DK165338B - PROCEDURE FOR CONTINUOUS TRICHROMI COLORING SYNTHETIC POLYAMIDE MATERIALS AND Aqueous COLOR FLOATS - Google Patents

Description

DK 165338 B

The present invention relates to a process for continuous trichromy staining of synthetic polyamide materials as well as aqueous color floats which can be used in the process of the invention.

Trichromy staining of synthetic polyamide materials again and again reveals an insufficient ozone depletion in the stains that do not meet the demands of today.

10 From EP Publication No. 92,512, trichromic dye mixtures containing the dyes of the formulas (15), (16) and (19) or (15), (16), (17) and (19) are known.

Further EP-A-99,859 discloses further trichromy dye mixtures containing the dyes of the formulas (15) and (19) listed below.

However, the known trichromi dye mixtures do not adequately meet all the requirements.

The object of the present object is to provide a process for dyeing synthetic polyamide materials with dyes suitable for combination according to the trichromy principle, thereby obtaining stains with extremely good ozone resistance.

This is achieved by the invention by continuously treating the synthetic polyamide materials with a dye web containing at least one fiber-reactive blue dye of the formula

DK 165338B

2

O NH

II I i

/ VVVS0H

in II II I 3 VVV Gl \ Λ (1) '

II I

O NH- · + - C3 wherein G3 and G5 are methyl, G4 is α, β-dibromo-propionylaminomethyl, α-chloro or α-bromoacryloylarepin-5-methyl, β- (β'-sulf atoethylsulfonyl) -propionylaminomethyl, α, β-dibromopropionylamino, -CH (COOH) -NH-CO-CHBr-CHyBr or chloroacetylaminomethyl, and G 2 means hydrogen, sulfo or chloroacetylaminomethyl or -CH (COOH) -NH-CO-CHBr - CH 2 Br, Or wherein G1 is hydrogen or methoxy, G2, G3 and G5 are hydrogen and G4 is sulfatoethylsulfonyl, chloroacetyl amino, α, β-dibromopropionylamino, vinylsulfonyl, 2-methoxy-4-fluoro-s-triazinylamino or 2-ethylamino. -4-fluoro-s-triazinylamino, or wherein G1, G2, G4 and G5 are hydrogen and G3 is chloroacetylamino or α, 3-dibromopropionylamino, 2,6-difluoro-5-chloropyrimidin-4-ylamino, 2- chloro-4-amino- or 4-N, N-dimethylamino-s-triazinylamino, or wherein G 1 is methyl, G 2 is β-sulfatethylsulfonyl, and G 3, G 4 and G 5 are hydrogen, or wherein one of G 1 and G2 is sulfo , G3 means α-bromoacryloylamino or N-methyl-N- [3- ((3-chloroethylsulfonyl) -benzoyl] -amino, and the other of G2 and G1 and G4 and G5 means hydrogen, 25 or G1, G2 and G5 hydrogen, G3 means methyl, and G4 means chloroacetylamino, or wherein G1 is methyl, G2 means 2,6-difluoro-5-chloropyrimidinyl amino, G4 means sulfo, and G3 and G5 means hydrogen, or at least one fiber-reactive blue dye of the formula

DK 165338 B

3 ^ ^ AA A - (SO 3 H) i-2 il il ((in (2),% \ / NH NH NH 8 NHY3 - (T) 1-2 wherein cyclohexyl, Y3 means 4- (4) 5 is chloroacetylaminomethyl and 5 wherein the dye contains a single sulfonic acid group or wherein Y 2 is isopropyl and Y 3 is a phenyl yl-sec-butyl group substituted with sulfo in the phenyl ring. chloroacetylaminomethyl, or a diphenyl ether group, which in the phenoxy group is substituted with sulfo and acryloylaminomethyl, or wherein Y 2 and Y 3 each represent a phenyl sec-butyl group substituted in the phenyl ring with sulfo and chloroacetylaminomethyl, or wherein Y and Y 3 respectively represent a 4-α-bromo-15-acryloylamino-3-sulfophenyl group, together with at least one red dye of the formula f · - · · - · * - <> - «- (> (3), t Tst „„ / \ H0- · · V /

NS03H

wherein A is hydrogen, optionally substituted C (1-4) alkyl, -SO.N ^ 1 »-CO-N ^ 1 or -SO, R 2 \ \ 23

DK 165338 B

4 wherein R 1 is C (1-4) alkyl, R 2 is optionally substituted C (5-7) -cycloalkyl or optionally substituted phenyl, and R 3 is optionally substituted phenyl or optionally substituted phenoxy, and B is hydrogen, halogen, C (2-4) -alkanoylamino, C (5-8) -cycloalkoxycarbonylamino, C (1-4) -alkoxycarbonylamino, C (1-4) -alkylsulfonylamino or optionally substituted phenylsulfonylamino, and at least one yellow or orange dye of the formula '.- / 2 .li / w »- <> - <\ ho3s g / ox c wherein Bi, B2 and Ei mean hydrogen, C (1-4) alkyl or C (1-4) -alkoxy, and X means straight or branched C (1-4) alkyl or straight or branched C (2-4) hydroxyalkyl, or

O VO

15 τ'Γ * Z1 A - N - c - C - CH3

H / Y

/ \

Z2-t 7 "SO3H

Z 3 * wherein Z 1, Z 2 and Z 3 each represent hydrogen, halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, or mixtures of dyes of formulas (4) and (5), or a yellow dye of formula

/ “Y Γ A

/ I / N! I i IJ

20 w / T / YV (6) · u

L 4 J

DK 165338 B

Wherein W is hydrogen, C (1-4) alkyl, C (1-4) alkoxy, halogen, C (2-4) alkanoylamino or an optionally substituted arylsylphonyl, aryloxy or arylcarbonyl group, W 2 represents hydrogen , halogen, an optionally substituted alkyl, aryloxy, aryloxysulfonyl group or a group of the formula

tf W

-SO / 5 or -CON ^ 5, \ \ W3 means an optionally substituted alkyl or aryl group, W4 represents hydrogen or alkyl, and W5 and Wg each represent hydrogen or an optionally substituted alkyl, cycloalkyl or aryl group, as well as water and possibly additional additives.

