, hydroxyl and ~hioL groups of ~ool and silk, or with the amino and, where relevant, carboxyl groups of synthetic polyamides to form covalent chemical bonds.
X is preferably a fibre-reactive radical of the aliphatic, aromatic or heterocyclic series which is bonded to the radical A1 and/or A3 either directly or via a bridge member.
X is preferably bonded to the radical A1 and/or A3 either directly or v;a an amino group which can be monoalky-lated, for example via -NH-, -N(CH3)-, -N(C2Hs)- or -N~C3H7)-, or via a br;d9e member conta;ning an amino group.
A fibre-react;ve radical X in the formula (1) can be for example one of the following aliphatic or aromatic radi-cals:
vinylsulfonyl~ ~-chloroethylsulfonyl, ~-sulfatoethyl-sulfonyl, ~-acetoxy-ethylsulfonyl, phosphonooxyethylsulfonyl, ~thiosulfatoethylsulfonyl, N-methyl-N-~-sulfatoethyl-sulfonyl)-amino, acryloyl, monochloroacryloyl~ dichloro-acryloyl or trichloroacryloyl such as -CO-CCl=CH2, -CO-CH=CH-Cl, -CO-CCl=CH-CH3; monobromo3cryloyl~ dibromo-acryloyl or tribromoacryloyl such as -CO-CBr=CH2, -CO-CH=CH-Br, -CO~CBr-CH-CH3i and also -CO-CCl=CH-COOH, -CO-CH=CCl-COOH, ~7~ria~
-- 4 ~
-CO-CBr=CH-COOH, -CO-C~=CBr-COOH; -CO-CCl=CCl-COOH, -CO-CBr=
CBr-COOH; precursors of the acryloyl radical and of the derivatives of the acryloyl radical, such as ~-chloropropionyl, ~-bromopropionyl, 3-phenylsulfonylpropionyl, 3-methylsulfonyl-propionyl, 3-chloro-3-phenylsulfonylpropionyl, 2,3-dichloro-prop;onyl, 2,~-d;bromoprop;onyl; and also 2-fluoro-2-chloro-3,3-d;fluorocyclobutane-1-carbonyl, 2,2,3,3-tetrafluorocyclo-butane-1-carbonyl or -1-sulfonyl, ~-(2,2,3,3-tetrafluorocyclo-but-1-yl)-acryloyl,~- or ~-alkylsulfonylacryloyl orarylsulfonyl-acryloyl groups such as ~- or ~-methylsulfonylacryloyl, propiolyl~ chloroacetyl, bromoacetyl, 4-(~-chloroethyl-sulfonyl)-butyryl, 4-vinylsulfonyl-butyryl, 5-(~-chlorethyl-sulfonyl)-valeryl, 5-vinylsulfonyl-valeryl, 6~ chloroethyl-sulfonyl)-caproyl, 6-vinylsulfonyl-caproyl; and also 4-fluoro-3-nitrobenzoyl, 4-fluoro-3-n;trophenylsulfonyl, 4-fluoro-3-methylsulfonylbenzoyl, 4-fluoro-3-cyanobenzoyl,
2-fluoro-5-methylsulfonylbenzoyl~
The fibre-reactive radical X can also be a member of the heterocyclic series, for example a 2,4-dichlorotriazin-6-yl or monohalogenopyrimidinyl, dihalogenopyrimidinyl or trihalogenopyrimidinyl radical, such as 2,4-dichloro-pyrimidin-6-yl, 2,4,5-trichloropyrimidin-6-yl, 2,4-dichloro-5-nitro- or -5-methyl- or -5-carboxymethyl- or -5-carboxy- or -5-cyano- or -5-vinyl- or -5-sulfo- or -5-monochloromethyl- or -5-dichloromethyl- or -5-trichloro-methyl or -5-methylsulfonyl-pyrimidin-6-yl, 2,5-dichloro-4-methylsulfonylpyrimidin-6-yl, 2-fluoro-4-pyrimidinyl, 2,6-difluoro-4-pyrimidinyl, 2,6-difluoro-5-chloro-4-pyrimidinyl, 2-fluoro-5,6-dichloro-4-pyrimidinyl, 2,6-di-fluoro-5-methyl-4-pyrimidinyl, 2,5-difluoro-6-methyl-4-pyr-imidinyl, 2-fluoro-5-methyl-6-chloro-4-pyrimidinyl, 2-fluoro-5-nitro-6-chloro-4-pyrimidinyl, 2-fluoro-5-nitro-6-chloro-4-pyrimidinyl, 5-bromo-2-fluoro-4-pyrimidinyl, 2-fluoro-5-cyano-4-pyrimidinyl, 2-fluoro-5-methyl-4-pyrimidinyl, 2,5,6-trifluoro-4-pyrimidinyl, 5-chloro-6-chloromethyl-2-fluoro-4-pyrimidinyl, 2,6-difluoro-5-bromo-4-pyrimidinyl, 2-fluoro-5-bromo-6-chloromethyl-4-pyrimidinyl, 2,6-di~luoro-5-chloro-~'~ 7~
methyl-4-pyrimidinyl, 2,6-difluoro-5-nitro-4-pYrimidinYl, 2-fluoro-6-methyl-4-pyr;m;dinyl, 2-fluoro-5-chloro-6-methyl-4-pyrimidinyl, 2-fluoro-5 chloro-4-pyr;midinYl, 2-fluoro-6-chloro-4-pyr;mid;nyl, 6-trifluorome~hyl-5-chloro-2-fluoro-4-pyrimidinyl, 6-trifluoromethyl-2-fluoro-4-pyrim;d;nYl, 2-fluoro-5-nitro-4-pyrimidinyl, 2-fluoro-5-trifluoromethYl-4-pyr;midinyl, 2-fluoro-5-phenyl- or -5-methylsulfonYl-4-pyrimidinyl, 2-fluoro-5-carboxamido-4-pyrim;d;nyl, 2-fluoro-5-carbomethoxy-4-pyrimidinyl, 2-fluoro-5-bromo-6-trifluoromethyl-4-pyr;m;dinyl, 2-fluoro-6-carboxam;do-4-pyrimidinyl, 2-fluoro-6-carbo-methoxy-4-pyr;m;dinyl, 2-fluoro-6-phenyl-4-pyrimid;nyl, 2-fluoro-6-cyano-4-pyr;m;d;nyl, 2,6-difluoro-5-methylsulfonyl-4-pyrimid;nyl, 2-fluoro-5-sulfonamido-4-pyr;m;dinyl, 2-fluoro-5-chloro-6-carbomethoxy-4-pyrimidinyl, 2,6-difluoro-5-tri-fluoromethyl-4-pyrimid;nyl; 2,4-bis-methylsulfonyl pyrimidin-4-yl, 2,5-bis-methylsulfonyl-5-chloropyrimidin-4-yl, 2-methyl-sulfonyl-pyrim;din-4-yl, 2-phenylsulfonyl-pyr;m;d;n-4-yl, 2-methylsulfonyl-5-chloro-6-methylpyr;midin-4-yl, 2-methylsulfonyl-5-bromo-6-methyl-pyrimidin-4-yl, 2-methylsulfonyl-5-chloro-6-ethyl-pyrimidin-4-yl, 2-methylsulfonyl-5-chloro-methylpyrimidin-4-yl, 2-methylsulfonyl-5-n;tro-6-methylpyrimidin-4-yl, 2,5,6-tris-methylsulfonyl-pyr;midin-4-yl, 2-methylsulfonyl-5,6-d;methylpyrimidin-4-yl, 2-ethylsulfonyl-5-chloro-6-methyl-pyrimidin-4-yl, 2-methylsulfonyl-6-chloro-pyrimidin-4-yl, 2,6-bis-methylsulfonyl-5-chloro-pyrimidin-4-yl, 2-methylsulfonyl-6-carboxy-pyrimidin-4-yl, 2-methylsulfonyl-5-sulfo-pyrimidin-4-yl, 2-methylsulfonyl-6-carbomethoxy-pyrim;din-4-yl, 2-methylsulfonyl-5-carboxy-pyrimidin-4-yl, 2-methylsulfonyl-5-cyano-6-methoxy-pyrim;d;n-4-yl, 2-methyl-sulfonyl-5-chloro-pyrimidin-4-yl, 2-sulfoethylsulfonyl-6-methyl-pyrimidin-4-yl~ 2-methylsulfonyl-5-bromo-pyrimidin-4-yl, 2-phenylsulfonyl-5-chloro-pyrimidin-4-yl, 2-carboxy-methylsulfonyl-5-chloro-6-methyl-pyrimidin-4-yl, 2,4-dichloro-pyrimidine-6-carbonyl or -6-sulfonyl, 2,4-dichloropyrimidine-5-carbonyl or -5-sulfonyl~ 2-chloro-4-methylpyrimidine-5-carbonyl, 5~L
2-methyl-4-chloropyrimidine-5-carbonyl, 2-methylthio 4-fluoropyrimidine-5-carbonyl, 6-methyl-2,4-dichloro-pyr;mid;ne 5-carbonyl, 2,4,6-trichloropyrimidine-5-carbonyl, 2,4-d;chloropyrimidine-5-sulfonyl, 2,4-dichloro-6-methylpyrim;d;ne-5-carbonyl or-5-sulfonyl~ 2-methyl-sulfonyl-6-chloropyr;midine-4- and -5-carbonyl, 2,6-bis-(methylsulfonyl)-pyrimidine-4- or -5-carbonyl, 2-ethylsulfonyl-6-chloropyrim;d;ne-5-carbonyl, 2,4-bis-(methylsulfonYl)-pyrimidine-5-sulfonyl, 2-methylsulfonyl-4-chloro-6-methyl-pyrimidine-5-sulfonyl or -5-carbonyl~ 2-chloroquinoxaline-3-carbonyl, 2- or 3-monochloroquinoxaline-6-carbonyl, 2- or 3-monochloroquinoxaline-6-sulfonyl, 2,3-dichloroquinoxaline-5 or -6-carbonyl, 2,3-dichloroquinoxaline-5- or -6-sulfonyl, 1~4-dichlorophthalazine-6-sulfonyl or -6-carbonyl, 2,4-dichloroquinazoline~7- or -6-sulfonyl or -carbonyl, 2,4,6-trichloroquinazoline-7- or -8-sulfonyl, 2- or 3- or 4-(4',5'-dichloropyridaz-6'-on-1'-yl)-phenylsulfonyl or -carbonyl, ~-~4',5'-dichloropyridazin-6'-on-1'-yl)-propionyl, 3,6-dichloro-pyridazine-4-carbonyl or -4-sulfonyl, 2-chlorobenzothiazole-5-or -6-carbonyl or -5- or -6-sulfonyl, 2-arylsulfonyl-benzo-thiazole- or 2-alkylsulfonylbenzothiazole-5- or -6-carbonyl or -5- or -6-sulfonyl, such as 2-methylsulfonylbenzothiazole-or 2 ethylsulfonylbenzothiazole-5- or -6-sulfonyl or -car-bonyl, 2-phenylsulfonylbenzothiazole-S- or -6-sulfonyl or -carbonyl and the corresponding 2-sulfonylbenzothiazole-5- or -6-carbonyl or -sulfonyl derivatives which contain sulfo groups in the fused-on benzene ring, 2-chlorobenzoxazole-5- or -6-carbonyl or -sulfonyl, 2-chlorobenzimidazole-5- or -6-carbonyL or -sulfonyl, 2-chloro-1-methylbenzimidazole-5- or -6-carbonyl or -sulfonyl, 2-chloro-4-methyl 1,3-thiazole-5-`carbonyl or -4- or -5-sulfonyl; ammonium-containing tri-azine rings, such as 2-trimethylammonium-4-phenylamino- or -4-(o-, m- or p-sulfophenyl)-amino-triazin-6-yl, 2-(1,1-dimethyl-hydrazinium)-4-phenylamino- or -4-(o-, m- or p-sulfophenyl)-aminotriazin-6-yl, 2-(2-isopropylidene-1,1-dimethyl)-hyd-razinium-4-phenylamino- or -4-(o-, m- or p-sulfophenyl)-amino-triazin-6-yl, 2-N-aminopyrrolidinium- or 2-N-aminopiperid-~ ~.
