TREA

Dyes for thermoplastics

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Information

  • Patent Grant
  • 3974123
  • Patent Number
    3,974,123
  • Date Filed
    Thursday, February 20, 1975
    49 years ago
  • Date Issued
    Tuesday, August 10, 1976
    48 years ago
Information
Abstract
Dyes of the formula ##SPC1##WhereD is the radical of the diazo component,R is hydrogen, alkyl or aryl,X is hydrogen, cyano or carbamoylA.sup.1 is A or ##SPC2##AndA is hydrogen or an optionally substituted hydrocarbon radical, are eminently suitable for coloring thermoplastic resinous material. Colorations stable to heat and with excellent fastness properties are obtained, the color strength of the dyes being remarkable.
Description

The invention relates to a process for coloring thermoplastics with dyes of the formula I ##SPC3##
wherein A.sup.1 is A or ##SPC4##
D is the radical of a diazo component,
R is hydrogen, alkyl, methylphenyl or phenyl,
X is hydrogen, carbamoyl or cyano,
Z is alkylene, cycloalkylene, aralkylene or arylene, and the alkylene can be interrupted by oxygen, sulfur or N-substituted imino, the
A's independently of one another are hydrogen, unsubstituted or substituted alkyl, cycloalkyl, aralkyl, phenyl or acyl, and two
A's together with the nitrogen are a saturated heterocyclic ring of five to seven members.
The radicals D are derived, in particular, from amines of the benzene, benzthiazole, benzisothiazole, thiazole, thiadiazole, thiophene, azobenzene or anthraquinone series.
Examples of substituents of the radicals D of the diazo component are:
In the benzene series: chlorine, bromine, nitro, cyano, trifluoromethyl, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, carbomethoxy, carbobutoxy, carbo-.beta.-ethylhexoxy, carbo-.beta.-methoxyethoxy, carbo-.beta.-hydroxyethoxy, optionally N-monosubstituted or N-disubstituted carboxylic acid amide or sulfonamide, methyl, ethyl, butyl, octyl, hexyl, methoxy or ethoxy; N-substituents of the carboxylic acid amides or sulfonamides are, eg., methyl, ethyl, propyl, butyl, .beta.-hydroxyethyl, .gamma.-hydroxypropyl, .beta.-methoxyethyl, .gamma.-methoxypropyl or .gamma.-ethoxypropyl, or groups which form the pyrrolidide, piperidide or morpholide.
In the azobenzene series: chlorine, bromine, nitro, cyano, methyl, ethyl, methoxy or ethoxy.
In the heterocyclic series: chlorine, bromine, nitro, cyano, methyl, C.sub.17 H.sub.35, ethyl, phenyl, methoxy, ethoxy, methylmercapto, .beta.-carbomethoxyethylmercapto, .beta.-carboethoxyethylmercapto, carbomethoxy, carboethoxy, carbo-.beta.-ethylhexoxy, acetyl, methylsulfonyl or ethylsulfonyl.
Preferred diazo components have at least one substituent, such as methylsulfonyl, phenylsulfonyl, ethylsulfonyl, carboalkoxy, optionally N-substituted carbamoyl and, in particular, cyano, chlorine or bromine.
The radical D can specifically be derived from, eg., the following amines: o-, m- or p-nitroaniline, o-, m- or p-cyanoaniline, 2,4-dicyanoaniline, 2,4,6-tribromoaniline, 2-chloro-4-nitroaniline, 2-bromo-4-nitroaniline, 2-cyano-4-nitroaniline, 2-methylsulfonyl-4-nitroaniline, 2-methyl-4-nitroaniline, 2-methoxy-4-nitroaniline, 4-chloro-2-nitroaniline, 4-methyl-2-nitroaniline, 2-hexyl-4-nitroaniline, 4-methoxy-2-nitroaniline, 1-amino-2-trifluoromethyl-4-chlorobenzene, 2-chloro-5-aminobenzonitrile, 2-amino-5-chloro-benzonitrile, 1,-amino-2-nitrobenzene-4-sulfonic acid n-butylamide or .beta.-methoxyethylamide, 2,4-dinitroaniline, 2,4-dinitro-6-chloroaniline, 2,4-dinitro-6-bromoaniline, 2,4-dinitro-6-cyanoaniline, 1-amino-2,4-dinitrobenzene-6-methylsulfone, 2,6-dichloro-4-nitroaniline, 2,6-dibromo-4-nitroaniline, 2-chloro-6-bromo-4-nitroaniline, 2,6-dicyano-4-nitroaniline, 2-cyano-4-nitro-6-chloroaniline, 2-cyano-4-nitro-6-bromoaniline, 1-aminobenzene-4-methylsulfone, 1-amino-2,6-dibromobenzene-4-methylsulfone, 1-amino-2,6-dichlorobenzene-4-methylsulfone, 1-amino-2,4-dinitrobenzene-6-carboxylic acid methyl ester or .beta.-methoxyethyl ester, 3,5-dichloroanthranilic acid propyl ester, 3,5-dibromoanthranilic acid .beta.-methoxyethyl ester, N-acetyl-p-phenylenediamine, 4-aminoacetophenone, 4- or 2-aminobenzophenone, 2- and 4-aminodiphenylsulfone, 5-nitroanthranilic acid methyl ester, isobutyl ester, methyldiglycol ester, .beta.-methoxyethyl ester, .beta.-butoxyethyl ester and .beta.-acetoxyethyl ester, 3- or 4-aminophthalic acid .beta.-hydroxyethylamide, 3-amino-6-nitrophthalic acid .beta.-hydroxyethylamide, methylsulfonic acid 2'-aminophenyl ester, 3'-aminophenyl ester or 4'-aminophenyl ester, ethylsulfonic acid 2'-aminophenyl ester, 3'-aminophenyl ester or 4'-aminophenyl ester, butylsulfonic acid 2'-aminophenyl ester, 3'-aminophenyl ester or 4'-aminophenyl ester, benzenesulfonic acid 2'-aminophenyl ester, 3'-aminophenyl ester or 4'-aminophenyl ester, 2-aminoanthraquinone, 1-amino-4-chloroanthraquinone, 2-aminobenzthiazole, 2-amino-benzthiazole-6-carboxylic acid methyl ester, 2-amino-6-methylsulfonylbenzthiazole, 2-amino-6-cyanobenzthiazole, 2-amino-6-nitrobenzthiazole, 5,6- or 6,7-dichloro-2-aminobenzthiazole, 4-amino-5-bromo-7-nitro-1,2-benzisothiazole, 3-amino-5-nitro-2,1-benzisothiazole, 3-amino-5-nitro-7-bromo-2,1-benzisothiazole, 2-aminothiazole, 2-amino-5-nitrothiazole, 2-amino-4-methylthiazole-5-carboxylic acid ethyl ester, 2-amino-4-methyl-5-acetylthiazole, 2-amino-3-cyano-4-methylthiophene-5-carboxylic acid esters of C.sub.1 - to C.sub.8 -alkanols or C.sub.1 - to C.sub.4 -alkoxyethanol, 2-phenyl-5-amino-1,3,4-thiadiazole, 3-methylmercapto-5-amino-1,2,4-thiadiazole, 3-.beta.-carbomethoxyethylmercapto-5-amino-1,2,4-thiadiazole and 2,4-dicyano-3,5-dimethylaniline.
Examples of suitable diazo components of the aminoazobenzene series are: 4-aminoazobenzene, 2',3-dimethyl-4-aminoazobenzene, 3',2-dimethyl-4-aminoazobenzene, 2,5-dimethyl-4-aminoazobenzene, 2-methyl-5-methoxy-4-aminoazobenzene, 2-methyl-4',5-dimethoxy-4-aminoazobenzene, 4'-chloro-2-methyl-5-methoxy-4-aminoazobenzene, 4'-nitro-2-methyl-5-methoxy-4-aminoazobenzene, 4'-chloro-2-methyl-4-aminoazobenzene, 2,5-dimethoxy-4-aminoazobenzene, 4'-chloro-2,5-dimethoxy-4-aminoazobenzene, 4'-nitro-2,5-dimethoxy-4-aminoazobenzene, 4'-chloro-2,5-dimethyl-4-aminoazobenzene, 4'-methoxy-2,5-dimethyl-4-aminoazobenzene, 4'-nitro-4-aminoazobenzene, 3,5-dibromo-4-aminoazobenzene, 2,3'-dichloro-4-aminoazobenzene, 3-methoxy-4-aminoazobenzene, 3-chloro-4-aminoazobenzene and 2',3-dichloro-4-aminoazobenzene.
Examples of radicals R other than hydrogen are ethyl, n- or i-propyl, butyl, pentyl, .alpha.-ethylpentyl, phenyl or methylphenyl and preferably methyl.
The radicals A can be identical or different. A can be hydrogen or, eg., the following substituents:
alkyl of 1 to 8 carbon atoms, alkyl optionally substituted by hydroxyl, cyano, alkoxy of 1 to 8 carbon atoms, phenoxy, phenoxyethoxy or benzyloxy; cyclohexyl, norbornyl, benzyl, phenylethyl, phenylhydroxyethyl, phenylpropyl, phenylbutyl, phenyl optionally substituted by chlorine, methyl, methoxy or ethoxy, polyalkoxyalkyl, hydroxypolyalkoxyalkyl, alkanoyloxyalkyl or alkoxycarbonylalkyl, alkanoyl, aralkanoyl, aroyl, alkylsulfonyl or arylsulfonyl.
Examples of radicals ##EQU1##0 are pyrrolidino, piperidino, morpholino, piperazino, N-methylpiperazino or hexamethyleneimino.
