SU584808A3 - Method of dyeing carpets made of polyamide fibres - Google Patents

Description

(54) METHOD FOR DYING CARPETS FROM POLYAMIDE HALOCON

The invention relates to the field of dyeing polyamide materials by padding, in particular, to the method of dyeing polyamide carpets with anthraquine dyes.

There is a method of dyeing polyamide carpets by padding them in an aminoanthraquine dye solution (11 of general formula 1

About MHRt U

KaOjS

0 JKV,

W-CHA-CH CH,

Gui Rj-

The disadvantage of this method is the unevenness of the color, due to the poor outgassing ability of the dye used, as well as its low migration capacity.

In order to improve the uniformity of color, 0.01-10 weight by weight of a compound of the general formula 11 is used as an amino-thraquine dye.

HR

NHRi

-5 where R is the residue of the formula

where R and R are each alkyl, containing from 1 to 4 carbon atoms, and together contain ke more than € carbon atoms, one Y is a sulfo group, the other is hydrogen;

RJ is an aromatic or heteroaromatic residue.

As Rj, alkyl residues containing 1-6 C atoms, possibly substituted, are used, whose chain can be interrupted by lines and gangways, for example, -O-, NRj-,

-CO-, -OCO-, - NRjCO-, HR, SOj-, and

Vj is an isomolecular alkyl or arylene residue, s particularly a phenyl residue. As R substituents, there may be F.CJ .Bi, NHa, OH, low molecular weight (with 1-4 C atoms) alkoxy, aryl, in particular phenyl, acylamino and acyloxy. S means preferably aromatic, carbocyclic the residue, in particular the residue of the benzene and naphthalene series. These residues are either unsubstituted or contain one or more of the following substituents low molecular weight alkyl residues arylmethylene, aryloxy, arylthio, low molecular weight alkoxy, or alkklmerkapto, low molecular weight alkilsulfo nil, arylsulfonyl, preferably phenyl, methylphenyl, chlorophenyl, or methoxyphenylsulfonyl Ce, B, F, sulfo, sulphonamide, sulphonamide and carbonamide, substituted by low molecular weight alkyl, aralkyl, cycloalkyl or aryl, low molecular weight L carbalkoxy, cyano, amino, substituted alkyl, cyclo amino acid, acylamino, amino methylene and acylated aminomethylene. The following acyl residues are used: C-Cd-alkoxycarbonyl, C, -C, -alkanoyl, C-C-alkylsulfonyl, aroyl and arylsulfonide. Examples of such residues are Ztoxycarbonyl, acetyl, propionyl, methylsulfonyl, benzoyl, phenylsulfonyl, L-methylphenyl sulfonyl, p-chlorophenylsulfoyyl or p-methoxyphenylsulfonyl. The dyes used in the proposed method are obtained by treating an anthraquinone of the formula W O KH-R, and where Y and R have the specified expression values; Hafc is a chlorine, fluorine or bromine atom of a compound of formula IV — R. The condensation process is also carried out with the corresponding derivatives of the amino compound — acylated arylsulfonic acids, i.e., for example, toluenesulfonic acid amides or beisolsulfonic acids of the formula V-IJR-KI where V is the residue aromatic sulfonic acid. For condensation with anthraquinone, the Formula III is suitable, for example, the following amines or the corresponding acylated arylsulfonic acids of the compound: Aliphatic amines: methylamine, ethylamine, n-propylamine, isopropylamine, sec-butylamine, n-butylamine, isobutylamine, f-oxyslymine, sec-butylamine, n-butylamine, isobutylamine, f-oxylamine, sec-butylamine, n-butylamine, isobutylamine, f-oxylamine, sec-butylamine, n-butylamine, isobutylamine, f-oxylamine, n-propylamine, isopropylamine, sec-butylamine, n-butylamine, isobutylamine, f-oxylamine, n-propylamine, isopropylamine, sec-butylamine, n-butylamine, isobutylamine, p-oxylamine, p-oxylamine aminopentane, 3-methoxypropylamine, 1-phenyl-3-aminobutane, 1-phenyl-2-aminopropane, further phenylaminoalkyl, for example 4ep 1- (4-methylphenylamino) -2-amino groups. Aromatic amines: naphthylamine, O-, M-, p-toluidine, 3,4-dimethylaniline, 2, b-dimethylaniline, 2,6-dystilaniline, 2-ethyl-6-methylaniline, 2,4,6-trimethylaniline, 2,4-dimethyl-6-ethylaniline, 2,6-diethyl-4-methylaniline, p-tert-butylaniline, p-dodecylaniline, p-cyclohexylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, m-bromoaniline, p-phtoraniline, 3-chloro-4-methylaiylin, m-aminobenzenesulfonic acid, α-aminobenzonitrile, o-anisidine, m-anisidine, p-anisidine, 3-ethoxyaniline, 2- (Ji-oxy) -ethoxyaniline, 3- (- - ) -ethoxyaniline, 4- (-oxy) -ethoxyaniline, 4- {cyano) -ethoxyaniline, 4-methoxy-3-chloro nilin, 2-methyl-5-methoxyaniline, 2,5-diethoxy. xianiline, 4-amino) -benzylmethylamine, 4-aminobenzdioxane, 4-aminophenyl- (N, -diethylamino) methyl ester, aminohydroquinone dimethyl ether, 4- aminodiphenyl ether, 4-aminodiphenylmethane, 3,3-diaminodiphenylsulfone, N - (p-aminobenzylidene) -aniline, 4-amino-H-benzylidene aniline, (o-, M-, p -) - thioanididine, simple 4-aminodiphenylthioether, H-C-oxyethyl) -sulfonyl-anilnyl, 3-phenylsulfonyl-aniline, m-phenylenediamine, p-phenylenediamine, p-phenylennamin-2-sulphonic acid, m-phenylenediamine-4-sulphonic acid, aminodiphenylamine and his mono- or disulfonated in position 3 or 4 derivatives, 4,4-diaminostilbendisulfonic acid- (2,2), 1,3-diamino-2-methylbenzenesulfonic acid- (5), 3-aminoacetanilide, 4-aminoacetanilide, K-methyl -N-acetyl-p-phenylenediamine, m-cyclohexyl-N-acetyl-p-phenylenediamine, (4-amino) -anilide benzoic acid, K-ethyl-K-benzoyl-p-phenylenediamine, 3-acetylamino-4-methylaniline, N - 4-amino) -phenylpyrrolidone, 3-methoxy-4-acetylaminoaniline, glycolic acid (4-amino) -phenyl ester, 3-aminobenzenesulfonic acid, phenyl B, 2-aminobenzoate, 3-aminobenzoate oic acid, methyl 4-aminobenoic acid ester, 3-amino-4-methylbenzoic acid, 3-amino-6-chloro-benoic acid, p-acetylaniline, 2-aminobenzoic acid methyl ester, 3-aminobenzoic acid methyl ester, 3-amino amide -4-methoxybenzene sulfonic acid, diethylamide-3-acmnobenzenesulfonic acid, li-te-cyan) -ethylamide-4-amino-benzenesulfonic acid N - (| | -cyan) -ethyl ™ FT (| 5 acetoxy) -ethylamide-3-aminobe 1 sol-sulfonic acid, bis- (Ji-hydroxy) E:; nlamide-3-am-benzoyl sulfonic acid 3-amino-4-methoxy phenylmethyl sulfone, 2-amino-5 -acetylaminobenzoic acid, then diaryl disulfimides containing at least one aryl-drene capable of condensing with the anthraquinone of formula 1P an amine group, for example, 3-phenylsulfonylamino-sulfonyl-p-toluidine. Such residues are introduced into the antrichinone nucleus as follows. The compound of formula III is first reacted with arylamine, and the resulting compound, after introducing the sulfonic acid group into the aryl core, is converted by known methods to the sulfonic acid chloride, and the latter is converted into the corresponding sulfonic acid, which is reacted with sulfonic acid chloride. Heterocyclic amines: 2-aminothiazole, 2-amino-5-nitrothiazole, 2-amino-5-diathiazole, 2-amino-4-methyl-5-nitrothiazole, 2-amino-4-methylthiazole 2-amino-4- (4- chloro) -phenylthiazole, 3-am-nopyridine, 3-aminoquinoline, 3-aminopyrazole, 3 aminopyrazole 3-amino-1-phenylpyrazole, 3-aminoindazole, 3-amino 1, 2,. 4-triazole, 3-amino-1- (4-labels, siphenyl) -pyrazole, 2 aminobenzthiazole, 2-amino b-methylbenzthiazole, 2-amino-6-cyanbenthiazole, 2-amino-6-methoxybenzthiazole, 2 amino b-carbztoxybenzthiazole J 2 - amiko-6 chlorokszthiazole, 2-amino-6-methylsulfonylbenzimidazole, 2-aminobenztriazoleJ 2-amino-1, 3,4-thiadiazole, 2-amino 1, 3,5-thia diazole, 2-amino -4-phenyl or -4-methyl -1,3,5-hyadiazole. Preferably, 1-isopropylamino-6- or 7-sulfo-anthraquinos are used, containing in position 4 a phenylamino residue substituted by 1–3 methyl or methoxy groups, for example, 1-isopropylamino-4- (2-methyl-4-methoxy) -phenylamino b- or 7-sulfo-anthraquinone, as well as compounds containing in position 4 of an anthraquinous core a group of the formula Y SOi-MH-SO -R where R. is a molecular weight, a saturated, aliphatic residue unsubstituted or substituted by halogen, lower alkyl or lower alkoxyphenyl the remainder. Rj in the meaning of a saturated, aliphatic residue is this C, -alkyl residue which may be substituted by halogen, in particular chlorine or bromine, alkoxy, mono- or di-Cj-C j-alkylamido groups, for example ethyl, L-metho | , J-dimethylaminopropyl, p-chlorophenyl and p-bromophenyl. These colorants are distinguished by particularly pure, strong shades of blue-greenish color. The amino-compounds introduced at position 4 allow for the production of pure, yellowish-green dyes that color the polyamide without striation. The amino-amino compounds used are those of formula VI where Z is the residue of a number of naphthalene or benzene, acetoacetamide or a heteroaromatic residue} the benzene ring A can be substituted. If Z is a heterocyclic aromatic residue, it is, for example, an azolyl residue, possibly condensed, preferably with a benzene core. Examples are 2-lower-alkylindolyl- (3) -stocks, diazolyl-residues, especially pyrazolyl-residues, for example 2-lower alkyl-pyrazolyl- (3) or 1-aryl-3-lower alkyl-5-oxypyrazolyl- (4) - residues, wherein the name aryl is phenyl or phenyl, substituted by sulfo, chlorine or methyl, then 1-lower alkyl-indazolyl (3) residues or imidazolyl residues, for example benzimidazolyl (2) residues, or thiazolyl residues, for example thiazolyl - (2) - or benzthiazolyl (2) - residues. As the latter, it is also possible to use an azinyl group, for example, pyridyl groups, in particular a pyridyl- (3) -group. Carbocyclic-aromatic rings in Z, as well as the benzene ring A, may also contain other non-acidic water-dissociating substituents, especially halogens, for example fluorine, chlorine, or bromine, alkyl, oxyalkyl, alkoxy, alkoxycarbonyl, alkylsulfonyl, or alkylsulfonyloxy groups containing up to 5 carbon atoms or a nitro group. Z can also mean the residue of the active methylene compound used as the paint-forming component. In this case, acetoacetic acid amides are suitable, in particular, acetoacetic acid anilides, for example, N, M-dimethyl acetoacetamide, N-methoxypropyl acetoacetamide, N-methyl- or N-ethylanilide of acetoacetic acid, substituted for low-molecular alkyl or alkoxy-acetylide, or in the same place, or if you have a set of acetoacetic acid, substituted for low-molecular alkyl or alkoxyacetic acid, or N-methyl acetoacetate, substituted for low-molecular alkyl or alkoxyacetate, or N-methyl acetoacetate, substituted for low-molecular alkyl or alkoxyacetate, or

acetoacetic acid, N -benzylamide acetoacetic acid or

N-cyclohexylamide acetoacetic acid.

