DE2816735A1 - N-Substd. 5,8-di:amino-quinizarin dyestuff mixts. - giving blue-green colourations on polyester and cellulose tri:acetate fibres - Google Patents

Abstract

A dyestuff mixt. contains at least 5 wt. % each of either >=2 cpds. of formula (I) or >=1 cpd. of formula (I) and 1 of formula (II), where X1 and X2 are 1-3C n-alkyl; X3 is H or X1; Y is H or a radical of formula (III) where R1, R2 and R3 are independently H, Hal, -OH, 1-4C alkyl or 1-4C alkoxy. The mixts. are esp. suitable for dyeing synthetic fibres partic. polyester or cellulose triacetate fibres, giving clear blue-green dyeings which are fast to sublimation. Dyeing by the exhaustion method is pref., owing to the synergistically enhanced affinity and build-up capacity of the compsn.

Description

Anthraquinone dye mixtures

The invention relates to dye mixtures comprising a) at least two dyes of the formula or b) at least one dye each of the formula I and of the formula wherein X1 and X2 for C1-C3-n-alkyl, X3 for H or X1 and Y for the remainder of the formula or represent H, where the radicals R1-R3 mentioned above in any context independently of one another are H, OH, halogen (preferably chlorine), C1-C4-alkyl or C1-C4-alkoxy and the minimum proportion by weight of a mixture component is 5%, as well as their production and use for dyeing synthetic fiber material.

The individual components can be of the type and, in the case of R, too differ from one another according to the position of the substituents. The substituents R can take all theoretically conceivable positions, but preferably those where they do not cause steric hindrance.

Mixtures of 2 components of type I are preferred on the one hand, which differ in terms of the nature of the substituents R, and on the other hand 3 mixtures of 2 components of type I and 1 component of type II, their Substituents R according to type and position with the substituents R in one component are identical in type I.

Among these mixtures, preference is again given to those of the formulas given in which the grouping for isopropyl or particularly preferably t-butyl and R1-R3 independently of one another for H, CH3 or OCH3 and where the radicals R1-R3 occur only once in a phenyl radical.

4-component mixtures of 2 components are very particularly preferred of type I, which differ from one another with regard to the radicals R and 2 components of type II, the radicals R of which are identical to the radicals in type I in terms of type and position are.

The mixing ratio within a type and between 2 types can vary within wide limits.

The preferred minimum weight fraction of a component is 10%; the maximum proportion is 80%.

In the case of mixtures of two, the weight ratio is preferably within of type I and in the case of mixtures of type I with type II (Y = H) 2: 1 to 1: 2, in particular 1: 1. In contrast, this ratio is found for mixtures of type I and type II (Y [H) at 8: 1 to 1: 1, in particular 6: 1 to 2: 1.

The mixtures according to the invention can be prepared in various ways Methods are done.

In addition to the mechanical mixing of the individual components before, during or after the formation, the production-related mixing comes through use of mixtures of suitable starting materials into consideration.

The last-mentioned variant, in which the mixing already takes place during of the manufacturing process is particularly economical.

In addition, combinations of both variants are possible by a partial mixture is brought about during production and then carried out mechanical admixing of individual components or other partial mixtures the desired End product manufactures.

The individual components are known or in a manner known per se Easily accessible (see GB-PS 1,081,390 for type I and US-PS 3,558,670 for type II).

Type I is expediently made by reacting 5-sec-or-t-alkylamino-8-chloro-quinizarin produced with corresponding arylamines or arylamine niches.

Type II (Y f H) is obtained either through the gradual implementation of 5,8-dichloroquinizarin with arylamines of different constitution or by one-step Implementation with arylamines or mixtures of different arylamines. In the latter case In addition to the symmetrical compounds, one also obtains asymmetrical products, in where the substituents in the 1- and 4-positions are different from one another. Type II (Y = H) is best obtained by the action of 5-amino-8-chloroquinizarin corresponding arylamines or amine mixtures - or by the action of acidic agents to type I dyes (i.e. dealkylation according to e.g. GB-PS 1,081 390).

