CA1109063A - Azo dyes, processes for producing them, and their use - Google Patents
Azo dyes, processes for producing them, and their useInfo
- Publication number
- CA1109063A CA1109063A CA299,037A CA299037A CA1109063A CA 1109063 A CA1109063 A CA 1109063A CA 299037 A CA299037 A CA 299037A CA 1109063 A CA1109063 A CA 1109063A
- Authority
- CA
- Canada
- Prior art keywords
- formula
- alkoxy
- process according
- azo dye
- cyano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000987 azo dye Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 32
- 238000004043 dyeing Methods 0.000 claims abstract description 18
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 17
- 150000002367 halogens Chemical class 0.000 claims abstract description 17
- 229920000728 polyester Polymers 0.000 claims abstract description 12
- 229920002994 synthetic fiber Polymers 0.000 claims abstract description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 39
- 230000008878 coupling Effects 0.000 claims description 26
- 238000010168 coupling process Methods 0.000 claims description 26
- 238000005859 coupling reaction Methods 0.000 claims description 26
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 26
- 239000000460 chlorine Substances 0.000 claims description 25
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 18
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- -1 cyano, methoxy Chemical group 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 7
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 150000001989 diazonium salts Chemical class 0.000 claims description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 26
- 125000000547 substituted alkyl group Chemical group 0.000 abstract description 2
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 239000004744 fabric Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- QRMPKOFEUHIBNM-UHFFFAOYSA-N 1,4-dimethylcyclohexane Chemical compound CC1CCC(C)CC1 QRMPKOFEUHIBNM-UHFFFAOYSA-N 0.000 description 2
- LHRIICYSGQGXSX-UHFFFAOYSA-N 2-chloro-4,6-dinitroaniline Chemical compound NC1=C(Cl)C=C([N+]([O-])=O)C=C1[N+]([O-])=O LHRIICYSGQGXSX-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical class NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 101100450129 Caenorhabditis elegans hal-3 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- KYPOHTVBFVELTG-UHFFFAOYSA-N but-2-enedinitrile Chemical group N#CC=CC#N KYPOHTVBFVELTG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- VQTGUFBGYOIUFS-UHFFFAOYSA-N nitrosylsulfuric acid Chemical compound OS(=O)(=O)ON=O VQTGUFBGYOIUFS-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- 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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
- C09B29/0805—Amino benzenes free of acid groups
- C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
- C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
- C09B29/0811—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino
- C09B29/0813—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino substituted by OH, O-C(=X)-R, O-C(=X)-X-R, O-R (X being O,S,NR; R being hydrocarbonyl)
-
- 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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Abstract of the Disclosure New disperse azo dyes are disclosed which correspond to the formula
Description
1~39~ 3 The invention relates to new azo dyes of the disperse class, to processes for producing them, and to their use for dyeing and printing synthetic fibres, especially fibres containing ester groups, particularly polyester materials.
The new azo dyes free from water-solubilising groups correspond to the formula /N2 ORl ~ /~
02N~ ~-- N----N ~ NH - CH2 - CH - R2 \~ ~/ OH
wherein Xrepresents halogen, Rl represents unsubstituted alkyl, alkyl which is substituted by halogen, cyano, aIkoxy or ~-alkoxy ethylene, wherein the aIkoxy-part may be further substituted by cyano or cycloalkyl, '- R2 represents unsubstituted lower aIkyl, and R3 represents unsubstituted lcwer alkyl or lower alkyl which may be sub-- stituted by halogen, cyano or alkoxy.
In preferred azo dyes, X represents chlorine, Rl represents an aIkyl group which has 1 to 3 carbon atcms and which is substituted by chlorine, cyano, methoxy or ethoxy, and especially the group -CH2CH2OR4 in which R4 represents methyl or ethyl, and R2 and R3 independently of one another each represent methyl or ethyl.
The new azo dyes free from water-solubilising groups correspond to the formula /N2 ORl ~ /~
02N~ ~-- N----N ~ NH - CH2 - CH - R2 \~ ~/ OH
wherein Xrepresents halogen, Rl represents unsubstituted alkyl, alkyl which is substituted by halogen, cyano, aIkoxy or ~-alkoxy ethylene, wherein the aIkoxy-part may be further substituted by cyano or cycloalkyl, '- R2 represents unsubstituted lower aIkyl, and R3 represents unsubstituted lcwer alkyl or lower alkyl which may be sub-- stituted by halogen, cyano or alkoxy.
In preferred azo dyes, X represents chlorine, Rl represents an aIkyl group which has 1 to 3 carbon atcms and which is substituted by chlorine, cyano, methoxy or ethoxy, and especially the group -CH2CH2OR4 in which R4 represents methyl or ethyl, and R2 and R3 independently of one another each represent methyl or ethyl.
- 2 -- ' ' ~1~9~3 Preferred azo dyes are those of the formula N02 ORl"
02N - ~ N=N ~ Nl - C~12 - I1 2 OH
Hal 3 - 2a -~9~
wherein Hal represents chlorine or bromine, Rl" represents branched-chain or substituted alkyl, R2 represents unsubstituted lower alkyl, and R3" represents methyl, ethyl or propyl, which can be optionally substituted with halogen, particularly chlorine.