Dyes characterized by good selectivity and light fastness are obtained if amino-compounds of the formula yi are used, where 2 means unsubstituted phenyl residue or substituted with at least one and, preferably, no more than three substituents phenyl residue: nitro, chlorine, fluorine, alkyl, substituted alkyl for example, oxyalkyl, alkoxy and / or substituents of alkoxycarbonyl alkylsulfonyl or alkylsulfonyloxy, with alkyl and alkoxy units containing not more than 4 carbon atoms.

Particularly preferred are those compounds of formula VI in which Z is a phenyl group or a methyl substituted phenyl group. In these preferred compounds, the benzene ring is either unsubstituted or substituted methylgroup.

Examples of such amino-compounds:

,

Sh

OCHj

i "H, -Sn, NaON

ten

15

20

25

SI,

egn

thirty

, 11 M

40

"

"

"about

If the dyes of the formula C contain a free hydroxy or thio group or another primary or atoric amino group, then the products obtained by the proposed method can be subjected to additional acylation. Suitable acylating agents for this purpose are, for example, lower alkanoyl chlorides substituted by lower alkyl groups, lower alkoxy or halogen groups, benzoyl chlorides, sulfochlorides, for example, ethane methane, p-toluene or benzenesulfonyl chloride, then phenyl or alkyl chloroformate. In both latter cases, urethanes are obtained, which by further interaction with lower aliphatic amines, for example, hydroxyethylamine or 3-methoxypropylamine, can be converted to urea derivatives. Chloroformic acid thioesters are also suitable acylating agents.

In addition, the dyes present in the proposed 14x dyes are acylamino, e.g. acetylamino groups, e.g. by heating in 10% hydrochloric acid, and the amino compounds thus obtained are reacted with acylating agents, e.g. sulfochlorides or carboxylic acid chlorides, according to these higher ways.

Additional acylation is important, first of all, for the introduction of fiber-reactive acyl residues. For the purpose of this, a dye of formula I containing in position 4 a substituent with a primary or secondary amino group is treated with an acid anhydride or an acid halide, an acyl residue which can react with a fibrous material containing hydroxyl or amino groups to form a covalent bond.

As such anhydrides or acid halides with a reactive acyl residue, for example, the following may be mentioned: anhydrides and halides of aliphatic oL, p-unsaturated carboxylic acids, for example chloromeleic acid anhydride, propionic acid chloride, acrylic acid, acrylic acid, and in particular, halogen, acrylic acid and anhydride, halogen acid, acrylic acid and anhydride, halogen, acrylic acid, and halogen acid, acrylic acid, and halogen acid, anhydride, acyl acid anhydride, halide acid, acrylic acid chloride, acrylic acid, and halogen acid; halogen aliphatic carboxylic acids, for example, chloroacetyl chloride, sulfochloroacetic acid chloride, jb-bromo- or chloroacetyl chloride, oL chloride, | -dichloro- or dibromopropionic acid, fluorocyclobutanecarboxylic acid halides, for example, tri-chloride and tetrafluorocyclobutanecarboxylic acid chloride, c-chloride (.-chloro or f-hydrochloric acid or its bromide, then a heterocycle;

with at least 1 nitrogen atom, for example, 2-halobenzthiazole or oxazole-6-carboxylic or sulphonic acid chloride, 3,6-dichloropyr-dazine-5-carboxylic acid chloride, tetrachloropyridazine, 4,5-dichloropyridazone- (6) -yl chloride -propionic acid, 4,5-dichloro-1-phenylpyridazone-carboxylic or -sulfonic acid chloride, 1,4-dichloro-phthalazalinecarboxylic or -sulfonic acid chloride, 1,4-dichlorophthalazine-carboxylic acid or -sulfonic acid chloride, 2,4-dichlorohinazolinecarboxylic chloride -sulfonic acid, 2,4,6-trichloro- or 2,4,6-tribromopyrimidine and its production one containing, for example, in position 5, a cyano, nitro, methyl, ethyl, carbamide, sulfamide, carbomethoxy, carbalkoxy, acyl (for example, benzoyl, acetyl, propionyl group), alkenyl group (for example, allyl - or chlorovinyl group), or a substituted alkyl group (for example, carboxy-methyl, chloromethyl-, or bromomethyl group), 2,4,5,6-tetrachloro- or 2,4,5,6-tetrabromopyridine, 2,6-dichloro or 2,6-dibromo-4-carboethoxypyrimidine, 2,4,5-tetrachloropyrimidine, 5-nitro-6-methyl-2,4-dichloropyrimidine, 2,4-dichloropyrimidine-6-carboxylic acid chloride, 2,4-dichloropyrimidine- 5-carboxylic acid, amides of 2,6-dichloro- or 2,6-dibromopyrimidine-4-, or-5-carboxylic acid or sulfonic acid or chloride 4-or-5-carboxylic acid, or sulfonic acid, 2,4-dichloropyrimidine- 5-sulfonic acid, 2,4-dichlo-5-chloromethyl-6-methyl-pyrimidine, 2,4-dibromo-5-bromomethyl-6-methylpyrimidine, 2,4-dichloro-5-chloromethylpyrimidine 2,4-dibrom-5 β-bromomethylpyrimidine, 2,5,6-trichloro-4-methylpyrimidine, 2,6-dichloro-4-trichloromethylpyrimidine or, in particular, 2-methanesulfonyl-4,5dichloro-6-methylpyrimidine, 2,4,6-trichloro-1, 3,5-triazine or 2,4,6-tribrom1, 3,5-triazine, 4,6-dichloro-1,3,5-triazines, substituted in p Position 2, namely, an aryl or alkyl residue, for example, phenyl, methyl, or ethyl residue, or an aliphatic or aromatic residue, bonded through sulfur atoms of a mercapto compound, or through an oxygen atom of a hydroxyl compound, or in particular the NHj group, or a residue linked through the nitrogen atom of an aliphatic, hydrothermal, or aromatic eidanocompound, as compounds whose residues can be linked in position 2 to the core of triazine, namely as a result of interaction with trihaloentriazine, For example, aliphatic or aromatic mercapto or hydroxyl compounds, for example, thiospheres, thioglycolic acid, thiourea, tivfenodsh, methyl, ethyl, isopropyl alcohol, glycolic acid, phenol, chlorophenols or nitrophenols, phenolcarboxylic acid, glycolic acid, phenol, phenol, chlorophenols or nitrophenols, phenolcarboxylic acid, glycolic acid, phenol, phenol, chlorophenols or nitrophenols, phenolcarboxylic acid, glycolic acid, phenol, phenol, chlorophenols or nitrophenols; and acylated amino groups containing hydroxylamine, hydrazine, phenylhydrazine, phenylhydrazine sulfonic acids, urea acid and its derivatives, seven- and thiosemicarbazides and carbazones, methyl, ethyl, and ropil-, metoksietil-, methoxypropylamine,. dimethyl-, diethyl-, methylphenyl-, ethylphenylamine-, chloroethylene, ethanolamines, propanolamines, benzylamine, cyclohexylamine, morpholine, piperidine, piperazine, aminouric esters, ethyl acetic acid esters, aminoethanesulfonic acid, aplymerate, maxites, acetyl acid, aminoacetic acid ethers, aminoethanesulfonic acid, apymelic acid; , N-methylaniline, toluidines, xylidines, chloanilines, p- or m-aminoacetanilide, nitranylines, aminophenols, nitrotoluidines, phenyldiamines, toluenediamines, anisidine, phenetidine, diphenylamine, naphthyl 1 dan, aminonaptols, diamine talin, and in particular anilines containing acidic groups, e.g. sulfanilic, metanilovuyu, ortanilovuyu acid anilindisulfonovuyu acid aminobenzilsulfokislotu, aniline with -metansulfonovuyu acid aminodibenzoynuyu acid naftilaminodi- and -trisulfonovuyu acid, aminobenzoic acid, such as 1 or 2-hydroxy-5 -aminobenoic acid, aminonaphtholmono-, di- and trisulfonic acids, aminobenzoic acid or -sulfonic acid. Further, one should also mention colored compounds or compounds with a dye character, for example, 4-nitro-4-aminostilbendisulfonic acid and amino azo dyes or amino anthraquinones or phthalocyanines containing at least one more reactive amino group.

