CA1126266A

CA1126266A - Disperse anthraquinone dyes

Info

Publication number: CA1126266A
Application number: CA321,505A
Authority: CA
Inventors: Urs Karlen
Original assignee: Individual
Current assignee: BASF Schweiz AG
Priority date: 1978-02-16
Filing date: 1979-02-14
Publication date: 1982-06-22
Also published as: CH642092A5; GB2015557B; JPS54120638A; DE2905653A1; FR2417528A1; CH642094A5; GB2015557A; DE2905653C3; JPS5833895B2; BR7900958A; CH642093A5; FR2417528B1; CH642091A5; DE2905653B2

Abstract

Abstract of the Disclosure There are described novel disperse anthraquinone dyes of the formula I

Description

11~6~66 Case 1-11596/E
DISPERSE ANTHRA~UINONE DYES
The invention relates to novel disperse anthraquinone dyes of the formula I

~., ,.~ ,!~ ,., 1I ll I N-(CH2)m-X (CH2)n (I) il i i1 in whicn X is oxygen or sulfur, m is an integer from 3 to 10 inclusive, n is an integer from 1 to 3 inclusive, and R is an aryl or aryloxy group which is unsubstituted or is substituted by nonionic substituents, or R is a heterocyclic radical which is unsubstituted or is substituted by nonionic substituents, and which is optionally bound by way of an oxygen atom to the -(CH2)n group.
, The number m is preferably 4 or 5, and particularly 3; and the number n is preferably 1 or 2. X is preferably an oxygen atom.
Suitable R groups are the phenyl, phenoxy, naphthyl . and naphthoxy groups, as well as heterocyclic radicals, for example the furyl, thiophene, pyrrole or pyridine radical, and also the corresponding hydrogenated hetero-~k ~ . , .

- 1~26~6 cyclic radicals, and these heterocyclic radicals can be optionally bound by way of an oxygen atom to the -~CH2)n group. All these R groups can be substituted by nonionic substituents, for example by halogen such as chlorine, bromine or fluorine; by lower alkyl such as methyl, ethyl, propyl, isopropyl and butyl, or by lower alkoxy such as methoxy, ethoxy or butoxy.
The CH2 group between the symbols X and R can be further substituted by an alkyl group having 1 to 3 ~ carbon atoms, so that iso-alkyl groups having a maximum 4 of 6 carbon atoms are formed.
In preferred dyes of the formula I, R is an unsubstituted or substituted phenyl or phenoxy group, with suitable substituents being in particular chlorine, methyl or methoxy.
The novel anthraquinone dyes can be produced by methods which are in general known, for example by reacting 1,4-diaminoanthraquinone-2,3-dicarboxylic acid imide with a primary amine of the formula II
H2N~(CH2)m~x-(cH2)n (II) in which X, m, n and R have the meanings defined above.
The compounds of the formula II are known and can be produced by known methods, for example by reaction of the corresponding alcohols or thioalcohols with lower alkylene nitriles, and subsequent hydrogenation of the condensation product. The reaction is performed at S0 to 250C, preferably at 80 to 180C, in an inert solvent, such as nitrobenzene, diethylene glycol monomethyl ether, toluene, xylene, Tetralin, and so forth, or in an excess of the ~ respective amine itself.
;, ,:, , ....
,;, .

The following are to be mentioned as specific examples of amines of the formula II:
3-(2'-phenoxy)-ethoxypropylamine, 3-(furyl-2)-methoxypropylamine, 3-(tetrahydrofuryl-2)-metho~ypropylamine, 3-(3'-phenyl)-propyloxypropylamine, 3-(phenyl)-methoxypropylamine, 3-(2'-pyridyl-3-oxy)-ethoxypropylamine, 3-(p-chlorophenyl)-methoxypropylamine, 3-(p-methoxyphenyl)-methoxypropylamine, 3-(2'-pyridyl-2)-ethoxypropylamine, 3-(pyridyl-4)-methoxypropylamine, 3-(thienyl-2)-methoxypropylamine, ~- 3-(tetrahydrothienyl-2)-methoxypropylamine, :~ 4-(2'-phenoxy)-ethoxybutylamine, 4-(3'-phenyl)-propyloxybutylamine, 4-(p-chlorophenyl)-methoxybutylamine, 4-(p-methoxyphenyl)-methoxybutylamine, 5-(phenyl)-methoxypentylamine, 3-(phenyl)-methylthiopropylamine, and 4-(2'-phenyl)-ethylthiobutylamine.
The processing of the novel anthraquinone dyes of the formula I into dye preparations is carried out in a manner generally known, for example by grinding in the presence of dispersing agents and/or fillers. The preparations, ; optionally dried in vacuo, can be used, after the addition of a greater or lesser amount of water, for dyeing, padding or printing in a so-called long or short liquor.
: From an aqueous suspension, the dyes have excellent affinity for textile material made from fully-synthetic or semi-synthetic, hydrophobic, high-molecular organic substances. The dyes are particularly suitable for dyeing and printing textile material made from cellulose-2 1/2-.. . .