Specific examples of radicals A, other than those mentioned above, are:
1. Unsubstituted or substituted alkyl: ##EQU2## CH.sub.3, C.sub.2 C.sub.5, n- or i-C.sub.3 H.sub.7, n- or i-C.sub.4 H.sub.9, C.sub.6 H.sub.13, ##EQU3## CH.sub.2 CH.sub.2 OH, (CH.sub.2).sub.3 OH, ##EQU4## (CH.sub.2).sub.4 OH, (CH.sub.2).sub.6 OH, ##EQU5## (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH, (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH, (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OH, (CH.sub.2).sub.2 CN, (CH.sub.2).sub.5 CN, (CH.sub.2).sub.6 CN, (CH.sub.2).sub.7 CN, (CH.sub.2).sub.2 O(CH.sub.2).sub.2 CN, (CH.sub.2).sub.3 O(CH.sub.2).sub.2 CN, (CH.sub.2).sub.2 O(CH.sub.2).sub.2 O(CH.sub.2).sub.2 CN, (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OCH.sub.3, (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5, (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH, (CH.sub.3)OC.sub.2 H.sub.4 OCH(CH.sub.3).sub.2, (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.4 H.sub.9, (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OCH.sub.2 C.sub.6 H.sub.5, (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.2 H.sub.4 C.sub.6 H.sub.5 ##SPC5##
(ch.sub.2).sub.3 oc.sub.2 h.sub.4 oc.sub.6 h.sub.5 ##EQU6## the corresponding radicals in which two or three groupings -OC.sub.2 H.sub.4 -, ##EQU7## or -OCH-CH.sub.2 - are present, CH.sub.2 CH.sub.2 OCH.sub.3, CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5, CH.sub.2 CH.sub.2 OC.sub.3 H.sub.7, CH.sub.2 CH.sub.2 OC.sub.4 H.sub.9, CH.sub.2 CH.sub.2 OC.sub.6 H.sub.5, (CH.sub.2).sub.3 OCH.sub.3, (CH.sub.2).sub.3 OC.sub.2 H.sub.5, (CH.sub.2).sub.3 OC.sub.3 H.sub.7, (CH.sub.2).sub.3 OC.sub.4 H.sub.9, ##EQU8## (CH.sub.2).sub.3 OC.sub.6 H.sub.13, (CH.sub.2).sub.3 OC.sub.8 H.sub.17, (CH.sub.2).sub.3 O--, (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5, (CH.sub.2).sub.3 OC.sub.2 H.sub.4 C.sub.6 H.sub.5, (CH.sub.2).sub.3 OC.sub.6 H.sub.5, ##EQU9## ##SPC6##
2. Unsubstituted or substituted cycloalkyl and polycycloalkyl: ##SPC7##
3. Aralkyl: ##EQU10## CH.sub.2 C.sub.6 H.sub.5, C.sub.2 H.sub.4 C.sub.6 H.sub.5, ##EQU11## and corresponding radicals with C.sub.6 H.sub.4 CH.sub.3 in place of C.sub.6 H.sub.5.
4. Unsubstituted or substituted phenyl radicals:
C.sub.6 h.sub.5, c.sub.6 h.sub.4 ch.sub.3, c.sub.6 h.sub.5 (ch.sub.3).sub.2, c.sub.6 h.sub.4 och.sub.3, c.sub.6 h.sub.4 oc.sub.2 h.sub.5, c.sub.6 h.sub.4 och.sub.2 ch.sub.2 oh and C.sub.6 H.sub.4 Cl;
5. CH.sub.2 CH=CH.sub.2, (CH.sub.2).sub.5 COOCH.sub.3, ##SPC8##
wherein n is 2, 3, 4 or 6, C.sub.2 H.sub.4 OCOCH.sub.3, C.sub.2 H.sub.4 OCHO, C.sub.2 H.sub.4 OCOCH.sub.3, (C.sub.2 H.sub.4 O).sub.2 COCH.sub.3, (C.sub.2 H.sub.4 O).sub.2 CHO, (CH.sub.2).sub.3 OCOH.sub.3 and (CH.sub.2).sub.3 OCHO.
6. CHO, CH.sub.3 CO, C.sub.2 H.sub.5 CO, C.sub.3 H.sub.7 CO, ##EQU12## C.sub.2 H.sub.5 CO, CH.sub.3 3C.sub.6 H.sub.4 CO, C.sub.6 H.sub.5 CH.sub.2 CO, C.sub.6 H.sub.5 OCH.sub.2 CO, CH.sub.3 SO.sub.2, C.sub.2 H.sub.5 SO.sub.2, C.sub.6 H.sub.5 SO.sub.2 and CH.sub.3 C.sub.6 H.sub.4 SO.sub.2.
Examples of preferred substituents A are hydrogen, CH.sub.2, C.sub.2 H.sub.5, n- or i-C.sub.3 H.sub.7, n- or i-C.sub.4 H.sub.9, C.sub.6 H.sub.13, ##EQU13## ##SPC9## (n= 2, 3, 6), CH.sub.2 CH.sub.2 OCH.sub.3, CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5, CH.sub.2 CH.sub.2 OC.sub.4 H.sub.9, (CH.sub.2).sub.3 OCH.sub.3, (CH.sub.2).sub.3 OC.sub.2 H.sub.5, (CH.sub.2).sub.3 OC.sub.3 H.sub.7, (CH.sub.2).sub.3 OC.sub.4 H.sub.9, ##SPC10## ##SPC11##
(ch.sub.2).sub.3 oc.sub.2 h.sub.4 och.sub.3, (ch.sub.2).sub.3 oc.sub.2 h.sub.4 oc.sub.4 h.sub.9, (ch.sub.2).sub.3 oc.sub.2 h.sub.4 oc.sub.6 h.sub.5, ##SPC12##
ch.sub.2 c.sub.6 h.sub.5, c.sub.2 h.sub.4 c.sub.6 h.sub.5, ##EQU14## c.sub.6 h.sub.5, c.sub.6 h.sub.4 ch.sub.3 and C.sub.6 H.sub.4 OCH.sub.3.
Examples of radicals Z are alkylene of 2 to 8 carbon atoms, cycloalkylene of 6 to 18 carbon atoms, with 1 to 3 rings, aralkylene of 7 to 10 carbon atoms and arylene of 6 to 15 carbon atoms. Specific examples are: --(CH.sub.2).sub.n -- (n = 2, 3, 4, 6, 8), ##EQU15## --(CH.sub.2).sub.3 (OC.sub.2 H.sub.4).sub.2 O(CH.sub.2).sub.3 --, --(CH.sub.2).sub.3 O(CH.sub.2).sub.4 O(CH.sub. 2).sub.3 --, ##EQU16## ##SPC13## --(CH.sub.2)OCH.sub.2 CH.sub.2 O(CH.sub.2).sub.3 --, ##SPC14##
Alkylene radicals are particularly preferred, specifically
--(CH.sub.2)p-- (p = 2, 3, 4, 6), as well as --CH.sub.2 --C(CH.sub.3).sub.2 --CH.sub.2 --, --(CH.sub.2).sub.3 OC.sub.2 H.sub.4 O(CH.sub.2).sub.3 -- and --(CH.sub.2).sub.3 O(CH.sub.2).sub.4 O(CH.sub.2).sub.3 --.
The dyes of the formula I may be prepared by reaction of a diazo compound of amines of the formula II
d--nh.sub.2
with coupling components of the formula III ##SPC15##
wherein R, X, A, and A.sup.1 are as defined above.
The amines are diazotized by conventional methods. The coupling reaction is also carried out by conventional methods, in an aqueous strongly acid to weakly acid medium, if appropriate with solvents added. Sparingly, soluble coupling components are suitably coupled in solvents.
Industrially valuable dyes and dye mixtures are particularly those of the formula Ia ##SPC16##
in which
A.sup.1 is A or ##SPC17##
D.sup.1 is phenyl substituted by chlorine, bromine, trifluoromethyl, methyl, ethyl, methoxy, nitro, cyano, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, C.sub.1 - to C.sub.8 -alkoxycarbonyl, C.sub.1 - to C.sub.4 -alkoxycarbonyl, C.sub.1 - to C.sub.4 -alkoxyethoxycarbonyl, .beta.-(C.sub.1 -C.sub.4 -alkoxyethoxy)-ethoxycarbonyl or N,N-C.sub.1 - to C.sub.4 -dialkylsubstituted sulfamoyl; phenylazophenyl; phenylazophenyl substituted by methyl, chlorine, bromine or nitro; benzthiazolyl; benzthiazolyl substituted by nitro, cyano, methylsulfonyl or ethylsulfonyl; benzisothiazolyl; benzisothiazolyl substituted by chlorine, bromine, cyano or nitro; thiazolyl substituted by cyano or nitro; thienyl substituted by methyl, ethyl, propyl, C.sub.17 H.sub.35, phenyl, cyano, nitro or C.sub.1 - to C.sub.8 -alkoxycarbonyl; or thiadiazolyl substituted by phenyl, methyl, chlorine, bromine, methylmercapto, ethylmercapto or C.sub.1 - to C.sub.4 -alkoxycarbonylethylmercapto;
R.sup.1 is hydrogen or alkyl of 1 to 3 carbon atoms;
X is hydrogen, carbamoyl or cyano;
A is hydrogen; C.sub.1 - to C.sub.8 -alkyl; C.sub.2 - to C.sub.8 -alkyl substituted by hydroxyl, OCHO, OCOCH.sub.3, OCOC.sub.3 H.sub.7, C.sub.2 - to C.sub.4 -hydroxyalkoxy, cyano, C.sub.1 - to C.sub.8 -alkoxy, C.sub.1 - to C.sub.8 -alkoxycarbonyl, phenoxy or phenyl; cyclohexyl, methylcyclohexyl, norbornyl, phenyl, .beta.-hydroxy-.beta.-phenylethyl or (CH.sub.2).sub.3 (OC.sub.2 H.sub.4).sub.m OT;
m is 1 or 2;
T is C.sub.1 - to C.sub.4 -alkyl, benzyl or phenyl, ##EQU17## is pyrrolidino, piperidino, morpholino, hexamethyleneimino, piperazino, N-methylpiperazino or N-.beta.-hydroxyethylpiperazino and
Z is C.sub.2 - to C.sub.8 -alkylene, ##EQU18## --(CH.sub.2).sub.3 --N--(CH.sub.2).sub.3 --, --(CH.sub.2).sub.3 --OC.sub.2 H.sub.4 -O--(CH.sub.2).sub.3 --, --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 O (CH.sub.2).sub.3 --, ##SPC18##
Particularly important dyes are those of the formula Ib ##SPC19##
in which
B is nitro, cyano, chlorine, bromine, trifluoromethyl, carbomethoxy, carboethoxy, .beta.-methoxycarboethoxy, methylsulfonyl, ethylsulfonyl, methyl, methoxy, phenylazo, chlorophenylazo or dichlorophenylazo,
B.sup.1 is hydrogen, nitro, chlorine, bromine, cyano, methyl, methoxy, carbomethoxy, phenylsulfonyl, carboethoxy, methylsulfonyl or ethylsulfonyl,
B.sup.2 is hydrogen, chlorine, bromine, cyano or methyl and the
A's, independently of one another, are hydrogen, unsubstituted or substituted alkyl, cycloalkyl, aralkyl, phenyl or acyl, and
A.sup.1 has the above meanings.