The introduction of hydroxyl residue substituted in position 2, mercapto or amino compounds or ammonia of triazine residues into the dyes offered is carried out in such a way that 2,4,6-trihalo-1,3,5-triazine, in particular cyanuric chloride, is reacted with the dye and one of several of the above compounds.

In addition, it is possible in the dyes obtained by this method, which have Jb-chloropropionyl-, cL, p-dichloyl or dibromopropionyl residue, can be converted in addition by the proposed method by cleaving the hydrogen halide with alkali-reactive agents, for example, acryl, chlorine or bromacrylate

Preferably, dyes of the formula 11 are used, wherein K is an amino-arylo residue, in particular an amino benzene residue or an amino aralkyl group, for example aminomethyl phenyl residue, and may also mean

. a - y - a

where a) And a means each aryl, in particular a possibly substituted phenylode, or a - aryl residue and a - a low molecular weight alkyl residue, and contains an acylated g1 -mino group and

y is a direct bond or a member of the bridge of the formula -O-,

, -SvKR3rr- Ha-N N -, - c; K -, - c 0- -S02-, -ОСО-, HRjCO-NUjSO-, or-ЗОа-МЯЗ-вОаn, K is hydrogen or a lower alkyl residue. B-substituents a and a are suitable, for example, halogen, as well as low molecular weight alkyl and alkoxy groups. As examples of the residuals of the formulas - HN - R, the following should be mentioned:

-HN

-HN4 7-iNg

NH

SOj-HH- O

where and C, -C

with, -C-alkyl. C, -C.-alkoxy. C, -C-alkanoyl. canoe .Si.

/ SI,

-O-C h

-NN l --WH -

SOj-MB-SO-CH CH-OHi-UHCH J

i3

O-CO-O

-nzhTtHo

and

Reactive groups, especially the acylamine residue, should be introduced only at the end of the reaction, since the latter are cleaved off during the condensation of the compounds of the formula and with the compounds of the formula S.

However, alkylene sulphonyl compounds, for example, vinyl sulphonyl or their starting compounds containing P-sulphatoethylsulphonyl groups, can be introduced into the compounds of the formula before condensation with the halo anthranine of the formula P1.

The resulting stains and packings are characterized by intense color, very good light fastness and durability in a wet state, for example, resistance to washing.

Example 1. 44.6 parts by weight of sodium salt of 1-isopropylamino-4-bromoanthraquinone-6-sulfonic acid are added together with 18.6 parts by weight. aniline and 20 weight.h. sodium bicarbonate to 30Q m of water and 80% by weight. Ethyl alcohol, This mixture is heated to 75-80 ° and 0.6 weight.h is added, with good stirring, for 10 minutes. powdered copper. To complete the reaction, stir an additional 15 hours at | 80-85 ° C. Excess aniline distilled off; water vapor. 300 parts by weight are added to the residue. ethyl alcohol and a hot alcohol-aqueous dye solution are separated by filtration from a small amount of a copper catalyst. The filtrate is acidified with dilute hydrochloric acid until & with speckles stains red congo paper blue. The dye precipitates in crystalline form. The precipitate is filtered off with suction and washed with dilute hydrochloric acid, which is then weighed into 300 parts by weight. water. The pH is adjusted to 7.5 with a dilute aqueous solution of sodium hydroxide, 300 parts by weight are heated to and below. 20% brine. Thus, a sodium salt of the dye of the following formula is obtained.

faOj $

kn14

well filtered. The dye is sucked off and dried in vacuum at 80 ° C. The dye dyes wool and synthetic polyamide fibers from acetic acid to sulfuric acid aanna in uniform, greenish-blue shades with excellent light fastness.