~7~S~
-- 7inium~4-phenylamino- or -4-to-, m- or p-sulfophenyl)-amino-triazin-6-yl, and also 4-phenylamino- or 4-(sulfophenylamino)-triazin-6-yl radicals which, in the 2-pos;tion, contain 1,~-bis-azabicycloC2.2.2~octane or 1,2-bis-azabicycloCO.3.3]-octane via a quaternary nitrogen bond, 2-pyridinium-ll-phenyl-amino- or -4-(o-, m- or p-sulfophenyl)-amino-triazin-6-yl and corresponding 2-oniumtriazin-6-yl radicals which are sub-stituted in the 4-position by alkylamino, such as methylamino, ethylamino or ~ -hydroxyethylamino, or alkoxy, such as methoxy or ethoxy, or aryloxy, such as phenoxy, or sulfo-phenoxy groupsn An interesting fibre-reactive radical can also be a chloro- or fluoro-1,3,5-triazine radical of the formula F, C1 V
where the substituent V on the triazine ring can be in par-ticular:
halogen, for example chlorine or fluorine, C1_8-alkoxy, for example methoxy, cyclohexyloxy, phenoxy, C1_6~
alkylmercapto, such as methylmercapto, phenylmercapto, -NH2, alkylamino, N,N-dialkylamino, cycloalkylamino, N,N-dicyclo-alkylamino, aralkylamino and arylamino groups, mixed-substituted amino groups, such as N-alkyl-N-cyclohexylamino and N-alkyl-N-arylamino groups, and also amino groups which contain heterocyclic radicals which can have further fused-on carbo-cyclic rings, and amino groups in which the amino nitrogen atom is a member of an N-heterocyclic ring which can contain further hetero atoms, as well as hydrazino and semicarbazido.
The abovementioned alkyl radicals can be straight-chain or branched and of low molecular weight or higher molecular weight and are preferably alkyl radicals having 1 to 6 carbon atoms; cycloalkyl, aralkyl and aryl radicals can be in par-ticular cyclohexyl, benzyl, phenethyl, phenyl and naphthyl radicals; heterocyclic radicals can be in particular furan, thiophene, pyrazole, pyridine, pyrimidine, quinoline, benzi-midazole, benzothiazole and benzoxazole radicals; and aminogroups in which the amino nitrogen atom is a member of an N-heterocyclic ring are preferably radicals of six-membered N-heterocyclic compounds Hhich can contain nitrogen, oxygen or sulfur as further hetero atoms. The abovementioned alkyl, cycloalkyl, aralkyl and aryl radicalsr the heterocyclic radicals and the N-heterocyclic rings can be further substi-tuted, for example by: halogen, such as fluorine, chlorine or bromine, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C1_4-alkyl, c1_4-alkoxY, acylamino groups, such as acetylamino or benzoylamino, ureido, hydroxyl, carboxyl, sulfomethyl or sulfo~ Examples of such amino groups are: -NH2, methylamino, ethylamino, propylamino, ;sopropylam;no, butylamino, hexylamino, ~-methoxyethylamino, ~-methoxypropylamino, ~-ethoxyethylamino, N,N-dimethylamino, N,N-diethylamino, ~-chloroethylamino, ~-cyanoethylamino, ~-cyanopropylamino, ~-carboxyethylamino, sulfomethylamino, ~-sulfoethylamino, ~-hydroxyethylamino, N,N-d;-~-hydroxy-ethylamino, ~-hydroxypropylamino, benzylamino, phenethyl-amino, cyclohexylamino, phenylamino, tolu;dino, xylidino, chloranilino, anisidino, phenetidino, N-methyl-N-phenylam;no, N-ethyl-N-phenylamino, N-~-hydroxyethyl-N-phenylamino, 2-,
The fibre-reactive radical X can also be a member of the heterocyclic series, for example a 2,4-dichlorotriazin-6-yl or monohalogenopyrimidinyl, dihalogenopyrimidinyl or trihalogenopyrimidinyl radical, such as 2,4-dichloro-pyrimidin-6-yl, 2,4,5-trichloropyrimidin-6-yl, 2,4-dichloro-5-nitro- or -5-methyl- or -5-carboxymethyl- or -5-carboxy- or -5-cyano- or -5-vinyl- or -5-sulfo- or -5-monochloromethyl- or -5-dichloromethyl- or -5-trichloro-methyl or -5-methylsulfonyl-pyrimidin-6-yl, 2,5-dichloro-4-methylsulfonylpyrimidin-6-yl, 2-fluoro-4-pyrimidinyl, 2,6-difluoro-4-pyrimidinyl, 2,6-difluoro-5-chloro-4-pyrimidinyl, 2-fluoro-5,6-dichloro-4-pyrimidinyl, 2,6-di-fluoro-5-methyl-4-pyrimidinyl, 2,5-difluoro-6-methyl-4-pyr-imidinyl, 2-fluoro-5-methyl-6-chloro-4-pyrimidinyl, 2-fluoro-5-nitro-6-chloro-4-pyrimidinyl, 2-fluoro-5-nitro-6-chloro-4-pyrimidinyl, 5-bromo-2-fluoro-4-pyrimidinyl, 2-fluoro-5-cyano-4-pyrimidinyl, 2-fluoro-5-methyl-4-pyrimidinyl, 2,5,6-trifluoro-4-pyrimidinyl, 5-chloro-6-chloromethyl-2-fluoro-4-pyrimidinyl, 2,6-difluoro-5-bromo-4-pyrimidinyl, 2-fluoro-5-bromo-6-chloromethyl-4-pyrimidinyl, 2,6-di~luoro-5-chloro-~'~ 7~
methyl-4-pyrimidinyl, 2,6-difluoro-5-nitro-4-pYrimidinYl, 2-fluoro-6-methyl-4-pyr;m;dinyl, 2-fluoro-5-chloro-6-methyl-4-pyrimidinyl, 2-fluoro-5 chloro-4-pyr;midinYl, 2-fluoro-6-chloro-4-pyr;mid;nyl, 6-trifluorome~hyl-5-chloro-2-fluoro-4-pyrimidinyl, 6-trifluoromethyl-2-fluoro-4-pyrim;d;nYl, 2-fluoro-5-nitro-4-pyrimidinyl, 2-fluoro-5-trifluoromethYl-4-pyr;midinyl, 2-fluoro-5-phenyl- or -5-methylsulfonYl-4-pyrimidinyl, 2-fluoro-5-carboxamido-4-pyrim;d;nyl, 2-fluoro-5-carbomethoxy-4-pyrimidinyl, 2-fluoro-5-bromo-6-trifluoromethyl-4-pyr;m;dinyl, 2-fluoro-6-carboxam;do-4-pyrimidinyl, 2-fluoro-6-carbo-methoxy-4-pyr;m;dinyl, 2-fluoro-6-phenyl-4-pyrimid;nyl, 2-fluoro-6-cyano-4-pyr;m;d;nyl, 2,6-difluoro-5-methylsulfonyl-4-pyrimid;nyl, 2-fluoro-5-sulfonamido-4-pyr;m;dinyl, 2-fluoro-5-chloro-6-carbomethoxy-4-pyrimidinyl, 2,6-difluoro-5-tri-fluoromethyl-4-pyrimid;nyl; 2,4-bis-methylsulfonyl pyrimidin-4-yl, 2,5-bis-methylsulfonyl-5-chloropyrimidin-4-yl, 2-methyl-sulfonyl-pyrim;din-4-yl, 2-phenylsulfonyl-pyr;m;d;n-4-yl, 2-methylsulfonyl-5-chloro-6-methylpyr;midin-4-yl, 2-methylsulfonyl-5-bromo-6-methyl-pyrimidin-4-yl, 2-methylsulfonyl-5-chloro-6-ethyl-pyrimidin-4-yl, 2-methylsulfonyl-5-chloro-methylpyrimidin-4-yl, 2-methylsulfonyl-5-n;tro-6-methylpyrimidin-4-yl, 2,5,6-tris-methylsulfonyl-pyr;midin-4-yl, 2-methylsulfonyl-5,6-d;methylpyrimidin-4-yl, 2-ethylsulfonyl-5-chloro-6-methyl-pyrimidin-4-yl, 2-methylsulfonyl-6-chloro-pyrimidin-4-yl, 2,6-bis-methylsulfonyl-5-chloro-pyrimidin-4-yl, 2-methylsulfonyl-6-carboxy-pyrimidin-4-yl, 2-methylsulfonyl-5-sulfo-pyrimidin-4-yl, 2-methylsulfonyl-6-carbomethoxy-pyrim;din-4-yl, 2-methylsulfonyl-5-carboxy-pyrimidin-4-yl, 2-methylsulfonyl-5-cyano-6-methoxy-pyrim;d;n-4-yl, 2-methyl-sulfonyl-5-chloro-pyrimidin-4-yl, 2-sulfoethylsulfonyl-6-methyl-pyrimidin-4-yl~ 2-methylsulfonyl-5-bromo-pyrimidin-4-yl, 2-phenylsulfonyl-5-chloro-pyrimidin-4-yl, 2-carboxy-methylsulfonyl-5-chloro-6-methyl-pyrimidin-4-yl, 2,4-dichloro-pyrimidine-6-carbonyl or -6-sulfonyl, 2,4-dichloropyrimidine-5-carbonyl or -5-sulfonyl~ 2-chloro-4-methylpyrimidine-5-carbonyl, 5~L