The dyes used in the process according to the invention are distinguished by the trichromy staining of uniform color structure, which is the affinity of the dye as a function of concentration, good dyeing properties, good nuance in different concentrations, good authenticity and good combinability. The 20 stains produced meet the ozone depletion requirements.

The color floats according to the invention are characterized in that they contain water, the dyes used in the process according to the invention mentioned above, and optionally 25 additional additives.

By trichromy is meant the additive color mixing of suitably selected yellow or orange, red or blue dyes, with which all desired shades in the visible color spectrum can be obtained by appropriate choice of 30 proportions of the dyes.

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6

By the method according to the invention, stains with good to very good ozone resistance are obtained.

Anthraquinone dyes defined by formulas 5 (1) and (2) contain all fiber-reactive groups of the kind capable of reacting with the hydroxy groups in cellulose, with the amino, carboxy, hydroxy and thiol groups in wool and silk, or with amino and optionally carboxy groups in synthetic polyamides to form 10 covalent chemical bonds.

As alkyl groups within the meaning of A, B ^, B £, E ^, R ^, X,

Z 1, Z 2 and Z 3 in formulas (3), (4) and (5) can be used independently of each other straight-chain or branched-chain alkyl groups, for example methyl, ethyl, propyl, isopropyl, butyl, 15 sec-butyl, isobutyl and tert .-butyl.

An alkyl group A may be substituted, for example, with halogen such as chlorine or bromine, especially fluorine, and A is as an alkyl group preferably a C 1-6 perfluoroalkyl group, especially a trifluoromethyl group.

An optionally substituted phenyl group R 2 and R 4 may be one with C 1-4 alkyl, C 1-4 alkoxy or halogen substituted phenyl group. Preferably R 2 or an unsubstituted phenyl group.

An optionally substituted phenoxy group may be one having 25 C ^ £alkalkyl, especially methyl, C ^^ - al alkoxy or halogen, in particular: chlorine, substituted phenoxy group. As a phenoxy group, R 2 is preferably an unsubstituted or chloro-substituted phenoxy group.

As halogen in the definitions B, Z 2, and Z 2 in formulas (3) and (5), fluorine, chlorine or bromine, especially chlorine, can be used.

For example, as C 2-4 alkanoylamino in the definition B of formula (3), acetylamino, propionylamino or buffered amine may be used.

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7

In particular, as C5-6 cycloalkoxycarbanylamino in the definition of B, cyclohexyloxycarbonylamino may be used.

As C 1-4 alkylsulfonylamino in the definition of B may be used methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl or sec.-butylsulfonylamino.

As phenylsulfonylamino group in the definition of B, a phenylsulfonylamino group substituted with C 1-6 alkyl, C 1-6 alkoxy or halogen. Preferably, an unsubstituted or methyl substituted phenylsulfonylamino group is used.

As alkoxy groups in the definition of B 2, B 2 # E 2, Z 2 and in formulas (4) and (5), for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy or tert-butoxy are used.

As the hydroxyalkyl group in the definition X of formula (4), a straight or branched hydroxyalkyl group, e.g. a β-hydroxyethyl, β-hydroxypropyl, β-hydroxybutyl or α-ethyl-β-hydroxyethyl group.

When C1-4 alkyl means, this group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.

When C 1-4 alkoxy means, this group may be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy or tert-butoxy.

When C2-4 alkanoylamino means, this group may be, for example, acetylamino, propionylamino or butyrylamino.

When an optionally substituted arylsulfonyl, aryl-oxy or arylcarbonyl group means, aryl preferably means a group of benzene or naphthalene group which may be further substituted, e.g. with C 1-4 alkyl groups such as methyl and ethyl, C 1-4 alkoxy groups such as methoxy or ethoxy, halogen such as fluoro, chloro or bromo, alkanoylamino groups

1 C Λ · »» * S 4- ΑΛΛ v. / «£ A Avw» a a Ml ·! MUST. Μ M

DK 165338 B

8 When W · and / or means halogen, these groups may be fluoro, chloro or bromo.

When W 2 represents a substituted aryloxy or aryloxy sulfonyl group, aryl means a group of the benzene or naphthalene series which may be further substituted, e.g. with C ^ ^ alkyl alkyl groups such as methyl and ethyl, C ^ _ ^ alkoxy groups such as methoxy and ethoxy, halogen such as fluorine, chlorine and bromine, alkanoylamino groups having 1-6 carbon atoms such as acetylamino, and hydroxy.

When W 1, W 2 or W g means an optionally substituted alkyl group, this independently of the others is preferably a straight or branched C 1-6 alkyl group, especially a C 1-4 alkyl group which may be further substituted, e.g. . with halogen, such as fluoro, chloro or bromo, hydroxy, cyano, C 1-4 alkoxy, such as methoxy or ethoxy, and alkanoyl groups of 1-6 carbon atoms, such as an acetyl or propionyl group, and a benzoyl group.

An alkyl group may also be substituted with sulfo. Examples of W 2, W 2, and W 5 as alkyl groups include methyl, ethoxy, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl and trifluoromethyl.

When Wg, Wg and Wg represent an optionally substituted aryl group, they independently of one another preferably belong to benzene or naphthalene series, and * may be further substituted, e.g. with C 1-4 alkyl groups such as methyl, C 1-4 alkoxy groups such as methoxy and ethoxy, halogen such as fluoro, chloro or bromo, trifluoromethyl, alkanoylamino groups of 1-6 carbon atoms such as acetyl. amino hydroxy and carboxy. The aryl group Wg may also be substituted with sulfo. Wg, Wg and Wg, as aryl groups, are in particular a phenyl group which may be substituted by methyl, trifluoromethyl and chlorine.

When W 1 is an alkyl group, it is preferably a straight or branched C 1-6 alkyl group, especially a C 1-6 alkyl group. Examples of these groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl- (1), pentyl- (3), heptyl- (1), heptyl- (3) and oxtyl- (1).

DK 165338 B

9 When W 2 and W g represent an optionally substituted cycloalkyl group, these groups are independently preferably cycloalkyl groups having 5- to 7-membered rings, which may be further substituted, e.g. with C 1-6 alkyl such as methyl. In particular, they are a cyclohexyl group.

