DE2300591C3 - Use of nitroanthraquinones for dyeing and printing synthetic fiber materials - Google Patents

Description

is where Ri and R2 independently of one another are Hydrogen, Ci - C4-alkyl, halogen, hydroxy, optionally by hydroxy or Ci- Q-alkoxy further substituted Ci - Ci-alkoxy or Ci - C5-AI-kylcarbonylamino stand.

3. Use of compounds according to claim 2, characterized in that Ri for Hydrogen, Cl, Br, hydroxy, Ci-Q-alkyl or Ci - C4-alkoxy, the alkoxy radical being substituted by hydroxy or Ci - Q-alkoxy can be further substituted, and R2 stand for hydrogen.

4. Use of compounds according to claims 1-3 for dyeing and printing Polyester and cellulose ester fiber materials.

5. Use of compounds according to Claims 1 -3 for dyeing polyester fiber materials.

The invention relates to the use of Sulphonic acid group-free compounds of the general form!

NH-R

in which R stands for an optionally substituted phenyl radical, one X stands for a nitro group, the other X stands for Are hydrogen, or their mixtures for dyeing and printing synthetic fiber materials.

Suitable substituents on R are alkyl, cycloalkyl, aralkyl, aryl, cycloalkoxy, aralkoxy, aryloxy, alkoxy, Alkoxycarbonyl, alkoxycarbonyloxy, acylamino, especially alkylcarbonylamino, alkylsulfonyl, arylsulfo-

nyl, alkylaminocarbonyloxy, acylaminocarbonyloxy, alkylajninocarbonylamino, acylaminocarbonylamino, Alkylaminothiocarbonylamino, alkylaminosulfonyloxy, acylaminosulfonyloxy, amino, mono- and dialkylamino, Aryicarbonyloxy, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, amino, alkylsulfonyloxy, arylsulfonyloxy, Alkoxysulfonyl, aryloxysulfonyl, alkoxycarbonyl, alkylaminosulfonyl, Arylaminosulfonyl, dialkylaminosulfonyl. Halogen such as F, Cl, Br, carboxy, cyan, nitro, Hydroxy and cycloalkylamino.

Alkyl as a substituent on R preferably has 1-12 carbon atoms and can have further substituents of the above mentioned group.

The other alkyl and alkoxy groups preferably contain 1-4 carbon atoms, cycloalkyl and cycloalkoxy groups and in particular those with 5-7 carbon atoms. The aryl radicals are preferably phenyl radicals. The groups mentioned can be further substituted by amino, hydroxy, carboxy, cyano, halogen or C 1 _{-C 4} -alkoxy.

Examples of J are i-AniJino-6- or -7-nitro-anthraquinone, 1- [methyl-, 2 ', 6'-dimethyl-, 2', 4 ', 6'-TYimethyl, Ethyl, 4'-tert-butyl, 4'-dodecyl, 2'-methyl-6'-ethyl, 2 ', 4'-dimethyl-6'-ethyl, chlorine, bromine, fluorine -, Cyano, methoxy, ethoxy, ^ -hydroxyethoxy,] 3-cyanoethoxy, S'-ChloM'-methoxy-, 2'-methyl-4'-methoxy-, 2 ', 5'-diethoxy, 4'-methylaminomethyl, 4'-phenyl, 4'-cyclohexyl, 2', 5'-dimethoxy, 2'-, 3'- or 4'-dimethylaminomethyl, 4'-phenoxy-, 4'-methylthio-, 4'-phenylthio-, 3 '- (j3-hydroxyethylsulfonyl) -, 3'-phenylsulfonyl, 2'-, 3'- or 4'-amino, acetylamino, N-methylacetylamino, N-Cyclohexyl-acetylamino-, Hydroxyacetylamino-, Methoxyacetylamino, phenylsulfonyloxy, methylsulfonyloxy, phenoxysulfonyl, ethoxysulfonyl, 4'-acetylamino-2'-carboxy-, methoxycarbonyl-, acetyl-, Phenylcarbonyl-, diethylaminosulfonyl-, N- (j3-hydroxyethyl) -N- (j3-cyanoethyl) -aminosulfonyl-, N, N-Di (jJ-cyanäthylamino) -sulfonyl-, ß-Phenyläthylaminosulfonyl-, j3-Hydroxyäthoxy-, y-Hydroxypropoxy-,] 3-Hydroxyäthylmercapto-, N - (/ 3-Hydroxyäthylamino) -carbonyl-, /? -)> - Dihydroxypropoxyphenyl, also methoxy-, cyclohexyloxy-, Benzyloxy and phenoxycarbonylamino, o-p-propyloxy; o-p-terL-butyloxy-; ο-, p-methoxyethoxy-; 4'- or 5'-chloro-2'-methoxy-; 4 ', 5'-dichloro-2'-methoxy-; 2'-, 3'- or 4'-hydroxy-; 3 ', 5'-dichloro-4'-hydroxy-; 4'-chloro-3'-hydroxy-; 2- or 3'-methoxy-4'-acetylamino] -anilino-6- or 7-nitro-anthraquinones. Furthermore, alkyl, hydroxy, alkoxy, amino substances. l-anilino-6, (7) -nitro-anthraquinones, which are im Aniline residue by one or more phthalimino-N-methylene, Caprolactam-N-methylene, propionylaminomethylene, Succinimidomethylene, benzoylaminomethylene, carbamoylaminomethylene or carbethoxyaminomethylene radicals are substituted.