If instead of 44.6 weight parts G-isopropylamino-4-bromanthraquinone-6-sulfoxl-layer of sodium is used

0 parts 1-isopropylamino-4-vromantrahinon-6-sulphate or -7-sulphate sodium, then get similar blue dyes with the same coloristic properties ,,

The use of 1-isopropylamino-45 bromanthraquinone-6-sulfonic acid is obtained, for example, by reacting 1-nitroanthraquinone-6-sodium sulfonic acid with isopropylamine in an autoclave when heated for several hours to 100-110 ° C and then brominating the resulting 1-isopropylamino anthraquinone-6 -sulfonic bromine in pyridine-Eudom solution with

Example2. To water suspension

5: 44.6 weight.h. 1-isopropylamino-4-brOmanthraquinone-b-sodium sulphate in 400 vol. water add an alcohol solution of 27.4 wt. 1-amino-2-methoxy-5-methylbenzene to 85 parts by weight ethyl

0% alcohol, the resulting mixture is heated until 20 parts by weight is added. sodium bicarbonate and then at 7580 ° C for 3 minutes 0.5. “Acupressure Copper Pors”

6 4 h prk internal temperature 88-EOS when heated under reflux. The greenish-blue solution is filtered on suction, the hydrochloric acid is brought to a koigo-acidic reaction, in this case the dye precipitates in a crystalline form, the dye precipitate is sucked off at 45 ° E and washed with a dilute / mixture of alcohol, water and acid until it is removed

S crezidine. The residue is brought into water to a volume of 800 ml and the aqueous solution of sodium hydroxide is adjusted to pH 7, and the dye dissolves at a temperature. At this temperature, precipitated with 10% sodium chloride for 1 vol. salt of the dye in the form of a well left in the bottom of the oil vessel. The aqueous mother liquor is removed by decanting, the solidifying precipitate of the dye is dried at 90-100 ° C in vacuum.

This dye formula

NaOj $ is dissolved in water to produce pure greenish-blue color and dyes wool and synthetic polyamide fibers from acetic acid to a sulfuric acid bath in uniform and completely pure greenish-blue shades with EXCELLENT light fastness. If instead of the amount used, 1-isopropylamino-4-bromoanthraquinone-6-sodium sulphate used a mixture of 44.6 parts by weight. 1-nzopropylamino-4-bromoantaquinone-6- or -7-sodium sulphate, which is obtained if anthraquinone-2-sulfoxis is nitrated in a mixture of 1-nitroanthraquinone-b- or -7-sulphonic acid, this mixture is converted by isopropylamine in an autoclave at a temperature of 90-110 C To the corresponding isomeric 1-isopropylamino-anthraquino-6- or-7-sulphonic acid mixture of sodium salt and by bromination in acetic acid, a mixture of 4-bromine compounds is obtained, giving a uniform greenish-blue color. Similar colors can also be obtained if instead of 44.6 pts.h 1-isopropylamino-4 - romantrahinon-6-sulfonic acid 48.6 parts by weight of sodium take 1-cyclohexylamino-4-bromanthraquinone-6-sodium sulphate or if 30.6 parts by weight The 1-amino-2,5-dimethoxybenzene is allowed to react with 44.6 parts by weight. 1-isopr, opylamino-4-bromanthraquinone-6-sodium sulfate .. IF 44.6 parts by weight are reacted. 1-isopropylamino-4-bromoanthine "quinone-6-sulphate sodium instead of 1-amino-2-mets) xi-5-methylbeneol" with the appropriate amount of amine Formula SOzNHSOato also get dye, painted wool and synthetic polyamide fibers in uniform, very pure greenish-blue shades, Example 3. 44.6 parts by weight Sodium salt of 1-iaopropylamino-4-bromoanthraquinone-b-sulfonic acid is weighed together with 20 parts by weight of mezidine and 20% by weight of sodium bicarbonate in 250% weight; h. water and 100 weight.Ch. ethyl alcohol. The resulting mixture was heated before stirring and npf stirring a mixture of 0.5 parts by weight was added to it over 3 minutes. copper and 0.5 weight.h. copper chloride. The mixture is stirred for 15 hours at 80-85 °, after which the blue solution is filtered and the aqueous hydrochloric acid is brought to a STRONG congo-acid reaction, in which the dye precipitates in crystalline form. The precipitate is filtered off with suction and washed with a diluted mixture of alcohol, water, and acid. The dye is further added to 300 parts by weight of water, diluted with an aqueous solution of sodium hydroxide, the mixture is brought to a pH of 7.5 and heated and 10% sodium chloride is added. So get the sodium salt of the dye of the formula LSH precipitate is sucked off to the dye dried in vacuum at. The resulting dye is dyed with synthetic polyamide fibers and also wool in bright shades of blue with excellent light fastness. If in the above example instead of 44.6 parts by weight 1-isopropylamino-4-bromotraquinone-6-sulphonic sodium is used in equal portions of 1-isopropylamino-4-bromo-thraquinone-7-sodium sulphate or 44.6 parts by weight. Mixing from 1-isopropylamino-4-bromoanthraquinone-6-sul sodium phosphate and g-isopropyllamino-4-bromo-sodium-1-sulphonone-7-sulphonic acid in a 1: 1 ratio, you get similar blue hues with the same coloristic properties. Example 4. A mixture consisting of 44.6 parts by weight 1-isopropylamino-4-bromantrahinoN-6-sulfonic acid and sodium 1-isopropylamino-4-bromantrahinon-7-sulfonic acid sodium obtained from the nitrided mixture of anthraquinone-2-sulfonic acid and translated izopropilamynom 1-izopropilaminoantrahinon-6, 7-sulphonic acid and optionally Brominated to the corresponding 4-bromo-anthraquin derivative, weighed together with 18 parts by weight 2,6-dimethylaniline and 20 weight.h, sodium bicarbonate in 250 weight.h. water and 100 parts by weight, ethyl alcohol. The resulting mixture is heated to 70 ° C and, with vigorous stirring, a mixture of 0.5 parts by weight is introduced over 3 minutes. copper and 0.5 wt.h copper chloride. The mixture is stirred for 15 hours at 80-85 ° C, after which the blue solution is filtered, the aqueous hydrochloric acid is brought to a strong CONGO-ACID reaction, and the dye precipitates in a crystalline form. The precipitate is sucked off; p is additionally washed with a diluted mixture of alcohol, water and acid. The dye is then added to 300 weight, h. water, diluted with an aqueous solution of sodium hydroxide, bring the solution to a pH of 7.5, heat to 10% sodium chloride and add. The precipitate of the sodium salt of the dye of the General formula

SOsHa

ten

V5

sH, - (j, rO

20

sucked off and the dye dried under vacuum at. This dye colors synthetic polyamide fibers in beautiful blue shades with excellent light fastness.