According to a preferred variant of the process, mixtures of 5-sec- or -t-alkylamino-8-chloroquinizarin are used and 1) 5-amino-8-chloroquinizarine or 2) 5,8-dichloro-quinizarine or 3) mixtures from 1) and 2) with defined arylamines or arylamine mixtures implemented with exchange of chlorine atoms.

It is particularly advantageous to use the quinizarin mixtures mentioned above to implement with defined amines and the respective reaction product with the corresponding To mix reaction product of another defined amine.

In this way one obtains mixtures with an even number of individual components, preferably mixes of 4 and 6.

In addition, one can in the preparation of such dye mixtures to which no particularly high demands are made in terms of the clarity of the color tone will / also start from the technical products of 5,8-dichloroquinizarins, which 15 - 30% 2,5,8-trichloroquinizarin, 5,7-dichloroquinizarin, 2,5,7-trichloroquinizarin, Contain 2,6,8-trichlorquinizarin and tetrachlorquinizarin as by-products can.

The use of 5,8-dichloroquinizarin in technical form is special advantageous because this is naturally cheaper and sometimes because of those by-products causes an additional improvement in the absorption and build-up capacity of the dyes.

The new dye mixtures are ideal for dyeing synthetic fibers, especially polyester and cellulose triacetate fibers all the usual processes in which they produce sublime-fast dyeings of blue-green shades result.

However, their suitability for dyeing by the exhaust method should be emphasized.

The prerequisite for this was a considerable improvement in the drawing and Build-up capacity of the dye mass, which is well above that normally to be expected Blending effect goes beyond; in other words: the new mixtures surprisingly show a real synergistic effect.

In comparison, the individual dyes or

Dye mixtures with other substituents are much worse Pulling behavior, which is why they are practically only used in the thermosetting process can be.

In the following, "parts" mean parts by weight.

EXAMPLE 1: a) A finely divided mixture of equals Parts by weight of the dyes obtained according to b) and c) after-dyes polyester fibers the pull-out method in clear blue cast tones of a very good level of fastness, especially very good fastness to sublimation and wet fastness.

b) 30 parts of 5-tert-butylamino-8-chloro-quinizarin, 15 parts of sodium acetate and 150 parts of p-anisidine are heated to 140-145 ° C. for 7 hours. One dilutes at 60 ° C. with 150 parts by volume of methanol, filtered at 60 ° C., washes the residue with hot methanol and water and dry. 30.3 parts of 5-tert-butylamino-8-p-anisidino-quinizarin are obtained.

c) 30 parts of 5-tert-butylamino-8-chloro-quinizarin, 15 parts of sodium acetate and 150 parts by volume of aniline are hardened for 5 hours at 180-185 ° C and as in b) be.ohrieben worked up.

29.3 parts of 5-tert-butylamino-8-anilinoquinizarin are obtained.

d) The 5-tert-butylamino-8-chloroquinizarin used in b) and c) can be obtained as follows: 495 parts of 5,8-dichloroquinizarin (7ig) are in 2400 parts by volume of nitrobenzene at 140-145 0C with vigorous turbines in the course 15 hours at a steady rate under reflux with 375 parts by volume of p-tert-butylamine offset. After a further 2 hours at the same temperature one teaches cold and 10 Hours after cold. It is filtered, washed with a little nitrobenzene, and finally with Methanol nitrobenzene-free and dries. 265 parts of an almost pure product are obtained.

Example 2s a) A finely divided mixture of the same Parts by weight of the dyes obtained according to b) and c) after-dyes polyester fibers the pull-out method in somewhat muted blue-green tones with a good level of fastness. With high amounts of dye, the already good drawability of the in la) used dye mixture is exceeded.

b) The reaction is carried out as in Example lb), but instead of the product obtained according to ld) the product obtained according to 2d) and works as follows: The fully reacted mixture is stirred in about 2000 parts of 2N hydrochloric acid a, stir until all the p-inisidine has gone into solution as the hydrochloride, filtered, washes successively with dilute hydrochloric acid and water until the drain is neutral. After adding 1 part of bicarbonate, the filter material is dried in vacuo. Obtain 38.5 parts of 5-tert-butylamino-8-p-anisidino-quinizarin are contaminated with approx. 25-30% other dyes (shade red-green), originating from or originating from the By-products of d).