2-methyl-4-chloropyrimidine-5-carbonyl, 2-methylthio 4-fluoropyrimidine-5-carbonyl, 6-methyl-2,4-dichloro-pyr;mid;ne 5-carbonyl, 2,4,6-trichloropyrimidine-5-carbonyl, 2,4-d;chloropyrimidine-5-sulfonyl, 2,4-dichloro-6-methylpyrim;d;ne-5-carbonyl or-5-sulfonyl~ 2-methyl-sulfonyl-6-chloropyr;midine-4- and -5-carbonyl, 2,6-bis-(methylsulfonyl)-pyrimidine-4- or -5-carbonyl, 2-ethylsulfonyl-6-chloropyrim;d;ne-5-carbonyl, 2,4-bis-(methylsulfonYl)-pyrimidine-5-sulfonyl, 2-methylsulfonyl-4-chloro-6-methyl-pyrimidine-5-sulfonyl or -5-carbonyl~ 2-chloroquinoxaline-3-carbonyl, 2- or 3-monochloroquinoxaline-6-carbonyl, 2- or 3-monochloroquinoxaline-6-sulfonyl, 2,3-dichloroquinoxaline-5 or -6-carbonyl, 2,3-dichloroquinoxaline-5- or -6-sulfonyl, 1~4-dichlorophthalazine-6-sulfonyl or -6-carbonyl, 2,4-dichloroquinazoline~7- or -6-sulfonyl or -carbonyl, 2,4,6-trichloroquinazoline-7- or -8-sulfonyl, 2- or 3- or 4-(4',5'-dichloropyridaz-6'-on-1'-yl)-phenylsulfonyl or -carbonyl, ~-~4',5'-dichloropyridazin-6'-on-1'-yl)-propionyl, 3,6-dichloro-pyridazine-4-carbonyl or -4-sulfonyl, 2-chlorobenzothiazole-5-or -6-carbonyl or -5- or -6-sulfonyl, 2-arylsulfonyl-benzo-thiazole- or 2-alkylsulfonylbenzothiazole-5- or -6-carbonyl or -5- or -6-sulfonyl, such as 2-methylsulfonylbenzothiazole-or 2 ethylsulfonylbenzothiazole-5- or -6-sulfonyl or -car-bonyl, 2-phenylsulfonylbenzothiazole-S- or -6-sulfonyl or -carbonyl and the corresponding 2-sulfonylbenzothiazole-5- or -6-carbonyl or -sulfonyl derivatives which contain sulfo groups in the fused-on benzene ring, 2-chlorobenzoxazole-5- or -6-carbonyl or -sulfonyl, 2-chlorobenzimidazole-5- or -6-carbonyL or -sulfonyl, 2-chloro-1-methylbenzimidazole-5- or -6-carbonyl or -sulfonyl, 2-chloro-4-methyl 1,3-thiazole-5-`carbonyl or -4- or -5-sulfonyl; ammonium-containing tri-azine rings, such as 2-trimethylammonium-4-phenylamino- or -4-(o-, m- or p-sulfophenyl)-amino-triazin-6-yl, 2-(1,1-dimethyl-hydrazinium)-4-phenylamino- or -4-(o-, m- or p-sulfophenyl)-aminotriazin-6-yl, 2-(2-isopropylidene-1,1-dimethyl)-hyd-razinium-4-phenylamino- or -4-(o-, m- or p-sulfophenyl)-amino-triazin-6-yl, 2-N-aminopyrrolidinium- or 2-N-aminopiperid-~ ~.
~7~S~
-- 7inium~4-phenylamino- or -4-to-, m- or p-sulfophenyl)-amino-triazin-6-yl, and also 4-phenylamino- or 4-(sulfophenylamino)-triazin-6-yl radicals which, in the 2-pos;tion, contain 1,~-bis-azabicycloC2.2.2~octane or 1,2-bis-azabicycloCO.3.3]-octane via a quaternary nitrogen bond, 2-pyridinium-ll-phenyl-amino- or -4-(o-, m- or p-sulfophenyl)-amino-triazin-6-yl and corresponding 2-oniumtriazin-6-yl radicals which are sub-stituted in the 4-position by alkylamino, such as methylamino, ethylamino or ~ -hydroxyethylamino, or alkoxy, such as methoxy or ethoxy, or aryloxy, such as phenoxy, or sulfo-phenoxy groupsn An interesting fibre-reactive radical can also be a chloro- or fluoro-1,3,5-triazine radical of the formula F, C1 V
where the substituent V on the triazine ring can be in par-ticular:
halogen, for example chlorine or fluorine, C1_8-alkoxy, for example methoxy, cyclohexyloxy, phenoxy, C1_6~
alkylmercapto, such as methylmercapto, phenylmercapto, -NH2, alkylamino, N,N-dialkylamino, cycloalkylamino, N,N-dicyclo-alkylamino, aralkylamino and arylamino groups, mixed-substituted amino groups, such as N-alkyl-N-cyclohexylamino and N-alkyl-N-arylamino groups, and also amino groups which contain heterocyclic radicals which can have further fused-on carbo-cyclic rings, and amino groups in which the amino nitrogen atom is a member of an N-heterocyclic ring which can contain further hetero atoms, as well as hydrazino and semicarbazido.
The abovementioned alkyl radicals can be straight-chain or branched and of low molecular weight or higher molecular weight and are preferably alkyl radicals having 1 to 6 carbon atoms; cycloalkyl, aralkyl and aryl radicals can be in par-ticular cyclohexyl, benzyl, phenethyl, phenyl and naphthyl radicals; heterocyclic radicals can be in particular furan, thiophene, pyrazole, pyridine, pyrimidine, quinoline, benzi-midazole, benzothiazole and benzoxazole radicals; and aminogroups in which the amino nitrogen atom is a member of an N-heterocyclic ring are preferably radicals of six-membered N-heterocyclic compounds Hhich can contain nitrogen, oxygen or sulfur as further hetero atoms. The abovementioned alkyl, cycloalkyl, aralkyl and aryl radicalsr the heterocyclic radicals and the N-heterocyclic rings can be further substi-tuted, for example by: halogen, such as fluorine, chlorine or bromine, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C1_4-alkyl, c1_4-alkoxY, acylamino groups, such as acetylamino or benzoylamino, ureido, hydroxyl, carboxyl, sulfomethyl or sulfo~ Examples of such amino groups are: -NH2, methylamino, ethylamino, propylamino, ;sopropylam;no, butylamino, hexylamino, ~-methoxyethylamino, ~-methoxypropylamino, ~-ethoxyethylamino, N,N-dimethylamino, N,N-diethylamino, ~-chloroethylamino, ~-cyanoethylamino, ~-cyanopropylamino, ~-carboxyethylamino, sulfomethylamino, ~-sulfoethylamino, ~-hydroxyethylamino, N,N-d;-~-hydroxy-ethylamino, ~-hydroxypropylamino, benzylamino, phenethyl-amino, cyclohexylamino, phenylamino, tolu;dino, xylidino, chloranilino, anisidino, phenetidino, N-methyl-N-phenylam;no, N-ethyl-N-phenylamino, N-~-hydroxyethyl-N-phenylamino, 2-,
3- or 4-sulfoanilino, 2,5-disulfoanilino, 4-sulfomethyl-anilino, N-sulfomethylanilino, 2-, 3- or 4-carboxyphenylamino, 2-carboxy-5-sulfophenylamino, 2-carboxy-4-sulfophenylamino,
4-sulfonaphth-1-ylamino, 3,6-disulfonaphth-1-ylamino, 3,6,8-trisulfonaphth-1-ylamino, 4,6,8-trisulfonaphth-1-ylamino, 1-sulfonaphth-2-ylamino, 1,5-disulfonaphth-2-ylamino, 6-sulfonaphth-2-ylamino, morpholino~ piperidino, piperazino, hydrazino and semicarbazido.
In particularly preferred embodiments of the process according to the invention9 ~ ~ 7 _ 9 _ a) a dye of the formula ::~ ll 1 2 \ /~
. i il il i_S03H (2) 0 NH~ 3 0-1 (X) 1-2 .
.~
in which X is as defined under the formula (1~ and the phenyl ring L1 can be monosubstituted, disubstituted, tr;substituted or tetrasubstituted by C1_4-alkyl, C1_4-alkoxy or phenoxy, is used;
b) a dye of the formula _ 0 NH-A . _-- (S03H) 1-2 ; :I~ ,¢ ,il~ ~i (3), \ 2 / ( ) 1-2 _ which A4 is a C1_6-alkyl or Cs_7-cycloalkyl radical, X is as defined under the formula t1) and the phenyl ring L2 can be monosubstituted, disubstituted or trisubstituted by C1_~-alkyl, C1_4-alkoxy, phenoxy or c1_4-alkYlphenoxy, is used;
'~
., ~ ~ 7 c) a dye of the formula 0 NH-A --(S03H) 1-2 :~
~ ! il i! i --(x) 1-2 / \ / \.~ ._.
~ ~H-(Cl 8-A1ky1~n)--~L3 ~ (4), ; ;n wh;ch A4 is as defined under the formula (3), X is as def;ned under the formula (1) and the phenyl ring L3 can be monosubstituted or disubstituted by C1_4-alkyl or C1_4-alkoxy, is used;
d) a dye of the formula ;
0 NH- (cl_8-alkYlene) o ~ ~ 3 T i1 i1 i (s), ~ / \ / \ ~
o NH-(Cl_8 alkyl~0_l \ _ Xso H
;n wh;ch X ;s as def;ned under the formula (1), ;s used.