A preferred group of dyes within the formula I corresponds to the formula

(H)

wherein R, and R2 independently of one another are hydrogen,

Hydroxy, C, -Q-alkyl, halogen, Ci-C ₄ -AlkOXy, amino or Ci-Cs-alkylcarbonylamino and X has the meaning given above. The alkoxy groups can be further substituted _{by hydroxy or Ci-C 4 -AlkOXy.}

Particularly preferred are compounds of the formula Π in which Ri is hydrogen, chlorine, bromine, hydroxy, Ci-C ₄ -alkyl or Ci-Q-alkoxy, where the alkoxy radical can be further substituted by hydroxy or Ci-C ₄ -AlkOXy, and R2 is hydrogen means, while X has the meaning given above

These compounds can be prepared by reacting 1,6- or 1,7-dinitro-anthraquinone with Amines of the general formula

HjN - R

wherein R has the meaning given in formula 1. It is technically and economically particularly advantageous however, to implement mixtures of 1,6- and 1,7-dinitro-antrhachinon. Such mixtures can be easily after separation of 1,5- and 1,8-dinitro-antraquinone win from the anthraquinone dinitration.

The reaction takes place in organic solvents at temperatures of 60-200 ° C, preferably at 80-150 ° C. The nitro groups in the j3 position are not attacked. Come as a solvent high-boiling halogenated or nitrated hydrocarbons, such as dichloroethane and tetrachloroethane, chlorobenzene, o-dichlorobenzene, trichlorobenzene and especially nitrobenzene, or those of a hydrophilic type, such as triethanolamine, Pyridine, dioxane, dimethyl sulfoxide, sulfolane and especially dimethylformamide are possible. It is beneficial also to use the bases of the formula III in excess as solvents.

Acid-binding agents can be used to neutralize the primarily split off nitrous acid, such as salts of weak inorganic or organic acids, for example the Na, K, Mg salts of the Carbonic acid or acetic acid, or organic or inorganic bases such as triethanolamine, pyridine, Add quinoline or magnesium oxide.

The reaction times depend on the type of amine to be converted, the chosen reaction temperature and the concentration of the reactants. The reaction times can vary within wide limits, depending on the choice of conditions; they lay usually between 4 - 10 hours. The isolation of the reaction products can be carried out in a manner known per se Way by diluting with low molecular weight alcohols or by evaporating the reaction mixture, preferably in Venuleth. If compounds of the formula III are used as solvents, can the reaction products also by dilution with, if appropriate, aqueous mineral acids or organic acids Acids are deposited.

Of course, you can carry out further chemical reactions after the reaction at R, for. B. acylate existing amino groups or saponify existing acylamino groups or convert hydroxyl groups into alkoxy groups by alkylation or into ester groups by acylation. By the action of halogens, such as chlorine or bromine, halogen-releasing agents, such as SO ₂ CI ₂ - or SOCI ₂ -, HNO ₁ - or HNO3-H2SO4 mixtures, compounds of the formula 1 can be prepared in which R is one or more Cl-, Contains Br or NO2 groups. The reaction with methylenakliven compounds, e.g. B.

N-methylolcaprolactam, allows the introduction of Residues that are bound via a methylene bridge. Sulfonyl radicals can be by sulfochlorination and introduce subsequent replacement of the chlorine with residues containing amino or hydroxyl groups.

