# US 7,410,594 B2 · Trichromatic dyeing process and dye mixtures used therein

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- Number: US 7,410,594 B2
- Document ID: US7410594B2
- Status: Granted
- Kind: B2
- Application number: 10/492,869
- Filed: 2002-10-14
- Published: 2004-12-16
- Granted: 2008-08-12
- Earliest claimed: 2001-10-17
- Assignees: Clariant Finance (BVI) Limited
- Inventors: Markus Gisler; Roland Wald
- Web page: https://patentgrep.com/patent/US7410594B2

## CPC

- C09B 67/0041: {mixtures containing one azo dye}
- D06P 1/0096: {Multicolour dyeing}
- D06P 1/38: using reactive dyes
- D06P 3/66: using reactive dyes
- D06P 3/10: using reactive dyes
- C09B: ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES {, e.g. PIGMENTS}; MORDANTS; LAKES (fermentation or enzyme using processes to synthesise a desired chemical compound C12P)
- D06P: DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM

## Abstract

The present invention relates to a process for the trichromatic dyeing or printing of hydroxy-group-containing or nitrogen-containing organic substrates with dye mixtures and also to such dye mixtures and hydroxy-group-containing or nitrogen-containing organic substrates dyed or printed therewith.

## Claims

### Claim 1

Trichromatic coloring process for coloring a hydroxy-group-containing or nitrogen-containing organic substrate comprising the step of coloring the substrate with a dye mixture comprising at least one red-dyeing compound of the formula (I)
wherein
R1 is a C1-4-alkyl group or a substituted C2-4-alkyl group,
R2 and R3 are independently from each other H; —OH; —CN; C1-2-alkyl;
—SO3H;
—COOH; —OC1-2-alkyl or —NH2,
X is a halogen radical and
Y —CH═CH2 or —CH2CH2-Z, wherein Z is a radical which can be eliminated by alkali,
at least one yellow or orange -dyeing compound is selected from the group consisting of: formula (II)
wherein
R4 and R5 signify independently from each other H or —SO3H,
A is a group of formula (i) or (ia)
wherein
X and Y are defined above,
R6 and R7 independently from each other H; unsubstituted C1-4alkyl or substituted C1-4alkyl,
B is
wherein R8 C1-4alkyl; —NH2 or —NHC1-4alkyl,
wherein the asterisk marks the bond to the —N═N— group;
of formula (III)
wherein
R9 —SO3H or —SO2Y, wherein Y is defined above,
R10 H or —SO3H,
R11 H; unsubstituted C1-4alkyl or substituted C1-4alkyl,
D is
wherein
X and Y are defined above and
R12 is H; unsubstituted C1-4alkyl or substituted C1-4alkyl;
and formula (IV)
wherein
R13 is H; methyl; methoxy, ethoxy; —NHCONH2 or —NHCOCH3,
R14 is H; methyl; methoxy or ethoxy,
RG is
wherein
R15 is H or chlorine,
Y is defined above;
and at least one blue-dyeing compound selected from the group consisting of: formula (V)
wherein
R16 is H or —SO3H,
R17 is
wherein
X and Y have the same meanings as defined above,
R18 and R19 are independently from one another H; unsubstituted C1-4alkyl or substituted C1-4alkyl,
n is 0 or 1,
T is
wherein
R16 has the meanings as defined above and Y has the meanings as defined above and
R20 is H; unsubstituted C1-4alkyl or substituted C1-4alkyl;
formula (VI)
in which
R21 is H or —COOH,
each of R22 and R24 is independently H; —COOH; —SO3H; —NHCOCH3; —NHCOCHY2—CH2Y1; —NHCOCY2═CH2 or —NHCOCH2Y1,
R23—COOH,
Y1 is chlorine; bromine; —OSO3H or —SSO3H and
Y2 is H; chlorine or bromine;
formula (VII)
in which
Y has the same meanings as defined above,
R25 H or —SO3H,
R26 H or —SO3H;
and formula (VIII)
wherein
each Y has independently from each other the same meaning as defined above,
R27 and R28 are independently from each other H;
unsubstituted C1-4alkyl or substituted C1-4alkyl.