In very particularly preferred embodiments of the process according to the invent;on e) a dye of the formula (2) or (3) is used;
f) use is made of anthraquinone dyes of the type defined by the invention ;n which X ;s a fibre~reactive radical of the aliphatic, aromatic or heterocyclic series which can be bonded v;a a bridge member of the formula .~ . .. .
~ ~7~
N{ (CO) .~
or via ~ICH --N- or -CH2-N , and R4 is hydrogen or C1_4-alkyl;
g) use is made of anthraquinone dyes of the type defined by the invention in which X is a chloroacetyl, bromoacetyl, acryloyl, ~ ,~-dichloropropionyl,~ ~ -dibromopropionyl, ~-bromoacryloyl or ~-chloroacryloyl radical which is bonded via -NH-, -CJH-NH- or -CH2-NH- or is a radical of the formula COOH
-~U- ~ \ / rr ~ ~U ~ \ F~ Cl R5 F, C1 in which Rs is C1_6-alkoxy, c1_6-alkYlmercapto or a radical of the formula ~R6 where R6 and R7, \R
independently of each other, are each hydrogen~ C1_6-alkyl or subs~ituted or unsubstituted phenyl or naphthyl, or is a vinylsulfonyl, ~-sulfatoethylsulfonyl, ~-acetoxyethylsulfonylf ~-chloroethylsulfonyl or ~ '-sulfatoethylsulfonyl)-propion-ylaminomethyl radical~
In three particularly interesting embodiments of the process according to the invention, use is made of ~7~
h) an anthraqu;none dye of the formula O NH
Il 1 2 11 11 i-S03H
' 'T~ 1\. ./ 2 O NH ~ -G (6) = .
in which G1, G3 and G5 are each methyl, G4 is ~-di-bromopropionylaminomethyl, ~-chloroacryloylaminomethyl~
~-bromoacryloylaminomethyl, ~ '-sulfatoethylsulfonyl)--propionylaminomethyl,~,~-dibromopropionylamino, ~r -CH ( COOH) -NH-CO-¢H
or chloroacetylaminomethyl and G2 is hydrogen, sulfo, chloroacetylaminomethyl or -CH~COOH)-NH-CO-CH~r-CH2Br or ;n which G1 is hydrogen or methoxy, Gz, G3 and Gs are each hydrogen and G4 is sulfatoethylsulfonyl, chloro-acetylamino, ~3-dibromopropionylamino, vinylsulfonyl, 2-methoxy-4-fluoro-s-triazinylarnino or 2-ehtylamino-4-fluoro-s-trizinylamino or in which G1, G2, G4 and Gs are each hydrogen and G3 is chloroacetylamino, ~ ~ -dibromo-propionylamino, 2,6-difluoro-5-chloro-pyrimidin-4-ylamino or 2-chloro-4-amino- or 4-N,N-dimethyl-amino-s-triazinyl-amino, or in which G1 is methyl, Gz is ~-sulfatoethyl-sulfonyl and G3, G4 and Gs are each hydrogen~ or in which G1 or G2 is sulfo, G3 ;s~-bromoacryloylamino or N-methyl-N-~3- ~ -chloroethylsulfonyl~-benzoyl~-amino and G2 or G1 and G4 and 65 are each hydrogen, or G1, G2 and Gs are each hydrogen, G3 is methyl and G4 is chloroacetylamino, or in which G1 is methyl, Gz is 2,6-difluoro-5-chloropyrimidinylamino, G4 is sulfo and G3 and Gs are each hydrogen;
", i : . , ~ r~
i) a dye of the formula (6) in which G1, Gz, G4 and Gs are each hydrogen and G3 is chloroacetylamino or ~,~)-dibromopropionylamino, or in which G1, G2, G3 and Gs are each hydrogen and G4 is vinylsuLfonyl, chloro-acetylamino, 2-methoxy- or 2-ethylamino-4-fluoro-s-triazinyl-amino or in which G1, G3 and G5 are each methyl, G2 is hydrogen and G4 is chloroacetylaminomethyl, ~,~-dibromo-propionylaminomethyL or -CH~COOH)-NH-CO-CHBr-CH2Br, or in which G1 is methoxy, G2, G3 and Gs are each hydrogen and G~ is ~-sulfatoethylsulfonyl~ or in which G1, G3 and Gs are each hydrogen and G2 and G4 are each chloroacetylaminomethyl or -cH(cooH)-N~-co-cHBr-cH2Br~
or in which G1, G3 and Gs are each methyl, G2 is ~, ~ -dibromopropionylamino and G4 is sulfo, or in which G1 is sulfo, G2, G4 and Gs are each hydrogen and G3 is ~-bromoacryloylamino, or in ~hich G1 is methyl, G2 is 2,6-difluoro-5-chloropyrimidYlamino, G3 and Gs are each hydrogen and G4 is sulfo; and j) an anthraquinone dye of the formula ~1) in which A1 is cyclohexyl, A2 is hydrogen, A3 is 4-(4'-methyl-phenoxy)-phenyl and X is chloroacetylaminomethyl and the dye contains only one sulfo group or ;n which A1 is isopropyl, A2 is hydrogen and A3, together with X, is a phenyl-sec. butyl radical which is substituted in the phenyl ring by sulfo and chloroacetylaminomethyl or is a 4-phenoxyphenyl radical which is substituted in the phenoxy radical by sulfo and acryloylaminomethyl, or in which A2 is hydrogen and A1 and A3, together with X, are both a 4-~-bromoacryloylamino-3-sulfophenyl radical or a phenyl-sec.-butyl radical which is substituted in the phenyl ring by sulfo and chloroacetylaminomethyl.
Of the dyes indicated in j), preference is given to the dye of the ~ormula (1) in which A1 is cyclohexyl, A2 is hydrogen and A3 iS 4-(4'-methylphenoxy)-phenyl, the phenyl ring of the phenoxy group being substituted by sulfo and chloroacetylaminomethyl.
A particularly important embodiment of the process Sf~
accord;ng to the invention comprises using a dye of the formula (6) in which G1, G2, G4 and Gs are each hydrogen and G3 is ~,~-dibromopropionylamino, or in which G1, G3, G4 and Gs are each hydrogen and G2 is vinyl-sulfonyl, chloroacetylamino, 2 methoxy-4-fluoro-s-triazinyl-amino or 2-ethylamino-4-fluoro-s-triazinylamino, or in which G1 is methyl~ G2 is 2,6-difluoro-5-chloropyrimidinylamino, G3 and Gs are both hydrogen and G4 is sulfo, or in which G1 is methoxy, G2, G3 and Gs are each hydrogen and G4 is p~-sulfatoethylsulfonyl~ or in which G1~ G3 and Gs are each methyl, G2 is hydrogen or -CH(COOH)-NH-CO-CHBr-CH2Br and G4 is ~,~-dibromopropionylaminomethyl or ~cH(cooH)-NH-co-cHBr-cH2Br~ or in which G1, G3 and Gs are each methyl, G2 is D~-dibromopropionylamino and G4 is sulfo, or in which G1 is sulfo, G2, G4 and Gs are each hydrogen and G3 is ~-bromoacryloylamino~
Very particularly important embodiments of the process according to the invention comprise using the dye of the formula .
1l NH 2 o\ ~- C~3 ~CH2NHCOCH2Cl ~--CH3 ( 7) .=,~
or the dye of the formula \ / \o/ ~o/ 3 - C~3 ~cH2~HcocH2cl (8), H ~ / 3 ~= b or the dye of the formula ~ ~ ~. R, ,~ ,S03H
i1 11 ~H~ -NH-CO-CH2Cl (9), ,~= o ~ 5 or the dye of the formula .--~
~H--~ H ~
CH -NH-C0-CH Cl -~ CH3 (10) In the process according to the invention, it is also possible to use mixtures of two or more anthraquinone dyes of the type defined. In particular, use is made of a mixture of two anthraquinone dyes whose individual components each contain one or two fibre-reactive groups and one or two sulfo groups.
Preferably, each individual component of the mixture corresponds to one of the anthraquinone dyes specified above under the formula (1).
It is very particularly preferred to use in the process according to the invention mixtures of anthraquinone dyes of the formulae t2), t3), t4) or t5), i.e. mixtures in which one component corresponds to a dye of the formula t2), t3), (4) or t5) and the other component corresponds to a dye of the formula t2), t3), t4) or t5). In particular, use is made of a mixture of two anthraquinone dyes in which one component corresponds to a dye of the formula t2) and the other component corresponds to a dye of the formula t2) or t3).
In an important mixture of anthraquinone dyes which can be used in the process according to the invention, one component corresponds to a dye of the formula t7), t8) or a dye of the formula t3) in which A4 is cyclohexyl, L2 is substituted bY P-methylphenoxy and X is chloro-acetylaminomethyl, and the dye of the formula t3) contains only one sulfo group, and the other component corresponds to a dye of the formula (6) in which G1, G2, G4 and ~2~
~ 16 -G5 are each hydrogen and G3 is ~,~-dibromopropionylamino, or in which G1, G3, G4 and G5 are each hydrogen and G2 is vinyLsulfonyl, chloroacetylam;no, 2-methoxy-4-fluoro-s-tr;az;nyla~;no or 2-ethylam;no-4-fluoro-s-tr;az;nylamino, or ;n wh;ch G1 ;s methyl, and G2 ;s 2,6-d;fluoro-5-chloro-pyr;m;dinylamino, G3 and G5 are both hydrogen and G4 ;s sulfo, or ;n wh;ch G1 is sulfo, G2, G4 and Gs are each hydrogen and G3 is ~-bromoacryloylamino, or in which G1, G3 and Gs are each methyl, and G2 is ~,¦~-dibromo-propionylam;nomethyl, -CH(COOH)-NH-C0-CHBr-CH2gr or ~C,~-dibromopropionylamino and G4 is hydrogen, -CH(COOH)-NH-C0-CH~r-CH2Br or sulfo, or in which G1 is methoxy, G2, G3 and Gs are each hydrogen and G4 is ~-sulfatoethyl-sulfonyl.
In a part;cularly ;mportant m;xture of anthraquinone dyes which can be used in the process according to the in-vent;on, one component corresponds to the dye of the formula (7) or (8) and the other component corresponds to the dye of the formula (3) ;n wh;ch A4 is cyclohexyl, L2 is substituted by p-methylphenoxy and X is chloroacetylamino-methyl and the dye of the formula (3) contains only one sulfo group.
