Process for the mass coloration of thermoplastics with anthraquinonylaminotraizines

Abstract

A process for the mass coloration of thermoplastics with anthraquinonylaminotriazines of the formula ##STR1## wherein each of X.sub.1 and X.sub.2 is an alkylmercapto or arylmercapto group or a group of the formula --NR.sub.1 R.sub.2, in which each of R.sub.1 and R.sub.2 is alkyl, cycloalkyl, aralkyl or aryl, and R.sub.2 can additionally be hydrogen, or R.sub.1 and R.sub.2 together with the nitrogen atom to which they are attached and optionally a further heteroatom form a 5- or 6-membered ring, one Y is a hydrogen or chlorine atom, a hydroxy, arylmercapto, alkanoylamino or aroylamino group, or a group of the formula ##STR2## and the other Ys are hydrogen atoms, Hal is a chlorine or bromine atom, and n is 0 or 1. Yellow to orange colored fibres of clear shade, good color strength and fastness properties are obtained.

Description

The present invention relates to a process for the mass colouration of thermoplastics with anthraquinonylaminotriazines of the formula ##STR3## wherein each of X.sub.1 and X.sub.2 is an alkylmercapto or arylmercapto group or a group of the formula --NR.sub.1 R.sub.2, in which each of R.sub.1 and R.sub.2 is alkyl, cycloalkyl, aralkyl or aryl, and R.sub.2 can additionally be hydrogen, or R.sub.1 and R.sub.2 together with the nitrogen atom to which they are attached and optionally a further heteroatom form a 5- or 6-membered ring, one Y is a hydrogen or chlorine atom, a hydroxy, arylmercapto, alkanoylamino or aroylamino group, or a group of the formula ##STR4## and the other Ys are hydrogen atoms, Hal is a chlorine or bromine atom, and n is 0 or 1.

Alkylmercapto groups represented by X.sub.1 and X.sub.2 in formula (1) are preferably those containing 1 to 6 carbon atoms. Suitable arylmercapto groups are e.g. naphthylmercapto groups and, in particular, phenylmercapto groups which are unsubstituted or substituted by chlorine atoms or alkyl or alkoxy groups, each of 1 to 6 carbon atoms. Where X.sub.1 and X.sub.2 are groups of the formula --NR.sub.1 R.sub.2, the preferred meanings of R.sub.1 and R.sub.2 are alkyl groups of 1 to 20 carbon atoms, alkoxyalkyl groups, cycloalkyl groups of 5 to 10 carbon atoms, benzyl or phenylethyl groups, or phenyl groups which are unsubstituted or substituted by chlorine atoms or alkyl or alkoxy groups, each of 1 to 6 carbon atoms, while R.sub.2 can additionally be hydrogen.

The two radicals R.sub.1 and R.sub.2 together with the nitrogen atom to which they are attached can also form e.g. a piperidine or morpholine ring.

An arylmercapto group Y is preferably a phenylmercapto group which can be substituted by chlorine atoms or alkyl or alkoxy groups, each of 1 to 6 carbon atoms. Y can also be an alkanoylamino group of 2 to 6 carbon atoms or a benzoylamino group which is unsubstituted or substituted by chlorine atoms or alkyl or alkoxy atoms of 1 to 6 carbon atoms, but is in particular a hydrogen atom or a OH group. n is preferably 0.

The anthraquinonylaminotriazine compounds to be used in accordance with the invention are known compounds. They are advantageously obtained by condensation of a chlorotriazine of the formula ##STR5## with the corresponding aminoanthraquinone, for example 1-aminoanthraquinone, 1-aminoanthraquinone-3-, -4-, -5-, -6- or -7-chloroanthraquinone, 1-aminoanthraquinone-4-hydroxyanthraquinone, 1-aminoanthraquinone-4-, -5- or -8-phenylmercaptoanthraquinone, 1-aminoanthraquinone-4- or -5-acetylaminoanthraquinone, 1-aminoanthraquinone-4- or -5-benzoylaminoanthraquinone.