Particularly preferred embodiments of the process of the invention are characterized by using at least one red dye of formula (3) wherein A is hydrogen, methyl, trifluoromethyl / R 10 -CON 2, -SO 9 N 2 x or -SO, R , R 2 is methyl or ethyl, R 2 is cyclohexyl or phenyl, and R 2 is phenyl, methylphenyl, phenoxy or chlorophenoxy, and B is hydrogen, chloro, acetylamino, propionylamino, cyclohexyloxycarbonylamino, phenylsulfonylamino or methylphenylsulfonylamino, since A and B cannot simultaneously represent hydrogen, and b) at least one yellow or orange dye of the formula '.- / CH3 ../l C * \ / * ~ N = N ~ * \) · -0-Χ (7 ) ho s- N; · - ·) ... / \ ../ i

J K

A 1 wherein A 1 represents hydrogen or methyl, means hydrogen or methyl, and means methyl, ethyl, β-hydroxyethyl, β-hydroxypropyl, β-hydroxybutyl or α-ethyl 2 -hydroxyethyl, or a mixture of at least one dye of the formula ( 7) and a yellow dye of the formula

DK 165338B

10 • fVsv </ '> T /' * 5 N'NT "TH3 (8),

vV

, _A

Z - + - H — SO H

6 v * wherein Z 2 and Z g each represent hydrogen, methyl or chlorine, or a yellow dye of the formula · - # φ / ^ «- N = N- · - / \

Al / ii-i-SO3H (9> · <k W4) wherein hydrogen, methyl, chloro, methoxy, ethoxy, o-methylphenoxy, phenoxy, acetylamino, phenylsulfonyl, p-methylphenylsulfonyl, p-chlorophenylsulfonyl, naphthylsulfonyl, p-methylbenzoyl or p-chlorobenzoyl, Vi 2 means hydrogen, chloro, methyl, trifluoromethyl, o-methylphenoxy, o-chlorophenoxy, o-chlorophenoxysulfonyl, -SC 2 N 2 / NC 2 -2-alkylaminosulfonyl, N, N-dimethylaminosulfony 1 , N-methyl 1-N-β-hydroxyethylaminosulfonyl, N-methyl 1-N-cyclohexylaminosulfonyl, N-phenylaminosulfonyl, No-methylphenylaminosulfonyl, No-chlorophenylaminosulfonyl, Nm-trifluoromethyl-phenylaminosulfonyl, N-ethyl phenylaminosulfonyl, -CONH 2 or -CON (CH 3) 2 / is methyl or phenyl, and W 4 is hydrogen, methyl, ethyl or octyl.

Particularly interesting embodiments of the process according to the invention are characterized by the use of 20 c) in particular a dye of formula (1) wherein G 1, G 3, G 2 and G 5 are hydrogen and G 3 is chloroacetylamino.

DK 165338 B

Or α, β-dibromopropionylamino, or wherein G 2, G 2, G g and G g represent hydrogen and G 4 represents vinylsulfonyl, chloroacetylamino, 2-methoxy- or 2-ethylamino-4-fluoro-s-triazinylamino, or wherein G ·, Gg and Gg are methyl, Gg 5 is hydrogen, and G4 is chloroacetylaminomethyl, α, β-dibromopropionylaminomethyl or -CH (COOH) -NH-CO-CHBr-CHgBr, or wherein G1 is methoxy, Gg, G g and G g represent hydrogen and G 1 represents β-sulfatoethylsulfonyl or wherein G

Gg and Gg represent hydrogen and Gg and G4 represent chloroacetyl-ΙΟ aminomethyl or -CH (COOH) -NH-CO-CHBr-CH 2 Br, or wherein G 2, Gg and Gg represent methyl, G 2 means α, β-dibromopropionylamino and G 2 is sulfo or wherein G 2 is sulfo, G 2, G 4 and G g are hydrogen and G g is α-bromoacryloylamino or wherein G 2 is methyl, G 2 is 2.6-15 difluoro-5-chloro -pyrimidylamino, Gg and Gg means hydrogen, and G 2 means sulfo, or d) a blue dye of formula (2) wherein cyclohexyl and Yg represent 4- (4'-methylphenoxy) phenyl and wherein the phenyl ring in the phenoxy group is substituted with sulfo and chloroacetylaminomethyl.

A particularly important embodiment of the process according to the invention is characterized by the use of a blue dye of formula (1) wherein G 1, G 2, G 2 and G g represent hydrogen and G g means α, β-dibromopropionylamino, or wherein G , Gg, G4 and Gg means hydrogen, and G2 means vinylsulfonyl, chloroacetylamino, 2-methoxy-4-fluoro-s-tri-azinylamino or 2-ethylamino-4-fluoro-s-triazinylamino, or wherein G1 means methyl, G2 means 2,6-difluoro-f-chloro-pyrimidinylamino, Gg and Gg means hydrogen, and G 1 means sulfo, or wherein G 2a means methoxy, G 2, Gg and Gg means hydrogen, and G 2 means β-sulfatoethylsulfonyl, or wherein G 1, Gg and Gg are methyl, G 1 is hydrogen or -CH (COOH) -NH-CO-CHBr-CH 2 Br, and G 4 is α, β-di-bromopropionylaminomethyl or -CH (COOH) -NH-CO -CHBr-CH 2 Br, or wherein G 1 is Gg and Gg is methyl, G 2 is α, β-dibromopropionylamino, and G 4 is sulfo, or wherein G 1 is sulfo, Gg, G 4 and Gg is hydrogen, and Gg is α-bromoacryloylamino, together with a red dye of the formula

DK 165338 B

12 (3) and the yellow or orange dyes of formulas (4) and / or (5) or (6).