Particularly valuable dyes are those of the formula ~2 ~Rl"
02N ~ N = N ~ NH-CH2-CH-(CH3, C2H
OH
(Br, Cl) NHCO-(CH3, C2H5) wherein Rl" has the same meaning as above, especially -CH2CH20CH3 and CH(CH3)2-In the above formulae, Rl" represents in particular abranched-chain alkyl group, or an alkyl group substituted by ether groups, and R2 and R3 independently of one another represent methyl or ethyl.
Suitable groups Rl and/or R3 are, for example, those of the ( 3)2~ CH2CH2Cl, -CH2CH2Br, -CHCl-CH2Cl -cH2cH2cN, -cH2-cH(OH)-cH2cl~ -CH2c6H5~ -CH2C6H4N02~ -CH2c6H4 -CH2CH2C6H5, -CH2CH20H, -CH2CH2-0-CH3, -CH2CH2-0-C4Hg -C4H8-o-c4H9~ -CH2CH2-0-cH2cH20cH3~ -CH2CH2-0-CH2CH2-OH~
-C H -CH -CH2CH2-0-CH2CH2-0COCH3' -CH2CH2-0-CH2CH2-CN' -CH2-CH2-0-COCH2Cl, -CH2CH2-0-CO-CHBr-CH2Br, -CH2-CH-(GCOCH3)-CH2-0-C6H5, -CH2-CH2-0-CO-CH=CH2, -cH2-cH(OcOcH3)-cH2ococH3 -(CH2)1-3--CO(H' CH3~ C2H5' C3H7 4 9)' (CH2)1-3-~H-cO(H~ CH3, C2H5, C3H7, C4H ) -(CH2)l_3-o-co(c6H5~ C6H4Cl, C6H4Br, C5H40CH3, C6H4CH3), -(CH2)1-3-0-CO-O(cH3. C2H5, C3H7, C4H9), '~
, -(CH2)1_3-0-CO-O-(C6H5, C6~14Cl, C6H4Br, C6H40CH3, C6H4CH3)~
-CH2CH2-0-C6H5 und -CH2CH2-0-CO-C~12-C6H5.
Lower alkyl groups in the present description are taken to be groups having 1 to 5 carbon atoms; and branched-chain alkyl is in particular isopropyl.
These azo dyes are obtained by coupling coupling components of the formula ORl ~: ~HCOR3 OH
. . .
wherein Rl, R2 and R3 have the same meaning as above, with the diazonium compound of a 2,4-dinitro-6-halogenoaniline of the : formula . ~0 $i O~N ~ NH2 wherein X has the same meaning as above.
The coupling components of the given formula are obtained by reaction of an amine of the formula , ORl with an epoxide of the formula ` CH - CH - R
~-: \20 / 2 whereby there are obtained, in addition to the main product '. of the formula , ~ - 4 -.
. . .
C9~
Ç~
or its isomers of the formula OR
-CH-CH -OH
~=~ , 2 N~ICOR3 R2 also bis-addition products together with a small amount of unreacted starting amine as a mixture.
The new water-insoluble azo dyes, their mixtures with each other and mixtures thereof with other azo dyes, are excellently suitable for dyeing and printing leather, wool, silk and, in particular, synthetic fibres, such as acrylic fibres or acrylo-nitrile fibres, from polyacrylonitrile, or copolymers from ,. . .
~^ - acrylonitrile and other vinyl compounds, such as acrylic esters, acrylic amides, vinylpyridine, vinyl chloride or vinylidene chloride, or from copolymers of dicyanoethylene and vinyl acetate, ' and also acrylonitrile-block copolymers, fibres from polyurethanes, , polypropylene fibres, especially from polypropylene fibres modified with metals, particularly with nickel, from cellulose s tri- and -2 1/2~acetate, and especially fibres from polyamides,` such as nylon-6, nylon-6.6 or nylon 12, and from aromatic ' polyesters, such as those from terephthalic acid and ethylene glycol or 1,4-dimethylcyclohexane, and copolymers from terephthalic ~ ~9~~
acid and isophthalic acid and ethylene glycol.
The present invention relates also to a process for dyeing and printing textile material based on synthetic fibres, in particular on polyester fibres, in which process there are used azo dyes which are free from water-solubilising groups and which correspond to the formula N02 ~ORl 02N ~ N = N ~ NH-CH2-CH-R2 / OH
wherein X, Rl, R2 and R3 have the same meanings as above.
For dyeing in aqueous liquors, the water-insoluble dyes according to the present invention are used advantageously in a finely divided form, and dyeing is performed with the addition of dispersing agents, such as sulphite cellulose liquor or synthetic detergents, or a combination of various wetting and dispersing agents. It is as a rule expedient to convert before dyeing the dyes to be used into a dye preparation containing a dispersing agent and finely divided dye in such a form that a fine dispersion is obtained on dilution of the dye preparations with water. Such dye preparations can be produced in a known manner, for example by grinding the dye in dry or wet form, with or without the addition of dispersing agents during the grinding operation.