Oxygen-free radicals A, and radicals A containing alkoxy groups, are preferred. Further, the dyes with A.sup.1 = A are preferred as being more easily obtainable.
The corresponding dyes which contain, as the diazo component, benzthiazole, benzisothiazole, thiazole, thiadiazole or thiophene which are unsubstituted or substituted by chlorine, bromine, cyano, methyl, methylmercapto, .beta.-carbomethoxyethylmercapto, .beta.-carboethoxyethylmercapto, carbomethoxy, carboethoxy or acetyl, are also particularly valuable.
Amongst the particularly valuable diazo components, the following may be mentioned specifically: 4-nitroaniline, 2-chloro-4-nitroaniline, 2-bromo-4-nitroaniline, 2-cyano-4-nitroaniline, 2-methoxy-4-nitroaniline, 2-amino-5-nitrophenylsulfonic acid dimethylamide, 2-amino-5-nitrophenylsulfonic acid butylamide, 2-amino-5-nitrophenylsulfonic acid .beta.-methoxyethylamide, 2-aminobenzonitrile, 3-chloro-4-aminobenzonitrile, 2-chloro-5-aminobenzonitrile, 2-amino-5-chlorobenzonitrile, 3,5-dichloro-2-aminobenzonitrile, 1-amino-2,4-dicyanobenzene, 1-amino-2,4-dicyano-6-chlorobenzene, 2-chloro-4-amino-5-nitrobenzonitrile, 2-amino-3-chloro-5-nitrobenzonitrile, 2-amino-3-bromo-5-nitrobenzonitrile, 2,6-dicyano-4-nitroaniline, 2,5-dichloro-4-nitroaniline, 2,6-dichloro-4-nitroaniline, 2,6-dibromo-4-nitroaniline, 2-chloro-6-bromo---4-nitroaniline, 2,4-dinitroaniline, 2,4-dinitro-6-chloroaniline, 2,4-dinitro-6-bromoaniline, 2-amino-3,5-dinitrobenzonitrile, 1-amino-4-nitrobenzene-2-methylsulfone, 1-amino-4-nitrobenzene-2-ethylsulfone, 4-methylsulfonylaniline, 1-amino-2-chlorobenzene-4-methylsulfone, 1-amino-2,6-dibromobenzene-4-methylsulfone, 1-amino-2,6-dichlorobenzene-4-methylsulfone, 2-amino-diphenylsulfone, 2-amino-5-nitrobenzoic acid esters, 2-amino-3-chloro-5-nitrobenzoic acid esters, 2-amino-3,5-dichlorobenzoic acid esters, 4-aminoazobenzene, 2,3'-dimethyl-4-aminoazobenzene, 2',3-dimethyl-4-aminoazobenzene, 2,5-dimethyl-4-aminoazobenzene, 3,5-dibromo-4-aminoazobenzene, 3-chloro-4-aminoazobenzene, 2,3-dichloro-4-aminoazobenzene, 2,4-dicyano-3,5-dimethylaniline, 2-trifluoromethylaniline and 2-trifluoromethyl-4-chloroaniline.
Examples of particularly valuable heterocyclic diazo components are 2-amino-4-methylthiazole-5-carboxylic acid ethyl ester, 2-amino-5-phenyl-1,3,4-thiadiazole, 3-phenyl-5-amino-1,2,4-thiadiazole, 3-methylmercapto-5-amino-1,2,4-thiadiazole, 3-.beta.-carbomethoxyethylmercapto-5-amino-1,2,4-thiadiazole, 3-.beta.-carboethoxyethylmercapto-5-amino-1,2,4-thiadiazole, 2-amino-6-cyanobenzthiazole, 2-amino-3-cyano-4-methylthiophene-5-carboxylic acid esters, 3-amino-5-nitro-2,1-benzisothiazole, 3-amino-5-nitro-7-chloro-2,1-benzisothiazole, 3-amino-5-nitro-7-bromo-2,1-benzisothiazole, 4-amino-7-nitro-1,2-benzisothiazole, 4-amino-5-bromo-1,2-benzisothiazole, 4-amino-5-cyano-7-nitro-1,2-benzisothiazole, 4-amino-5-chloro-7-nitro-1,2-benzisothiazole and 4-aminobenzisothiazole.
The dyes of the formula I are eminently suitable for mass-coloring thermoplastics at temperatures of up to about 300.degree.C. This property of azo dyes of the formula I was unforseeable since azo disperse dyes are usually not as stable to heat as this. In particular, it is surprising that it is especially the azo dyes free from nitro groups which prove very stable to heat on incorporation into molten polyamide. Examples of thermoplastics which can be colored with the above dyes are polystyrene, rigid polyvinyl chloride, polyethylene, polyamides, polyesters, polypropylene, polycarbonates, styrene-butadiene, copolymers are acrylonitrile-butadiene-styrene copolymers. The colorations obtained have excellent fastness properties, especially fastness to light, weathering and plasticizers. The fastness to plasticizers can be modified by selection of the radicals A, whilst the fastness to light depends essentially on D and X.
Compared to dyes of similar hue conventionally used for mass coloring thermoplastics, the dyes of the formula I are of outstanding color strength, which may be up to about 3.5 times that of conventional dyes. Accordingly, the amounts required for coloration are low, being of the order of from 0.01 to about 1% by weight, based on the thermoplastic to be colored. Normally, from 0.03 to 0.05% of dye suffices. As a rule, transparent colorations are obtained, since most of the dyes are soluble in the substrate. Opaque colorations can be obtained by adding, eg., about 1% of titanium dioxide.
The coloration of the thermoplastics is carried out by conventional methods as described, eg., in U.S. Pat. 3,006,882 or British Patent 888,996 (which are incorporated herein by reference).
In the Examples which follow, parts and percentages are by weight, unless stated otherwise.





EXAMPLE 1
22.2 parts of 1.3-propylenediamine are added, in portions, to a mixture of 200 parts by volume of N-methylpyrrolidone, 71 parts of triethylamine and 99 parts of 2,6-dichloro-3-cyano-4-methylpyridine at room temperature. The mixture is then stirred for 5 hours at from 45.degree. to 55.degree.C, diluted with 1,500 parts by volume of water and acidified to pH 1.5 - 2 with hydrochloric acid. The precipitate which separates out is filtered off, washed with water and dried. 97 parts of a product of the formula ##SPC20##
which contains small proportions of the products of the formulae ##SPC21##
are obtained. 11.4 parts of this mixture are stirred, without prior purification, with 30 parts by volume of methoxypropyleneamine for 5 hours at 150.degree.C; the resulting melt is then caused to dissolve in water by acidifying with hydrochloric acid. This gives a solution of the coupling component of the formula ##SPC22##
(which still contains small portions of the coupling components of the formulae ##SPC23##
The mixture obtained is cooled to room temperature and added in portions to a solution of 7 parts of 2-aminobenzonitrile which has been diazotized by conventional methods. The coupling mixture is stirred for 15 minutes at pH 1.5 to 0 and is then buffered to pH 2.5 - 3 with sodium acetate at from 0.degree. to 10.degree.C. The product is filtered off, washed with water and dried; 18 parts of a dye powder are obtained, consisting essentially of the compound of the formula ##SPC24##
with a proportion of the dyes of the formulae ##SPC25##
and ##SPC26##
0.5 part of this dye mixture is thoroughly mixed with 1,000 parts of polystyrene granules or powder by conventional methods, and the mixture is then fused. Hereupon, the dye dissolved; it proves stable in the melt at up to 300.degree.C. On solidification, polystyrene having a strong yellow coloration of excellent fastness to light is obtained. The dye proves equally heat-stable when incorporated into fused polyamide, and the mass-colored polyamide is also very fast to light. The dye is also very suitable for the mass coloring of polypropylene, polyethylene, polyvinyl chloride and polyesters.
EXAMPLE 2
78 parts of 1-amino-2-trifluoromethyl-4-chloro-benzene are dissolved in 400 parts of 96% strength sulfuric acid at from 0 to 20.degree.C. The mixture is cooled to from 0.degree. to 4.degree.C, 130 parts of 45% strength nitrosulfuric acid are added and the batch is stirred at from 0.degree. to 5.degree.C for 3 hours. It is then poured onto 1,200 parts of ice, whilst stirring, and the mixture is stirred for a further 30 minutes and then filtered. After destroying excess nitrous acid, 258 parts of the coupling component of the formula ##SPC27##
(dissolved in dimethylformamide) are added to the diazonium salt solution and the pH of the coupling solution is raised to 2 - 3 by adding sodium hydroxide solution at from 0.degree. to 5.degree.C. When the coupling reaction has ended, the dye which has precipitated, of the formula ##SPC28##
is filtered off, washed with water and dried.
1,000 parts of polystyrene are colored with 0.5 part of this dye, analogously to Example 1; a yellow polystyrene of very good fastness to light is obtained.
The dyes characterized by their substituents in the table which follow can also be used, in the above manner, for mass colorating purposes and give the hues shown in the table.