; ~
, ~

acetate, cellulose triacetate or synthetic polyamides, and particularly textile materials made from aromatic polyesters, for example those made from terephthalic acid and ethylene glycol or 1,4-dimethylolcyclohexane, and fibres made from copolymers formed from terephthalic acid and isophthalic acid and ethylene glycol.
- For dyeing from aqueous liquors, the dyes are advantageously used in a finely dispersed form, dyeing being performed in the presence of dispersing or wetting agents, or in the presence of a combination of various wetting agents and dispersing agents.
In order to obtain intense dyeings on polyethylene terephthalate fibres from an aqueous dye liquor, it is appropriate to add a carrier to the dye liquor, or to perform the dyeing process under pressure at a temperature above 100C. Suitable carriers are for example benzene-dicarboxylate, o-phenylphenol, chlorobenæene or alkyl naphthalene.
When the dye is applied by padding or printing, the polyester fabric, advantageously after drying, is heated, for example in steam or in warm air, to temperatures above c 100C, for example to temperatures between 180 and 210C.
The dyeings obtained according to the invention can be subjected to an aftertreatment, for example by heating in an aqueous solution of a nonionic detergent.
r Cellulose-2 1/2-acetate fibres are dyed preferably at temperatures of 80-85C, whereas cellulose triacetate fibres are dyed advantageously at the boiling point of the dye liquor. The use of carriers or swelling agents is superfluous when dyeing cellulose-2 1/2 acetate or polyamide fibres.
Of particular interest with regard to dye yield are . .
. , .

11262~

mixtures of dyes, which contain at least one dye of the formula I given in the foregoing. Suitable mixtures of this kind are for example:
a) a mixture of at least two dyes of the above formula I;
b) a mixture of at least one dye of the above formula I
and at least one other 1,4-diaminoanthraquinone-2,3-dicarboxylic acid imide dye which is not embraced by the above formula I, for example a dye of the formula Il 1 11 .\ ~.\ /N tCH2)3-OCH3 il i -c) a mixture of at least one dye according to the above formula I and at least one azo dye, for example an azo dye of the formula 02N~ N N ~ /alkyl (Cl-C4) \ / alkyl (Cl-C
CN NHCO-alkyl Cl-C4 wherein X is halogen, particularly Br, or CN or NO2, of which the proportion in the mixture is preferably at most 15%, relative to the mixture, in order to preserve the shade of the anthraquinone dye; and d) a mixture of at least one dye of the above formula I
and at least one other 1,4-diaminoanthraquinone-2,3-dicarboxylic acid imide dye which is not embraced by the above formula I, and at least one azo dye according to c) in the given amounts.
The preferred mixture is that according to b).

, ~

~ 6~ 6 The mixtures contain the dye of the formula I
preferably in amounts of 45 to 90 % by weight, and the 1,4-diaminoanthraquinone-2,3-dicarboxylic acid imide dye, which is not embraced by the formula I, preferably in amounts of lO to 65 % by weight, relative to the mixture.
The dyes according to the invention are distinguished by their brilliance, and they yield on synthetic textile material brilliant blue dyeings having very good general fastness properties. To be emphasised are the resistance to heat hardening, the fastness to thermofixing, pleating, exhaust gases, cross-dyeing, dry-cleaning and chlorine, and also the good fastness to wetting, for example to water, sea water, washing and perspiration, above all however their good fastness to sublimation and to light.
Furthermore, these dyes are distinguished by good sub-stantivity and build-up properties on the stated material.
The dyes have good affinity for the fibres and a good exhaustion property. The dyeings are fast to lubricants, ozone, flue gases, rubbing and solvents, and the resist of wool and cotton and the resistance to high temperature are good. The dischargeability and the pH stability are good.
Since variations in the pH value during dyeing cannot be avoided, the novel dyes are more applicable and less dependent on the dyeing conditions than are the known dyes.
It is also possible to use the novel water-insoluble anthraquinone dyes for dope dyeing (dyeing in the melt) of polyamides, polyesters and polyolefines. The polymers intended for dyeing are advantageousLy dyed in the form of powders, granules or flakes, or as they come out of the spinning solution; or they are mixed in the melted state with the dye, which is introduced in the dry condition or in the form of a dispersion or in the form of a solution in a solvent which can be volatile. After the dye has been 1'1 2~ 6 , homogeneously dispersed in the solution or melt of the polymer, the mixture can be processed in a known manner, by casting, moulding or extrusion, into the form of fibres, yarns, monofilaments, films, and the like.
In the German Patent Specification No. 945,112, there are described dyes which differ from the dyes according to the invention by the fact that the former carry on the imide nitrogen atom a group of the formula -(CH2)p-0-Rl, in which Rl is an alkyl or alkoxyalkyl group having not more than 4 carbon atoms, and p is an integer from 1 to 4 inclusive. Compared with these known dyes, the dyes according to the invention are surprisingly dis-tinguished by improved fastness to sublimation with equally good, or in some cases better, substantivity and build-up properties. Relative to the molecular weight of the dyes used, the dye yield in the case of the dyes according to the invention is moreover unexpectedly improved.
The invention is illustrated by the following Examples without being limited to them. The temperature values are given in degrees Centigrade; and except where otherwise stated, 'parts' and 'percentages' relate to the weight.