To obtain strong dyeings on polyethylene terephthalate fibres, it proves advantageous to add a swelling agent to the ',,-,. , ~3'9~
dye bath; or to perform the dyeing process under pressure at temperatures above 100C, for example at 130C. Suitable swelling agents are aromatic carboxylic acids, for example salicylic acid, phenols, such as o- or p-oxydiphenyl, or aromatic halogen compounds, such as o-dichlorobenzene or diphenyl.
For thermofixing the dye, the padded polyester fabric is heated, advantageously after prior drying, e.g. in a warm stream of air, at temperatures of above 100C, for example between 180 and 210C.
The dyeings obtained according to the present process can be subjected to an aftertreatment, for example by heating in an aqueous solution of an ion-free detergent.
The stated dyes can be applied according to the present process not only by impregnation but also by printing. For this purpose there is used, for example, a printing paste which contains the finely dispersed dye together with the auxiliaries customarily used in printing, such as wetting and thickening agents.
Full dyeings and printing having good fastness properties are obtained by the present process.
Full dyeings are likewise obtained with application of the new dyes from organic solvents, where the dye is applied from a solvent, in which it is dissolved or is present as a fine dispersion, to the textile article to be dyed. Suitable solvents are, e.g., petroleum fractions and, in particular, chlorinated hydrocarbons (e.g. perchloroethylene), which can be used on their 9.~
own, or as a dispersion together with water.
The new water-insoluble dyes can be used also for the solution dyeing of polyamides, polyesters and polyolefins.
The polymer to be dyed is advantageously mixed in the form of powders, granules or chips, as a finished spinning solution or in the melted state, with the dye, which is introduced in the dry condition or in the form of a dispersion or solution in an optionally volatile solvent. After homogeneous dispersion of the dye in the solution or melt of the polymer, the mixture is processed in a known manner, by casting, moulding or extrusion, into the form of fibres, yarns, monofilaments, films, and so forth.
The new dyes are suitable also for the so-called transfer or sublimation printing process, in which the dye is sublimated in the hot state from an auxiliary carrier (e.g. paper) onto the sheet material to be printed (e.g. made from polyester fibres).
Except where otherwise stated in the Examples which follow, parts are parts by weight, percentages are per cent by weight, and temperatures are in degrees Centigrade.
" ~ .
.
Example 1 21.75 g of 2,4-dinitro-6-chloroaniline is suspended in 50 ml of H2S04 (88%), and 16.8 ml of a 40% nitrosylsulphuric acid is added at 10-15 in the course of 30 minutes. After 3 hours, the clear diazo solution is added dropwise to a clear acidified solution of 43.6 g of the coupling component of the formula ~ Or~H2CH20CH3 H2-cH3 I OH
in 200 ml of ice water, the temperature being held below 5 by the addition of ice.
A pH value of about 3 is obtained by the simultaneous dropwise addition of conc. sodium hydroxide solution. The resulting dye of the formula 02N ~ N=N ~ _ NU-CH2-clu-cH2 3 is filtered off, and washed with hot water until the filtrate is colourless. After drying, there remains 50 g of a navy blue powder. The dye produces on polyester fabrics deeply coloured blue dyeings having good fastness to light and to sublimation.
The coupling component uséd in this Example is obtained by reacting the amine of the formula -- g _ ~ .
~ 9 OC21140C~H3 Ç~_ NH2 ..
at 20 - 30 in glacial acetic acid, with an equimolar amount of 1,2-butylene oxide.
Example 2 21.75 g of 2,4-dinitro-6-chloroaniline is diazotised as described in Example 1. The diazo solution is added dropwise to a solution consisting of 40 g of a coupling component of the formula IOC~(CH3)2 CH2 ~CH CH2-CH3 ~: l H
. NHCOCH3 dissolved in 200 ml of ice water and 12 parts by volume of conc.
hydrochloric acid. The resulting dye of the formula Cl OCH(CH3)2 02N ~ N=N ~ ~ - NH-CH2-~H-CH -CH
N2. NHCOCH3 is filtered off and washed with hot water. After drying, there is obtained 51 g of a navy blue dye which, applied in the HT process to polyester fabric, is distinguished by very good - fastness properties, and also by a high rate of absorption.
The coupling component is obtained by addition of equimolar amounts of 1,2-butylene oxide to the amine of the formula OCH(CH3)2 Example 3 The dye of the formula Cl OCH2CH20CH3 o2N~<$N=N ~ NH- CU2 - CII- CH2- C1:3 NO2 NHCOCH2CH3 . OH
; is obtained in a manner analogous to that described in Example 1 by using, in place of the coupling component described in Example 1, 32.5 g of the coupling component of the formula : ~ ~H-cH2-fH-cH2-CH3 OH
There is obtained 51 g of a navy blue disperse dye having very good build-up properties on polyester fabrics.