The triazines of the formula (2) are obtained by the stepwise replacement of two chlorine atoms in cyanuric chloride by the amines or mercaptans X.sub.1 H and X.sub.2 H.

The following amines are cited as examples: methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, n-hexylamine, n-octylamine, n-decylamine, n-dodecylamine, n-hexadecylamine, or n-octadecylamine, dimethylamine, diethylamine, di-n-propylamine or di-n-butylamine, .beta.-methoxyethylamine, .gamma.-methoxy-n-propylamine or .gamma.-isopropoxy-n-propylamine, cyclohexylamine, dicyclohexylamine, benzylamine, phenylethylamine, aniline, o-, m- or p-toluidine, N-methylaniline, N-ethylaniline or N-n-butylaniline, 1-aminonaphthalene, piperidine or morpholine.

Table I lists a number of anthraquinonylaminotriazines of the formula ##STR6## wherein A is the 1-anthraquinonyl radical, m is 1, and the meanings of X.sub.1 and X.sub.2 are indicated in columns II and III.

TABLE I______________________________________No. X.sub.1 X.sub.2______________________________________1 .beta.-methoxyethylamino .beta.-methoxyethylamino2 .gamma.-methoxypropylamino .gamma.-methoxypropylamino3 .gamma.-isopropoxypropylamino .gamma.-isopropoxypropylamino4 benzylamino benzylamino5 phenylethylamino phenylethylamino6 n-hexadecylamino n-hexadecylamino7 n-octadecylamino n-octadecylamino8 methylamino ethylamino9 methylamino n-butylamino10 methylamino n-hexadecylamino11 ethylamino n-octadecylamino12 methylamino dimethylamino13 methylamino diethylamino14 methylamino di-n-propylamino15 methylamino di-n-butylamino16 ethylamino dimethylamino17 methylamino anilino18 ethylamino anilino19 isopropylamino anilino20 n-butylamino anilino21 n-hexadecylamino anilino22 n-octadecylamino anilino23 methylamino N-methyl-anilino24 ethylamino N-methyl-anilino25 dimethylamino diethylamino26 dimethylamino diisopropylamino27 dimethylamino di-n-butylamino28 dimethylamino N-methyl-anilino29 di-isopropylamino N-methyl-anilino30 di-n-butylamino N-methyl-anilino31 anilino N-methyl-anilino32 N-methyl-anilino N-ethyl-anilino34 ethylmercapto methylmercapto35 ethylmercapto n-propylmercapto36 ethylmercapto n-butylmercapto37 ethylmercapto n-hexadecylmercapto38 ethylmercapto n-octadecylmercapto39 methylmercapto phenylmercapto40 ethylmercapto phenylmercapto41 anilino phenylmercapto42 N-methylanilino phenylmercapto43 N-ethylanilino phenylmercapto44 methylamino methylmercapto45 methylamino ethylmercapto46 methylamino n-propylmercapto47 methylamino n-butylmercapto48 methylamino n-hexadecylmercapto49 methylamino n-octadecylmercapto50 ethylamino methylmercapto51 diethylamino methylmercapto52 dimethylamino methylmercapto53 dimethylamino ethylmercapto54 diethylamino ethylmercapto55 di-n-butylamino ethylmercapto56 dimethyamino n-propylmercapto57 anilino methylmercapto58 anilino ethylmercapto59 anilino n-propylmercapto60 anilino n-butylmercapto61 anilino n-hexadecylmercapto62 anilino n-octadecylmercapto63 N-methylanilino methylmercapto64 N-ethylanilino methylmercapto______________________________________

Table II lists further anthraquinonylaminotriazines of the formula (3), wherein m is 2, A is the anthraquinone radical which is bonded to the triazinylamino groups in the positions indicated in column II, and X.sub.1 and X.sub.2 have the meanings given in columns III and IV.