;
~- ~
.-, . ~., 1~ 26;~66 ExamPle 1 59 parts of moist 1,4-diaminoanthraquinone-2,3-dicarboxylic acid imide and 39 parts of 3-(2'-phenoxy)-ethoxypropylamine are introduced into 120 parts of nitrobenzene. The temperature is raised to 100, and 27 parts of water are distilled off. After the tempera-ture has reached 120, the mixture is stirred for one further hour, and is subsequently allowed to cool to room temperature, in the course of which the dye, 1,4-diaminoanthraquinone-N-(3'-l2'`-phenoxy]-ethoxypropyl)-

2,3-dicarboxylic acid imide, of the formula I~ ,D~ CH2CH2CH2ocH2cH2~

precipitates in the form of beautiful crystals. These are filtered off and then washed with 60 parts of nitro-benzene and 150 parts of methanol to thus obtain 38.9 parts of the dye of the said formula.
When this dye is applied as a disperse dye to polyester fibres by the customary dyeing processes, brilliant blue dyeings having very good fastness properties are obtained.
Examples 2 - 23 If the procedure is carried out analogously to that described in Example 1 except that, instead of the

3-(2'-phenoxy)-ethoxypropylamine given therein, there are used equivalent amounts of those amines listed in Table 1, column 2, there are obtained the disperse dyes of the formula , , ' .
, ' ~ .

6;~66 ~0\ /11~

il i i1 in which R' has the meaning given in column 3. From an aqueous suspension, these dyes yield on polyester fabric likewise brilliant blue dyeings having similarly good fastness properties.

LZ6~

_ , Table 1 Ex. No. Amine .

2 H2N- (CH2) 3-o-CH24~ ( 2) 3 CH2 3 H2N- (CH2) 3--CH2~ - (CH2) 3-0-CH2~

4 H2N- (CH2) 3-- (CH2) 3~ - (CH2) 3-0- (C~2)3-e3 H2N- (CH2) 3-o-CH2~9 _ (CH2) 3-o-CH2~3 6 H2N- (CH2) 3--CH2~C ~ (CH2) 3--CH2~Cl 7 H2N- (CH2) 3-0-CH2g~0CH3 - (CH2) 3-0-CH2~g'~.'H3 8 H2N- (CH2) 3-- (CH2) 2~ _ (CH2) 3-0- (CH2)2~;9 9 H2N- (CH2) 3-0 CH2~N _ (CH2) 3-0-CH2~N

H2N- (CH2) 3-o-CH24~ (CH2) 3 CH2 11 H2N- (CH2) 3-o-CH24~ (C 2) 3 CH2~

12 H2N- (CH2)4~~ (CH2) 2 ~3 _ (cH2)4-O- (CH2) 2 ~3 13 H2N- (CH2) 4-- (~H2) 3~ _ (CH2) 4-- (CH2) 3~

1~6'Z66 Table 1 (continuation) Ex............ Amine :
. . _ _ . . . ~
14 2N (CH2 ) 4--CH2~ Cl - (CH2 ) 4_o-cH2~cl H2N- (CH2 ) -0-CH ~OCH - (CH2 ) 4_o-CH2~3CH3 16 H2N- (CH2 ) 5 CH2~ (CH2 ) 5 0 C 2~3 17 H2N- (C~2) 3 S CH2~3 _ (CH2) 3 S CH2~