c) The reaction is carried out as in Example lc), but instead the product obtained according to ld) incorporates the product obtained according to 2d) and works, as described in b). 35 parts of 5-tert-butylamino-8-anilino-quinizarin are obtained, contaminated with approx. 25-30% red-green dyes, originating or originating from the by-products of d).

d) One carries out the reaction of example ld), but works as follows: Most of the nitrobenzene is distilled off in vacuo at approx. 110-1200C, the residue diluted strongly with methanol, filtered cold, with a little methanol and copiously washed with water and dried. 510 parts of crude 5-tert-butylamino-8-chloro-quinizarin are obtained, including 5-tert-butylamino-2,8-dichloro-quinizarine, 8-tert-butylamino-2,5-dichloro-quinizarine and contains 5-tert-butylamino-7-chloro-quinizarine (originated on 3 the by-products of the crude 5,8-dichloroquinizarin used by exchange of the a chlorine atoms).

EXAMPLE 3s a) A mixture of 25% each according to Example 1 b) and 1 c) and products obtained according to b) and c) give polyester fabric a strong color and really in clear blue-green tones.

Similar colorations with a significantly greener or bluer shade are possible obtained when dyeing with 10% each of 3 c) + 3 d) and 40 k 1 b) and 1 c) or with 40 k 3 c) + 3 d) each and 10 ffi 1 b) + 1 c) each.

b) 20 parts of the 5-tert-butylamino-8-p-anisidino-quinizarin obtained according to Example 1 b) are in 240 parts of nitrobenzene and 6 parts of p-toluenesulfonic acid for 1 hour at 140-1450C be -; ^. delt. It is diluted with 520 parts of methanol, stirred cold, filtered, washes with methanol and water. 5-Amino-8-p-anisidino-quinizarin is obtained.

c) 25 parts of 5-amino-8-chloro-quinizarin, 75 parts of aniline, 12 parts Sodium acetate is stirred at 175-1800C until there is no more feedstock is demonstrable. Now it is stirred cold, from 800C it is diluted with 120 parts by volume of methanol, filtered at 600G, washed with methanol and water and dried.

17.6 parts of 5-amino-8-anilino-quinizarin are obtained.

d) The 5-Mnino-8-chloro-quinizarin used in c) can be used as follows obtained: 495 parts of 5,8-Diohlorquinizarin (75%) are in 2400 parts by volume Nitrobenzene at 140-145 ° C with vigorous turbines over the course of 15 hours 375 parts by volume of p-tert-batylamine were added quickly at reflux. After further Approx. 10 ffi are distilled off from the batch for 2 hours at the same temperature, and the mixture is set 80-90 parts of p-toluenesulfonic acid and holds at 140-145 until chromatographically 5-p-tert-butylamino-8-chloro-quinizarin is no longer detectable (30 minutes to 2 hours required). Now it is distilled to dryness in a vacuum. The residue (720 parts) is extracted with twice the amount of cold water. It left behind after drying 450 parts of 5-amino-8-chloroquinizarin content: 65-70%.

Example 4: a) 2 parts of the dye mixture obtained in b) and 1 part of the paraffin mixture obtained according to o) is mixed and used according to the usual Methods brought into finely dispersed form. Polyester fabrics are thus or dyed HT process. Clear green dyeings of good lightfastness are obtained and very good fastness to sublimation.

b) 50 parts of 5-tert-butylamino-8-chloro-quinizarin, 75 parts of p-anisidine, 150 parts of p-toluidine and 20 parts of sodium acetate are heated to 160-17000 until no more input material can be detected. It is now cooled to 70 ° C, with Dilute 240 parts of methanol, stir cold, filter, the residue with methanol and water washed and dried.

A mixture of 5-tert-butylamino-8-anisidinoquinizarin is obtained and 5-tert-butylamino-8-p-toluidino-quinizarine.

c) 60 parts of 5,8-dichloroquinizarin, 40 parts of sodium acetate, 100 parts p-Anisidine and 200 parts of p-toluidine are stirred at 175-1800C. After about an hour Reaction in the mixture are no feedstock and no half-way conversion products more available. The melt is now diluted with 300 parts of diethylene glycol monoethyl ether, sucks off at 50-60 C, washes the Nutachgut one after the other with diethylene glycol monomethyl ether, Ethanol, water, dilute hydrochloric acid and again water.