Table 1__________________________________________________________________________ HueExam- of the mass-ple Z R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 coloredNo. polystyrene__________________________________________________________________________3 --CH.sub.2 CH.sub.2 -- H (CH.sub.2).sub.2 OCH.sub.3 C.sub.3 H.sub.7 CN H yellow4 " " (CH.sub.2).sub.3 OCH.sub.3 CH.sub.3 " " "5 " " " " " Cl "6 " " C.sub.2 H.sub.5 " " H "7 " " CH.sub.3 " " " "8 " " (CH.sub.2).sub.3 OCH(CH.sub.3).sub.2 " " " "9 " " (CH.sub.2).sub.2 OCH.sub.3 " " " "10 " " " " " Cl "11 " " " " CF.sub.3 H "12 " " (CH.sub.2).sub.3 OCH.sub.3 CH.sub.3 CF.sub.3 Cl "13 " " C.sub.2 H.sub.5 " CN H "14 " " " " CF.sub.3 H "15 " " " " " Cl "16 --CH.sub.2 CH.sub.2 CH.sub.2 -- " CH.sub.2 CH.sub.2 OH " CN H "17 " " (CH.sub.2).sub.3 OH " " " "18 " " " " CF.sub.3 Cl "19 " " CH.sub.2 CH.sub.2 OCH.sub.3 " " H "20 " " H " " " "21 " " CH.sub.2 CH.sub.2 OCH.sub.3 C.sub.3 H.sub.7 " " "22 " " C.sub.2 H.sub.5 CH.sub.3 COOCH.sub.3 " "23 " " CH.sub.2 CH.sub.2 OCH.sub.3 " " " "24 " " " " " Cl "25 " " " " CN " "26 " " (CH.sub.2).sub.3 OCH(CH.sub.3).sub.2 " CF.sub.3 H "27 " " CH.sub.2 CH.sub.2 OH " " " "28 " " C.sub.2 H.sub.5 " CN Cl "29 " " " C.sub.3 H.sub.7 " " "30 " " " " CF.sub.3 H "31 " " CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.3 " " "32 " " " " CN " "33 " " " " COOCH.sub.3 Cl "34 --(CH.sub.2).sub.3 -- " H CH.sub.3 CN H "35 " " " " CF.sub.3 " "36 " " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " CN " "37 " " " H SO.sub.2 C.sub.6 H.sub.5 " "38 " " CH.sub.2 CH.sub.2 OH CH.sub.3 CN " "39 " " CH.sub.2 CH.sub.2 OCH.sub.3 " " " "40 " " " C.sub.3 H.sub.7 " " "41 " " " CH.sub.3 " Cl "42 " " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " " H "43 " " CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 " " " "44 " " " " " Cl "45 " " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " " H "46 " " CH.sub.2 CH.sub.2 OH " " " "47 " " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " " " " CH.sub.3 .vertline.48 --CH.sub.2 --C--CH.sub.2 -- " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " " " " .vertline. CH.sub.349 " " CH.sub.2 CH.sub.2 OH " " " "__________________________________________________________________________
Exam-ple Z R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5No.__________________________________________________________________________50 --(CH.sub.2).sub.3 -- (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5 H CH.sub.3 CN H yellow51 " (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5 " " " " "52 " (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH " " " " "53 " (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.4 H.sub.9 " " " " "54 " C.sub.6 H.sub.5 " " " " yellow55 " " " " ` Cl orange56 " C.sub.6 H.sub.4 CH.sub.3 " " " H "57 " " " " " yellow CH.sub.3 .vertline.58 " --CH(CH.sub.2).sub.3 C--OH " " " " " .vertline..vertline. CH.sub.3 CH.sub.359 " " " " " "60 " " " " " "61 " CH.sub.2 CH.sub.2 OCH.sub.3 " H SO.sub.2 C.sub.6 H.sub.5 " "62 " " CH.sub.3 CN " "63 " (CH.sub.2).sub. 3 OCHCH.sub.2 OCH.sub.3 " " " " " .vertline. CH.sub.364 " (CH.sub.2).sub.3 OCH.sub.2 CHOC.sub.6 H.sub.5 " " " " " .vertline. CH.sub.3__________________________________________________________________________
Table 2__________________________________________________________________________No. D Z Hue__________________________________________________________________________65 --CH.sub.2 --CH.sub.2 -- yellow66 " --(CH.sub.2).sub.3 -- "67 " --(CH.sub.2).sub.4 -- "68 " --(CH.sub.2).sub.6 -- "69 " --CH.sub.2 --CH-- " .vertline. CH.sub.370 " "71 " "72 "73 " "74 --CH.sub.2 --CH.sub.2 -- red75 " --(CH.sub.2).sub.3 -- "76 " --(CH.sub.2).sub.4 -- "77 " --(CH.sub. 2).sub.6 -- "78 " --(CH.sub.2).sub.8 -- "79 " --CH.sub.2 --CH-- " .vertline. CH.sub.380 red81 " --CH.sub.2 --CH.sub.2 --CH.sub.2 --N--CH.sub.2 --CH.sub.2 --CH.sub.2 -- red .vertline. CH.sub.382 --CH.sub.2 --CH.sub.2 -- orange83 " --(CH.sub. 2).sub.3 -- "84 " --(CH.sub.2).sub.4 -- "85 " --(CH.sub.2).sub.6 -- "86 " --CH.sub.2 --CH-- " .vertline. CH.sub.387 " --(CH.sub.2).sub.3 --N--(CH.sub.2).sub.3 -- " .vertline. CH.sub.388 --CH.sub.2 --CH.sub. 2 -- "89 " --(CH.sub.2).sub.3 -- "90 " --(CH.sub.2).sub.4 -- "91 " --(CH.sub.2).sub.6 -- "92 " --CH.sub.2 --CH-- " .vertline. CH.sub. 393 " --(CH.sub.2).sub.3 --N--(CH.sub.2).sub.3 -- .vertline. CH.sub.394 " "95 --CH.sub.2 --CH.sub.2 -- red96 " --(CH.sub.2).sub.3 -- "97 " --(CH.sub.2).sub.4 -- "98 " --(CH.sub.2).sub.6 -- "99 --(CH.sub.2).sub.8 -- "100 " --CH.sub.2 --CH-- " .vertline. CH.sub.3101 " " bluish102 --(CH.sub.2).sub.3 -- red103 --(CH.sub.2).sub.4 -- "__________________________________________________________________________
Table 3__________________________________________________________________________No. D R.sup.1 Z Hue__________________________________________________________________________104 C.sub.2 H.sub.5 --(CH.sub.2).sub.3 O(CH.sub.2).sub.4 O(CH.sub. 2).sub.5 yellow105 " " "106 " " red C.sub.2 H.sub.5 OC .parallel. O107 " (CH.sub.2).sub.3 OCH.sub.3 --(CH.sub.2).sub.3 -- "108 " " --(CH.sub.2).sub.4 -- "109 " --(CH.sub.2).sub.3 --O(CH.sub.2).sub.4 O(CH.sub.2).sub.3 -- yellowish red110 " C.sub.2 H.sub.5 " "111 " C.sub.3 H.sub.7 (n) --(CH.sub.2).sub.3 -- "112 " C.sub.2 H.sub.5 --(CH.sub.2).sub.3 --N--(CH.sub.2).sub.3 "- .vertline. CH.sub.3113 " " red114 " " --(CH.sub.2).sub.3 O(CH.sub.2).sub.4 O(CH.sub. 2).sub.3 -- "__________________________________________________________________________
Table 4__________________________________________________________________________No. D R Z Hue__________________________________________________________________________ C.sub.3 H.sub.7 (n)115 N.angle. --(CH.sub.2).sub.3 O(CH.sub.2).sub.4 O(CH.sub.2).su b.5 yellow C.sub.3 H.sub.7 (n)116 " --(CH.sub.2).sub.2 -- "117 " " --(CH.sub.2).sub.3 -- "118 " " "119 " " "120 " " "121 " "122 " " red123 " " yellow- ish red124 " " red .parallel. O125 HN--C.sub.2 H.sub.5 " yellow- .vertline. ish red126 NN--H --(CH.sub.2).sub.3 -- red CH.sub.3 OC .parallel. O__________________________________________________________________________
Table 5__________________________________________________________________________No. D R.sup.1 Z X Hue__________________________________________________________________________127 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 --(CH.sub.2).sub.3 -- CN reddish blue128 " " " CONH.sub.2 blue129 " " " H "130 " (CH.sub.2).sub.3 OC.sub.4 H.sub.9 " CN violet131 " " " red CH.sub.3 OC .parallel. O132 " (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5 " " "133 " " " bluish red134 " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " " "135 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 --(CH.sub.2).sub.2 -- CN orange136 " CH.sub.2 CH.sub.2 OCH.sub.3 " " "137 " " --(CH.sub.2).sub.4 -- " yellowish red138 " CH.sub.2 CH.sub.2 OH --(CH.sub.2).sub.3 -- " orange139 " " " H red140 " CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 " CN orange141 --(CH.sub.2).sub.3 -- CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 CN orange142 " " CH.sub.2 CH.sub.2 OCH.sub.3 " "143 " " CH.sub.2 C.sub.2 C.sub. " H.sub.5 "144 " CH.sub.2 CH.sub.2 OCH.sub.3 CONH.sub.2 red145 " " " H "146 " " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " "147 " " " CONH.sub.2 "148 " " " bluish red149 " " " H "150 " " " CONH.sub.2 "151 " " CH.sub.2 C.sub.2 --C.sub.6 H.sub.5 " "152 " CH.sub.2 CH.sub.2 OCH.sub.3 CN yellowish red153 " " CH.sub.2 CH.sub. 2 CH.sub.2 OCH.sub.3 " "154 " " " "155 " " CH.sub.2 CH.sub.2 OCH.sub.3 " "156 " " " red157 " " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " "158 --(CH.sub.2).sub.3 -- CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CN bluish red159 " " CH.sub.2 CH.sub.2 OCH.sub.3 " "160 " " " yellow161 " " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " "162 --(CH.sub.2).sub.4 -- " CN red163 " " " CONH.sub.2 "164 " " " H "165 " --(CH.sub.2).sub.2 -- C.sub.4 H.sub.9 (n) " "166 --(CH.sub.2).sub.4 -- CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CN brown167 " --(CH.sub.2).sub.3 -- H " yellow- brown168 " " " yellow169 " " " orange170 " " " "171 " " CN red172 --(CH.sub.2).sub.3 -- CH.sub.2 CH.sub.2 OCH.sub.3 CN red173 " " " yellowish red174 " " " " H.sub.5 C.sub.2 .vertline.175 " (CH.sub.2).sub.3 OCH.sub.2 CH " red .vertline. (n)H.sub.9 C.sub.4176 " CH.sub.2 CH.sub.2 OCH.sub.3 H orange177 " CH.sub.2 CH.sub.2 OCH.sub.3 CN yellowish red178 " (CH.sub.2).sub.6 OH " "179 " " (CH.sub.2).sub.3 OCH.sub.3 " orange180 --CH.sub.2 CH.sub.2 CH.sub.2 NCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CN yellow .vertline. CH.sub.3181 --(CH.sub.2).sub.3 -- " " yellow- ish red182 " " (CH.sub.2).sub.2 CH.sub.2 OCOCH.sub.3 " yellow183 " (CH.sub.2).sub.6 OH " red C.sub.2 H.sub.5 .vertline. CH.sub.2 CHC.sub.4 H.sub.9 (n)184 " CH.sub.2 CH.sub.2 OCH.sub.3 " orange185 " " " "186 " --(CH.sub.2).sub.3 OCH.sub.3 " reddish yellow187 " " C.sub.6 H.sub.5 " orange188 " (CH.sub.2).sub.3 OCH.sub.3 " reddish yellow189 " " " "__________________________________________________________________________
Table 6__________________________________________________________________________No. D R.sup.1 R.sup.2 Z Hue__________________________________________________________________________190 H H --(CH.sub.2).sub.3 -- orange191 " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " red192 H H " orange193 " CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 " red194 H H " "195 " CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 " "196 (CH.sub.2).sub.3 OCH.sub.3 H " red197 CH.sub.3 O--C " " " violet .parallel. O__________________________________________________________________________
EXAMPLE 198
29.5 parts of 2-aminobenzonitrile are dissolved in 800 parts by volume of water and 80 parts by volume of 30% strength hydrochloric acid at room temperature. 750 parts of ice are then added, followed, at from 0.degree. to 5.degree.C, by 77 parts by volume, added all at once, of a 23% strength sodium nitrite solution. After stirring for two hours at from 0.degree. to 5.degree.C, the following suspension is added to the clear or turbid diazonium salt solution: 66.0 parts of 2,6-bis-(.beta.-methoxyethylamino)-3-cyano-4-methylpyridine are dissolved in 80 parts by volume of warm dimethylformamide, 12.5 parts of an adduct of about 23 moles of ethylene oxide to 1 mole of sperm oil alcohol are then added, and the solution is introduced into a mixture of 30 parts by volume of 30% strength hydrochloric acid and 1,000 parts by volume of water, whilst stirring.