A particularly important embodiment of the process according to the invention is characterized by the use of the blue dye of the formula 8 p2 / \ AA / ° 3η in ii 5 f \ AA /% .CH HHC0CH.C1 H fc-s \ -ch cco ), or the dye of formula. A ^ 2 / vVV 3 I II Π Γ% / \ / \ / C ^ 3 / H NHCOCH Cl 8 fc— / \ _CH and cil3 XCH2NHC0CH2C1 or the dye of formula II Fa. A A A / ° 3h • · · ·

I II II I

10% AA / · · · · · 8 lb— ^ VNH-CO-CH Cl (12) or the dye of formula 8 fKO · / v'v \ I 11 11 1% / \ / \ / CH-NH-CO -CH Cl '8 K> - <T> -CH3' (33,

DK 165338 B

13

In the process of the invention, mixtures of two or more of the above-defined anthraquinone dyes may also be used. In particular, a mixture of two anthraquinone dyes is used, the individual components of which each contain one or two fiber-reactive groups and one or two sulfonic acid groups.

Preferably, the individual components of the mixture correspond to one of the anthraquinone dyes defined above under formula (2).

An important mixture of anthraquinone dyes which can be used in the process of the invention is characterized in that one component corresponds to a dye of formula (10}, (11) or a dye of formula · - · 8 F <H>

15, A / \ / \ SO3H

I II II I, ,, (14) \ / \ / \ / - (CH NHC0CH2C1> ΰ hi- · ^ · - ♦ '. =. V <> -CH3 - · * · * and the other component corresponds to a dye of the formula (1) wherein G 1 is G 2, G 4 and G g means hydrogen and G 2 represents α, β-dibromopropionylamino, or wherein G 1, G 2, G 4 and G 5 are hydrogen and G 2 is vinylsulfonyl. chloro-acetylamino, 2-methoxy-4-fluoro-s-triazinylamino or 2-ethylamino-4-fluoro-s-triazinylamino, or wherein G G. means methyl, G2 means 2,6-difluoro-5-chloropyrimidinylamino, G represents hydrogen, and G 1 represents sulf o, or wherein G 1 represents sulf o, G 2, G 4 and G 5 means hydrogen, and G 2 represents α-bromoacryloylamino, or wherein G 2, G 2 and G 5 methyl, G2 means α, β-dibromopropionylamino-methyl, -CH (COOH) -NH-CO-CHBr-CH2Br or α, β-dibromopropionylamino, and G4 means hydrogen, -CH (COOH) -NH-CO-CHBr-

DK 165338B

C1-6 Br or sulfo, or in which G1- means methoxy, G2, G2 and G1j represent hydrogen, and G2 means β-sulfatoethylsulfonyl.

A particularly important mixture of anthraquinone dyes which can be used in the process of the invention is characterized in that one component corresponds to the dye of formula (10) or (11) and the other component corresponds to the dye of formula (14).

Another particularly important blend of anthraquinone dyes, which can be used in the process of the invention, is characterized in that one component corresponds to the dye of formula (10) or (11) and the other component corresponds to the dye of formula (1). wherein G 2, G 2, G 2 and G 5 are hydrogen and G 3 is chloroacetylamino.

A particularly important mixture of anthraquinone dyes which can be used in the process of the invention is characterized in that one component corresponds to the dye of formula (11) and the other component corresponds to the dye of formula (13). Preferably 20 is the weight ratio of the dyes of formula (11) to (13) 90:10 to 70:30, especially 80:20.

Usually, the weight ratio of the anthraquinone dyes in the blends used in the process of the invention may vary widely. A weight ratio 25 of 90:10 to 10:90, especially 70:30 to 30:70 has been found to be advantageous.

The anthraquinone dyes of formula (2) used in the process of the invention or the components of the mixtures of the anthraquinone dyes preferably contain only a single sulfonic acid group.

DK 165338B

15

In the process of the invention, preferably a red dye is used e) a red dye of formula (3) wherein A is hydrogen, N-methyl-N-cyclohexylsulfamoyl, phenylsulfonyl, N-ethyl-N-phenylsulfamoyl, phenoxysulfonyl or trifluoromethyl, and B means hydrogen, acetylamino or cyclohexyloxycarbonylamino, and in particular f) a red dye of formula (3) wherein A means hydrogen and B means acetylamino or cyclohexyloxycarbonylamino, or

A represents trifluoromethyl, and B represents acetylamino, or A

means phenylsulfonyl, N-methyl-N-cyclohexylsulfamoyl, N-ethyl-N-phenylsulfamoyl or phenoxysulfamoyl, and B means hydrogen and the yellow or orange dye of formula (4) to (6) (g) the yellow dye of formula. / “I 15 / \ -0CH3 (15) ·» · · «» Bl s £ 3h or the orange dye of the formula / 0CH3, · - · i- «· - · H03S“ * \) -N = N-. () - N = N - (VoCH (16) c3 or a mixture of the yellow dye of formula (15) with an orange dye of formula '(16) 20 or a mixture of the dyes of formulas (15) and / or (16) with the dye having the formula * a * · = · \ lyh / Y (17! .A / 1 in! l H03S /

DK 165338 B

16 wherein the weight ratio of the dyes of formulas (15) and (16) is 60:40 to 40: 60 / especially 1: 1 and the weight ratio of the dyes to formulas (15) or (16) and (17) is 80:20 to 20:80, especially 70:30, and the weight ratio of the dyes 5 to formulas (15), (16) and (17) is 60:20:20, 20:60:20 to 20:20:60, especially 1: 1. : 1, or the yellow dye of formula AA / ° 3h: r; rr ((v / yyv

* V * H

A particularly preferred embodiment of the process according to the invention is characterized in that a blue dye of formula (10), (11), (12) or (13) or a mixture of the dyes of formulas (11) and (13) is used. in a weight ratio of especially 70:30, together with a red dye of the formula h3c-n- <7> i ~ so, <19> I H2 \ _.

V · · = · X * HO— (\ · - ·

Xs ° 3H

o- · x · L ^ i2 H2V.

/ \ - N = N - / # \ (20) or I} \ = / X · W- / \ \ o3h

DK 165338 B

17? F3 H2 \ _ \ -N = N- · ^ hn-l} w <21) i0 V HO- <> I N · - · '

CH3 XS03H

the yellow dye of formula (15), (16) or (18) or a mixture of the yellow dye of formula (15) and (17) in the weight ratio 70:30.

A particularly important embodiment of the process according to the invention is characterized by the use of a dye of formula (10) or (111) with a dye of formula (1p) and the dye of formula (16).