After drying, 71.3 parts of a product are obtained, which, like earomatograms show about 50-60 ffi from 5-p-toluidino-8-p-anisidino-quinizarin and 20-25 each ffi consists of 5,8-di-ptoluidino-quinizarine and 5,8-di-p-anisidino-quinizarine.

Example 5: a) Equal parts of the dye mixture obtained in b) and the dye obtained according to Example 3 c) verden on polyester fibers applied by the exhaust process. Very well built-up blue-green colorations are obtained. If only the dye mixture obtained according to b) is used, a bluish tinge is obtained green colorations.

b) 50 parts of 5-isopropylamino-8-bromo-quinizarin and 30 parts.

tert-Butylamino-8-bromo-quinizarin with 320 parts of aniline and 35 parts of sodium acetate are stirred at 160 ° until a sample is taken no significant quantities of the feedstock ppshr are detectable. Men cools, diluted with 350 parts of methanol, stirred cold, filtered, washed with methanol and dries0 A mixture of 5-isopropylamino-8-anilino-quinizarin is obtained and 5-tert-butylamino-8-anilinoquinizarine.

A very similar mixture is obtained if, instead of the bromine compounds the analogous chlorine compounds start at 170-1750C.

c) The frying ties used in b) can be retained either by partial exchange of the bromine in 5,8-dibromoquinizarin analogously to in Example 1 d) described procedure or by bromination of 5-isopropylamino- or 5-tert-butylamino-quinizarin using bromine in 230% HC1.

The 5-isopropylamino- or 5-tert-butylamino-quinizarine can e.g. from 5-nitro-quinizarin by exchanging the nitro group for isopropylamine or tert-butylamine can be obtained.

Example 6: a) 2 parts each of the following dyes 5-tert. -Butylamino-anilino-quinizarin, obtained according to example 1 c), 5-amino-8-anilino-quinizarin, obtained according to example 3 c) and 1 part of the dye 5,8-di-anilinoquinizarin, obtained according to DAS 1 288 067 Example 43 are brewed in finely divided form and thus polyester fabric treated according to the pull-out procedure.

Blue-green colorations are obtained. The mixture of dyes has very good airflow.

Example 7s a) Polyester fibers are mixed with mixtures according to b) and c) the dyes obtained are colored in a ratio of 3-1 to 1-3. A bluish tinge is obtained green colorations with good - very good all-round fastness properties.

b) 25 parts of 5-sec-butylamino-8-chloro-quinizarine, 100 parts of m-toluidine and 10 parts of soda are heated at 160-170 ° C until one is removed and chromatographed sample no more input material can be detected. One dilutes with 150 parts of methanol, filtered off at 400C, washed successively with methanol and Water. 18.6 parts of 5-sec-butylamino-8-m-toluidino-quinizarin are obtained.

c) 25 parts of 5-sec-butylamino-8-chloro-quinizariil, 100 parts of p-phenitidine and 10 parts of sodium acetate are heated at 160 cm until in a chromatographed Sample only a little input material is detectable. After work-up as in 6) 5-sec-butylamino-8-p-phenetidino-quinizarin is obtained.

Example 8: a) Equal parts of the dye mixtures obtained according to b) and c) are mixed and brought into finely dispersed form. Be with this mixture Polyexter fibers dyed in a blue-green tone. You can only color with those according to b) or c) mixtures obtained, blue-green colorations are also obtained, whose Drawing and air building capacity is significantly lower.

b) 50 parts of a reaction mixture of 5-tert-butylamino-8-chloro-quinizarin, 5-Amino-8-chloro-quinizarin, obtained according to d) and 25 parts of sodium acetate are with 150 parts by volume of aniline kept at 170-1800C until there is no feedstock in a sample is more detectable. Now you dilute slowly at 700C with 120 parts of methanol, stirred for several hours at 40 ° C., filtered off, washed successively with methanol and water and dry. A dye mixture of approx. 60% 5-tert.- Butylamino-8-anilino-quinizarine and 40% 5-amino-8-anilino-quinizarine.

c) 50 parts of a reaction mixture of 5-tert-butylamino-8-chloroquinizarin and 5,8-dichloroquinizarin, obtained according to e), are mixed with 150 parts of p-toluidine and 25 parts of sodium acetate kept at 170 ° C. until there was no starting material in a sample more verifiable piste Now work on as described in b). Is received a dye mixture of approx.