In a further particularly important mixture of anthraquinone dyes which can be used in the process accord-ing to the invention, one component corresponds to the dye of the formula t7) or (8) and the other component corres-ponds to the dye of the formula (6) in which G1, Gz, G4 and Gs are each hydrogen and G3 is chloroacetylamino~
In a very particularly important mixture of anthra-quinone dyes which can be used in the process according to the invention, one component corresponds to the dye of the formula (8) and the other component corresponds to the dye of the formula (10). Prefarably the weight ratio of the dyes of the formulae (8) to (10) is 90:10 to 70:30~ in particular 80:20.
In general the weight ratio of the anthraquinone dyes in the mixtures used according to the invention can , ~ .
S~
vary within wide l;mits. A weight rat;o of 90:10 to 10:90 and in particular of 70:30 to 30:70, has been found to be advantageous.
The anthraquinone dyes of the formula (1) or the components of the mixtures used in the process according to the invention preferably contain only one sulfo group.
The anthraquinone dyes used in the process accord-ing to the invention are known per se or can be prepared analogously to known methods. For ;nstance, the dyes of the formula (1) can be prepared as indicated in German Offenlegungsschr;ft 2,305,206, Sw;ss Patent 466,~70 and British Patent 903,590.
The dyes used in the process according to the in-vention are either in the form o-f the;r free sulfonic acid or preferably ;n the form of its salts.
Examples of su;table salts are the alkali metal, alkaline earth metal and ammonium salts and the salts of organic amines. Examples are the sodium, lithium, potassium and ammonium salts and the salt of triethanolam;ne.
The dyes used ;n the process according to the ;n-vent;on generally conta;n further additives, such as sod;um chloride or dextrin.
The process according to the invention for dyeing synthetic polyamide mater;als can be appl;ed to the customary dyeing methods.
The dyeing liquors, in addition to water and the dyes, can contain further additives, for example wetting agents, anti-foams, levelling agents or agents which affect the nature of the text;le material, for example softeners, f;re retardants or soil , water- or oil-repellent agents, and water-softening agents and natural or synthetic thick-eners, for example alginates or cellulose ethers.
The process according to the invention is par-ticularly su;table for cont;nuous dyeing.
The dyes used ;n the process accord;ng to the in-vention are d;stinguished by uniform build-up, good ex-haustion properties and good fastness properties, in ~ ~7~
particular good ozone fastness.
The particularly noteworthy ozone fastness of the dye;ngs obtained with the process accord;ng to the in-vention on synthetic polyamide materials is determined by American Associa~ion of Textile Chemists and Colorists test methods 109-1975 and 129-1975.
The process according to the invention is suitable for dye;ng synthetic polyamide materials, for example nylon or Perlon, in particular nylon 6.6 and preferably nylon 6.
Said textile material can be dyed at various stages in processing, for example as fibre, yarn, woven fabric or knitted fabric and in particular as carpet.
In a particularly interesting embodiment of the process according to the invention, nylon carpets are con-tinuously dyed with anthraquinone dyes of the formula (1) or mixtures of anthraquinone dyes of the formula t1), in particular the anthraquinone dyes of the formulae (2) or ~6).
If mixtures of dyes are used in the process accord-ing to the invention, these can be prepared by mixing the individual dyes. This mixing process is effected for ex-ample in suitable mills, for example ball and pin mills, and kneaders or mixers.
The mixtures of dyes can also be prepared by spray-drying the aqueous mixtures of dyes.
The amounts in which the dyes or mixtures are used in the dyebaths can vary within wide limits, depending on the desired depth of shade~ but in general amounts of 0.001 to 6% by weight on weight of fibre has been found to be advantageous.
The liquor ratio can be chosen from within a wide range, from 1:1 to 5:1 for continuous dyeing methods and from 5:1 to 50:1, preferably 8:1 to 25:1, for discontinuous exhaust methods.
Dyeing is effected from aqueous liquor, for example by the exhaust method, for example at temperatures between 70 and 130C, preferably at around the boil, i.e. at 95 '
In particularly preferred embodiments of the process according to the invention9 ~ ~ 7 _ 9 _ a) a dye of the formula ::~ ll 1 2 \ /~
. i il il i_S03H (2) 0 NH~ 3 0-1 (X) 1-2 .
.~
in which X is as defined under the formula (1~ and the phenyl ring L1 can be monosubstituted, disubstituted, tr;substituted or tetrasubstituted by C1_4-alkyl, C1_4-alkoxy or phenoxy, is used;
b) a dye of the formula _ 0 NH-A . _-- (S03H) 1-2 ; :I~ ,¢ ,il~ ~i (3), \ 2 / ( ) 1-2 _ which A4 is a C1_6-alkyl or Cs_7-cycloalkyl radical, X is as defined under the formula t1) and the phenyl ring L2 can be monosubstituted, disubstituted or trisubstituted by C1_~-alkyl, C1_4-alkoxy, phenoxy or c1_4-alkYlphenoxy, is used;
'~
., ~ ~ 7 c) a dye of the formula 0 NH-A --(S03H) 1-2 :~
~ ! il i! i --(x) 1-2 / \ / \.~ ._.
~ ~H-(Cl 8-A1ky1~n)--~L3 ~ (4), ; ;n wh;ch A4 is as defined under the formula (3), X is as def;ned under the formula (1) and the phenyl ring L3 can be monosubstituted or disubstituted by C1_4-alkyl or C1_4-alkoxy, is used;
d) a dye of the formula ;
0 NH- (cl_8-alkYlene) o ~ ~ 3 T i1 i1 i (s), ~ / \ / \ ~
o NH-(Cl_8 alkyl~0_l \ _ Xso H
;n wh;ch X ;s as def;ned under the formula (1), ;s used.
In very particularly preferred embodiments of the process according to the invent;on e) a dye of the formula (2) or (3) is used;
f) use is made of anthraquinone dyes of the type defined by the invention ;n which X ;s a fibre~reactive radical of the aliphatic, aromatic or heterocyclic series which can be bonded v;a a bridge member of the formula .~ . .. .
~ ~7~
N{ (CO) .~
or via ~ICH --N- or -CH2-N , and R4 is hydrogen or C1_4-alkyl;
g) use is made of anthraquinone dyes of the type defined by the invention in which X is a chloroacetyl, bromoacetyl, acryloyl, ~ ,~-dichloropropionyl,~ ~ -dibromopropionyl, ~-bromoacryloyl or ~-chloroacryloyl radical which is bonded via -NH-, -CJH-NH- or -CH2-NH- or is a radical of the formula COOH
-~U- ~ \ / rr ~ ~U ~ \ F~ Cl R5 F, C1 in which Rs is C1_6-alkoxy, c1_6-alkYlmercapto or a radical of the formula ~R6 where R6 and R7, \R
independently of each other, are each hydrogen~ C1_6-alkyl or subs~ituted or unsubstituted phenyl or naphthyl, or is a vinylsulfonyl, ~-sulfatoethylsulfonyl, ~-acetoxyethylsulfonylf ~-chloroethylsulfonyl or ~ '-sulfatoethylsulfonyl)-propion-ylaminomethyl radical~
In three particularly interesting embodiments of the process according to the invention, use is made of ~7~
h) an anthraqu;none dye of the formula O NH
Il 1 2 11 11 i-S03H
' 'T~ 1\. ./ 2 O NH ~ -G (6) = .
in which G1, G3 and G5 are each methyl, G4 is ~-di-bromopropionylaminomethyl, ~-chloroacryloylaminomethyl~
~-bromoacryloylaminomethyl, ~ '-sulfatoethylsulfonyl)--propionylaminomethyl,~,~-dibromopropionylamino, ~r -CH ( COOH) -NH-CO-¢H
or chloroacetylaminomethyl and G2 is hydrogen, sulfo, chloroacetylaminomethyl or -CH~COOH)-NH-CO-CH~r-CH2Br or ;n which G1 is hydrogen or methoxy, Gz, G3 and Gs are each hydrogen and G4 is sulfatoethylsulfonyl, chloro-acetylamino, ~3-dibromopropionylamino, vinylsulfonyl, 2-methoxy-4-fluoro-s-triazinylarnino or 2-ehtylamino-4-fluoro-s-trizinylamino or in which G1, G2, G4 and Gs are each hydrogen and G3 is chloroacetylamino, ~ ~ -dibromo-propionylamino, 2,6-difluoro-5-chloro-pyrimidin-4-ylamino or 2-chloro-4-amino- or 4-N,N-dimethyl-amino-s-triazinyl-amino, or in which G1 is methyl, Gz is ~-sulfatoethyl-sulfonyl and G3, G4 and Gs are each hydrogen~ or in which G1 or G2 is sulfo, G3 ;s~-bromoacryloylamino or N-methyl-N-~3- ~ -chloroethylsulfonyl~-benzoyl~-amino and G2 or G1 and G4 and 65 are each hydrogen, or G1, G2 and Gs are each hydrogen, G3 is methyl and G4 is chloroacetylamino, or in which G1 is methyl, Gz is 2,6-difluoro-5-chloropyrimidinylamino, G4 is sulfo and G3 and Gs are each hydrogen;
", i : . , ~ r~
i) a dye of the formula (6) in which G1, Gz, G4 and Gs are each hydrogen and G3 is chloroacetylamino or ~,~)-dibromopropionylamino, or in which G1, G2, G3 and Gs are each hydrogen and G4 is vinylsuLfonyl, chloro-acetylamino, 2-methoxy- or 2-ethylamino-4-fluoro-s-triazinyl-amino or in which G1, G3 and G5 are each methyl, G2 is hydrogen and G4 is chloroacetylaminomethyl, ~,~-dibromo-propionylaminomethyL or -CH~COOH)-NH-CO-CHBr-CH2Br, or in which G1 is methoxy, G2, G3 and Gs are each hydrogen and G~ is ~-sulfatoethylsulfonyl~ or in which G1, G3 and Gs are each hydrogen and G2 and G4 are each chloroacetylaminomethyl or -cH(cooH)-N~-co-cHBr-cH2Br~
or in which G1, G3 and Gs are each methyl, G2 is ~, ~ -dibromopropionylamino and G4 is sulfo, or in which G1 is sulfo, G2, G4 and Gs are each hydrogen and G3 is ~-bromoacryloylamino, or in ~hich G1 is methyl, G2 is 2,6-difluoro-5-chloropyrimidYlamino, G3 and Gs are each hydrogen and G4 is sulfo; and j) an anthraquinone dye of the formula ~1) in which A1 is cyclohexyl, A2 is hydrogen, A3 is 4-(4'-methyl-phenoxy)-phenyl and X is chloroacetylaminomethyl and the dye contains only one sulfo group or ;n which A1 is isopropyl, A2 is hydrogen and A3, together with X, is a phenyl-sec. butyl radical which is substituted in the phenyl ring by sulfo and chloroacetylaminomethyl or is a 4-phenoxyphenyl radical which is substituted in the phenoxy radical by sulfo and acryloylaminomethyl, or in which A2 is hydrogen and A1 and A3, together with X, are both a 4-~-bromoacryloylamino-3-sulfophenyl radical or a phenyl-sec.-butyl radical which is substituted in the phenyl ring by sulfo and chloroacetylaminomethyl.