18 H2N- (CH2 ) 4-S tCH2 ) 2-e3 . - (CH2 ) 4-S- (CH2 ) 2~3 19 H2N- ~CH2 ) 3-0 (CH2 ) 2,o~3 Cl _ (CH2 ) 3-0- (CH2 ) 2 , -e3 Cl 2 2 4 ( 2)2 ~ -(C~2)4-0-(C32)2-0 21 H2N- (CH2 ) 3-0-CH CH2 ~ _ (CH2 ) 3-0-CH-CH2 ~

2 2 C 2 H 5 ~C 1 C 2 H 5 ~:1 2 3 H2N- (CH2 ) 3-0-CH2-C~ H-0~ - (CH2 ) 3-0-CH2-CI H-0 Example 24 A mixture of 1.5 parts of the dye described in Example 1 and 1 part of the dye of the formula llZ6266 ~., ,!1, ,!~ ,!1, !~ ,., ,i1, ~ i, N- (CH2 ) 3--CH3 il i i1 dyes, from an aqueous dispersion, polyester fabric in brilliant blue shades having good fastness properties, and exhibits better substantivity than that exhibited by the two individual dyes.

Example 25 .

The build-up and the strength on polyester materials can be greatly improved with a mixture of the following anthraquinone and azo dyes O NH2 o -(CH2)30(CH2)2o--~ ~- and ~CN

02N~ N=N~ N (C H ) The gain in strength between the two dyes is shown in the following table.

_ ,~

.:

` ~ ~Z S26 Table . _ Anthra- Azo Calculated Required.Gain in %
quinone dye amount of amount of of calculated dye . dye for dye for value (in parts) (in parts) ~reference 1/1 RT in %
type strength` ~

100 0 1.5 1.5 0 97.5 2.5 1.29 1.0 22.5 1.13 0.8 29.2 .90 10 0.91 0.6 34.0 0.57 0.35 38.6 0.35 0.22 37.1 0 100 0.2 0.2 0 Example 26 If the mixture of Example 24 is mixed with the azo dye of Example 25, the build-up and the strength on polyester materials can likewise be improved:
...
Anthra- Azo dye Calculated Required Gain in quinone (in parts) amount of amount of % of mixture . dye for dye for calculatec (in parts) . 1/1 RT 1/1 RT value 100 0 1.2 1.2 0 97.5 2.5 1.07 0.8 25.2 o.s6 o.6433.3 0.8 0.4840.0 0-53 0.2847.2 0.34 0.1750.0 0 100 0.2 0.2 0 . ': . ..

6;~6~

Example 27 A mixture of equal parts of the dyes described in Examples 1 and 4 dyes, from an aqueous dispersion, polyester fabrics in brilliant blue shades having good fastness properties, and exhibits better substantivity than that of the two individual dyes.
Example 28 2 parts of the dye obtained according to Example 1 are suspended in 4000 parts of water. To this dispersion are added as swelling agent 12 parts of the sodium salt of o-phenylphenol and also 12 parts of diammonium phosphate, and 100 parts of polyethylene glycol terephthalate yarn are dyed for 1 1/2 hours at 95 to 98. The dyeing is rinsed, and aftertreated with aqueous sodium hydroxide solution and a dispersing agent. A brilliant blue dyeing having fastness to washing, light and sublimation is obtained.
A brilliant blue dyeing having very good fastness to washing and to sublimation is obtained by replacing in the above Example the 100 parts of polyethylene glycol terephthalate yarn by 100 parts of cellulose triacetate, dyeing under the conditions described, and subsequently rinsing with water.
hxample 29 In a pressure dyeing apparatus, 2 parts of the dye obtained according to Example 7 are finely suspended in 2000 parts of water containing 4 parts of oleyl polyglycol ether. The pH value of the dye bath is adjusted to 4 to 5 with acetic acid. 100 parts of polyethylene glycol terephthalate yarn are introduced at 50; the bath is heated within 30 minutes to 140, and dyeing is performed for S0 minutes at this temperature. The dyeing is subsequently rinsed with water, soaped and dried. There is obtained under these conditions a brilliant blue dyeing having fastness to washing, perspiration, light and sublimation.
The dyes described in the other Examples yield by this process dyeings equal in quality.
Example 30 Polyethylene glycol terephthalate fabric is impregnated on a padding machine at 40 with a liquor of the following composition:
parts of the dye mixture according to Example 24 finely dispersed in parts of sodium alginate, parts of triethanolamine, parts of octyl phenol polyglycol ether, and 930 parts of water.
The fabric, squeezed out to about 100%, is dried at 100, and subsequently fixed for 30 seconds at a tempera-ture of 210. The dyed material is rinsed with water, soaped and dried. There is obtained under these con-ditions a brilliant blue dyeing having fastness to washing, rubbing, light and sublimation.
The dyes described in the other Examples yield by this process dyeings which are equal in quality.