TABLE II______________________________________ Posi-No. tion X.sub.1 X.sub.2______________________________________65 1,4 .beta.-methoxyethylamino .beta.-methoxyethylamino66 1,5 .beta.-methoxyethylamino .beta.-methoxyethylamino67 1,4 .gamma.-methoxypropylamino .gamma.-methoxypropylamino68 1,5 .gamma.-methoxypropylamino .gamma.-methoxypropylamino69 1,4 .gamma.-isopropoxypropyl- .gamma.-isopropxypropylamino amino70 1,5 .gamma.-isopropoxypropyl- .gamma.-isopropxypropylamino amino71 1,4 benzylamino benzylamino72 1,5 benzylamino benzylamino73 1,4 n-hexadecylamino n-hexadecylamino74 1,5 n-hexadecylamino n-hexadecylamino75 1,4 methylamino methylamino76 1,5 methylamino methylamino77 1,4 butylamino butylamino78 1,5 butylamino butylamino79 1,4 dimethylamino dimethylamino80 1,5 dimethylamino dimethylamino81 1,4 morpholyl morpholyl82 1,5 morpholyl morpholyl83 1,4 anilino anilino84 1,5 anilino anilino85 1,4 phenylmercapto phenylmercapto86 1,5 phenylmercapto phenylmercapto87 1,4 n-butylmercapto n-butylmercapto88 1,5 n-butylmercapto n-butylmercapto89 1,4 n-hexadecylmercapto n-hexadecylmercapto90 1,5 n-hexadecylmercapto n-octadecylmercapto91 1,4 n-octadecylmercapto n-octadecylmercapto92 1,5 n-octadecylmercapto n-octadecylmercapto93 1,4 methylamino anilino94 1,5 methylamino anilino95 1,4 methylamino N-methylanilino96 1,5 methylamino N-methylanilino97 1,4 dimethylamino anilino98 1,5 dimethylamino anilino99 1,4 methylmercapto anilino100 1,5 methylmercapto anilino101 1,4 methylmercapto N-methylanilino102 1,5 methylmercapto N-methylanilino103 1,4 n-butylmercapto anilino104 1,5 n-butylmercapto anilino105 1,4 n-octadecylmercapto anilino106 1,5 n-octadecylmercapto anilino107 1,4 methylmercapto phenylmercapto108 1,5 methylmercapto phenylmercapto109 1,4 n-butylmercapto phenylmercapto110 1,5 n-butylmercapto phenylmercapto111 1,4 methylmercapto n-hexadecylmercapto112 1,5 methylmercapto n-hexadecylmercapto113 1,4 methylamino dimethylamino114 1,5 methylamino dimethylamino115 1,4 methylmercapto morpholinyl116 1,5 methylmercapto morpholinyl117 1,4 n-hexadecylamino anilino118 1,5 n-hexadecylamino anilino119 1,4 isopropylamino anilino120 1,5 isopropylamino anilino121 1,4 anilino N-methylanilino122 1,5 anilino N-methylanilino123 1,4 methylamino methylmercapto124 1,5 methylamino methylmercapto125 1,4 dimethylamino methylamino126 1,5 dimetylamino methylamino127 1,4 dimethylamino methylmercapto128 1,5 dimethylamino methylmercapto129 1,5 ethylamino butylamino______________________________________

Table III lists compounds of the formula ##STR7## wherein X.sub.1 and X.sub.2 have the meanings given in columns II and III and Y is as defined in column IV. Column V indicates the position of Y.

TABLE III______________________________________No. X.sub.1 X.sub.2 Y Position______________________________________130 ethylamino butylamino hydroxy 4131 cyclohexyl- cyclohexyl- hydroxy 4 amino amino132 dimethyl- dimethyl- 2,4-bisanilino- 4 amino amino triazinyl-6- amino133 N-methyl- phenylamino 2,4-bisethyl- 4 anilino aminotriazinyl- 6-amino134 N-methyl- phenylamino 2,4-bisethyl- 5 anilino aminotriazinyl- 6-amino135 N-methyl- phenylamino 2,4-bisphenyl- 4 anilino mercapto-tria- zinyl-6-amino______________________________________

It is also possible to use mixtures of different dyes.