About from 500 to 1,000 parts of ice are added to the coupling solution, followed by about 65 parts of 50% strength sodium hydroxide solution to bring the pH of the mixture to 2.5 - 3.2. After the coupling reaction has terminated, the mixture is warmed to 70.degree.C and the product is filtered off and washed with hot water. After drying, about 97 to 98 parts of a yellow powder of the formula ##SPC29##
are obtained; the powder gives a yellow solution in dimethyl/formamide.
0.5 part of this dye are mixed thoroughly with 1,000 parts of polystyrene granules or powder by conventional processes. The mixture is then fused, which causes the dye to dissolve. The dye is stable in the melt at up to 300.degree.C. After solidification, a deep yellow polystyrene of excellent fastness to light is obtained. The dye shows equal heat stability when incorporated into fused polyamide. The dye is also very suitable for the mass coloring of polypropylene, polyethylene, polyvinyl chloride or polyesters.
EXAMPLE 199
78 parts of 1-amino-2-trifluoromethyl-4-chlorobenzene are dissolved in 400 parts of 96% strength sulfuric acid at from 0 to 20.degree.C. The mixture is cooled to from 0.degree. to 4.degree.C, 130 parts of 45% strength nitrosylsulfuric acid are added and the batch is stirred for 3 hours at from 0.degree. to 5.degree.C. It is then poured onto 1,200 parts of ice, whilst stirring, stirred for a further 30 minutes and filtered. After destroying excess nitrous acid, 117 parts of the coupling component of the formula ##SPC30##are added to the diazonium salt solution and the pH of the coupling solution is brought to from 2 to 3 by adding sodium hydroxide solution at from 0 to 5.degree.C. After the coupling reaction has terminated, the dye of the formula ##SPC31##
which has precipitated is filtered off, washed with water and dried.
On coloring 1,000 parts of polystyrene with 0.5 part of this dye analogously to EXAMPLE 198, a yellow polystyrene of very good fastness to light is obtained.
Table 7__________________________________________________________________________Exam- R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 Hueple of the mass-No. colored polystyrene__________________________________________________________________________200 CH.sub.2 CH.sub.2 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 C.sub.3 H.sub.7 CN H yellow201 " (CH.sub.2).sub.3 OCH.sub.3 CH.sub.3 " " "202 " " " " Cl "203 " C.sub.2 H.sub.5 " " H "204 " CH.sub.3 " " " "205 " (CH.sub.2).sub.3 OCH(CH.sub.3).sub.2 " " " "206 C.sub.2 H.sub.5 (CH.sub.2).sub.2 OCH.sub.3 " " " "207 CH.sub.2 CH.sub.2 OH " " " " "208 " " " CF.sub.3 " "209 CH.sub.2 CH.sub.2 OH (CH.sub.2).sub.3 OCH.sub.3 CH.sub.3 CF.sub.3 Cl "210 C.sub.2 H.sub.5 C.sub.2 H.sub.5 " CN H "211 " " " CF.sub.3 H "212 " " " " Cl "213 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 OH CH.sub.3 CN H "214 " (CH.sub.2).sub.3 OH " " " "215 " " " CF.sub.3 Cl "216 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 " " H "217 C.sub.6 H.sub.5 H " " " "218 " CH.sub.2 CH.sub.2 OCH.sub.3 " " " "219 C.sub.2 H.sub.5 C.sub.2 H.sub.5 " COOCH.sub.3 " "220 " CH.sub.2 CH.sub.2 OCH.sub.3 " " " "221 " " " " Cl "222 C.sub.4 H.sub.9 (n) " " CN " "223 (CH.sub.2).sub.3 OCH(CH.sub.3).sub.2 (CH.sub.2).sub.3 OCH(CH.sub.3).sub.2 " CF.sub.3 H "224 C.sub.6 H.sub.13 (n) CH.sub.2 CH.sub.2 OH " " " "225 H C.sub.2 H.sub.5 " CN Cl "226 " " C.sub.3 H.sub.7 " " "227 " " " CF.sub.3 H "228 " CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.3 " " "229 " " " CN " "230 " " " COOCH.sub.3 Cl "231 CH.sub.2 CH.sub.2 OCH.sub.3 H CH.sub.3 CN H "232 " " " CF.sub.3 H "233 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " CN H "234 " " H SO.sub.2 C.sub.6 H.sub.5 " "235 CH.sub.2 CH.sub.2 --C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 OH CH.sub.3 CN " "236 " CH.sub.2 CH.sub.2 OCH.sub.3 " " " "237 " " C.sub.3 H.sub.7 " " "238 " " CH.sub.3 " Cl "239 " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " " H "240 " CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 " " " "241 " " " " Cl "242 CH.sub.2 CH--O--C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " " H " .vertline. CH.sub.3243 CH.sub.2 CH.sub. 2 CH.sub.2 OC.sub.6 H.sub.5 CH.sub.2 CH.sub.2 OH " " " "244 CH.sub.2 --CH--C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " " " " .vertline.- OH245 (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5 " " " " "246 " CH.sub.2 CH.sub.2 OH " " " "247 (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5 CH.sub.2 --CH--CH.sub.3 CH.sub.3 CN H " .vertline. OH248 (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5 CH.sub.2 CH.sub.2 OH " " " "249 (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH " " " " "250 (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.4 H.sub.9 " " " " "251 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " " " yellow252 " " " " Cl orange253 C.sub.6 H.sub.4 CH.sub.3 " " " H "254 " " " " yellow CH.sub.3 .vertline.255 --CH(CH.sub.2).sub.3 C--OH " " " " " .vertline..vertline. CH.sub.3 CH.sub.3256 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH " " " "257 CH.sub.2 CH.sub.2 OCH.sub.3 " " " "258 CH.sub.2 CH.sub.2 OCH.sub.3 " H S0.sub.2 C.sub.6 H.sub.5 " "259 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.3 CN " "260 (CH.sub.2).sub.3 OCHCH.sub.2 OCH.sub.3 " " " " " .vertline. CH.sub.3261 (CH.sub.2).sub.3 OCH.sub.2 CHOC.sub.6 H.sub.5 CH.sub.2 CH.sub.2 OH " " " " .vertline. CH.sub.3262 (CH.sub.2).sub.6 OH CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.3 CN H "263 (CH.sub.2).sub.5 --CN " " " " "264 CH.sub.2 CH.sub.2 OCH.sub.3 " C.sub.6 H.sub.5 " " "265 " CH.sub.2 CH.sub.2 OCH.sub.3 " CF.sub.3 Cl "266 " " H " " "267 " " C.sub.2 H.sub.5 CN " "268 (CH.sub.2).sub.5 COOCH.sub.3 " CH.sub.3 " H "269 (CH.sub.2).sub.5 COOC.sub.2 H.sub.5 " " " " "270 (CH.sub.2).sub.5 COOC.sub.3 H.sub.7 " " " " "271 (CH.sub.2).sub.5 COOC.sub.4 H.sub.9 " " " " "272 CH.sub.2 CH.sub.2 OCH.sub.3 " " " "273 CH.sub.2 CH=CH.sub.2 " " " " "274 CH.sub.2 CH=CH.sub.2 CH.sub.2 CH=CH.sub.2 " " " "275 CH.sub.2 CH.sub.2 CH.sub.2 OH (CH.sub.2).sub.3 OCH.sub.3 " " " "276 CH.sub.2 CH--C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 OH " " " " .vertline. CH.sub.3277 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 SO.sub.2 CH.sub.3 " " " "278 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 COC.sub.6 H.sub.5 CH.sub.3 CN H yellow279 " SO.sub.2 C.sub.6 H.sub.5 " " " "280 CH.sub.2 CH.sub.2 OCH.sub.3 " " " " "__________________________________________________________________________
Table 8__________________________________________________________________________Exam- R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 Hueple of the mass-No. colored polystyrene__________________________________________________________________________281 H C.sub.2 H.sub.5 H NO.sub.2 H yellow282 " (CH.sub.2).sub.3 OCH.sub.3 " " " "283 " (CH.sub.2).sub.3 OCH(CH.sub.3 ).sub.2 " " " "284 " (CH.sub. 2).sub.3 OCH.sub.3 CH.sub.3 " " orange285 " " OCH.sub.3 " " red-orange286 C.sub.2 H.sub.5 C.sub.2 H.sub.5 " " " scarlet287 " " H " " orange288 " " CN " " yellowish red289 " C.sub.3 H.sub.7 (n) " " " "290 " " " " C1 bluish red291 " C.sub.2 H.sub.5 " " " "292 (CH.sub.2).sub.3 OCH.sub.3 " " " " "293 " " " " " yellowish red294 (CH.sub.2).sub.3 OCH.sub.3 C.sub.2 H.sub.5 Cl NO.sub.2 H yellowish red295 H " " " " orange296 " (CH.sub.2).sub.3 OCH.sub.3 " " " "297 " " NO.sub.2 " " red298 C.sub.2 H.sub.5 " " " " bluish red299 " " CN " Br "300 CH.sub.2 CH.sub.2 OCOCH.sub.3 C.sub.2 H.sub.5 " H H yellow301 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 OCOCH.sub.3 " " " "302 CH.sub.2 CH.sub.2 OC.sub. 6 H.sub.5 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 Cl NO.sub.2 " orange303 " " CN " " Yellowish red304 CH.sub.2 CH.sub.2 CH.sub.2 OC.sub.6 H.sub.5 " " " " scarlet305 " " Cl " " orange306 (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5 " " " " "307 (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5 " CN " " yellowish red308 " " " " Cl bluish red309 " " " " Br "310 " CH.sub.2 CH.sub.2 OH " " " "311 (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 OH Cl NO.sub.2 H orange312 " " CN " " yellowish red313 (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 C.sub.6 H.sub.5 " " " " scarlet314 (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5 " " " " "315 " " Cl " " orange316 " CH.sub.2 CH.sub.2 OCH.sub.3 " " " "317 " " CN " " yellowish red318 " " NO.sub.2 " " red319 " CH.sub.2 CH.sub.2 OH " " " "320 " " Br " " red-orange321 " " COOCH.sub.3 " " "322 " " H " " orange323 " " SO.sub.2 CH.sub.3 " " red324 " " CH.sub.3 " " orange325 " " OCH.sub.3 " " "326 " " SO.sub.2 CH.sub.3 Cl " golden yellow327 " CH.sub.2 CH.sub.2 OCH.sub.3 CN NO.sub.2 NO.sub.2 bluish red328 " " " " CN "329 " " Cl " Cl yellow- brown330 (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5 CH.sub.2 CH.sub.2 OCH.sub.3 H SO.sub.2 CH.sub.3 Cl yellow331 " " Cl " H "332 " " Br NO.sub.2 Br yellow- brown333 " CH.sub.2 CH.sub.2 OH COOCH.sub.3 Cl Cl yellow334 " " Cl SO.sub.2 C.sub.6 H.sub.5 H "335 " " CN CN " orange336 " " Cl Cl Cl yellow337 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " " " "338 " " " SO.sub.2 CH.sub.3 " "339 " " H N=N--C.sub.6 H.sub.5 H orange340 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 " " " "341 " " Cl SO.sub.2 CH.sub.3 " yellow__________________________________________________________________________ proportions