In an analogous manner are obtained the dyes of the formula X ORl .
02N~N=N~ f which likewise dye polyester fabrics in deep navy blue shades.
9~
__ ~ t No. X Rl R2 3 _ 21 Cl -CH(CH3)2 _CC231~ CH2CH3 4 ll ll ll -CH3Cl " . -CH2CH2Cl 6 ll ll -c2~5 "
7 ll .. ll -CH2 8 Br .. ll ll 11 . . -C"H3 CH2CH2Cl 12 l . , CC235 -CH3 14 . l . CH2CH3 ll ll -C2~lS "
16 Cl -CH2CH20CH3 -CH -CH3 17 .l l .l -CH2CH3 18 Br 19 . ll C2H,5 ll ll -CH3 .
21 ll ll -CH3 ll 22 ~l l CH2Cl 23 ll ll ll -CH2CH2Cl 24 l l C2H5 "
" ll . " -CH2 26 Cl " .. ll ll 27 ll ll ll -CH2CH2Cl .
28 . " . -CH
29 ll ll " -CH2 Cl -CH2CH(CH3)2 -C2~15 -CH3 ' . _ . . _ . - 13 - _ .__ "';
: ~ .
- ~
- --~ - ~
No. X R.l R2 R3 .' ~
; 31 Br -CH3 C2H5 -CH3 .i 3323 .l CH2C 20CH2CH3 A C1~2CH3 . 34 ll ll ll -CH2 . 35 ll ll -CH3 -CH3 ( 36 ll ll ll CCHH2CH13 " 39 Cl . "C2H5 CH23CH3 ll ll ll -CH2 ' 41 ll ll -.CH3 -CH3 42 ,l. Il ,l CH2CH3 . 43 ll ll ll -CH2 : 44 Cl -cH2cH2ocH(cH3)2 ,l -CH3 i 45 ll ll ll -CH2CH3 .~ 46 ll ~l ll -CH2Cl 47 Br ~l ll -CH .
!: 48 ll It . '' CcH3cHl3 ' Sl ll ll - "C2H5 CHH32CH3 . ' - . S2 ,l l l -CH2Cl ,.~ 53 Cl ~ ~ C 2 3 .~ 56 Cl -~H2cH2ocH2cH2c~l2cH3 - " -CH3 57 ll . Il ll -CH2CH3 . S8 Br l l CCHH23CH3 - 60 Cl - CH(CH3)2 -CH3 CH2CH2C 3 ;
~ - 14 -. . .
. . , . . . . ~
No. _ _ _ _ 2 _ _ 61 Cl- C~l(C113)2 -C2H5 -CH2C~2C~1 62 Br ll ll ..
63 ,l l -C113 64 Cl~ CH2CH20CH3 l l .l " C2H5 "
66 Br ll " .
67 ll ll -CH3 ll 68 Cl " . ll -CH(CH3)2 69 .l-CH2CH20CH2CH2CN C2H5 CH3 ll ~. I ., -C~12CH3 71 ,l-CH2CH2CN l . -72 " ll ll -C~3 73 ll ll -C~
74 l -CH2CH2Cl C2H5 l I~ .l .l CH2CH3 76 ll ~ -CH3 -CH3 77 .l .l l CH2CH3 78 l l l -CH2C
79 . -CH3 l -CH2CH2C
ll ll C2H5 -CH3 81 ll ll ll . -CH2CH3 82 - . l : -CH2CH2C
83 ll . ll -CH2 84 Br ll ll j, ll ~, . -CH2CH3 86 .. -CH2Cl ¦
., ~ .
.
.
~ 15 -
02N - ~ N=N ~ Nl - C~12 - I1 2 OH
Hal 3 - 2a -~9~
wherein Hal represents chlorine or bromine, Rl" represents branched-chain or substituted alkyl, R2 represents unsubstituted lower alkyl, and R3" represents methyl, ethyl or propyl, which can be optionally substituted with halogen, particularly chlorine.
Particularly valuable dyes are those of the formula ~2 ~Rl"
02N ~ N = N ~ NH-CH2-CH-(CH3, C2H
OH
(Br, Cl) NHCO-(CH3, C2H5) wherein Rl" has the same meaning as above, especially -CH2CH20CH3 and CH(CH3)2-In the above formulae, Rl" represents in particular abranched-chain alkyl group, or an alkyl group substituted by ether groups, and R2 and R3 independently of one another represent methyl or ethyl.