The compounds of the formula I are particularly suitable for dyeing and printing synthetic materials Fibers such as cellulose triacetate, polyamide and especially polyester fibers. Also in solvent dyeing can they be used. Polyester fibers can be used in a known manner after the carrier, high temperature or colored by thermosol processes.

Also available as base products for brown, navy blue, dark blue and black dye settings 5 they are extremely suitable. B. by combining with commercially available blue (green) dyes make real navy blue polyester dye.

The dyeings and prints obtained are distinguished by good fastness properties.

example 1

a) 10 g of strand material made of polyethylene terephthalate are in a liquor of 400 ml of water, 0.4 g of one Mixture of l-anilino-6- and -7-nitro-anthraquinone in finely divided form, 3.4 g of a mixture of 0-, m-, p-cresotinic acid methyl ester and 0.6 g of a mixture from equal parts of an anionic dispersant and a nonionic polyglycol ether

κι addition of sulfuric acid until a pH value of 4.5 2 hours e colored at 96-98 ° C, then it is rinsed and dried. A deep reddish purple coloration is obtained which is very good is lightfast.

i> b) The dye mixture used in a) can be obtained as follows: 298 g of a mixture of 1,6- and 1,7-dinitro-anthraquinone (80.4%) are stirred into 900 ml of aniline and kept at 100-105 ° C. for this period stirred until there is no more feed material in a sample

4 (i is detectable (about 8 hours required), man diluted at 50-60 ° C within 2 hours with 900 ml of methanol, stirred for 2 hours, sucks the crystalline precipitated reaction product from, it was washed with a solution of 150 g of aniline in 300 ml of methanol, finally with 300 ml of methanol and hot water and dried at 80 ° C. 277 g of one are obtained Mixture of l-anilino-6-and-7-nitro-antrhachinon.

c) The dinitro-anthraquinone used can be obtained as follows: 10 kg of anthraquinone are dissolved in 40 kg of 20% oleum, in 2 hours below 50 ° C. with 20.6 kg of a mixture consisting of 33% HNO ₃ and 67% H ₂ SO ₄ , added, heated to 90 ° C. in 2 hours and kept at this temperature until anthraquinone and monoitration product are no longer detectable -Dinitro-anthraquinone and washes the suction filter in portions with 37 kg of anhydrous sulfuric acid.

W) water is added, causing the temperature to rise to 80 - 85 ° C. After a further 30 minutes, the product is filtered off with suction at 80 ° C. and washed with 20 kg of 88% strength H ₂ SO ₄ . After washing neutral and drying, 3.3 kg of a product that \ Ae following composition:

1,6-dinitro-anthraquinone
1,7-dinitro-anthraquinone
1,8-donilro-anthraquinone

41.8%
38.6%
12.0%

1,5-dinitro-anthraquinone 1.6%

2,6- + 2,7-dinitro-anthraquinone <1.0%

Hydroxy-dinitro-anthraquinone 1.2%

Example 2

a) 10 g of a rag made of polyethylene terephthalate are in a liquor with a pH of 4.5 from 400 ml of water and 0.4 g of the finely divided dye mixture of l-ni-toluidino-6- -7-nitro-anthraquinone and 0 , 3 g of a mixture of equal parts of an anionic dispersant and a nonionic polyglycol ether stained for 2 hours at 120-130 ⁰ C. After rinsing and drying, a deep purple color is obtained.

b) If cellulose triacetate is treated according to one of the in Example la) and 2a) given instructions with the same dye mixture are also obtained purple tints.

c) The dye used in a) and b) can be mixed by reacting 1,6- and 1,7-dinitro-anthraquinone with m-toluidine analogously to that given in Example Ib) Prescription can be obtained.

Example 3

a) A fabric made of polyethylene glycol terephthalate fibers is impregnated with a liquor on the padder, in 1000 g 20 g of the finely divided dye 1 - (p-tert-butyl-anilino) -6-nitro-anthraquinone and 10 g of a polyether described in Belgian patent specification 6 15 102 as a thermosol auxiliary contains.