If in the above example, instead of a mixture of 44.6 parts by weight 1-isopropylamino-4-bromanthraquinone-b-sodium sulphate and 1-isopropyl-1-mino-4-bromoantraquinone-7-sulphate sodium were used for 48.6 p.w. 1-Cyclohexylamino-4-bromanthraquinone-b-sodium sulphate or 7-sulphate sodium or 46 parts by weight 1-sec-butylamino-4-bromanthraquinone-6-sulphate or -7-sulphate sodium, similar blue shades with the same coloristic properties are obtained.

Dyes with similar properties are obtained if, instead of 2,6-dimethylaniline, an equivalent amount of the following amines is used.

25

tYN

H,

thirty

jf-SO Ctts

40

4S

.

H, H

МН2 а2 5Н5НН2-СН2 CH2-CH2-0 JHj

Example 5. 92 weight.h. 1-sec-iivciuiauHHo-4-6poMaHTpaxHHOH-6-sulfonic sodium and 60 parts by weight l of aminoazobenzene is dissolved at 1000 rpm. 50% aqueous alcohol. At this temperature, 40 parts by weight are then added. sodium bicarbonate and, within an hour, add a mixture of 1 weight.h. copper powder and 0.8 weight.h. copper sulfate. The mixture is then boiled at reflux for 40 hours, and the resulting green dye dissolves. The catalyst and a small amount of unreacted aminobenzene are filtered off under suction and the dye is crystallized out by cooling to 20-25 ° C. Sucked off, dried in vacuum at and once weighed in benzene, the further p-aminobenzo containing dye is separated. The resulting dye of the formula O NH-CH N CH dyes wool and synthetic polyamide fibers in very uniform uniform green shades with excellent light fastness. If a and the above example, 92 weight.h. The 1-sec-butylamino-4-bromanthraquinone-b-sodium sulfonic acid is replaced by 89.2 parts by weight. 1-isopropylamino-4-bromanthraquinone-6-sodium sulphate 89.2 parts by weight a mixture consisting of 1-propylamino-4-bromanthraquinone-b- and -7-sodium sulphate, then similar green dyes are obtained. The above method can also be varied in the sense that instead of 60 weight, hours 120 weight parts of p-aminobenzene are used. p- (f-p-toluenes pho) amino-azobenzene with so pl. 156-157 ° which is reacted with 90 parts by weight. 1-sec-butylamino-4-bromanthraquinone-6-sulfonic sodium in an aqueous-alcoholic solution in an autoclave at 100-100 ° C, followed by saponification of the resulting toluene-sulfonated dye with concentrated sulfuric acid and subsequent processing. Similar green shades are also obtained if 60 wt.h. p-aminobenzene is replaced by 60 parts by weight. 3-aminobenzene or 70 weight.h. 4-amino-3,2-dimethylazobenzene or 90 weight.h. 4- (1-phenyl-3-methyl-6-hydroxypyrazolyl (4) -a-o) -1-aminoben ashes. EXAMPLE 6 48.6 ppm, 1-cyclohexylamino-4-bromoanthraquinone-6-sodium sulphate and 30 pts.w. 1-phenyl-3-aminobutane is dissolved in 500 vol. 40% aqueous hydrochloride at 60 ° C, added to 20 parts by weight. sodium bicarbonate and then 0.6 parts by weight powdered copper and the reaction mixture is heated for 20 h to reflux temperature. The resulting dye solution is separated after completion of the reaction from the copper catalyst (filtration) and then brought to a CONGO-ACID reaction with aqueous hydrochloric acid. The dye precipitates in crystalline form. The residue is filtered off with suction and the residue is washed with aqueous hydrochloric acid to an amine-free state. Sediment. then neutralized to 400 weight.h. water with an aqueous solution of sodium hydroxide and at pH 7.5, the sodium salt of the formula O III-CH- is isolated by filtration (C, pCH2- / which is dried at 80-90 ° C in vacuum. Wool and polyamide are dyed with acetic acid – sulfuric acid Baths to produce very pure blue shades with good light fastness. If in the above example 48.6 parts by weight of 1-cyclohexylamino-4-bromanthraninon-6-sodium sulfate are replaced by 44.6 parts by weight of 1-isopropylamino-4-bromanthrahinon -6-sulphate or 7-sulphate sodium or mixtures thereof, then similar homogeneous greenish-blue colors are obtained nki with good light fastness (polyamide and wool). Example 7. 44.6 parts by weight of sodium salt of 1-isopropylamino-4-bromo-anthricinone-6-sulfonic acid are added together with 27 parts by weight of glycolic ester of p-aminobenzoic acid and 20 parts by weight of sodium bicarbonate to 250 parts by weight of water and 100 parts by weight of ethyl alcohol. The resulting mixture is heated to 70 ° C and 1 part by weight of copper is added to it with vigorous stirring over 3 minutes. 15 h at ZO-VZs. Then the blue solution is filtered, the aqueous hydrochloric acid is brought to a CONGO-ACID reaction, and the dye is precipitated. It is filtered off with suction and washed with a dilute mixture of alcohol, water, and hydrochloric acid. The dye is then weighed from 300 weight.4. water diluted with an aqueous solution of sodium hydroxide is brought to pH 7.5, heated to and added 10% sodium chloride, and the sodium salt of the dye of the formula I n-CI I CH, SOjKa I COjCHjCHjOH O NH is formed