Table 9__________________________________________________________________________Exam- D R.sup.1 R.sup.2 X Hueple of the mass-No. colored polystyrene__________________________________________________________________________342 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CN reddish blue343 " " " CONH.sub.2 blue344 " " " H "345 " (CH.sub.2).sub.3 OC.sub.4 H.sub.9 CH.sub.2 CH.sub.2 OCH.sub.3 CN violet346 " " " red347 " (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub. " " "348 " " " bluish red349 " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " "350 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CN orange351 " CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 " "352 " C.sub.6 H.sub.5 " " yellowish red353 " CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 OH " orange354 " " " H red355 " CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 CN orange356 CH.sub.3 OOCC.sub.2 H.sub.4 S " " " "357 " CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 " "358 " CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 " "359 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 CONH.sub.2 red360 " " " H "361 " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " "362 " " " CONH.sub.2 "363 " " " bluish red364 " " " H "365 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OH CONH.sub.2 bluish red366 " CH.sub.2 CH.sub.2 --C.sub.6 H.sub.5 " " "367 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 CN yellowish red368 " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " scarlet369 " " " "370 " CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 " "371 " " " red372 " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " "373 " " " bluish red374 " CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 " "375 " " " yellow376 " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " "377 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CN red378 " " " CONH.sub.2 "379 " " " H "380 " C.sub.4 H.sub.9 (n) C.sub.4 H.sub.9 (n) " "381 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CN brown382 " H (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OCH.sub.3 " yellow- brown383 H H " yellow384 " " " orange385 " " " "386 " " CN red387 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 CN red388 " " " yellowish red389 " CH.sub.2 CH.sub.2 OH " scarlet H.sub.5 C.sub.2 .vertline.390 (CH.sub.2).sub.3 OCH.sub.2 CH (CH.sub.2).sub.2 O(CH.sub.2).sub.2 "H red .vertline. (n)H.sub.9 C.sub.4391 H H H orange392 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 CN yellowish red393 (CH.sub.2).sub.6 OH (CH.sub.2).sub.6 OH " "394 " (CH.sub.2).sub.3 OCH.sub.3 CH.sub.2 CH.sub. 2 OCCH.sub.3 " orange .parallel. O395 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CHOCOCH.sub.2 OC.sub.6 H.sub.5 CN yellow396 " " " " "397 " (CH.sub.2).sub.2 CH.sub.2 OCOCH.sub.3 (CH.sub.2).sub.2 CH.sub.2 OCOCH.sub.3 " "398 (CH.sub.2).sub.6 OH (CH.sub.2).sub.6 OH " red C.sub.2 H.sub.5 .vertline. CH.sub.2 CHC.sub.4 H.sub.9 (n)399 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 " orange400 " " " "401 --(CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 " reddish yellow402 " C.sub.6 H.sub.5 " " orange403 (CH.sub.2).sub.3 OCH.sub.3 " " reddish yellow404 " " " "__________________________________________________________________________
Table 10__________________________________________________________________________Exam- D R.sup.1 R.sup.2 Hueple of the mass-No. colored polystyrene__________________________________________________________________________405 H H orange406 " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 red407 H H orange408 " CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 red409 H H "410 " CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 "__________________________________________________________________________
Table 11__________________________________________________________________________Exam-ple D R.sup.1 R.sup.2 R.sup.3 HueNo.__________________________________________________________________________411 H O.sub.4 H.sub.9 (n) CH.sub.3 red412 " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " "413 " C.sub.6 H.sub.13 (n) " "414 " CH.sub.2 CH--C.sub.4 H.sub.9 (n) " " .vertline. C.sub.2 H.sub.5415 " " "416 " " "417 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " "418 " " C.sub.3 H.sub.7 (r) "419 C.sub.4 H.sub.9 (n) C.sub.4 H.sub.9 (n) CH.sub.3 "420 C.sub.6 H.sub.13 (n) C.sub.6 H.sub.13 (n) " "414 " " " "415 C.sub.4 H.sub.9 (n) C.sub.4 H.sub.9 (n) " "416 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " "417 H " " "418 H C.sub.4 H.sub.9 (n) CH.sub.3 red419 H " C.sub.3 H.sub.7 (n) "420 H C.sub.6 H.sub.13 (n) CH.sub.3 "421 H C.sub.4 H.sub.9 (n) CH.sub.3 " H.sub.3 COC .parallel. O422 H CH.sub.2 --CH--C.sub.4 H.sub.9 (n) " " .vertline. C.sub.2 H.sub.5423 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OH.sub.3 " ruby424 " " C.sub.2 H.sub. "425 " C.sub.4 H.sub.9 (n) CH.sub.3 "426 C.sub.4 H.sub.9 (n) " " "427 C.sub.6 H.sub.13 (n) C.sub.6 H.sub.13 (n) " "428 H --CH.sub.2 --CH.sub.2 --CH.sub.2 --OCH.sub.3 CH.sub.3 red429 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " CH.sub.3 ruby430 C.sub.4 H.sub.9 (n) C.sub.4 H.sub.9 (n) " "431 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 " "432 " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " "433 H H " red434 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 CH.sub.3 ruby C.sub.2 H.sub.5 --CO .parallel. O435 CH.sub.2 CH.sub. 2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 " "436 C.sub.4 H.sub.9 (n) C.sub.4 H.sub.9 (n) " " C.sub.17 H.sub.35 (n)437 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 " " C.sub.2 H.sub.5 OC .parallel. O438 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " "439 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 " yellow440 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 " yellow441 " " C.sub.3 H.sub.7 (n) "442 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.3 "443 H " " yellow444 C.sub.4 H.sub.9 (n) C.sub.4 H.sub.9 (n) " golden yellow445 CH.sub.2 CH.sub.2 CH.sub. 2 OCH.sub.3 C.sub.6 H.sub.5 " orange446 C.sub.4 H.sub.9 (n) C.sub.4 H.sub.9 (n) " red- orange447 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " "448 " " yellowish red__________________________________________________________________________
EXAMPLE 449
29.5 parts of 2-aminobenzonitrile are dissolved in 800 parts by volume of water and 80 parts by volume of 30% strength hydrochloric acid at room temperature. 750 parts of ice are then added, followed, at from 0.degree. to 5.degree.C, by 77 parts by volume, added all at once, of a 23% strength sodium nitrite solution. After stirring for 2 hours at from 0.degree. to 5.degree.C, the following suspension is added to the clear or turbid diazonium salt solution: 65.5 parts of 2-N,N-diethylamino-3-cyano-4-methyl-6-methoxyethylaminopyridine are dissolved in 80 parts by volume of warm dimethylformamide, 12.5 parts of an addition product of about 23 moles of ethylene oxide to 1 mole of sperm oil alcohol and then added, and the solution is introduced into a mixture of 30 parts by volume of 30% strength hydrochloric acid and 1,000 parts by volume of water, whilst stirring.