Examples of thermoplastics are polyolefins, such as polyethylene, polypropylene or polyisobutylene, also polyvinyl chloride, polystyrene, as well as copolymers of styrene, such as ABS, and especially linear polyesters.

Suitable linear polyesters are in particular those which are obtained by polycondensation of terephthalic acid or an ester thereof with a glycol of the formula HO--(CH.sub.2).sub.n --OH, in which n is an integer from 2 to 10, or with 1,4-di(hydroxymethyl)cyclohexane, or by polycondensation of a glycol ether of a hydroxybenzoic acid, for example p-(.beta.-hydroxyethoxy)-benzoic acid. The term "linear polyesters" also comprises copolyesters which are obtained by partial replacement of terephthalic acid by another dicarboxylic acid or by a hydroxycarboxylic acid and/or by partial replacement of the glycol by another diol. However the preferred linear polyester are polyethylene terephthalates.

Colouration is effected by the conventional methods, for example by mixing the colourants with the plastics material in granulate or particulate form and extruding the mixture to fibres, sheets or granules. These latter can then be moulded to objects by injection moulding.

The colouration obtained, especially in polyester, are distinguished by good fastness to light, washing, dry cleaning, cross-dyeing, thermofixation, bleeding and chlorite bleaching, as well as by clear shades and good colour strength.

Russian Pat. No. 192.993 and German Auslegeschrift No. 1 644 532 describe anthraquinone dyes which in the 4-position contain an arylamino group. In contradistinction thereto, the colourants employed in the present invention colour polyester in shades of distinctly better fastness to light and resistance to atmospheric influences.

The invention is illustrated by the following Examples, in which parts and percentages are by weight.

EXAMPLE 1

A non-delustred polyethylene terephthalate granulate suitable for fibre manufacture is shaken in a closed vessel for 15 minutes on a mechanical shaker together with 1% of 1-(2',4'-bis-N-methyl-N-phenylamino-1',3',5'-triazinyl-6')-aminoanthraquinone. The uniformly coloured granules are then spun in a melt spinning machine (285.degree. C..+-.3.degree. C., sojourn time in the spinning machine about 5 minutes) to filaments, which are stretched and wound on a draw twister. The solubility of the colourant in polyethylene terephthalate results in a strong yellow colouration which is distinguished by outstanding light-fastness, excellent fastness to washing, dry cleaning, cross-dyeing, sublimation and rubbing after thermofixation, and also by excellent resistance to chlorite bleaching and good viscosity values.

EXAMPLE 2

1000 parts of polyethylene terephthalate granules, 10 parts of titanium oxide (Kronos RN 40) and 1 part of finely divided 1-(2',4'-bis-N-methyl-N-phenylamino-1',3',5'-triazinyl-6')-amino-4-hydroxyanthraquinone are mixed in a closed vessel for 2 hours on a roller gear table. The coloured granules are extruded at about 260.degree. C. to strands of 2 mm, which are re-granulated. The resultant granules are processed at 270.degree.-280.degree. C. in a screw injection moulding machine to mouldings. The red coloration obtained is of very good light-fastness.

EXAMPLES 3-42

Table IV lists further colourants of the formula (3) which were used for colouring polyethylene terephthalate by the methods described in Examples 1 and 2. A is the anthraquinonyl radical. The meanings of X.sub.1, X.sub.2 and m are indicated in columns II, III and IV respectively. The position of the triazinylamino group in the anthraquinone radical is indicated in column V.