21 Suction is dried and the dye is dried under vacuum at 80 ° C. The dye paints synthetic polyamide fibers in uniform, greenish-blue shades of excellent light fastness. If in the above example, instead of 27 weight.h. of glycolic ester of p-amine of nobenoic acid, 27 weights of glycolic ester of p-aminobenzoic acid are used, then similar blue dyes with the same color properties are obtained. Example 8. 69,8 weight.h. 1-io propylamino-4- (3, 4-dimethyl-5) 3-aminophenyl-1 (-disulfimido) -phenylaminoanthraquinone-b-sulfonic acid is dissolved in 1200 ppm by weight. water at pH 6-7 and room temperature. Adding 10 weight.h. the bicarbonate is adjusted to a pH of 7.8-8 by three and added dropwise at 15–20 ° C over 1/2 h to 26.3 ppm by weight (,, JS-dibromopropionyl chloride, dissolved in 20 vol. of acetone. The pH value of the reaction solution was kept at 6.5 -7 by adding 10% bicarbonate solution. Continued to stir for 2 hours at 15-20 C. The solution partially precipitated. By adding 7.5% sodium chloride per 1 vol. the dye is completed. The dye precipitates. The resulting anthraquinone dye, which reacts with the fiber, conforms to the formula “- and-“ “. It is sucked off, washed 20. % salt and dried at 40–5 (L: in vacuum. Dark blue powder soluble in water is obtained, dyeing wool preferably in the presence of leveling agents (condensation product from higher aliphatic amines with ethylene oxide) from acetic acid baths giving very beautiful shades of a greenish blue color with good wet strength and lightfastness. If instead of 26.3 parts by weight of dibromopionyl chloride, 17.5 weight of c-brocrylic acid chloride is used,

22 4 access according to the above example, then a similar fiber-reactive dye with the same color properties is obtained. The 1-isopropylamino-4 (3, 4-D11methyl-5-) 3-aminophenyl-1 disulfimido) -phenylaminoanthraquinone-6-sulfonic acid used as the starting product is obtained if 46.1 parts by weight 3,5-diamino-5,6-dimethyldibenzopsulfimide is dissolved in 450 ppm by weight. at pH 7-8 and 44.6 ppm by weight is added to this solution. 1-isopropylamino-4-bromanthraquinone-6-sodium sulphate. The reaction mixture is heated to 85-87 ° C and a mixture of 0.5 parts by weight is added to the solution in portions within an hour. copper powder and 20 weight.h. sodium bicarbonate. Leave to react for 4 hours at 80-85 ° C, filter the dye solution, remove the insoluble parts, and precipitate the dye of formula OI 1 CH using 12% sodium chloride per 1 h. dye. Then filtered off and optionally washed with 10% sodium chloride solution. Polyamide-fiber reactive anthraquinone dyes with similar valuable properties are also obtained if, in Example 8, equivalent amounts of aminoanthraquinone dyes of the formulas listed above are used and equivalent quantities of the dyes mentioned above are used, instead of 2,4-dichloropyramidine-5-carboxylic acid chloride, are equivalent amounts of acylating agents.

23

SOjH

-SOjH

6/7 - SOgH

-CHCj, H-CjH -CH3 mixture)

7- SOjH

H

6/7 - SOjH mixture

example 9. 67,7 weight.h. The 1-isopropylamino-4- (3, 4-dimethyl-5-methylaminopropyl-1-disulfimido) phenylaminoanthraquinone-b-sulfonic acid is dissolved in 1000 wt. H. water at pH 6-7 and room temperature. Adding 10 weight.h. the sodium bicarbonate is adjusted to pH 7.8-8 and added dropwise at 15-20 ° C over half an hour to 26.3 parts by weight. tjt, Jb -dibromopropionyl chloride, dissolved in 20 vol.h. acetone, with the addition of 10%

24

CY, CH, g - "

CH,

Cl If Cl

Yy

Ns-sK

fil

CHj

/%

I J CHj

x

H H

-CH

ce- CO-from 5cc €

CK,

Jj t

Cl- (Je-lf-f PC

JH5 W (C} l5) 2

the sodium bicarbonate solution to the reaction solution hold the pH value of 6.5-7. Continue to mix for another 3 hours at 15-20 seconds, with the dye partially precipitating. By adding 10% salt per volume part of the dye to complete the precipitation of the acylated dye. The resulting new anthraquine dye reacts with the fiber and corresponds to the formula

25

a05 $

It is filtered off with suction, washed with 10% brine and dried in vacuum at 40-50 C. A water-soluble dark blue dye, dyed wool and polyamide material are obtained, preferably in the presence of levelers (condensation products from higher aliphatic amines with ethylene oxide) from an acetic acid bath, with a very clean color of greenish-blue shades with excellent light fastness.

If instead of 67.7 parts by weight, 1-isopropylamino-4- (3, 4-dimethyl-5) 3 -methamyophenyl-1 - (disulfimido) -phenylaminoanthraquinone-6-sulfonic acid, 66.3 parts by weight are used. 1-isopropylamino-4- (4-methyl-3-) 3-methylaminopropyl-1 - (disulfimido) -phenylaminoanthraquinone-6-sulfonic acid or 66.3 parts by weight 1-isopropylamino4, 3- (4-methylaminobutyl-1-disulfimido) -phenylaminoanthraquinoi-6-sulfonic acid and acylated in the above example, then 15% sodium chloride is used in the I ob.ch. dye. Filtered off additionally and washed with 10% sodium chloride solution. Requirement to obtain the blue base of anthraquinone Z-amio-5,6-dimethylphenyl 3-methylamophenyl disulfimide, for example, from 3-nitro-5,6-dimethyl sulfamide by condensation with y-hl propane sulfonyl chloride to obtain 3-nitro-3-nitro with 5,6-dimethyl-3-chloropropyl disulfimide, by reacting with an aqueous solution of monometh ilamine in the corresponding compound z-methylaminopropyl disulfimide with the subsequent reduction of the nitro compound in an aqueous solution with iron to give the corresponding amine.

26

Br I

Vg

Ш5

SOj HSOa-CH 2-С Hj-lf-CO-CH - СНа

Fiber-reactive dyes with good color properties.