Suitable groups Rl and/or R3 are, for example, those of the ( 3)2~ CH2CH2Cl, -CH2CH2Br, -CHCl-CH2Cl -cH2cH2cN, -cH2-cH(OH)-cH2cl~ -CH2c6H5~ -CH2C6H4N02~ -CH2c6H4 -CH2CH2C6H5, -CH2CH20H, -CH2CH2-0-CH3, -CH2CH2-0-C4Hg -C4H8-o-c4H9~ -CH2CH2-0-cH2cH20cH3~ -CH2CH2-0-CH2CH2-OH~
-C H -CH -CH2CH2-0-CH2CH2-0COCH3' -CH2CH2-0-CH2CH2-CN' -CH2-CH2-0-COCH2Cl, -CH2CH2-0-CO-CHBr-CH2Br, -CH2-CH-(GCOCH3)-CH2-0-C6H5, -CH2-CH2-0-CO-CH=CH2, -cH2-cH(OcOcH3)-cH2ococH3 -(CH2)1-3--CO(H' CH3~ C2H5' C3H7 4 9)' (CH2)1-3-~H-cO(H~ CH3, C2H5, C3H7, C4H ) -(CH2)l_3-o-co(c6H5~ C6H4Cl, C6H4Br, C5H40CH3, C6H4CH3), -(CH2)1-3-0-CO-O(cH3. C2H5, C3H7, C4H9), '~
, -(CH2)1_3-0-CO-O-(C6H5, C6~14Cl, C6H4Br, C6H40CH3, C6H4CH3)~
-CH2CH2-0-C6H5 und -CH2CH2-0-CO-C~12-C6H5.
Lower alkyl groups in the present description are taken to be groups having 1 to 5 carbon atoms; and branched-chain alkyl is in particular isopropyl.
These azo dyes are obtained by coupling coupling components of the formula ORl ~: ~HCOR3 OH
. . .
wherein Rl, R2 and R3 have the same meaning as above, with the diazonium compound of a 2,4-dinitro-6-halogenoaniline of the : formula . ~0 $i O~N ~ NH2 wherein X has the same meaning as above.
The coupling components of the given formula are obtained by reaction of an amine of the formula , ORl with an epoxide of the formula ` CH - CH - R
~-: \20 / 2 whereby there are obtained, in addition to the main product '. of the formula , ~ - 4 -.
. . .
C9~
Ç~
or its isomers of the formula OR
-CH-CH -OH
~=~ , 2 N~ICOR3 R2 also bis-addition products together with a small amount of unreacted starting amine as a mixture.
The new water-insoluble azo dyes, their mixtures with each other and mixtures thereof with other azo dyes, are excellently suitable for dyeing and printing leather, wool, silk and, in particular, synthetic fibres, such as acrylic fibres or acrylo-nitrile fibres, from polyacrylonitrile, or copolymers from ,. . .
~^ - acrylonitrile and other vinyl compounds, such as acrylic esters, acrylic amides, vinylpyridine, vinyl chloride or vinylidene chloride, or from copolymers of dicyanoethylene and vinyl acetate, ' and also acrylonitrile-block copolymers, fibres from polyurethanes, , polypropylene fibres, especially from polypropylene fibres modified with metals, particularly with nickel, from cellulose s tri- and -2 1/2~acetate, and especially fibres from polyamides,` such as nylon-6, nylon-6.6 or nylon 12, and from aromatic ' polyesters, such as those from terephthalic acid and ethylene glycol or 1,4-dimethylcyclohexane, and copolymers from terephthalic ~ ~9~~
acid and isophthalic acid and ethylene glycol.
The present invention relates also to a process for dyeing and printing textile material based on synthetic fibres, in particular on polyester fibres, in which process there are used azo dyes which are free from water-solubilising groups and which correspond to the formula N02 ~ORl 02N ~ N = N ~ NH-CH2-CH-R2 / OH
wherein X, Rl, R2 and R3 have the same meanings as above.
For dyeing in aqueous liquors, the water-insoluble dyes according to the present invention are used advantageously in a finely divided form, and dyeing is performed with the addition of dispersing agents, such as sulphite cellulose liquor or synthetic detergents, or a combination of various wetting and dispersing agents. It is as a rule expedient to convert before dyeing the dyes to be used into a dye preparation containing a dispersing agent and finely divided dye in such a form that a fine dispersion is obtained on dilution of the dye preparations with water. Such dye preparations can be produced in a known manner, for example by grinding the dye in dry or wet form, with or without the addition of dispersing agents during the grinding operation.
To obtain strong dyeings on polyethylene terephthalate fibres, it proves advantageous to add a swelling agent to the ',,-,. , ~3'9~
dye bath; or to perform the dyeing process under pressure at temperatures above 100C, for example at 130C. Suitable swelling agents are aromatic carboxylic acids, for example salicylic acid, phenols, such as o- or p-oxydiphenyl, or aromatic halogen compounds, such as o-dichlorobenzene or diphenyl.
For thermofixing the dye, the padded polyester fabric is heated, advantageously after prior drying, e.g. in a warm stream of air, at temperatures of above 100C, for example between 180 and 210C.
The dyeings obtained according to the present process can be subjected to an aftertreatment, for example by heating in an aqueous solution of an ion-free detergent.
The stated dyes can be applied according to the present process not only by impregnation but also by printing. For this purpose there is used, for example, a printing paste which contains the finely dispersed dye together with the auxiliaries customarily used in printing, such as wetting and thickening agents.
Full dyeings and printing having good fastness properties are obtained by the present process.