TABLE IV______________________________________Exam- Posi-ple X.sub.1 X.sub.2 m tion Colour______________________________________3 methylamino methylamino 1 1 yellow4 methylamino methylamino 2 1,5 yellowish orange5 ethylamino ethylamino 1 1 yellow6 ethylamino ethylamino 2 1,5 yellowish orange7 n-butylamino n-butylamino 1 1 yellow8 dimethylamino dimethylamino 1 1 yellow9 diethylamino diethylamino 1 1 yellow10 diisopropyl- diisopropyl- 1 1 yellow amino amino11 di-n-butyl- di-n-butyl 1 1 yellow amino amino12 piperidyl piperidyl 1 1 yellow13 morpholyl morpholyl 1 1 yellow14 anilino anilino 1 1 yellow15 N-methylani- N-methylani- 1 1 yellow lino lino16 N-methylani- N-methylani- 2 1,4 violet lino lino17 N-methylani- N-methylani- 2 1,5 reddish lino lino yellow18 diphenylamino diphenylamino 1 1 yellow19 phenylmercapto phenylmercapto 1 1 yellow20 methoxypropio- methoxypropio- 1 1 yellow nylamino nylamino21 isopropoxy- isopropoxy- 1 1 yellow propylamino propylamino22 methoxyethyl- methoxyethyl- 1 1 yellow amino amino23 amino amino 1 1 yellow24 benzylamino benzylamino 1 yellow25 phenylethyl- phenylethyl- 1 1 yellow amino amino26 diisopropyl- diisopropyl- 2 1,5 orange amino amino27 diisopropyl- phenylmercapto 1 1 yellow amino28 diisopropyl- p-toluidino 1 1 yellow amino29 dimethylamino methylmer- 1 1 yellow capto30 methylmer- methylmer- 1 1 yellow capto capto31 methylmer- butyl-2-mer- 1 1 yellow capto capto32 methylmer- methylmer- 2 1,5 reddish capto capto yellow33 N-methyl- N-methyl- 2 1,8 reddish anilino anilino yellow34 methylmercapto anilino 1 1 yellow35 methylmercapto phenylmercapto 1 1 greenish yellow36 methylmercapto o-phenetidino 1 1 greenish yellow37 methylmercapto p-phenetidino 1 1 yellow38 methylmercapto 4-chlorophenyl- 1 1 yellow mercapto39 methylmercapto 2,5-dichlor- 1 1 yellow phenyl40 methylmercapto 4-methylphenyl 1 1 yellow41 phenylmercapto morpholino 1 1 yellow42 phenylmercapto cyclohexyl-1- 1 1 yellow amino______________________________________

EXAMPLES 43-82

Table IV lists further colourants of the formula (4) which were used to colour polyethylene terephthalate by the methods described in Examples 1 and 2. A is the anthraquinonyl radical. The meanings of X.sub.1, X.sub.2 and Y are given in columns II, III and IV respectively. Column V indicates the position of Y in the anthraquinonyl radical and column VI the shade of the coloured polyester fibres.