Used for example as a starting material, 1-isopropylamino-4 (3, 4-dimethyl-5-) 3-methylaminopropyl-i - (disulfimido) -phenyl-1-minoanthraquinone-6-sulfonic acid is obtained if 43.5 parts by weight 3-amino-5,6-dimethylphenyl-3-methylaminopropionylsulfimide is dissolved in 450 wt. Parts. The temperatures and pH values are 7-8 / and 44.6 parts by weight are added to the solution obtained. 1-isopropylamino-4-bromanthraquinone-6-sodium sulphate. The reaction mixture is heated to 85-90 ° C and a mixture of 0.5 weight parts is introduced in portions within an hour. copper powder and 20 weight.h. sodium bicarbonate. The reaction takes place at 85-90 ° C for 4 hours, the dye solution is filtered, removing a large amount of copper precipitate and precipitating the dye of the formula

SNS

SO, -S02- СЫГ- СН, - Example 10. 50.4 pts.w. The sodium salt of 1-acetylamino-4-aminophenyl-2-sulfonic acid is weighed out together with 44.6 wt. hours. sodium salt of 1-isopropylamino-4-bromanthracnon-6-sulfonic acids and 20 parts by weight sodium bicarbonate in 350 weight.h. water. The resulting mixture is heated to and a mixture of 0.6 parts by weight is introduced with an intensive crossing over of E1 III for 3 min. copper and 0.4 weight.h. copper chloride. Continue to stir for 15 hours at. The resulting dye is precipitated by the addition of aqueous hydrochloric acid, which is then filtered off with suction, and the dye is washed with a diluted mixture of alcohol, water and acid. Get the dye of the formula

ABOUT

Then the dye with a mixture of 500 wt. ethanol and 500 weight.h. hydrochloric acid; (36%) is heated to reflux temperature until fully hydrolyzed to the acetyl group. The resulting dye is filtered off with suction and the residue is washed thoroughly with a mixture of alcohol, water and hydrochloric acid. The dye is then transferred to 300 parts by weight, water, diluted with an aqueous solution of sodium hydroxide, adjusted to pH 7.5 and the sodium salt of the dye of Formula 14.4 parts by weight is precipitated with 10% sodium chloride. this dye is dissolved in 200 parts by weight. water at pH 6-7 at room temperature. Addition of 2.5 weight.h. sodium bicarbonate, pH 7.8–8 and added dropwise at 15–20 ° C over half an hour 3.1 vol, h of cCjjb-dibromoproponyl chloride, dissolved in 5 vol. acetone. The pH of the reaction mixture is maintained at 6.5-7 by the addition of 10% sodium bicarbonate solution. Continue stirring for another 2 hours at 15–20 ° C, then precipitate is given with 1b% sodium chloride and the greenish-blue anthraquinone is sucked off, which reacts with the fiber dye of the formula CH3 $ O, 1Ha –CH-CH-CH1 91 I 0 Bg Bf which is washed with 10% brine and dried at 40-50 ° C in vacuum. Such a greenish-blue dye that reacts with the fiber is obtained if instead of 14.4 parts by weight 1-from-propylamino-4- (3-sulfo-4-amino) -phenyl aminoanthraquinone-6-sulfonic acid

used are J14,4 weight parts 1-of Opropyl mino-4- {3-sulfo-4-amino} -phenylamvoanthraquinone-7-sulfonic acid.

Claims (1)

Yar and mep 11. 49.5 weight.h. 1-isopropylamino-4- (2-mutoxy-5-aminomethane) -phenylaminoanthraquinone-6-sulfonic acid is dissolved in 1000 ppm by weight. water at pH 6-7 and the solution is cooled to 0-5s. 18.4 ppmw was added to the solution. cyanuric chloride, dissolved in 40 vol. acetone. The mixture is stirred for 1-2 hours, and the pH is maintained at 6-7 by adding sodium carbonate. Then add a solution of 20 sodium methanylate at 200 ppm. water. The mixture is heated up and sodium carbonate is adjusted to pH 6-6.7. After completion of the condensation, the dye is precipitated with sodium chloride, filtered, washed with Rossol and dried. The resulting dye of the formula dyes cotton in pure greenish shades. Recipe for dyeing 1. In a bath containing 500 parts by weight water, -0.5 weight.h. Glauber's salt, 0.4 vol. CR of acetic acid and 0.2 parts by weight of dye according to example 2, served at 10 weight, about wool flannel. The temperature is raised evenly for 30 minutes to the boiling point and the flange is colored for another 1 hour at the boiling point. The material then is washed and processed. A variegated greenish-blue color is obtained. If sulfuric acid is used instead of acetic acid in the same dyeing process, a greenish-blue color is also obtained. The formulation of dyeing and B dye bath containing 500 parts by weight water, 0.40 weight.h. 40% acetic acid, 0.23 weight.h. sulphonate butyl ester of ricinolic acid and 0.20 weight.h. dye according to example 5. p "5Day for Y h synthetic polyamide fabric. The temperature will evenly swell for 30 minutes to the boiling point and continue to color for another 1 hour at low boiling. The fabric is then washed and dried. A uniform, free-striping yellowish-green banding with good light fastness and wet strength is obtained. Formulation dyeing m 2 weight.h. the dye obtained according to an example is dissolved in 4000 parts by weight. water, add 10 weight.h. crystalline sodium sulfate and 100 parts by weight are supplied to the solution. well soaked wool, at a temperature of 40-. Then 2 weight parts are added. 40% acetic acid is boiled for 30 minutes and stained for 45 minutes at boiling. Then the wool is washed with cold water and dried. A blue color is obtained with horsin light resistance and wet strength. DETAILED DESCRIPTION A method for dyeing carpets with polyamide fibers by squeezing them in an amino-anthracion dye solution, using either one or another, so that 0.01-10% by weight is used as an amino-thrissinone dye. of the weight of the carpet of a compound of the general formula </ BR> where R is the remainder of the fomula — CHCjg in which R and R are each –g | alkyl containing from 1 to 4 carbon atoms, and together contain no more than B. carbon atoms, one Y is a sulfo group, the other is HYDROGEN) 1 - arsclastic iln heteroarctic residue. Sources of information taken into account in the examination: 1. French patent (f 2064426, 06 P, 1971.