Of the dyes indicated in j), preference is given to the dye of the ~ormula (1) in which A1 is cyclohexyl, A2 is hydrogen and A3 iS 4-(4'-methylphenoxy)-phenyl, the phenyl ring of the phenoxy group being substituted by sulfo and chloroacetylaminomethyl.
A particularly important embodiment of the process Sf~
accord;ng to the invention comprises using a dye of the formula (6) in which G1, G2, G4 and Gs are each hydrogen and G3 is ~,~-dibromopropionylamino, or in which G1, G3, G4 and Gs are each hydrogen and G2 is vinyl-sulfonyl, chloroacetylamino, 2 methoxy-4-fluoro-s-triazinyl-amino or 2-ethylamino-4-fluoro-s-triazinylamino, or in which G1 is methyl~ G2 is 2,6-difluoro-5-chloropyrimidinylamino, G3 and Gs are both hydrogen and G4 is sulfo, or in which G1 is methoxy, G2, G3 and Gs are each hydrogen and G4 is p~-sulfatoethylsulfonyl~ or in which G1~ G3 and Gs are each methyl, G2 is hydrogen or -CH(COOH)-NH-CO-CHBr-CH2Br and G4 is ~,~-dibromopropionylaminomethyl or ~cH(cooH)-NH-co-cHBr-cH2Br~ or in which G1, G3 and Gs are each methyl, G2 is D~-dibromopropionylamino and G4 is sulfo, or in which G1 is sulfo, G2, G4 and Gs are each hydrogen and G3 is ~-bromoacryloylamino~
Very particularly important embodiments of the process according to the invention comprise using the dye of the formula .
1l NH 2 o\ ~- C~3 ~CH2NHCOCH2Cl ~--CH3 ( 7) .=,~
or the dye of the formula \ / \o/ ~o/ 3 - C~3 ~cH2~HcocH2cl (8), H ~ / 3 ~= b or the dye of the formula ~ ~ ~. R, ,~ ,S03H
i1 11 ~H~ -NH-CO-CH2Cl (9), ,~= o ~ 5 or the dye of the formula .--~
~H--~ H ~
CH -NH-C0-CH Cl -~ CH3 (10) In the process according to the invention, it is also possible to use mixtures of two or more anthraquinone dyes of the type defined. In particular, use is made of a mixture of two anthraquinone dyes whose individual components each contain one or two fibre-reactive groups and one or two sulfo groups.
Preferably, each individual component of the mixture corresponds to one of the anthraquinone dyes specified above under the formula (1).
It is very particularly preferred to use in the process according to the invention mixtures of anthraquinone dyes of the formulae t2), t3), t4) or t5), i.e. mixtures in which one component corresponds to a dye of the formula t2), t3), (4) or t5) and the other component corresponds to a dye of the formula t2), t3), t4) or t5). In particular, use is made of a mixture of two anthraquinone dyes in which one component corresponds to a dye of the formula t2) and the other component corresponds to a dye of the formula t2) or t3).
In an important mixture of anthraquinone dyes which can be used in the process according to the invention, one component corresponds to a dye of the formula t7), t8) or a dye of the formula t3) in which A4 is cyclohexyl, L2 is substituted bY P-methylphenoxy and X is chloro-acetylaminomethyl, and the dye of the formula t3) contains only one sulfo group, and the other component corresponds to a dye of the formula (6) in which G1, G2, G4 and ~2~
~ 16 -G5 are each hydrogen and G3 is ~,~-dibromopropionylamino, or in which G1, G3, G4 and G5 are each hydrogen and G2 is vinyLsulfonyl, chloroacetylam;no, 2-methoxy-4-fluoro-s-tr;az;nyla~;no or 2-ethylam;no-4-fluoro-s-tr;az;nylamino, or ;n wh;ch G1 ;s methyl, and G2 ;s 2,6-d;fluoro-5-chloro-pyr;m;dinylamino, G3 and G5 are both hydrogen and G4 ;s sulfo, or ;n wh;ch G1 is sulfo, G2, G4 and Gs are each hydrogen and G3 is ~-bromoacryloylamino, or in which G1, G3 and Gs are each methyl, and G2 is ~,¦~-dibromo-propionylam;nomethyl, -CH(COOH)-NH-C0-CHBr-CH2gr or ~C,~-dibromopropionylamino and G4 is hydrogen, -CH(COOH)-NH-C0-CH~r-CH2Br or sulfo, or in which G1 is methoxy, G2, G3 and Gs are each hydrogen and G4 is ~-sulfatoethyl-sulfonyl.
In a part;cularly ;mportant m;xture of anthraquinone dyes which can be used in the process according to the in-vent;on, one component corresponds to the dye of the formula (7) or (8) and the other component corresponds to the dye of the formula (3) ;n wh;ch A4 is cyclohexyl, L2 is substituted by p-methylphenoxy and X is chloroacetylamino-methyl and the dye of the formula (3) contains only one sulfo group.
In a further particularly important mixture of anthraquinone dyes which can be used in the process accord-ing to the invention, one component corresponds to the dye of the formula t7) or (8) and the other component corres-ponds to the dye of the formula (6) in which G1, Gz, G4 and Gs are each hydrogen and G3 is chloroacetylamino~
In a very particularly important mixture of anthra-quinone dyes which can be used in the process according to the invention, one component corresponds to the dye of the formula (8) and the other component corresponds to the dye of the formula (10). Prefarably the weight ratio of the dyes of the formulae (8) to (10) is 90:10 to 70:30~ in particular 80:20.
In general the weight ratio of the anthraquinone dyes in the mixtures used according to the invention can , ~ .
S~
vary within wide l;mits. A weight rat;o of 90:10 to 10:90 and in particular of 70:30 to 30:70, has been found to be advantageous.
The anthraquinone dyes of the formula (1) or the components of the mixtures used in the process according to the invention preferably contain only one sulfo group.
The anthraquinone dyes used in the process accord-ing to the invention are known per se or can be prepared analogously to known methods. For ;nstance, the dyes of the formula (1) can be prepared as indicated in German Offenlegungsschr;ft 2,305,206, Sw;ss Patent 466,~70 and British Patent 903,590.
The dyes used in the process according to the in-vention are either in the form o-f the;r free sulfonic acid or preferably ;n the form of its salts.
Examples of su;table salts are the alkali metal, alkaline earth metal and ammonium salts and the salts of organic amines. Examples are the sodium, lithium, potassium and ammonium salts and the salt of triethanolam;ne.
The dyes used ;n the process according to the ;n-vent;on generally conta;n further additives, such as sod;um chloride or dextrin.
The process according to the invention for dyeing synthetic polyamide mater;als can be appl;ed to the customary dyeing methods.
The dyeing liquors, in addition to water and the dyes, can contain further additives, for example wetting agents, anti-foams, levelling agents or agents which affect the nature of the text;le material, for example softeners, f;re retardants or soil , water- or oil-repellent agents, and water-softening agents and natural or synthetic thick-eners, for example alginates or cellulose ethers.
The process according to the invention is par-ticularly su;table for cont;nuous dyeing.
The dyes used ;n the process accord;ng to the in-vention are d;stinguished by uniform build-up, good ex-haustion properties and good fastness properties, in ~ ~7~
particular good ozone fastness.
The particularly noteworthy ozone fastness of the dye;ngs obtained with the process accord;ng to the in-vention on synthetic polyamide materials is determined by American Associa~ion of Textile Chemists and Colorists test methods 109-1975 and 129-1975.
The process according to the invention is suitable for dye;ng synthetic polyamide materials, for example nylon or Perlon, in particular nylon 6.6 and preferably nylon 6.
Said textile material can be dyed at various stages in processing, for example as fibre, yarn, woven fabric or knitted fabric and in particular as carpet.
In a particularly interesting embodiment of the process according to the invention, nylon carpets are con-tinuously dyed with anthraquinone dyes of the formula (1) or mixtures of anthraquinone dyes of the formula t1), in particular the anthraquinone dyes of the formulae (2) or ~6).
If mixtures of dyes are used in the process accord-ing to the invention, these can be prepared by mixing the individual dyes. This mixing process is effected for ex-ample in suitable mills, for example ball and pin mills, and kneaders or mixers.
The mixtures of dyes can also be prepared by spray-drying the aqueous mixtures of dyes.
The amounts in which the dyes or mixtures are used in the dyebaths can vary within wide limits, depending on the desired depth of shade~ but in general amounts of 0.001 to 6% by weight on weight of fibre has been found to be advantageous.
The liquor ratio can be chosen from within a wide range, from 1:1 to 5:1 for continuous dyeing methods and from 5:1 to 50:1, preferably 8:1 to 25:1, for discontinuous exhaust methods.
Dyeing is effected from aqueous liquor, for example by the exhaust method, for example at temperatures between 70 and 130C, preferably at around the boil, i.e. at 95 '
5~
to 105C, or in the case of continuous dyeing methods at temperatures between 60 and 98C. In continuous methods, the liquor padded or sprayed on the cloth is preferably hot.
The pH of the dyeing liquor can vary within the range from 5 to 9. In general, a pH of 6 to 8.5 has been found to be advantageous. In the process according to the invention it can be advantageous to vary the pH during the dyeing, ;n particular to start the dyeing at a pH of 9 and to bring the dyeing l;quor to pH 5 in the course of the dyeing.
The dye time for d;scontinuous exhaust methods is generally 10 to 50 minutes. With continuous methods, the dye time depends on the dyeing apparatus or machines used a In the following examples, parts are by weight.
The temperatures are given in degrees centigrade. Parts by weight relate to parts by volume as the gramme relates to the cubic centimetre.