The dyes used in the process according to the invention for trichromy staining are known or can be prepared analogously to known methods. Thus, for example, the dyes of formulas (1) and (2) can be prepared as described in DE Publication No. 2,305,206 and No. 3,142,852, in Swiss Patent No. 466,470, in GB patent no.

No. 15,903,590, the dyes of formula (3) can be prepared as described in DE Patent Nos. 702,932 and No. 2,063,907, and in DE Publication No. 2,712,170, and the dyes of formulas (4) and (5) can be prepared as disclosed in DE Publication Publication No. 2,142,412 and DE Publication Publication No. 20,100,846.

When dye mixtures are used in the process according to the invention, these can be prepared by mixing the individual dyes. This mixing process can be carried out, for example, in suitable mills, e.g. ball or pin mills, and in kneading or mixing apparatus.

Furthermore, the mixtures of the dyes can be prepared by spray drying the aqueous dye mixtures.

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18

The dyes used in the process according to the invention are either in the form of free sulfonic acids or preferably as salts thereof.

As salts, for example, alkali metal, alkaline earth metal or ammonium salts or salts of an organic amine are used. Examples of these salts include sodium, lithium, potassium or ammonium salts or salts with triethanolamine.

The dyes used in the process according to the invention usually contain other substances, such as e.g. sodium chloride or dextrin.

The present method for trichromy staining can be applied to the usual continuous color processes. In addition to water and the dyes, the dye floats may contain other additives, such as wetting agents, anti-foaming agents, leveling agents or agents for affecting the properties of the textile material, such as plasticizers, fire retardants or dirt, water and oil repellents, and water softeners and natural softeners and water softeners. such as alginates and cellulose ethers.

The method of the invention is particularly suitable for staining with card floats, such as, for example, by the continuous color method and / or continuous foam color methods.

The process of the invention is suitable for continuous dyeing of synthetic polyamide materials, e.g. "Nylon" or "Perlon" ®, especially polyamide-6,6 and preferably polyamide-6 materials.

Said textile material may be available in various forms of processing, e.g. fibers, yarns, weaves, knitwear 19

DK 165338 B

• they last and especially in the form of blankets.

The good ozone resistance, which should be particularly emphasized in connection with the dyes produced by the process of the invention, is determined according to the regulations of the American Association of Textile Chemists and Colorists, test method 109-1975 or 129-1975.

The amounts in which the dyes or mixtures are used in the dye baths may vary within wide limits depending on the desired color depth, and it is usually advantageous to use amounts of from 0.001 to 6% by weight based on the material to be dyed.

The raft ratio can be selected within a wide range, especially from 1: 1 to 1: 5.

The staining is carried out with aqueous floats at temperatures between 60 and 98 ° C. Advantageously, hot foularding or hot spraying is done on the product.

The pH value of the color float can range from 5 to 9. It is usually advantageous to use a pH value in the range of 6-8.5.

The process according to the invention is further illustrated in the following 20 examples in which the parts listed are by weight. The ratio between weight parts and volume parts is the same as 3 between g and cm.

Example 1.

An aqueous solution containing 0.65 g / l of the dye 25 of formula * 20

DK 165338B

ho3s - <> _> - n = n - <^ >> - m-.Q..0CH3 0.29 g / l of the dye of formula · - · H3C “N“ * \ H / * I · - ·

Γ2 "V

/ XJ-N »n- / \ <19) ·. · · = · Χ · HO— (\ ^ y · - ·

n SO 3 H

and 0.57 g / l of the dye of the formula 0 NH II I ^ ^ \ / \ /% srjj rso3H (11) V WX ^ CH_NHCOCH0C1 ii i -3 2 2 0 NH- · '/ * - CH · H3C XCH2NHC0CH2C1 and 3 g / l anionic wetting agent is adjusted with Na 2 PO 2 at pH 8.2.

This raft is applied to a non-wetted polyamide-6 raw carpet in an amount of 300%, based on the weight of the rug, at a raft temperature of 22 ° C and at a carpet speed of 8 m / min.

The saturated carpet is then fed to a steam treatment plant, where it is treated for 4 minutes with saturated steam of a temperature of 98-100 ° C.

After washing in a broad washing machine, a carpet colored with a uniform brown hue is obtained, both with respect to the surface and the individual fibers, with good ozone resistance.

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21

The ozone content of the dye produced is determined using Regulation AATCC [American Association of Textile Chemists and Colorists] 120-1975, and the color change is assessed by the gray mass (SNV Swiss Norm Association -5 Norm 95805), where the number 1 expresses the worst rating and the number 5 the best rating.

The staining obtained with the above dyes has the authenticity number 4.

When, instead of the cold raft in the above example 10, a raft with a temperature of 90 ° C is used, a similar uniform tan is obtained without the use of a steam treatment plant or with a residence time of 1 minute in saturated steam of 98-100 ° C. good ozone-proof carpet with an authenticity of 4.

Example 2.

An aqueous solution containing 0.15 g / l of the dye 15 of the formula ._. / OCH 3 H O 3 S “# \) -N = N- (> -N = N- /) -0CH (16)

· = · · = · · = · J

0.1 g / l of the dye of formula · - · (19) Γ2 "v,.

/yN=N./ \ • · · = · v “° - <> · - ·

'' SOjH

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22 0.125 g / l of the dye of formula

0 NH II I

.A ./\/\_ so h l 'i' i 1 3. (10) \ / \ / \ SH c ch 'nhcoch9ci II IJL Δ o NH- · ζ) —CH3 · = · 2.0 g / 1 ammonium sulfate ester of ethoxylated nonylphenol and 0. 5 g / l of ethoxylated nonylphenol, adjusted on pH 8.0 with a mixture of Na₂HPO ^ and NaI₂PO₂, heated to 96-98 ° C. This hot solution is sprayed in a closed chamber at a pressure of 3 atm through a series of nozzles on a polyamide 66 blanket which is continuously passed through the chamber. The blanket residence time in the chamber is approx. 5 seconds. The beautiful shooting out-10 makes approx. 500%, based on the weight of the carpet. A uniform brown colored polyamide 66 blanket having an ozone resistance of 3-4 is obtained, with the evaluation of the ozone toughness being carried out as in Example 1.