75-80% 5-tert-butylamino-8-p-toluidino-quinizarine and SG-25S; 5-di-p-toluidino-quinizarine.

d) The mixture of 5-tert-butylamino-8-chloroquinizarin used in b) and 5-Amino-8-chloroquinizarine is obtained as follows: 160 parts 5,8-dichloroquinizarine At 140-145 ° C. in 960 parts of nitrobenzene, 76.8% strength is uniform over the course of 20 hours quickly mixed with 180 parts by volume of tert-butylamine; now about 100 is distilled Parts of nitrobenzene in vacuo, 14 parts of p-toluenesulfonic acid are added and the mixture is kept 30 Minutes at 140 ° C. Most of the nitrobenzene is now distilled in vacuo drives off remaining nitrobenzene in the weakly soda-alkaline range by means of water distillation off, filtered, washes with water and dries. To be preserved 162 parts, containing about 65-70% of a mixture of 5-tert-butylamino-8-chloro-quinizarin and 5-amino-8-chloro-quinizarin in a ratio of approx. 3: 2 and approx. 25-30% other 5-amino- and 5-tert-butylamino-quinizarines were formed from the by-products of the crude 5,8-dichloro-quinizarine used (5-chloro-, 5,7-dichloro-, 2,5,7- and 2,5,8-Trichlorquinizarine) by exchanging cb-position chlorine atoms for tert-butylamine and subsequent dealkylation.

e) The mixture of 5-tert-3utylamino-8-chloroquinizarin used in c) and 5,8-dichloroquinizarine can be obtained as follows: 160 parts of 5,8-dichloroquinizarine 76, $ ig in 960 parts of nitrobenzene become evenly quick with 140 in 8 hours Volume pasting tert-butylamine at 140-145 ° C with vigorous turbines is then added 100 parts are distilled off in vacuo, and sufficient MgO is added to the residue up to an alkaline one in a sample taken and stirred with hot water Titer is evident. It is distilled to dryness at 110-120 ° C. in vacuo. The pulverized residue is extracted with dilute HCl and washed neutral and dried. 176 parts of a mixture are obtained which contain 25-30 ffi impurities - Mainly from reactions of the by-products of the 5,8-dichloro [hinizarin] used sta = end-5-tert-butylamino-8-chloroquinizarine and 5, 8-dichloroquinizarine in the ratio of approx. 4: 1 contains.

Example 9 a) Fiber material made of polyester is mixed with a mixture from the dye mixture obtained according to b) and that obtained according to Example 8b Dyestuff mixture dyed in a ratio of 3: 1-1: 1. Strong blue colorations are obtained.

b) 50 parts of the mixture of 5-tert-butylamino-8-chloro-quinizarin obtained according to Example 8d and 5-amino-8-chloro-quinizarin are mixed with 35 parts of sodium acetate and 250 parts of 3-chloro-aniline Stirred at 1800C until only a small amount of input material can be detected. Man lets cool, - sucks off the precipitate, washes with about S3-chloroaniline-good with hot Methanol and water. A dye mixture is obtained which essentially consists of 5-amino-8-m-chloro-anilino-quinizarin and 5-tert. -Butylamino-8-m-chloro-anilino-quinizarin consists.

Example 10 a) Polyester fabric is mixed with the dye mixture obtained in b) Dyed in bluish green tones using the carrier process.

b) 50 parts of 5-tert-butylamino-8-chloro-quinizarin, 250 parts of a technical xylidine mixture that consists of about 10% 2.6-, 60% 2.4-, 25% 2.5 and 1-2 8 each of 2,3-, 3,4- and 3,5-xylidine and 25 parts of sodium acetate are stirred at 170-180 ° C until only a little is left in a sample taken Input material is detectable. Most of the is distilled in vacuo Xylidins from, carries out the residue in excess 10% hydrochloric acid, filtered, washes neutral and dries. You get 61 parts of a product that is completely predominantly from a mixture of isomeric 5-tert-butylamino-8-xylidino-quinizarin consists. The product was created with approx. 5-10% 5-amino-8-xylidino-quinizarin ( contaminated by dealkylation of the tert-butyl group).