Example 1: 10 parts of nylon 6 carpet yarn CAllied 3B-39]
are introduced at 40 into a dyebath which contains 500 parts of water, 1 part of NaH2po4, 0.15 part of Na2HP04 and 0.02 part of the dye of the formula O N~12 I ll l~ 1 3 ~./-\./-\.~-. _ .~
0 NH ~ \ /--NHCOCH2Cl The temperature is uniformly raised to the boil in the course of 30 minutes, and dyeing is continued at that tem-perature for 1 hour. The blue-dyed yarn is then rinsed and dried.
The ozone fastness of the dyeing obtained is tested in accordance with AATCC CAmerican Association of Textile Chemists and Colorists] test method 129-1975, and the colour change is evaluated against the standard grey scale ~SNV
~:7~X~l (Swiss Standards Institute) standard 95805] where 1 is worst and 5 is best.
The dyeing obtained with the above dye has a fastness level of 4-5~
Replacing the dye given in the above example by one of the dyes indicated in column II of the following table or by one of the dye mixtures indicated likewise affords blue dyeings having the fastness levels indicated in column III of the table for the colour change after said o~one fastness test.
. .
~ ;~7~5~
E x amp L e II III
~ .__ _ ._ o~ \ / \ /-~ ~S03H
2 I i1 i1 i . 4 ~ 1 2 .
Exampl Dye of the formula Fastness level ~ .. . _ . _ _ _ 4 1 N~ CH3 , 502CH2CH2oso3H
to 105C, or in the case of continuous dyeing methods at temperatures between 60 and 98C. In continuous methods, the liquor padded or sprayed on the cloth is preferably hot.
The pH of the dyeing liquor can vary within the range from 5 to 9. In general, a pH of 6 to 8.5 has been found to be advantageous. In the process according to the invention it can be advantageous to vary the pH during the dyeing, ;n particular to start the dyeing at a pH of 9 and to bring the dyeing l;quor to pH 5 in the course of the dyeing.
The dye time for d;scontinuous exhaust methods is generally 10 to 50 minutes. With continuous methods, the dye time depends on the dyeing apparatus or machines used a In the following examples, parts are by weight.
The temperatures are given in degrees centigrade. Parts by weight relate to parts by volume as the gramme relates to the cubic centimetre.
Example 1: 10 parts of nylon 6 carpet yarn CAllied 3B-39]
are introduced at 40 into a dyebath which contains 500 parts of water, 1 part of NaH2po4, 0.15 part of Na2HP04 and 0.02 part of the dye of the formula O N~12 I ll l~ 1 3 ~./-\./-\.~-. _ .~
0 NH ~ \ /--NHCOCH2Cl The temperature is uniformly raised to the boil in the course of 30 minutes, and dyeing is continued at that tem-perature for 1 hour. The blue-dyed yarn is then rinsed and dried.
The ozone fastness of the dyeing obtained is tested in accordance with AATCC CAmerican Association of Textile Chemists and Colorists] test method 129-1975, and the colour change is evaluated against the standard grey scale ~SNV
~:7~X~l (Swiss Standards Institute) standard 95805] where 1 is worst and 5 is best.
The dyeing obtained with the above dye has a fastness level of 4-5~
Replacing the dye given in the above example by one of the dyes indicated in column II of the following table or by one of the dye mixtures indicated likewise affords blue dyeings having the fastness levels indicated in column III of the table for the colour change after said o~one fastness test.
. .
~ ;~7~5~
E x amp L e II III
~ .__ _ ._ o~ \ / \ /-~ ~S03H
2 I i1 i1 i . 4 ~ 1 2 .
Exampl Dye of the formula Fastness level ~ .. . _ . _ _ _ 4 1 N~ CH3 , 502CH2CH2oso3H
6 t~ S03H 4 ~' 't' 't~ C~3 ,cH2NHcocEI2cl \o=~/ 3 H3 CH2l~lcocH
~ ~7~r ._ . ~
Exampl Dye of the formu~a Fastness level i I II III
__ ~ ..
~- 8 ,~ /S03H
~ ~7~r ._ . ~
Exampl Dye of the formu~a Fastness level i I II III
__ ~ ..
~- 8 ,~ /S03H
7 ~ -CH 4 C~3 CH2NHcocH-cH
8 t~ 1/ C~ 4 \.=./ 3 1 ¦
CH3 ICH-NH-CO-CH- lCH2 COOH Br Br . 9 .~ \ / \./ ~1/ 3 COOH 4 I~H0~ ~--CH3 Br Br CHj ICH-NHCO- ICH- ICH2 COOH Br Br .
.
25~3~
- 2~ -_ Exampl Dye of the-formula ¦Fastness level¦
II ! III
Mixture of 80 parts by weight of the dye of the formula 1~ " ,.
CH3 CH2NHCOCH2Cl and 20 parts by weight of the dye of the formula 4 .
NH; ~ H
I~H~ 0- -~ ~-CH
H2NHCOCH2Cl . I
: Mixture of 80 parts by weight of the dye of the formula ,3~ ~- CH~ ~cH2NHcocH2cl \.= ~/ 3 C~3 CH2NHCOCH2Cl. .
11 a~d 2~ part~ by ight of the dye of the form~la 4 b l~H--~ ~-0-~ -CH3 .
H2NHCOCH2Cl .. __ . . __ . - ._~
~ ~ 7~ rj ~F~
_ _ _ _ .
Examplle Dye of the formula Fastness level¦
I II III
-Mixture of 90 parts by weight of the dye of the formula ~ \ / \ /e~ ~S03H ' . ~./ \./ \ ~ C\3 ~CH2NHcOcH2C
~ ~H - O\ / C 3 and C~ CH NHCOCX2Cl .
12 10 parts by weigh~ of the dye of the formula 4 ; i~2 d ~H-~ -NHCOCH2C1 l i Mixture of 50 parts by weight of the dye of the formula ¦ i ~ I .
.~ S03H
and CH3 CH2NHCOCH2C1 13 50 parts by weight of the dye of the formula 4 ~ -NHCOCH2~1 .
:~ ~ 7~' ~
Example¦ 3ye oF the formu~a Fastness level I ¦ II III
Mixture of 80 parts by.wei~ht of the dye of the formula CH\3 and '.=.' 3 .
14 C~ CH NHCOCH Cl gh~ o th2e dye 2f the formula 4 b ~ ~ ~-UHCOCH2C.
lS ~ 4 16 d ~ ~o U
_ c/~ r[~ .
,, ;...
................ ... .
. .
~ ~:7~
, ~xampl~ Dye of the formula Fastness level I II III
._ ... . .. _ ___ . ____ 17 ~ 3CO C CU
18 ~ _0_~ -CU3 H2NHCOCH2Cl 19 ~\/S\.`~lf 4 ~ \~ ~
~ ;~7~S~3~L
-- 2~ --_ Example Dye of the IfIrmUla III
-- ~ \0~ ./ 3 __ .. ~ ~' f `~ ~ ~ HcH ~cH3 Comparative example:
Replacing the 0.02 part of the dye in Example 1 by 0.02 part of the non-fibre-reactive dye of the formula I~ \il/ \il/ ~i-S03H
O NH ~ ~ ~ -NE~COCH3 produces a blue dyeing which, on testing in accordance with the AATCC ozone fastness test method 129-1975, has a fastness level in terms of colour change ~SNV standard 95805] of only 2-3.
CH3 ICH-NH-CO-CH- lCH2 COOH Br Br . 9 .~ \ / \./ ~1/ 3 COOH 4 I~H0~ ~--CH3 Br Br CHj ICH-NHCO- ICH- ICH2 COOH Br Br .
.
25~3~
- 2~ -_ Exampl Dye of the-formula ¦Fastness level¦
II ! III
Mixture of 80 parts by weight of the dye of the formula 1~ " ,.
CH3 CH2NHCOCH2Cl and 20 parts by weight of the dye of the formula 4 .
NH; ~ H
I~H~ 0- -~ ~-CH
H2NHCOCH2Cl . I
: Mixture of 80 parts by weight of the dye of the formula ,3~ ~- CH~ ~cH2NHcocH2cl \.= ~/ 3 C~3 CH2NHCOCH2Cl. .
11 a~d 2~ part~ by ight of the dye of the form~la 4 b l~H--~ ~-0-~ -CH3 .
H2NHCOCH2Cl .. __ . . __ . - ._~
~ ~ 7~ rj ~F~
_ _ _ _ .
Examplle Dye of the formula Fastness level¦
I II III
-Mixture of 90 parts by weight of the dye of the formula ~ \ / \ /e~ ~S03H ' . ~./ \./ \ ~ C\3 ~CH2NHcOcH2C
~ ~H - O\ / C 3 and C~ CH NHCOCX2Cl .
12 10 parts by weigh~ of the dye of the formula 4 ; i~2 d ~H-~ -NHCOCH2C1 l i Mixture of 50 parts by weight of the dye of the formula ¦ i ~ I .
.~ S03H
and CH3 CH2NHCOCH2C1 13 50 parts by weight of the dye of the formula 4 ~ -NHCOCH2~1 .
:~ ~ 7~' ~
Example¦ 3ye oF the formu~a Fastness level I ¦ II III
Mixture of 80 parts by.wei~ht of the dye of the formula CH\3 and '.=.' 3 .
14 C~ CH NHCOCH Cl gh~ o th2e dye 2f the formula 4 b ~ ~ ~-UHCOCH2C.
lS ~ 4 16 d ~ ~o U
_ c/~ r[~ .
,, ;...
................ ... .
. .
~ ~:7~
, ~xampl~ Dye of the formula Fastness level I II III
._ ... . .. _ ___ . ____ 17 ~ 3CO C CU
18 ~ _0_~ -CU3 H2NHCOCH2Cl 19 ~\/S\.`~lf 4 ~ \~ ~
~ ;~7~S~3~L
-- 2~ --_ Example Dye of the IfIrmUla III
-- ~ \0~ ./ 3 __ .. ~ ~' f `~ ~ ~ HcH ~cH3 Comparative example:
Replacing the 0.02 part of the dye in Example 1 by 0.02 part of the non-fibre-reactive dye of the formula I~ \il/ \il/ ~i-S03H
O NH ~ ~ ~ -NE~COCH3 produces a blue dyeing which, on testing in accordance with the AATCC ozone fastness test method 129-1975, has a fastness level in terms of colour change ~SNV standard 95805] of only 2-3.