Proceeding in the same manner as described above in Example 1 and instead of the combination of dyes of formula (16), (19) and (11) listed in Example 1, they use the table below in Examples 3- 12 combinations of dyes in the quantities indicated there are also blankets colored uniformly in olives to brown shades with good ozone authenticity, the ozone authenticity being carried out in the same manner as in Example 1.

DK 165338B

23

Table

Ex. Dye Authenticity ~ 0.83 g /; l of the dye of formula 3_4 '/ 0CH3 H03S "\ /" n = n "\> -N = N- <X-0CH3 (16) · = · · = · · = · Ci3 1.78 g / l of the dye of formula · - · H3CT <H>? ° 2 = 2? A / "% (19) · '* -Ν = Ν- · / χ · I II \ / • · · = · ^ / / \ * / · \ v · - ·

io H

and 0.98 g / l of the dye of formula · - · e ψ- \ H>

A AA

% Λ Λ / JH2-NH-CO-CH Cl 8 Ah-A / -CH3 · = · · φ * έθ3Η 4 0.92 g / l of the dye of formula (16) 4 1.67 g / l of the dye with formula (19) and 0.76 g / l of the dye of formula fl AA /% / SO3h Γ Π.] Τ (22) ^ / \ / \ ^ • · · · - · 8 ta-A V ~ nh-co -c = ch0 \ = / I 2 S ^ 3H Br

DK 165338 B

24 "" Authenticity

Dye No. ___ rai_ 5 0.90 g / l of the dye of formula (16), 4. 1.30 g / l of the dye of formula (19) and 1.02 g / l of the dye of formula o P2 / vVV ° 3h VVV1 (23) B Oh— / ^ .- ch3 · = · ci3 '' NH-CO-CHBr-CH Br 6 0.92 g / l of the dye of formula (16) ^ 3-4 1.33 g / i of the dye of formula (19)) 0c 1.89 g / i of the dye of formula

il Ψ2 Qn H

/ vVV3% AÅ / C ^ 3 / Η2ΝΗ000Η201 (10) • · · 8 <) - ° ¾ · - · ci3 7 0.86 g / l of the dye of formula (18), 3-4 1.67 g / l . of: 'the dye of formula (19) and 1.60 g / l of dye of formula. i ft «, i ί li i <12> • v · ·. · ^ / \ / \ ^ • · · · - · 8 ^ * - nh-co-ch2ci · = ·

DK 165338 B

Ex. Authenticity f: No. Dye in 8 1.18 g / l of the dye of formula (16), 4 1.99 g / l of the dye of formula (17) and 1.14 g / l of the mixture of the dyes of formula (10) and (13) containing :: 80% by weight of the dye of formula (10) and 20% by weight of the dye of formula (13), calculated on the total mixture 9 1.97 g / l of the dye of formula 4 <> 1 ° 2 "* A" "A Λ" <18) r ii ~ NN-s-rs ·. ·. ···.

V / V V V

1 'i'

\ / H

2.47 g / l of the dye of formula (19) and 1.08 g / l of the mixture of the dyes of formulas (LO.) And (L3) containing 80% by weight of the dye of formula (10) and 20 % by weight of the dye of formula (13), calculated on the total mixture. 10 1.89 g / l of the dye of formula 4. / CH 3 °

\ / N = N / "N = N— '/ - ° ce3 V

· = · · = · · = ·

S ^ H

1.06 g / i of the dye of formula n - / "\ ^ o2x ../ h2ji (20) * -N = Ν- · χ χ · I II \ / ·. · · = · V" o- <> V /

io3H

DK 165338 B

26 - - - .____ _ ----. . - -------- - --- - —------ - - ---- ·

Ex. Dye Authenticity

No .__ tal_I

i in and! . · In 1/06 g / l of the dye of formula (10) j ί 11 2.03 g / l of the mixture of the dyes with the four formulas (15) and S * ~ \ * -o-so - · N · \ / 2 \ / · = · f = · (17),

Cl N = N-g-C-CH 3

* / Y

A / C1 in li

ho3s 7 V

the mixture containing 70% by weight of the dye of formula (15) and 30% by weight of the dye of formula (17), based on the total mixture, 0.89 g / l of the dye of formula

f3 H2? IN

/ \ # \ • * -N = N- · · / o -i \ ____ I il \ / (21) CO * H0% / and I · - · '

ch3 io3H

1.30 g / l of the mixture of the dyes of formulas (11) and (13) using 80% by weight of the dye of formula (11) and 20% by weight of the dye of formula (13), calculated on the total mixture ii} ---------

DK 165338B

27 μΓ. Dye Color No. ___________ Number 12 1.82 g / l of the dye of formula (16), 4. 2.32 g / l of the dye of formula (19) and 5 1.19 g / l of the dye of formula β2 / vVV ° 3H (24)

I II II I T

VVV .- / ° 3h 8 'nh- / \ q. ^ c £ 3 W /> j ________ 'v \ -! ....... f ..... "..... * '" 1 - .................. 1 1 11 »I, - I ...

Comparative Example 1.

When in Example 1, instead of 0.57 g / L of the dye of formula (11), 1.26 g / L of the non-fiber reactive dye of formula I / I / S is used. ·

10 · '· · · CH

VW 3 (25) 8 Oh- /) * _ ch3 · = ·

NS02NHCH2CH20H

and otherwise proceeds in the same manner as described in Example 1, a brown hue blanket is obtained which, when tested for ozone no. authenticity according to AATCC 129-1975 achieves an authenticity figure for the color change [SNV-Standard 95805] of only 2.

Comparative Example 2.

Proceeding in the same manner as described in Example 1, and instead of 0.57 g / l of the dye of formula (11) use 1.09 g / l of the non-fiber reactive dye of formula

DK 165338B

28 O F2

/ \ /% / SO3H

t il ii * / "%% AA / cl3 / h2-nh-co -. (\ • · · · - · · = · ΰ ltai - / * - CH3 (26) · = · rf3 obtains a rug colored in brown shades, the ozone of which is tested in the same way as described in Comparative Example 1, corresponds to an authenticity of 2.