Full dyeings are likewise obtained with application of the new dyes from organic solvents, where the dye is applied from a solvent, in which it is dissolved or is present as a fine dispersion, to the textile article to be dyed. Suitable solvents are, e.g., petroleum fractions and, in particular, chlorinated hydrocarbons (e.g. perchloroethylene), which can be used on their 9.~
own, or as a dispersion together with water.
The new water-insoluble dyes can be used also for the solution dyeing of polyamides, polyesters and polyolefins.
The polymer to be dyed is advantageously mixed in the form of powders, granules or chips, as a finished spinning solution or in the melted state, with the dye, which is introduced in the dry condition or in the form of a dispersion or solution in an optionally volatile solvent. After homogeneous dispersion of the dye in the solution or melt of the polymer, the mixture is processed in a known manner, by casting, moulding or extrusion, into the form of fibres, yarns, monofilaments, films, and so forth.
The new dyes are suitable also for the so-called transfer or sublimation printing process, in which the dye is sublimated in the hot state from an auxiliary carrier (e.g. paper) onto the sheet material to be printed (e.g. made from polyester fibres).
Except where otherwise stated in the Examples which follow, parts are parts by weight, percentages are per cent by weight, and temperatures are in degrees Centigrade.
" ~ .
.
Example 1 21.75 g of 2,4-dinitro-6-chloroaniline is suspended in 50 ml of H2S04 (88%), and 16.8 ml of a 40% nitrosylsulphuric acid is added at 10-15 in the course of 30 minutes. After 3 hours, the clear diazo solution is added dropwise to a clear acidified solution of 43.6 g of the coupling component of the formula ~ Or~H2CH20CH3 H2-cH3 I OH
in 200 ml of ice water, the temperature being held below 5 by the addition of ice.
A pH value of about 3 is obtained by the simultaneous dropwise addition of conc. sodium hydroxide solution. The resulting dye of the formula 02N ~ N=N ~ _ NU-CH2-clu-cH2 3 is filtered off, and washed with hot water until the filtrate is colourless. After drying, there remains 50 g of a navy blue powder. The dye produces on polyester fabrics deeply coloured blue dyeings having good fastness to light and to sublimation.
The coupling component uséd in this Example is obtained by reacting the amine of the formula -- g _ ~ .
~ 9 OC21140C~H3 Ç~_ NH2 ..
at 20 - 30 in glacial acetic acid, with an equimolar amount of 1,2-butylene oxide.
Example 2 21.75 g of 2,4-dinitro-6-chloroaniline is diazotised as described in Example 1. The diazo solution is added dropwise to a solution consisting of 40 g of a coupling component of the formula IOC~(CH3)2 CH2 ~CH CH2-CH3 ~: l H
. NHCOCH3 dissolved in 200 ml of ice water and 12 parts by volume of conc.
hydrochloric acid. The resulting dye of the formula Cl OCH(CH3)2 02N ~ N=N ~ ~ - NH-CH2-~H-CH -CH
N2. NHCOCH3 is filtered off and washed with hot water. After drying, there is obtained 51 g of a navy blue dye which, applied in the HT process to polyester fabric, is distinguished by very good - fastness properties, and also by a high rate of absorption.
The coupling component is obtained by addition of equimolar amounts of 1,2-butylene oxide to the amine of the formula OCH(CH3)2 Example 3 The dye of the formula Cl OCH2CH20CH3 o2N~<$N=N ~ NH- CU2 - CII- CH2- C1:3 NO2 NHCOCH2CH3 . OH
; is obtained in a manner analogous to that described in Example 1 by using, in place of the coupling component described in Example 1, 32.5 g of the coupling component of the formula : ~ ~H-cH2-fH-cH2-CH3 OH
There is obtained 51 g of a navy blue disperse dye having very good build-up properties on polyester fabrics.
In an analogous manner are obtained the dyes of the formula X ORl .
02N~N=N~ f which likewise dye polyester fabrics in deep navy blue shades.
9~
__ ~ t No. X Rl R2 3 _ 21 Cl -CH(CH3)2 _CC231~ CH2CH3 4 ll ll ll -CH3Cl " . -CH2CH2Cl 6 ll ll -c2~5 "
7 ll .. ll -CH2 8 Br .. ll ll 11 . . -C"H3 CH2CH2Cl 12 l . , CC235 -CH3 14 . l . CH2CH3 ll ll -C2~lS "
16 Cl -CH2CH20CH3 -CH -CH3 17 .l l .l -CH2CH3 18 Br 19 . ll C2H,5 ll ll -CH3 .
21 ll ll -CH3 ll 22 ~l l CH2Cl 23 ll ll ll -CH2CH2Cl 24 l l C2H5 "
" ll . " -CH2 26 Cl " .. ll ll 27 ll ll ll -CH2CH2Cl .
28 . " . -CH
29 ll ll " -CH2 Cl -CH2CH(CH3)2 -C2~15 -CH3 ' . _ . . _ . - 13 - _ .__ "';
: ~ .