Claims (16)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for preparing ozone-fast dyeings on synthetic polyamide fibre material from aqueous liquor with anthraquinone dyes which comprises using an anthraquinone dye of the formula (6) in which G1, G3 and G5 are each methyl, G4 is .alpha.-chloracryloylamino-methyl,.alpha.-bromo-acryloylaminomethyl, .alpha.,.beta.-dibromopropionylaminomethyl, .beta.-(.beta.'-sulfato-ethylsulfonyl)-propionyl-aminomethyl, .alpha.,.beta.-dibromopropionylamino or -CH(COOH)-NH-CO-CHBr-CH2Br and G2 is hydrogen, sulfo or -CH(COOH)-NH-CO-CHBr-CH2Br, or in which G1, G2, C3 and G5 are each hydrogen and G4 is .alpha.,.beta.-dibromopropionylamino, vinylsulfonyl, 2-methoxy-4-fluoro-s-triazinyl-amino or 2-ethylamino-4-fluoro-s-triazinylamino, or in which G1, G2, G4 and G5 are each hydrogen and G3 is .alpha.,.beta.-dibromopropionylamino, 2,6-difluoro-5-chloropyrimidin-4-ylamino or 2-chloro-4-amino- or 4-N,N-dimethylamino-s-triazinylamino, or in which G1 or G2 is sulfo, G3 is N-methyl-N-[3-(.beta.-chloroethylsulfonyl)-benzoyl]-amino and G2 or G1 and G4 and G5 are each hydrogen, or an anthraquinone dye of the formula (1) , in which A2 is hydrogen and A1 and A3, together with X are both a 4-.alpha.-bromo-acryloylamino-3-sulfophenyl radical or a phenyl-sec.-butyl radical which is substituted in the phenyl ring by sulfo and chloroacetylaminomethyl, in a continuous dyeing process and a liquor ratio from 1:1 to 5:1.
2. A process according to claim 1, wherein use is made of a dye of the formula (6) in which G1, G2, G4 and G5 are each hydrogen and G3 is .alpha.,.beta.-dibromopropionylamino, or in which G1, G2, G3 and G5 are each hydrogen and G4 is vinylsulfonyl, 2-methoxy- or 2-ethylamino-4-fluoro-s-triazinyl-amino, or in which G1, G3 and G5 are each methyl, G2 is hydrogen and G4 is .alpha.,.beta.-dibromopropionylaminomethyl or -CH(COOH)-NH CO-CHBr-CH2Br, or in which G1, G3 and G5 are each methyl and G2 and G4 are each -CH(COOH)-NH-CO-CHBr-CH2Br, or in which G1, G3 and G5 are each methyl, G2 is .alpha.,.beta.-dibromo-propionylamino and G4 is sulfo.
3. A process for preparing ozone-fast dyeings on synthetic polyamide fibre material from aqueous liquor with mixtures of anthraquinone dyes, which comprises using a mixture of anthraquinone dyes, in which each individual component corresponds to an anthraquinone dye of the formula (2) , in which X is a fibre-reactive radical, which is bonded either directly or via a bridge member and the phenyl ring L1 can be monosubstituted, di-substituted, trisubstituted or tetrasubstituted by C1-4-alkyl, C1-4-alkoxy or phenoxy, or (3) in which A4 is a C1-6-alkyl or C5-7-cycloalkyl radical, X is as defined under formula (2) and the phenyl ring L2 can be monosubstituted, disub-stituted or trisubstituted by C1-4-alkyl, C1-4-alkoxy, phenoxy or C1-4-alkylphenoxy, or (4) , in which A4 is as defined under the formula (3), X is as defined under formula (2) and the phenyl ring L3 can be monosubstituted or disubstituted by C1-4-alkyl or C1-4-alkoxy, or (5) , in which X is as defined under formula (2), in a continuous dyeing process and a liquor ratio from 1:1 to 5:1.
4. A process according to claim 3, wherein use is made of anthraquinone dyes in which X is a fibre-reactive radical of the aliphatic, aromatic or heterocyclic series which can be bonded via a bridge member of the formula or via or , and R4 is hydrogen or C1-4-alkyl.
5. A process according to claim 4, wherein use is made of anthraquinone dyes in which X is a chloroacetyl, bromoacetyl, acryloyl, .alpha.,.beta.-dichloro-propionyl, .alpha.,.beta.-dibromopropionyl, .alpha.-bromoacryloyl or .alpha.-chloroacryloyl radical which is bonded via -NH-, or -CH2-NH or is a radical of the formulae or in which R5 is C1-6-alkoxy, C1-6-alkylmercapto or a radical of the formula where R6 and R7, independently of each other, are each hydrogen, C1-6-alkyl or substituted or unsubstituted phenyl or naphthyl, or is a vinylsulfonyl, .beta.-sulfatoethylsulfonyl, .beta.-acetoxyethylsulfonyl, .beta.-chloroethylsulfonyl or .beta.-(.beta.'-sulfatoethylsulfonyl)-propionylaminomethyl radical.
6. A process according to claim 3, wherein mixtures of two anthraquinone dyes as defined in claim 3 are used.
7. A process according to claim 3, wherein a mixture of two anthraquinone dyes is used, in which one component corresponds to a dye of the formula (2) and the other component corresponds to a dye of the formula (2) or (3).
8. A process according to claim 6. wherein a mixture where one component corresponds to a dye of the formula (6) , in which G1, G3 and G5 are each methyl, G2 is hydrogen or chloroacetylamino-methyl and G4 is chloroacetylaminomethyl, and the other component corresponds to the dye of the formula (3) .
in which A4 is cyclohexyl, L2 is substituted by p-methylphenoxy and X is chloroacetylaminomethyl and the dye of the formula (3) contains only one sulfo group is used.
in which A4 is cyclohexyl, L2 is substituted by p-methylphenoxy and X is chloroacetylaminomethyl and the dye of the formula (3) contains only one sulfo group is used.
9. A process according to claim 3, wherein a mixture is used, in which each individual component corresponds to a monosulfo-containing dye of the formula (2), (3), (4) or (5).
10. A process according to claim 1 or 3, wherein synthetic poly-amide carpets are dyed.
11. A process according to claim 1 or 3, wherein nylon 6 fibre material is dyed.
12. A process according to claim 1 or 3,wherein the aqueous liquor is hot.
13. An aqueous dyeing liquor which contains water and a dye according to claim 1 in a liquor ratio from 1:1 to 5:1 and which can contain further additives.
14. An aqueous dyeing liquor which contains water and a mixture of dyes according to claim 3 in a liquor ratio from 1:1 to 5:1 and which can contain further additives.
15. The synthetic polyamide fibre material dyed using the process according to claim 1 or 3 and/or the dyeing liquor according to claim 13 or 14.
16. The synthetic polyamide carpet material dyed according to claim 15.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US66954884A | 1984-11-08 | 1984-11-08 | |
| US669,548 | 1984-11-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1272561A true CA1272561A (en) | 1990-08-14 |
Family
ID=24686757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000494710A Expired - Lifetime CA1272561A (en) | 1984-11-08 | 1985-11-06 | Process for dyeing synthetic polyamide materials with fibre-reactive anthraquinone dyes |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0181293B1 (en) |
| JP (1) | JPS61113884A (en) |
| KR (1) | KR860004201A (en) |
| CA (1) | CA1272561A (en) |
| DE (1) | DE3580241D1 (en) |
| DK (1) | DK513585A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242681A (en) * | 2012-02-13 | 2013-08-14 | 浙江舜龙化工有限公司 | High-performance anthraquinone cobalt blue mixed reactive printing dye |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0601970A1 (en) * | 1992-12-03 | 1994-06-15 | Ciba-Geigy Ag | Anthraquinone dyes, process for their manufacture and use thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1016230B (en) * | 1953-12-15 | 1957-09-26 | Ciba Geigy | Process for producing real tints |
| GB1009955A (en) * | 1961-07-06 | 1965-11-17 | Sandoz Ltd | Process for the level dyeing of textile materials of polyamide fibers possessing irregular affinity for dyestuffs |
| CH425713A (en) * | 1964-07-07 | 1967-06-15 | Sandoz Ag | Process for dyeing polyamide fibers with water-soluble, non-metallizable dyes |
| NL130308C (en) * | 1964-12-22 | |||
| DE2834997C2 (en) * | 1978-08-10 | 1980-08-28 | Hoechst Ag, 6000 Frankfurt | Process for dyeing synthetic polyamide fibers with reactive dyes using the exhaust method |
| DE3363011D1 (en) * | 1982-03-12 | 1986-05-22 | Ciba Geigy Ag | Process for dyeing fibrous material from natural polyamides |
| US4514187A (en) * | 1982-07-21 | 1985-04-30 | Ciba-Geigy Corporation | Process for dyeing differential-dyeing polyamide fibres |
| 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 |
| EP0162811B1 (en) * | 1984-05-22 | 1989-10-11 | Ciba-Geigy Ag | Process for the photochemical stabilisation of materials containing polyamide fibres |
| EP0181292B1 (en) * | 1984-11-08 | 1990-07-25 | Ciba-Geigy Ag | Process for the continuous trichromatic dyeing of synthetic polyamide materials |
-
1985
- 1985-11-04 EP EP85810511A patent/EP0181293B1/en not_active Expired - Lifetime
- 1985-11-04 DE DE8585810511T patent/DE3580241D1/en not_active Expired - Lifetime
- 1985-11-06 CA CA000494710A patent/CA1272561A/en not_active Expired - Lifetime
- 1985-11-07 KR KR1019850008310A patent/KR860004201A/en not_active Application Discontinuation
- 1985-11-07 DK DK513585A patent/DK513585A/en not_active Application Discontinuation
- 1985-11-08 JP JP60250605A patent/JPS61113884A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242681A (en) * | 2012-02-13 | 2013-08-14 | 浙江舜龙化工有限公司 | High-performance anthraquinone cobalt blue mixed reactive printing dye |
Also Published As
| Publication number | Publication date |
|---|---|
| KR860004201A (en) | 1986-06-18 |
| DK513585A (en) | 1986-05-09 |
| JPS61113884A (en) | 1986-05-31 |
| DK513585D0 (en) | 1985-11-07 |
| EP0181293A3 (en) | 1987-10-14 |
| EP0181293B1 (en) | 1990-10-24 |
| EP0181293A2 (en) | 1986-05-14 |
| DE3580241D1 (en) | 1990-11-29 |
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