TABLE V______________________________________Ex- Po-am- si-ple X.sub.1 X.sub.2 Y tion Colour______________________________________43 ethylamino ethylamino hydroxy 4 red44 ethylamino ethylamino benzoyl- 5 reddish amino yellow45 anilino anilino hydroxy 4 red46 N-methyl- N-methyl- hydroxy 4 red anilino anilino47 N-methyl- N-methyl- benzoyl- 5 reddish anilino anilino amino yellow48 N-methyl- N-methyl- benzoyl- 5 reddish anilino anilino amino yellow49 N-methyl- N-methyl- phenylmer- 4 red anilino anilino capto50 N-methyl- N-methyl- phenylmer- 5 yellow anilino anilino capto51 butylamino butylamino benzoyl- 4 red amino52 cyclohexyl- cyclohexyl- benzoyl- 4 claret amino amino amino53 diethyl- diethyl- benzoyl- 4 red amino amino amino54 diisopro- diisopro- hydroxy 4 red pylamino pylamino55 methylmer- methylmer- 4-chlorben- 4 red capto capto zoylamino56 methylmer- butyl-2- 4-chlorben- 4 red capto mercapto zoylamino57 methylmer- dimethyl- phenylmer- 5 yellow capto amino capto58 methylamino methylamino phenylmer- 5 brown- capto ish yellow59 N-methyl- N-methyl- phenylmer- 5 yellow anilino anilino mercapto60 N-methyl- N-methyl- 4-chlorphe- 5 yellow anilino anilino nylmercapto61 N-methyl- N-methyl- phenylmer- 8 yellow anilino anilino capto62 methylmer- anilino chlorine 3 green- capto ish yellow63 methylmer- 2-chlor- chlorine 3 green- capto anilino ish yellow64 methylmer- 3-chlor- chlorine 3 green- capto anilino ish yellow65 methylmer- anilino chlorine 4 yellow capto66 methylmer- o-anisidino chlorine 4 yellow capto67 methylmer- p-anisidino chlorine 4 yellow capto68 methylmer- anilino chlorine 6 yellow capto69 methylmer- o-toluidino chlorine 5 yellow capto70 p-toluidino p-toluidino chlorine 5 yellow71 methylmer- anilino chlorine 6(7) yellow capto72 methylmer- p-chlorani- chlorine 6(7) yellow capto lino73 methylmer- m-toluidino chlorine 6(7) yellow capto74 dimethyl- dimethyl- 2-chloro- 4 red amino amino benzoyl- amino75 dimethyl- dimethyl- 3-chloro- 4 claret amino amino benzoyl- amino76 dimethyl- dimethyl- 2-fluoro- 4 claret amino amino benzoyl- amino77 dimethyl- dimethyl- acetyl- 4 claret amino amino amino78 methylmer- phenylmer- hydroxy 4 red capto capto79 methylmer- phenylmer- benzoyl- 4 red capto capto amino80 methylmer- phenylmer- benzoyl- 5 yellow capto capto amino81 phenylmer- cyclohe- hydroxy 4 red capto xylamino82 phenylmer- morpholino hydroxy 4 red capto______________________________________

Claims

1. A process for the mass coloration of a thermoplastic in the melt in which the coloration is effected by

incorporating in said thermoplastic in the melt an effective amount of an anthraquinonylaminotriazine of the formula (1) ##STR8## wherein each of X.sub.1 and X.sub.2 is an alkylmercapto or arylmercapto group or a group of the formula --NR.sub.1 R.sub.2, in which each of R.sub.1 and R.sub.2 is alkyl, cycloalkyl, aralkyl or aryl, and R.sub.2 can additionally be hydrogen, or R.sub.1 and R.sub.2 together with the nitrogen atom to which they are attached form a 5- or 6-membered ring or are morpholino, one Y is a hydrogen or chlorine atom, a hydroxy, arylmercapto, alkanoylamino or aroylamino group, or a group of the formula ##STR9## and the other Ys are hydrogen atoms, Hal is a chlorine or bromine atom, and n is 0 or 1.

2. A process according to claim 1, where in the compound of the formula (1), each of X.sub.1 and X.sub.2 is a group of the formula --NR.sub.1 R.sub.2, in which R.sub.1 and R.sub.2 are alkyl groups of 1 to 20 carbon atoms, alkoxyalkyl groups, cycloalkyl groups of 5 to 6 carbon atoms, benzyl or phenylethyl groups or phenyl groups which are unsubstituted or substituted by chlorine atoms, alkyl or alkoxy groups, each of 1 to 6 carbon atoms, and R.sub.2 can additionally be hydrogen.

3. A process according to claim 1, where in the compound of the formula (1), X.sub.1 is an alkylmercapto group of 1 to 6 carbon atoms or a group of the formula --NR.sub.1 R.sub.2, in which R.sub.1 and R.sub.2 are as defined in claim 2 and X.sub.2 is an alkylmercapto group of 1 to 6 carbon atoms.

4. A process according to claim 1, where the compound of the formula (1) is ##STR10##

5. A process according to claim 1, where the compound of the formula (1) is ##STR11##

6. A process according to claim 1, where the compound of the formula (1) is ##STR12##

7. A process according to claim 1, where the compound of the formula (1) is ##STR13##

8. A process according to claim 1, where the compound of the formula (1) is ##STR14##

9. A thermoplastic mass colored by the process according to claim 1.

10. A linear polyester mass colored by the process according to claim 1.