About from 500 to 1,000 parts of ice are added to the coupling solution, followed by about 65 parts of 50% strength sodium hydroxide solution to bring the pH of the mixture to from 2.5 to 3.2. After the coupling reaction has terminated, the mixture is warmed to 60.degree.C and the product is filtered off and washed with hot water. After drying, about 97 to 98 parts of a yellow powder of the formula ##SPC32##
are obtained; the powder gives a yellow solution in dimethyl/formamide.
0.5 part of this dye are mixed thoroughly with 1,000 parts of polystyrene granules or powder by conventional processes. The mixture is then fused, which causes the dye to dissolve. The dye is stable in the melt at up to 300.degree.C. After solidification, a deep yellow polystyrene of excellent fastness to light is obtained. The dye shows equal heat stability when incorporated into fused polyamide. The mass colored polyamide is also very fast to light. The dye is also very suitable for the mass coloring of polypropylene, polyethylene, polyvinyl chloride and polyesters.
EXAMPLE 450
78 parts of 1-amino-2-trifluoromethyl-4-chlorobenzene are dissolved in 400 parts of 96% strength sulfuric acid at from 0.degree. to 20.degree.C. The mixture is cooled to from 0.degree. to 4.degree.C, 130 parts of 45% strength nitrosylsulfuric acid are added and the batch is stirred for 3 hours at from 0.degree. to 5.degree.C. The mixture is then poured onto 1,200 parts of ice, whilst stirring, stirred for a further 30 minutes and filtered. After destroying excess nitrous acid, 123 parts of the coupling component of the formula ##SPC33##
are added to the diazonium salt solution and the pH of the coupling solution is brought to from 2 to 3 by adding sodium hydroxide solution at from 0.degree. to 5.degree.C. After the coupling reaction has terminated, the dye of the formula ##SPC34##
which has precipitated is filtered off, washed with water and dried.
On coloring, 1,000 parts of polystyrene with 0.5 part of this dye analogously to Example 449, a yellow polystyrene of very good fastness to light is obtained.
The dyes characterized, in the table which follows, by their substituents, can also be used for mass coloration in the above manner, giving the hues shown in the table.
Table 12__________________________________________________________________________Exam- R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 Hueple of the mass-No. colored polystyrene__________________________________________________________________________451 N(C.sub.2 H.sub.5).sub.2 (CH.sub.2).sub.2 OCH.sub.3 C.sub.3 H.sub.7 CN H yellow452 " (CH.sub.2).sub.3 OCH.sub.3 CH.sub.3 " " "453 " " " " Cl "454 " C.sub.2 H.sub.5 " " H "455 " CH.sub.3 " " " "456 " (CH.sub.2).sub.3 OCH(CH.sub.3).sub.2 " " " "457 N(CH.sub.3).sub.2 (CH.sub.2).sub.2 OCH.sub.3 " " " "458 N(C.sub.3 H.sub.7).sub.2 " " " " "459 " " " CF.sub.3 " "460 " (CH.sub.2).sub.3 OCH.sub.3 CH.sub.3 CF.sub.3 Cl "461 N(CH.sub.3).sub.2 C.sub.2 H.sub.5 " CN H "462 " " CF.sub.3 H "463 " " " Cl "464 N(CH.sub.3).sub.2 CH.sub.2 CH.sub.2 OH " CN H "465 " (CH.sub.2).sub.3 OH " " " "466 " " " CF.sub.3 Cl "467 N(C.sub.2 H.sub.5).sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " " H "468 N--C.sub.6 H.sub.5 H " " " " .vertline. C.sub.2 H.sub.5469 " CH.sub.2 CH.sub.2 OCH.sub.3 " " " "470 N(CH.sub.3).sub.2 C.sub.2 H.sub.5 " COOCH.sub.3 " "471 " CH.sub.2 CH.sub.2 OCH.sub.3 " " " "472 " " " " Cl " CH.sub.2 OH473 N.angle. " " CN " " C.sub.2 H.sub.5474 N(CH.sub.3).sub.2 (CH.sub.2).sub.3 OCH(CH.sub.3).sub.2 " CF.sub.3 H "475 N(C.sub.4 H.sub.9).sub.2 CH.sub.2 CH.sub.2 OH " " " " C.sub.6 H.sub.5476 N.angle. C.sub.2 H.sub.5 " CN Cl " CH.sub.2 CH.sub.2 OH477 " " C.sub.3 H.sub.7 " " "478 " " " CF.sub.3 H "479 " CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.3 " " "480 " " " CN " "481 " " " COOCH.sub.3 Cl "482 N(CH.sub.2 CH.sub.2 OCH.sub.3).sub.2 H " CN H "483 " " " CF.sub. 3 H "484 " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " CN H "485 " " H SO.sub.2 C.sub.6 H.sub.5 " "486 " CH.sub.2 CH.sub.2 OH CH.sub.3 CN " "487 " CH.sub.2 CH.sub.2 OCH.sub.3 " " " " CH.sub.2 CH.sub.3488 N.angle. " C.sub.3 H.sub.7 " " " C.sub.4 H.sub.9 (n)489 N[CH(CH.sub.3).sub.2 ].sub.2 " CH.sub.3 " Cl "490 " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " " H "491 " CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 " " " " C.sub.2 H.sub.5492 N.angle. " " " Cl " C.sub.4 H.sub.9 (n)493 " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.2 " " H "494 " CH.sub.2 CH.sub.2 OH " " " "495 N CH.sub.2 CH(CH.sub.3).sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " " " " CH.sub.2 CH.sub.2 CH.sub.3 N.angle.496 CH--CH.sub.2 CH.sub.2 " " " " " .vertline. CH.sub.3497 " CH.sub.2 CH.sub.2 OH " " " "498 N(C.sub.2 H.sub.5).sub.2 (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5 " " " "499 " (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5 " " " "500 " (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH " " " "501 " (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.4 H.sub.9 " " " "502 " C.sub.6 H.sub.5 " " " "503 " C.sub.6 H.sub.4 OCH.sub.3 (m) " " Cl orange504 " C.sub.6 H.sub.4 CH.sub.3 " " H "505 " " " " yellow CH.sub.3 .vertline.506 " --CH(CH.sub.2).sub.3 C--OH " " " " .vertline..vertline. CH.sub.3 CH.sub.3507 " " " " "508 " " " " "509 " CH.sub.2 CH.sub.2 OCH.sub.3 H SO.sub.2 C.sub.6 H.sub.5 " "510 " CH.sub.3 CN " "511 " (CH.sub.2).sub.3 OCHCH.sub.2 OCH.sub.3 " " " " .vertline. CH.sub.3512 " (CH.sub.2).sub.3 OCH.sub.2 CHOC.sub.6 H.sub.5 " " " " .vertline. CH.sub.3513 " (CH.sub.2).sub.6 OH " " " "514 " (CH.sub.2).sub.5 --CN " " " "515 " CH.sub.2 CH.sub.2 OCH.sub.3 C.sub.6 H.sub.5 " " "516 " " " CF.sub.3 Cl "517 " " H " " "518 " " C.sub.2 H.sub.5 CN " "519 " (CH.sub.2).sub.5 COOCH.sub.3 CH.sub.3 " H "520 " (CH.sub.2).sub.5 COOC.sub.2 H.sub.5 " " " "521 " (CH.sub.2).sub.5 COOC.sub.3 H.sub.7 " " " "522 " (CH.sub.2).sub.5 COOC.sub.4 H.sub.9 " " " "523 " CH.sub.2 CH.sub.2-- " " " "524 " CH.sub.2 CH=CH.sub.2 " " " "525 N(CH.sub.3).sub.2 CH.sub.2 CH=CH.sub.2 " " " "526 N(C.sub.2 H.sub.5).sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OH " " " "527 " CH.sub.2 CH--C.sub.6 H.sub.5 " " " " .vertline. CH.sub.3528 N(CHCH.sub.2 CH.sub.3).sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " " " " .vertline. CH.sub.3529 N(C.sub.2 H.sub.5).sub.2 COC.sub.6 H.sub.5 CH.sub.3 CN H "530 " SO.sub.2 C.sub.6 H.sub.5 " " " "531 N(C.sub.3 H.sub.7).sub.2 " " " " "__________________________________________________________________________
Table 13__________________________________________________________________________Exam- R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 Hueple of the mass-No. colored polystyrene__________________________________________________________________________532 N(C.sub.2 H.sub.5).sub.2 C.sub.2 H.sub.5 H NO.sub.2 H yellow533 " (CH.sub.2).sub.3 OCH.sub.3 " " " "534 " (CH.sub.2).sub.3 OCH(CH.sub.3).sub.2 " " " "535 " (CH.sub.2).sub.3 OCH.sub.3 CH.sub.3 " " orange536 " " OCH.sub.3 " " red- orange537 " C.sub.2 H.sub.5 " " " yellowish red538 " " H " " orange539 " " CN " " yellowish red540 " C.sub.3 H.sub.7 (n) " " " scarlet541 " " " " Cl bluish red542 " C.sub.2 H.sub.5 " " " "543 N(C.sub.3 H.sub.7).sub.2 " " " " "544 N(C.sub.4 H.sub.9).sub.2 " " " " yellowish red545 N(C.sub.2 H.sub.5).sub.2 " Cl " H "546 N(C.sub.3 H.sub.7).sub.2 " " " " orange547 " (CH.sub.2).sub.3 OCH.sub.3 " " " "548 " " NO.sub.2 " " red549 N(C.sub.3 H.sub.5).sub.2 " " " " bluish red550 " " CN " Br "551 N(CH.sub.2 CH.sub.2 OCCH.sub.3).sub.2 C.sub.2 H.sub.5 " H H yellow .parallel. O552 " CH.sub.2 CH.sub.2 OCOCH.sub.3 " " " "553 N(C.sub.2 H.sub.5).sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 Cl NO.sub.2 " orange554 " " CN " " yellowish red555 N(C.sub.4 H.sub.9).sub.2 " " " " scarlet556 " " Cl " " orange557 " " Br " " "558 " " CN " " yellowish red559 " " " " Cl bluish red560 " " " " Br "561 " CH.sub.2 CH.sub.2 OH " " " "562 N(C.sub.2 H.sub.5).sub.2 (CH.sub.2).sub.3 OC.sub.2 H.sub.5 Cl " H orange563 " " CN " " yellowish red564 N(CH.sub.2 CH.sub.2 OCH.sub.3).sub.2 " " " " "565 N(CH.sub.3).sub.2 " " " " "566 N(C.sub.3 H.sub.7).sub.2 " Cl " " orange567 " (CH.sub.2).sub.2 OC.sub.2 H.sub.5 " " " "568 " " CN " " yellowish red569 " " NO.sub.2 " " red570 N(C.sub.2 H.sub.5).sub.2 " " " " "571 " " Br " " red-orange572 " " COOCH.sub.3 " " "573 " " H " " orange574 " " SO.sub.2 CH.sub.3 " " red575 " " CH.sub.3 " " orange576 " " OCH.sub.3 " " "577 " " SO.sub.2 CH.sub.3 Cl " yellow578 " " CN NO.sub.2 NO.sub.2 bluish red579 " " " " CN "580 " " Cl " Cl yellow- brown581 " CH.sub.2 CH.sub.2 OCH.sub.3 H SO.sub.2 CH.sub.3 " yellow582 " " Cl " H "583 " " Br NO.sub.2 Br yellow- brown584 " CH.sub.2 CH.sub.2 OH COOCH.sub.3 Cl Cl yellow585 " " Cl SO.sub.2 C.sub.6 H.sub.5 H "586 " " CN CN " orange587 " " Cl Cl Cl yellow588 N(C.sub.3 H.sub.7).sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " " " "589 " " " SO.sub.2 CH.sub.3 " "590 " " H N=N--C.sub.6 H.sub.5 H orange591 " CH.sub.2 CH.sub.2 OCH.sub.3 " " " "592 N(C.sub.2 H.sub.5).sub.2 " Cl SO.sub.2 CH.sub.3 " yellow__________________________________________________________________________