The fabric is then squeezed off to a weight increase of 70% and dried in a floating nozzle dryer or in a drying cabinet at 80 ° -12 ° ^C. The fabric is then treated in a tenter or in a Düsenhot-Flue about 45 seconds at 190-200 ⁰ C with heißter air, rinsed hereinafter, may be post-treated reductively and dried. The reductive aftertreatment for the purpose of removing the dye components adhering to the surface of the fibers can be carried out in such a way that the fabric is placed in a 3 to 5 cm volume with the fabric at 25 ° C. Sodium hydroxide solution of 38 ° Be and 1-2g / ltr. Hydroxulfite (concentrated) containing liquor enters, heated to 70 ° C within about 15 minutes and left at 70 ⁰ C for a further 10 minutes. Then it is rinsed hot, with 2-3cmVltr. 85 ° / cent formic acid at 5O ⁰ C acidified, rinsed and dried. A clear violet dyeing is obtained, which is distinguished by good fastness to light, heat-setting, rubbing and washing.

A very similar color is obtained if polyester fibers are used instead of polyethylene terephthalate fibers from M-bis-hydroxy-methylcyclohexane and terephthalic acid used.

b) The product used in a) can be obtained as follows: 15 g of 1,6-dinitro-anthraquinone and 30 ml of p-tert-butyl-aniline are ^{stirred at 125 °} C. until no more dinitro-anthraquinone can be detected is (about 6 hours required). It is diluted in the warm with 30 ml of ethylene glycol monomethyl ether, stirred cold, filtered off with suction and washed successively with ethylene glycol monomethyl ether and water. 13.9 g of 1 - (p-tert-butyl anilino) -6-nitro-anlhraquinone are obtained.

Example 4

a) A pre-cleaned and heat-set fabric made of polyethylene terephthalate fibers is coated with a printing paste printed, which consists of the following components:

40 g of a mixture of l- [m (p) -acetylamino-

anilino] -6 (7) -nitro-anthraquinone,
475 g water,

465 g crystal rubber (1: 2) and
'"20 g sulfated castor oil.

Aiginate thickening can also be used instead of crystal rubber. The printed and dried goods are used to fix the dye

π 190-200 ⁰ C driven over a high-performance stenter frame or through a condensation apparatus. The exposure time is 30-60 seconds. The fixed pressure obtained is then rinsed cold, with 1-2 g / ltr. anionic detergent at 70-80 ° C

Soaped for about 10 minutes, first rinsed hot and then cold and dried. A purple print is obtained which is distinguished by good fastness properties.

b) The components used in a) can be obtained from the technical mixture of 1,6- and 1,7-dinitro-an-

2-, anthraquinone (see Example Ic) either by reaction with m- or p-acetylamino-aniline with the addition of dimethylformamide at 130- 14O ⁰ C or by reaction in an excess of m- or p-phenylenediamine and subsequent acetylation in pyridine as a solvent

in received.

Example 5

j-, a) A fabric made of cellulose triacetate is, as in Example 3a) described, but each with 15 g of 1-m-anisidmo-6 (7) -nitro-anthraquinone and l-p-anisidino-b (7) -nitro · anthraquinone padded and then as there described, but treated with hot air at 210 C.

A deep bluish violet coloration of is obtained very good fastness to light and sublimation.

b) The dyes used in a) are obtained by reacting 1,6- and 1,7-dinitro-anthraquinone mil m- or p-anisidine either analogous to that in example la)

r, given rule, the implementation with m-anisidine requires a longer reaction time than that with p-anisidine, or one puts dinitroanthraquinone in 2-3 times the amount of nitrobenzene at 150-160 ° C with the addition of 2 moles of anisisidine / mole of dinitroanthra-

-, ii chinon around.

Example 6

a) 100 g of a fabric made of textured polyethylene ,, lenterephthalate fibers are used without pre-cleaning Room temperature brought into a dye bath that consists of

1 g of l- (p-hydroxy-anilino) -6-and

-7-nitro-anthraquinone and
1000 g tetrachlorethylene

is prepared. ^{The bath is heated to 115 °} C. within 10 minutes with vigorous liquor circulation and held at this temperature for 30 minutes. The liquor is then separated off and the dyed material with fresh solvent ,,, 5 minutes at about 40 C ^c rinsed. After the rinsing liquor has been separated off, the material to be dyed is centrifuged and dried in a stream of air. A blue-tinged ruby coloration with a very good color is obtained

Fastness to sublimation and good fastness to washing and rubbing.