Claims (13)

Method for continuous trichromy staining of synthetic polyamide materials, characterized in that these materials are treated continuously with a dye float containing at least one fiber-reactive blue dye of the formula 0 NH u [S \ y \ -so_a I 11 II I 3 VVV Cl \ / 2 (1) ' 0 HH - · () · -03 · =: · <X wherein G 1, G 3 and G 5 are methyl, G 4 is or, / 3-dibromo-10 propionylaminomethyl, or-chloro or α-bromoacryloylamino methyl 1, 3 - (/ 3 '-Sulf ato-ethylsulfony 1) -propionyl 1-aminomethyl 1, α, 3-dibromopropionylamino, -CH (COOH) -NH-CO-CHBr-CH 2 Br or chloro-acetyl aminomethy 1, and G 2 means hydrogen, sulf o or chloro ace ty laminome thyl or -CH (COOH) -NH-CO-CHBr-CH2Br, or wherein Θχ means hydrogen or methoxy, G2, G3 and G5 means hydrogen and G4 means sulfatoethylsulfonyl, chloroacetyl amino, α , / 3-dibromopropionylamino, vinyl sulphonyl, 2-methoxy-4-fluoro-s-triazinylamino or 2-ethylamino-4-fluoro-s-triazinylamino, or wherein G 1, G 2, G 4 and G 5 are hydrogen, and G3 means chloroacetylamino or or, 3-dibromo-prionyl amino, 2,6-difluoro-5-chloropyrimidin-4-ylamino, 2-chloro-4-amino- or 4-N, N-dimethylamino-s-triazinylamino, Or wherein Θχ is methyl, G2 is β-sulfatoethylsulfonyl, and G3, G4 and G5 are hyd or wherein one of G 2 and G 2 is sulfo, G 3 is α-bromoacryloylamino or N-methyl-N- [3- (3-chloroethylsulfonyl) benzoyl] amino, and the other of G 2 and Θχ and G4 and DK 165338 BG 5 means hydrogen, or ϋχ, G2 and G5 means hydrogen, G3 means methyl, and G4 means chloroacetylamino, 5 or wherein Gx means methyl, G2 means' 2,6-difluoro-5-chloropyrimidinyl amino, G4 means sulfo, and G3 and G5 means hydrogen, or at least one fiber-reactive blue dye of the formula. S Γ1 __ (S0jOm * il i * (2), \ / \ / \ / Process according to claim 1, characterized in that the blue dyes of formulas 8 Ψζ, A / \ A / ° 3h V \ A / ^ / h2 »hcoch2ci 8 Åh- / · ~ εΗ3 * • s # Ci3 are used. ^ \ / \ /% / S03H • · · · \ Å / C? 3 ^ / HjSBCOCHjCI B ί ^ Η - / '"A · = · ci3 xch2nhcoch2ci DK 165338B ft ^ 2 / v \ A / ° 3h I li II I ^ / \ / \ f H Ah— ^ \ -nh-co-ch2ci (12) • SS # · - · 0 ¥ H- <H> MA * '* I II II I SAA / ch2-nh-co- ch Cl ML / \ / t \ Process according to claim 1, characterized in that mixtures of two anthraquinone dyes are used with the definition of claim 1. 3 Bi wherein Βχ, Bø and Εχ means hydrogen, C (1-4) alkyl or C (1-4) alkoxy, and X means straight or branched C (1-4) alkyl or straight or branched C ( 2-4) -hydroxyalkyl, or / 2/2. h A - N - c — C - CH 3 h / Y / \ Zn-4- * —Ή — SO 2 H 2 · · 3 * / h 'wherein Ζχ, Z2 and Z3 each represent hydrogen, halogen, C (1- 4) -alkyl or C (1-4) -alkoxy, or mixtures of dyes of formulas (4) and (5), or a yellow dye of formula DK 165338B N «M-L - * - s \ A Ά ' Wherein L is hydrogen, C (1-4) alkyl, C (1-4) alkoxy, halogen, C (2-4) alkanoylamino or an optionally substituted arylsylphonyl, aryloxy - or arylcarbonyl group, Wg means hydrogen, halogen, an optionally substituted alkyl, aryloxy, aryloxysulfonyl group or a group of the formula W w -s ° 2 <or -cot / 5 Process according to claim 3, characterized in that a mixture is used, wherein one component is a dye of formula (1), (10) or (11) and the other component is a dye of formula. ϊ Γ® * ^ \ \ ^ 3 Wherein X is methyl or ethyl, R2 is cyclohexyl or phenyl, and R3 is phenyl, methylphenyl, phenoxy or chlorophenoxy, and B is hydrogen, chloro, acetylamino, propionylamino, cyclohexyloxycarbonylamino, phenylsulfonylamino or methylphenylsulfonylamino. A and B cannot both mean hydrogen. Process according to one of claims 1 and 3, characterized in that monosulfo group-containing dye of formula (2) is used. DK 165338 B Process according to claim 1, characterized in that at least one red dye of formula (3) is used, wherein A is hydrogen, methyl, trifluoromethyl, -CON 2, -SO, N 2 x or -SO, R, Process according to claim 6, characterized in that a red dye of formula (3) is used, wherein A is hydrogen, N-methyl-N-cyclohexylsulfamoyl, phenylsulfonyl, N-ethyl-N-phenylsulfamoyl, phenoxysulfonyl or trifluoromethyl, and B means hydrogen, acetylamino or cyclohexyloxycarbonyl amino. Process according to claim 7, characterized in that a red dye of formula (3) is used, wherein A 20 is hydrogen and B is acetylamino or cyclohexyloxycarbonyl amino or A is trifluoromethyl and B is acetylamino or A is phenylsulfonyl. , N-methyl-N-cyclohexylsulfamoyl, N-ethyl-N-phenylsulfamoyl or phenoxysulfonyl, and B means hydrogen. 