Example 11 a) A finely dispersed mixture of the b) and c) obtained dyes in the ratio 2: 1-1: 2 are by the HT process applied to polyester.

A bluish green coloration is obtained. The pure dyes themselves have only a low affinity for polyester fibers.

b) 50 parts of 5-amino-8-chloro-quinizarin, 200 parts of 4-amino-2-chloro-anisole and 35 parts of sodium acetate are stirred for about 12 hours at 180-1850C, then diluted with 200 parts by volume of ethanol, and the precipitated product is filtered off with suction at 75.degree and washed in the usual way. 56 parts of 5-amino-8- (p-methoxym-chloro-anilino) are obtained -chinizarin.

c) 50 parts of 5-isopropylamino-8-chloro-quinizarin, 200 parts of 2-methoxy-5-ethylaniline, 25 parts of sodium acetate are heated at 180-185 ° C. until one is removed Sample can no longer be detected by chromatography. One dilutes from 60 ° C with 300 parts by volume of methanol, stir cold, filter, wash successively with hot methanol and water and dry. 52 parts of 5-isopropylamino-8 are obtained (2-methoxy-5-ethyl) anilinoquinizarine.

Claims (11)

Claims 1. Dyestuff mixtures containing a) at least two dyestuffs of the formula or b) at least one dye each of the formula I and of the formula wherein X1 and X2 are C1-C3-n-alkyl, X3 is H or X1 and v is the remainder of the formula, where the or for H radicals R1-R3 mentioned above in any context, independently of one another, denote H, OH, halogen (between chlorine), C1-C4-alkyl or C1-C4-alkoxy and the minimum proportion by weight of a mixture component is 5 t. 2. dye mixtures according to claim 1, characterized in that the grouping for isopropyl or t-butyl and R1-R3 independently of one another for H, CH3 or OCH3 and where the radicals R1-R3 occur only once in a phenyl radical. 3. dye mixtures according to claim 1 or 2, characterized in that that X1-X3 are methyl. 4. dye mixtures according to claims 1 - 3, characterized in that that this consists of 2 components of type I, which differ in terms of the nature of the substituents R, and from 2 components of type II, whose substituents according to Art and position with the substituents in type I are identical. 5. Dye mixture according to claim 1, consisting of 5-t-butylamino-8-anilino-quinizarin and 5-t-butylamino-8-p-anisidino-quinizarine. 6. Dye mixture according to claim 1, consisting of S-t-butylamino-8-arlilino-quinizarine 5-t-butylamino-8-p-anisidino-quinizarine 5-amino-8-p-anisidino-quinizarine and 5-Pmino- ß-anilino-quinizarin 7. dye mixture according to claim 1, consisting from 5-t-butylamino-8-anilino-quinizarine. 5-t-butylamino-8-p-anisidino-quinizarine 5, 8-dianilino.ohinizarin and 5,8-di-p-anisidino quinizarin .. 8. Dye mixture according to claim 1 or 2 characterized by that the weight ratio of types to type II (y Z H) 8: 1 to 1: 1, preferably 6: 1 to 2: 1. 9. Dye mixture according to claim 1 or 2, characterized in that that the weight ratio of type I to type II (y = H) is 2: 1 to 1: 2. 10. A process for the preparation of dye mixtures according to claim 1, characterized in that dyes of the types mentioned in claim 1 are used I and II mixed together. 11. A process for the preparation of dye mixtures according to claim 4, characterized in that mixtures of 5-sec- or -t-alkylamino-8-chloroquinizarin and a) 5-amino-8-chloroquinizarine or b) 5,8-dichloro-quinizarine or c) mixtures from a) and b) with defined arylamines or arylamine mixtures with exchange which converts chlorine atoms.