An equivalent dyeing was carried out in the same way on a fabric made of polycyclohexane-dimethylene-terephthalate fibers obtain.

If the tetrachlorethylene is replaced by the same amount of 1,1,2-trichloroethane, it is equivalent Color received.

b) 100 g of yarn made from acetate threads are in introduced a dye bath from

1.0 g of the dye used in Example 6a), 1000.0 g of tetrachlorethylene, 1.5 g of oleic acid ethanolamide, 1.5 g of oleyl alcohol heptaethylene glycol ether and 6.0 g of water

is prepared. The bath is heated to 78 ° C. within minutes and held there for 45 minutes Temperature. After separating the dye liquor and rinsing with fresh tetrachlorethylene, the Dyed material freed from adhering solvent by suction and drying in a stream of air. You get one bluish ruby color.

c) The in a) and b) dye mixture employed may be from 1 -p-anisidino-6 (7) -nitro-anthraquinone by ether cleavage in 10g 78-8O ° / cent H ₂ SO ₄ at 40 ⁰ C (about 6 hours required) can be obtained in quantitative yield.

If you dye or print according to one of the rules described in Examples 1-6, polyethylene terephthalate or cellulose triacetate fibers with the dyes of the formula listed in the table

20th

O ₂ N

in this way, violet dyeings or prints with a strong reddish - weak bluish tint are obtained. Means in the second column the indication 6 or 7 that with a pure dye whose nitro group in the specified Position stands, was colored, while the indication 6, 7 indicates the use of a dye mixture.

Tabel

Position of substituent in NO; j

7 8 9 II) II 12 13 14

6th Il 6.7 CH 7th H <> H ο. ^ H CU (1.7 CH -ι C. Il 6.7 H 6.7 H 6.7 H 6th Il 6.7 H 6. " H 6th H

H H H H CH, H H CH, H CH, H H H CH, H CH. Cl H H Cl Cl Cl H N-
I.
CH, - NH- CO- CH, H H < Br H NH. H

N —CO —CH,

H H H H H H H H H H H CH H CH H H H H H H H H H H H H H H H H H H

CH-.

- CH - N

24 6th CH, NH -CH. SO-NH; C; H. 25th 7th SO; - H CH, 26th 6.7 H H -O 27 6.7 H H -S

CH.

H CH H H H H H H

NH-CO-CH

CH,

9 (Continuation) H NH CH, 23 00 591 3 10 4th Il ₆ ; Tabel Position as a subsidiary in
NO, ₂ H H S-CH ₂ -CH ₂ -OH Il H E.g. 7th H H CN H Il Il 29 6th SO ₁ -O- CH, OH
ι Il H 30th 6th H I.
-CO-CH ₂ N - CO - CH,
I. 31 H H Il CH, H 6th H H 32 H H - S - CII, H H 7th H H CII, H H 33 7th H CH, Cl Il H 34 6.7 H CT, H Il H 35 7th Il Il C ₂ H, CH, H 36 6.7 Il cn, II Il H 37 6.7 OCH, H C ₁₂ H ₂ , Il Il 38 ή OCH, Il NH-CH, Il H 39 6th H H Il Il 40 6.7 H NH-CO —CH, CH, Il Il 41 6.7 H H O Il H 42 6.7 - Ο —CiIi-CII ₂ H H Il H 43 6.7 H H H H H 44 7th H OCH, Il H H 45 6.7 OCH, H OH H H 4h 6.7 H OH H H H 47 7th H - OH H H H H 48 6.7 CH, Il OC ₂ H, H II 49 6.7 OC ₂ H, H OCH ₇ OCH, H 50 6th OCH, H H H H 51 6.7 OCH, Oil Cl Cl H 52 6th OCH, Cl OH H H 53 7th OC ₂ H, H OCH, CH, Il 54 6.7 Q- (C ₃ H ₄ OtCH, H H OCH, Il 55 6.7 H Cl CH, H ; 56 6th H Cl Il HI 57 6.7 H NH-COCH, OC ₂ H, H ': 58 6.7 H H H H 59 6.7 H H H 6Ü 7th 61

Claims (2)

Patent claims: 1. Use of compounds of the formula
O NH-R in which R stands for an optionally substituted phenyl radical, one X stands for a nitro group, the other X stand for hydrogen, or mixtures thereof for dyeing and printing synthetic fiber materials. 2. Use of compounds according to claim 1, characterized in that R is for