- ~
- --~ - ~
No. X R.l R2 R3 .' ~
; 31 Br -CH3 C2H5 -CH3 .i 3323 .l CH2C 20CH2CH3 A C1~2CH3 . 34 ll ll ll -CH2 . 35 ll ll -CH3 -CH3 ( 36 ll ll ll CCHH2CH13 " 39 Cl . "C2H5 CH23CH3 ll ll ll -CH2 ' 41 ll ll -.CH3 -CH3 42 ,l. Il ,l CH2CH3 . 43 ll ll ll -CH2 : 44 Cl -cH2cH2ocH(cH3)2 ,l -CH3 i 45 ll ll ll -CH2CH3 .~ 46 ll ~l ll -CH2Cl 47 Br ~l ll -CH .
!: 48 ll It . '' CcH3cHl3 ' Sl ll ll - "C2H5 CHH32CH3 . ' - . S2 ,l l l -CH2Cl ,.~ 53 Cl ~ ~ C 2 3 .~ 56 Cl -~H2cH2ocH2cH2c~l2cH3 - " -CH3 57 ll . Il ll -CH2CH3 . S8 Br l l CCHH23CH3 - 60 Cl - CH(CH3)2 -CH3 CH2CH2C 3 ;
~ - 14 -. . .
. . , . . . . ~
No. _ _ _ _ 2 _ _ 61 Cl- C~l(C113)2 -C2H5 -CH2C~2C~1 62 Br ll ll ..
63 ,l l -C113 64 Cl~ CH2CH20CH3 l l .l " C2H5 "
66 Br ll " .
67 ll ll -CH3 ll 68 Cl " . ll -CH(CH3)2 69 .l-CH2CH20CH2CH2CN C2H5 CH3 ll ~. I ., -C~12CH3 71 ,l-CH2CH2CN l . -72 " ll ll -C~3 73 ll ll -C~
74 l -CH2CH2Cl C2H5 l I~ .l .l CH2CH3 76 ll ~ -CH3 -CH3 77 .l .l l CH2CH3 78 l l l -CH2C
79 . -CH3 l -CH2CH2C
ll ll C2H5 -CH3 81 ll ll ll . -CH2CH3 82 - . l : -CH2CH2C
83 ll . ll -CH2 84 Br ll ll j, ll ~, . -CH2CH3 86 .. -CH2Cl ¦
., ~ .
.
.
~ 15 -
Claims (40)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An azo dye of the formula wherein X represents halogen, R1 represents unsubstituted alkyl, alkyl which is substituted by halogen, cyano, alkoxy or .beta.-alkoxy ethylene, wherein the alkoxy-part may be further substituted by cyano or cycloalkyl, R2 represents unsubstituted lower alkyl, and R3 represents unsubstituted lower alkyl or lower alkyl which may be substituted by halogen, cyano or alkoxy.
2. An azo dye according to claim 1 wherein X represents chlorine.
3. An azo dye according to claim 1 wherein R1 represents alkyl which is substituted by halogen, cyano, alkoxy or .beta.-alkoxy ethylene, wherein the alkoxy-part may be further substituted by cyano.
4. An azo dye according to claim 3 wherein R1 represents an alkyl group which has 1 to 3 carbon atoms and which is substitut-ed by chlorine, cyano, methoxy or ethoxy.
5. An azo dye according to claim 4 wherein R1 represents the group -CH2-CH2-O-R4, in which R4 represents methyl or ethyl.
6. An azo dye according to claim 1 wherein R2 represents methyl or ethyl.
7. An azo dye according to claim 1 wherein R3 represents methyl or ethyl.
8. An azo dye which corresponds to the formula wherein Hal represents chlorine or bromine, R1" represents branched-chain alkyl or alkyl which is sub-stituted by halogen, cyano, alkoxy or ?-alkoxy ethylene, wherein the alkoxy-part may be further substituted by cyano, R2 represents unsubstituted lower alkyl, and R3" represents methyl, ethyl or propyl, which can be optionally substituted with halogen.
9. An azo dye according to claim 8 wherein R3" represents methyl, ethyl or propyl substituted with chlorine.
10. An azo dye which corresponds to the formula wherein R1" has the same meaning as in claim 8.
11. An azo dye which corresponds to the formula
12. An azo dye which corresponds to the formula
13. An azo dye which corresponds to the formula
14. An azo dye which corresponds to the formula
15. An azo dye which corresponds to the formula
16. An azo dye which corresponds to the formula
17. An azo dye which corresponds to the formula
18. An azo dye which corresponds to the formula
19. A process for producing azo dyes of the formula wherein X represents halogen, R1 represents unsubstituted alkyl, alkyl which is substituted by halogen, cyano, alkoxy or .beta.-alkoxy ethylene, wherein the alkoxy-part may be further substituted by cyano, or cyclo-alkyl, R2 represents unsubstituted lower alkyl, and R3 represents unsubstituted lower alkyl or lower alkyl which may be substituted by halogen, cyano or alkoxy, in which process coupling components of the formula wherein R1, R2 and R3 have the same meaning as above, are coupled with the diazonium compound of a 2,4-dinitro-6-halogeno-aniline of the formula wherein X has the same meaning as above.