Table 14__________________________________________________________________________Exam- D R.sup.1 R.sup.2 X Hue ofple the mass-No. colored polystyrene__________________________________________________________________________593 N(C.sub.2 H.sub.5).sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CN reddish blue594 " " " CONH.sub.2 blue595 " " " H "596 " " CH.sub.2 CH.sub.2 OCH.sub.3 CN violet597 " " red CH.sub.3 OC .parallel. O598 " N(C.sub.3 H.sub.7).sub.2 " " "599 " " " bluish red600 " N(C.sub.2 H.sub.5).sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " "601 " " " orange602 " " CH.sub.2 CH.sub.2 OCH.sub.3 " "603 " N(C.sub.3 H.sub.7).sub.2 " " yellowish red604 " " CH.sub.2 CH.sub.2 OH " orange605 " " " H red606 " " CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 CN orange CH.sub.3 OOCC.sub.2 H.sub.4 S607 " " " "608 " " CH.sub.2 CH.sub.2 OCH.sub.3 " "609 " " CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 " "610 " CH.sub.2 CH.sub.2 OCH.sub.3 CONH.sub.2 red611 " " " H "612 " N(C.sub.2 H.sub.5).sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " "613 " " " CONH.sub.2 "614 " " " bluish red615 " " " H "616 " CH.sub.2 CH.sub.2 OH CONH.sub.2 "617 " N(CH.sub.3).sub.2 " " " 618 N(C.sub.2 H.sub.5).sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CN yellowish red scarlet619 " " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 "620 " " " "621 " " CH.sub.2 CH.sub.2 OCH.sub.3 " "622 " " " red623 " " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " "624 " " " bluish red625 " " CH.sub.2 CH.sub.2 OCH.sub.3 " "626 " " " yellow627 " " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " "628 " " " red629 " " " CONH.sub.2 "630 " " " H "631 " " C.sub.4 H.sub.9 (n) " "632 " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CN brown633 " " (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OCH.sub.3 " yellow- brown634 " H " yellow635 " " " orange636 " " " "637 " " " red638 " CH.sub.2 CH.sub.2 OCH.sub.3 " "639 " " " yellowish red640 " CH.sub.2 CH.sub.2 OH " scarlet641 (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH " red642 " H H orange643 " CH.sub.2 CH.sub.2 OCH.sub.3 CN yellowish red644 " (CH.sub.2).sub.6 OH " scarlet645 " " CH.sub.2 CH.sub.2 OCCH.sub.3 " orange .parallel. O646 CH.sub.2 CHOCOCH.sub.2 OC.sub.6 H.sub.5 " yellow647 " NO " " "648 " " (CH.sub.2).sub.2 CH.sub.2 OCOCH.sub.3 " "649 (CH.sub.2).sub.6 OH " red C.sub.2 H.sub.5 .vertline. CH.sub.2 CHC.sub.4 H.sub.9650 NO CH.sub.2 CH.sub.2 OCH.sub.3 " orange651 " " " "652 (CH.sub.2).sub.3 OCH.sub.3 " reddish yellow653 " " " orange654 " " " reddish yellow655 " " " "__________________________________________________________________________
Table 15__________________________________________________________________________ Hue ofExam- the mass-ple coloredNo. D R.sup.1 R.sup.2 polystyrene__________________________________________________________________________656 H orange657 " " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 red658 " H orange659 " NN--H CH.sub.2 CH.sub.2 OCH.sub.3 red660 N(C.sub.2 H.sub.5).sub.2 H "661 " " CH.sub.2 CH.sub.2 OCH.sub.3 "662 " " "__________________________________________________________________________
Table 16__________________________________________________________________________Exam-pleNo. D R.sup.1 R.sup.2 Hue__________________________________________________________________________ C.sub.2 H.sub.5663 CH.sub.2 CH.sub.2 OCH.sub.3 N.angle. ruby C.sub.2 H.sub.5664 " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " "665 " C.sub.4 H.sub.9 (n) " "666 " H " red667 " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 ruby668 " N(C.sub.2 H.sub.5).sub.2 "669 " " N(CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3).su b.2 "670 " CH.sub.2 CH.sub.2 OCH.sub.3 N(CH.sub.2 CH.sub.2 OCH.sub.3).sub.2 "671 " C.sub.4 H.sub.9 (n) N(C.sub.4 H.sub.9 (n)).sub.2 "672 " N(C.sub.2 H.sub.5).sub.2 red673 " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 " "674 " CH.sub.2 CH.sub.2 OCH.sub.3 " "675 " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 N(CH.sub.2 CH.sub.2 OCH.sub.3).sub.2 "676 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 N(C.sub.2 H.sub.5).sub.2 red677 " C.sub.4 H.sub.9 (n) " "678 C.sub.4 H.sub.9 (n) red- orange__________________________________________________________________________
Claims
  • 1. A thermoplastic resinous material which has been colored by mixing with a dye and distributing the dye homogeneously in the melt, said dye having the formula ##SPC35##
  • wherein
  • A.sup.1 is A or ##SPC36##
  • D.sup.1 is thienyl substituted by cyano, C.sub.1 - to C.sub.3 -alkyl, C.sub.17 H.sub.35, phenyl or C.sub.1 - to C.sub.8 -alkoxycarbonyl;
  • R.sup.1 is hydrogen or alkyl of 1 to 3 carbon atoms;
  • X is hydrogen, carbamoyl or cyano;
  • A is hydrogen; C.sub.1 to C.sub.8 -alkyl; C.sub.2 - to C.sub.8 -alkyl substituted by hydroxy, OCHO, OCOCH.sub.3, OCOC.sub.2 H.sub.5, OCOC.sub.3 H.sub.7, C.sub.2 - to C.sub.4 -hydroxyalkoxy, cyano, C.sub.1 - to C.sub.8 -alkoxy, C.sub.1 - to C.sub.8 -alkoxycarbonyl, phenoxy or phenyl; cyclohexyl; methylcyclohexyl; norbornyl; phenyl; .beta.-hydroxy-.beta.-phenylethyl; or (CH.sub.2).sub.3 (OC.sub.2 H.sub.4).sub.m OT;
  • m is 1 or 2;
  • T is C.sub.1 - to C.sub.4 -alkyl, benzyl or phenyl; ##EQU19## is pyrrolidino, piperidino, morpholino, hexamethyleneimino piperazino, N-methylpiperazino or N-.beta.-hydroxyethylpiperazino and
  • Z is C.sub.2 - to C.sub.8 -alkylene, --, --, ).sub. ##EQU20## --(CH.sub.2).sub.3 --N--(CH.sub.2).sub.3, --(CH.sub.2).sub.3 --OC.sub.2 H.sub.4 --O--(CH.sub.2).sub.3, --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 O (CH.sub.2) .sub.3 --, ##SPC37##
  • 2. A thermoplastic resinous material according to claim 1 containing as the dye a compound of the formula in claim 1, wherein X is cyano and R.sup.1 is methyl.
  • 3. A thermoplastic resinous material according to claim 1 containing as the dye a compound of the formula in claim 1, wherein
  • A is hydrogen, C.sub.1 - to C.sub.8 -alkyl, C.sub.1 - to C.sub.8 -alkoxy, substituted C.sub.2 - or C.sub.3 -alkyl, phenoxyethyl, phenoxypropyl, cyclohexyl, methylcyclohexyl, norbornyl, phenyl-C.sub.1 - to C.sub.4 -alkyl or phenyl and
  • A.sup.1 is A.
  • 4. A thermoplastic resinous material according to claim 1 containing as the dye a compound of the formula in claim 1, wherein Z is C.sub.2 - to C.sub.6 -alkylene, ##EQU21## ##SPC38##
  • 5. Thermoplastic resinous material according to claim 1 containing the dye of the formula ##SPC39##
  • 6. A thermoplastic resinous material according to claim 1 colored with 0.01 to 1% of the dye according to the formula in claim 1.
  • 7. A thermoplastic resinous material according to claim 1 wherein said material is polystyrene, a polyamide, polyethylene, polypropylene, a polyester, a polycarbonate or polyvinyl chloride.
Priority Claims (3)
Number Date Country Kind
2409754 Mar 1974 DT
2437203 Aug 1974 DT
2438130 Aug 1974 DT
US Referenced Citations (4)
Number Name Date Kind
3507951 Morecroft et al. Apr 1970
3640674 Berrie et al. Feb 1972
3725383 Austin et al. Apr 1973
3817975 Berrie et al. Jun 1974
Non-Patent Literature Citations (1)
Entry
Modern Plastics Encyclopedia, for 1963 (vol. 40, No. 1A), Sept. 1962, p. 496.