Claims

WHAT IS CLAIMED IS:

1. A disperse anthraquinone dye of the formula I

(I) in which X is oxygen or sulfur, m is an integer from 3 to 10 inclusive, n is an integer from 1 to 3 inclusive, and R is an aryl or aryloxy group which is unsubstituted or is substituted by nonionic substituents, or R is a heterocyclic radical which is unsubstituted or is substituted by nonionic substituents, and which is optionally bound by way of an oxygen atom to the -(CH2)n- group-

2. An anthraquinone dye according to Claim 1, wherein m is 3, 4 or 5.

3. An anthraquinone dye according to Claim 1, wherein m is 3.

4. An anthraquinone dye according to Claim 1, wherein the CH2 group between the symbols X and R is further sub-stituted by an alkyl group having 1 to 3 carbon atoms to form an iso-alkyl group.

5. An anthraquinone dye according to Claim l, wherein n is 1 or 2.

6. An-anthraquinone dye according to Claim 1, wherein X is oxygen.

7. An anthraquinone dye according to claim 1, wherein R is an unsubstituted phenyl or phenoxy group, or a phenyl or phenoxy group substituted by halogen, lower alkyl or lower alkoxy each with up to 4 carbon atoms.

8. An anthraquinone dye according to claim 1, wherein R is an unsubstituted phenyl group, or a phenyl group substituted by Cl, CH3 or OCH3.

9. An anthraquinone dye according to claim 1, wherein R is an unsubstituted phenoxy group.

10. A mixture of dyes which contains at least one dye of the formula I given in claim 1.

11. A mixture of at least one dye of the formula I given in claim 1 and at least one other 1,4-diaminoanthraquinone-2,3-dicarboxylic acid imide dye which is not embraced by the formula I
given in claim 1.

12. A mixture of at least one dye of the formula I given in claim 1 and a dye of the formula

13. A mixture of at least two dyes of the formula I given in claim 1.

14. A mixture of at least one dye of the formula I given in claim 1 and at least one azo dye of the formula in which X is halogen, the proportion of which in the mixture is at most 15 per cent by weight, relative to the mixture.

15. A mixture according to claim 14 wherein the azo dye is of the formula given in claim 14 in which X is Br2CN or NO2.

16. A mixture of dyes which comprises at least one dye of the formula I given in claim 1, and at least one other 1,4-diamino-anthraquinone-2,3-dicarboxylic acid imide dye which is not embraced by the formula I, and at least one azo dye according to claim 14 in amounts of at most 15 per cent by weight, relative to the mixture.

17. A process for producing anthraquinone dyes of the formula I according to claim 1 (I) in which X is oxygen or sulfur, m is an integer from 3 to 10 inclusive, n is an integer from 1 to 3 inclusive, and R is an aryl or aryloxy group which is unsubstituted or is substituted by nonionic substituents, or R is a heterocyclic radical which is unsubstituted or is substituted by nonionic substituents, and which is optionally bound by way of an oxygen atom to the -(CH2)n group, which process comprises reacting 1,4-diaminoanthraquinone-2,3-dicarboxylic acid imide with a primary amine of the formula II
H2N-(CH2)m-X-(CH2)n (II) in which X, m, n and R have the meanings defined above.

18. A dye preparation which contains at least one disperse dye of the formula I

(I) in which X is oxygen or sulfur, m is an integer from 3 to 10 inclusive, n is an integer from 1 to 3 inclusive, and R is an aryl or aryloxy group which is unsubstituted or is substituted by nonionic substituents, or R is a heterocyclic radical which is unsubstituted or is substituted by nonionic sub-stituents, and which is optionally bound by way of an oxygen atom to the -(CH2)n group, as well as a dispersing agent and/or an organic solvent.

19. A dye preparation according to claim 18, which contains at least one finely ground disperse dye together with a dispersing agent.

20. A process for dyeing or printing semi- and fully-synthetic fibres, which process comprises using a dye liquor or printing paste each containing at least one dye or dye mixture which contains at least one dye according to claim 1.

21. A process for dyeing or printing semi- and fully-synthetic fibres containing ester groups, which process comprises using a dye liquor or printing paste each containing at least one dye or dye mixture according to claims 1 and 10.

22. The dyed or printed textile material obtained by the process according to claim 20.

23. The material according to claim 22 made from cellulose-2 1/2-acetate or cellulose triacetate, or from aromatic polyester fibres.