20. A process according to claim 19 wherein there is used a diazonium compound in which X represents chlorine or bromine.
21. A process according to claim 19 wherein there is used a coupling component in which R1 represents alkyl which is sub-stituted by halogen, cyano, alkoxy or .beta.-alkoxy ethylene, wherein the alkoxy-part may be further substituted by cyano.
22. A process according to claim 21 wherein there is used a coupling component in which R1 represents an alkyl group which has 1 to 3 carbon atoms and which is substituted by chlorine, cyano, methoxy or ethoxy.
23. A process according to claim 22 wherein there is used a coupling component in which R1 represents the group of the formula -CH2CH2OR4, wherein R4 represents methyl or ethyl.
24. A process according to claim 19 wherein there is used a coupling component in which R2 represents methyl or ethyl.
25. A process according to claim 19 wherein there is used a coupling component in which R3 represents methyl or ethyl.
26. A process according to claim 19 wherein there is used a coupling component of the formula in which R1" represents branched-chain alkyl or alkyl which is substituted by halogen, cyano, alkoxy or .beta.-alkoxy ethylene, wherein the alkoxy-part may be further substituted by cyano, R2 represents unsubstituted lower alkyl, and R3" represents methyl, ethyl or propyl which can be optionally substituted with halogen.
27. A process according to claim 26 wherein R3" in the coupling component represents methyl, ethyl or propyl substituted with chlorine.
28. A process according to claim 26 wherein there is used a coupling component of the formula wherein R1" has the same meaning as in claim 26.
29. A process according to claim 19 wherein there is used a coupling component of the formula
30. A process according to claim 19 wherein there is used a coupling component of the formula
31. A process according to claim 19 wherein there is used a coupling component of the formula
32. A process according to claim 19 wherein there is used a coupling component of the formula
33. A process according to claim 19 or 20 wherein there is used a coupling component of the formula
34. A process according to claim 19 or 20 wherein there is used a coupling component of the formula
35. A process according to claim 19 or 20 wherein there is used a coupling component of the formula
36. A process according to claim 19 or 20 wherein there is used a coupling component of the formula
37. A process of dyeing or printing, which comprises using an azo dye according to claim 1 for dyeing or printing synthetic fibres.
38. A process according to claim 37, for dyeing or printing fibres containing ester groups.
39. A process according to claim 37, for dyeing or printing polyester fibres.
40. The synthetic fibre material dyed and printed with the azo dyes according to claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| LU76960 | 1977-03-16 | ||
| LU76960A LU76960A1 (en) | 1977-03-16 | 1977-03-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1109063A true CA1109063A (en) | 1981-09-15 |
Family
ID=19728501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA299,037A Expired CA1109063A (en) | 1977-03-16 | 1978-03-14 | Azo dyes, processes for producing them, and their use |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS53113831A (en) |
| CA (1) | CA1109063A (en) |
| CH (1) | CH633306A5 (en) |
| DE (1) | DE2811067C3 (en) |
| FR (1) | FR2383994A1 (en) |
| GB (1) | GB1600893A (en) |
| LU (1) | LU76960A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6069276A (en) * | 1999-03-05 | 2000-05-30 | Milliken & Company | Oxyalkylene-substituted m-amidoaniline intermediate |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE634032A (en) * | ||||
| FR1361053A (en) * | 1963-06-22 | 1964-05-15 | Hoechst Ag | Water insoluble monoazo dyes and their preparation |
| FR1534269A (en) * | 1966-08-12 | 1968-07-26 | Mitsui Kagaku Kogyo Kabushiki | New monoazo dyes |
| GB1352059A (en) * | 1970-05-06 | 1974-05-15 | Sandoz Ltd | Monoazo compounds of low solubility in water their production and use as dyes |
| GB1565531A (en) * | 1976-02-05 | 1980-04-23 | Ici Ltd | Diperse monoazo dyestuffs |
-
1977
- 1977-03-16 LU LU76960A patent/LU76960A1/xx unknown
-
1978
- 1978-03-06 JP JP2460278A patent/JPS53113831A/en active Pending
- 1978-03-13 CH CH269778A patent/CH633306A5/en not_active IP Right Cessation
- 1978-03-13 GB GB988378A patent/GB1600893A/en not_active Expired
- 1978-03-14 DE DE19782811067 patent/DE2811067C3/en not_active Expired
- 1978-03-14 CA CA299,037A patent/CA1109063A/en not_active Expired
- 1978-03-15 FR FR7807515A patent/FR2383994A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| CH633306A5 (en) | 1982-11-30 |
| DE2811067B2 (en) | 1981-01-08 |
| FR2383994A1 (en) | 1978-10-13 |
| LU76960A1 (en) | 1978-10-18 |
| DE2811067C3 (en) | 1981-12-03 |
| FR2383994B1 (en) | 1980-06-13 |
| GB1600893A (en) | 1981-10-21 |
| DE2811067A1 (en) | 1978-09-21 |
| JPS53113831A (en) | 1978-10-04 |
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| MKEX | Expiry |