8 Ah- (> -o- <,> - ch3 {13) · = · · ± · io3B 8 NHY3 - <T) i 10 wherein Υχ means cyclohexyl, Y3 means 4- (4'-methyl-phenoxy) -phenyl, and T means chloroacetylaminomethyl, and wherein the dye contains a single sulfonic acid group, or wherein Υχ means isopropyl, and Y3 means a phenyl yl-sec-butyl group substituted in the phenyl ring by sulfo and chloroacetylaminomethyl, or a diphenyl ether group which in the phenoxy group is substituted by sulfo and acryloylaminomethyl, or wherein Υχ and Y -butyl group substituted in the phenyl ring with sulfo f 20 and chloroacetylaminomethyl, or wherein Υχ and Y 3 each represent a 4-α-bromo-acryloylamino-3-sulfophenyl group, together with at least one red dye of the formula in S ) -N = N- (; · (3), · = / · = · / \ H0 -., · \ Ο3η) wherein A means hydrogen, optionally substituted C (1-4) alkyl. N 1 = -CO-N 1 or -SO_R 2 \ \ 23 * 2 z where C 1 -C 4 alkyl, R 2 optionally substituted C (5-7) -cy cloalkyl or optionally substituted phenyl, and Rø means optionally substituted phenyl or optionally substituted phenoxy, and B represents hydrogen, halogen, C (2-4) -alkanoylaxnino, C (5-8) -cycloalkoxycarbonyl-araino, C (1-4) ) -alkoxycarbonylamino, C (1-4) -alkylsulfonylamino or optionally substituted phenylsulfonylamino, and at least one yellow or orange dye of the formula / 2, for example · · · · · · · · · · · · · (4) / · · Is · β · \ ηο, γ ox Process according to claim 1, characterized in that at least one yellow or orange color of the formula 'is used. / “» / 1 at! <>: «- <> ™ - <> - ° Λ (7> HO ^ S— · / * m * · * · Ai DK 165338 B wherein Αχ means hydrogen or methyl, Fi means hydrogen or methyl, and Χχ means methyl, ethyl, β-hydroxyethyl, β-hydroxypropyl, β-hydroxybutyl or α-ethyl-β-hydroxyethyl, or a mixture of at least one dye of formula (7) and a yellow dye having the formula · - · · - ♦ / \ -o-so2- <> T / "5 ^ -nc # 3 (s)," / VS \ wherein Z5 and Z5 each represent hydrogen, methyl or chlorine, and a yellow dye of formula Process according to claim 9, characterized in that the yellow dye of the formula is used .- / "i '... * \ / · _Ν" Ν' · \ V * -N- · ^ \ -0CHj (15) · => «·« · · <= · Is 3H 5 or the orange dye of formula ../ ”3 H03S— (\ -n = N- · ^ \ -n = N- · ^ ^ * - 0CH3 (16) · = · · = · · = · ° i3 or a mixture of the yellow dye of formula (15) with the orange dye of formula (16), or a mixture of the dyes of formulas (15) and / or 10 (16) with the dye of the formula · - · «<> - ° -sv <> • = · ^ · = · C1 N = NCC-CH3 h / Y (17) Λ / 1 1 · HC ^ S7 V, the weight ratio of the dyes to the formulas (15) and (16) are 60:40 to 40:60, especially 1: 1, and the ratio of the dye of formula (15) or (16) to (17) is 15 80:20 to 20:80, especially 70 : 30, and the weight ratio of the dyes of formulas (15), (16) and (17) is 60:20:20, 20:60:20 to 20:20:60, especially 1: 1: 1, or DK 165338 B yellow dye of formula <> - ° 2 '=' AA / S 03h i it — N - N—, ♦. ·, ···. · V S V V v! I! |% / H 10 XI) * "N = N" Li * \ 4 — SO H (9), / · φ · · · · · · i · K <Y · W4 wherein Wi means hydrogen, methyl, chloro, methoxy, ethoxy, o -methylphenoxy, phenoxy, acetylamino, phenylsulfonyl, p-methylphenylsulfonyl, p-chlorophenylsulfonyl, naphthylsulfonyl, p-methylbenzoyl or p-chlorobenzoyl, W2 means hydrogen, chloro, methyl, trifluoromethyl, o-methylphenoxy, o-chlorophenoxy o-chlorophenoxy , -SO2NH2, NC (1-2) -alkylaminosulfonyl, Ν, Ν-dimethylaminosulfonyl, N-methyl-N- [hydroxyethylaminosulfonyl, N-methyl-N-cyclohexylamino-sulfonyl, N-phenylaminosulfonyl, N-methyl-phenyl amino -20 sulfonyl, No-chlorophenylaminosulfonyl, Nm-trifluoro-methylphenylaminosulfonyl, N-ethyl-N-phenylaminosulfonyl, -CONH 2 or -CON (CH 3) 2, W 3 means methyl or phenyl, and W 4 means hydrogen, methyl, ethyl or octyl. DK 165338 B 10 I Γι M 7 (1 *) i 1 'S i - (CH.NHCOCH.Cl) „^ / \ / \ *? 2 212 • · · * —v a ^ '\ X /% · ”° - <> -®3 • S · m W 3 represents an optionally substituted alkyl or aryl group, W 4 represents hydrogen or alkyl, and W 5 and W 5 each represent hydrogen or an optionally substituted alkyl, cycloalkyl or aryl group, as well as water and optionally additional additives. Process according to claim 1, characterized in that a blue dye of formula (10), (11), (12) or (13) or a mixture of the dye with formulas (11) and (13) is used in weight ratio in particular at 70:30 with a red dye of the formulas H3C-N- <7> i - S02 <19> 1 ΗΛ .. i> - «- <> ho— (V / XS03H ° - <> f2 'H2 \ _ # f \ s. (20) or ·. · V H0- <> \ o3h? f3 * 2 \ / \ - N., N - / '\ ra-i' i> <(21) co H% ^ 1 · And the yellow dye of formula (15), (16) or (18) or the mixture of the yellow dyes of formulas (15) and (17) in the weight ratio 70:30. Process according to claim 11, characterized in that one of the blue dyes of formula (10) or (11) is used together with the red dye of formula · - · H3C-N -. (H (19) • · - > · Γ * -N = N- · ^ I II \ /% / / = \ • H ° -% / \ o3h and the orange dye of the formula / CH3 10 ho3s- () .- N = N -. () -och3 (16) · = · · = · · = * Aqueous color lotteries, characterized in that they contain water, a dye mixture according to claim 1 as well as any additional additives.