### Claim 2 (depends on 1)

Trichromatic coloring process according to claim 1, wherein the dye mixture comprises at least one red-dyeing compound of the formula (Ia)
wherein
X′ is Cl or F,
R′1 is a C1-2-alkyl, especially —C2H5, or a C2-4-alkyl group, which is monosubstituted by Cl, F, Br, —OH, —CN or —NH2,
R′2 and R′3 are independently from each other H; C1-2-alkyl; —SO3H or —OC1-2alkyl,; —CH3; —SO3H or —OCH3 and
the —SO2Y group is attached to the phenylring at position 3, 4 or 5, wherein Y is as defined in claim 1.

### Claim 3 (depends on 1)

Trichromatic coloring process according to claim 1, wherein the dye mixture comprises at least one yellow or orange -dyeing compound selected from the group consisting of formula (IIa), (IIb), (IIc)
wherein A is
formula (IIIa), (IIIb)
wherein D is
formula (IVa) and (IVb)
wherein RG is

### Claim 4 (depends on 1)

Trichromatic coloring process according to claim 1, wherein the dye mixture comprises at least one blue-dyeing compound selected from the group consisting of formula (Va), (Vb), (Vc), (Vd), (Ve) (Vf)
wherein T is
formula (VIa), (VIb)
formula (VIIa), (VIIb)
and formula (VIIIa)

### Claim 5 (depends on 1)

A hydroxy-group-containing or nitrogen-containing organic substrate colored by a trichromatic coloring process as claimed in claim 1.

### Claim 6 (depends on 1)

Trichromatic coloring process according to claim 1, wherein the coloring step further comprises the step of dyeing or printing the substrate.

### Claim 7 (depends on 1)

Trichromatic coloring process according to claim 1, wherein Y is bonded in a meta or para position with respect to the azo group.

### Claim 8 (depends on 1)

A dye mixture comprising:
at least one red-dyeing compound of the formula (I)
wherein
R1 is a C1-4-alkyl group or a substituted C2-4-alkyl group,
R2 and R3 are independently from each other H; —OH; —CN; C1-2-alkyl; —SO3H; —COOH; —OC1-2-alkyl or —NH2,
X is a halogen radical and
Y is —CH═CH2 or —CH2CH2-Z, wherein Z is a radical which is eliminated by alkali,
at least one yellow or orange -dyeing compound is selected from the group consisting of: formula (II)
wherein
R4 and R5 signify independently from each other H or —SO3H,
A signifies a group of formula (i) or (ia)
wherein
X and Y are defined above,
R6 and R7 signify independently from each other H; unsubstituted C1-4alkyl or substituted C1-4alkyl,
B is
wherein R8 C1-4alkyl; —NH2 or —NHC1-4alkyl,
and the asterisk marks the bond to the —N═N— group;
of formula (III)
wherein
R9 —SO3H or —SO2Y, wherein Y is defined above,
R10 H or —SO3H,
R11 H; unsubstituted C1-4alkyl or substituted C1-4alkyl,
D is
wherein
X and Y are defined above and
R12 is H; unsubstituted C1-4alkyl or substituted C1-4alkyl;
and formula (IV)
wherein
R13 is H; methyl; methoxy, ethoxy; —NHCONH2 or —NHCOCH3,
R14 is H; methyl; methoxy or ethoxy,
RG is
wherein
R15 is H or chlorine,
Y is defined above;
and at least one blue-dyeing compound selected from the group consisting of: formula (V)
wherein
R16 is H or —SO3H,
R17 is
wherein
X and Y have the same meanings as defined in claim 1,
R18 and R19 are independently from one another H; unsubstituted C1-4alkyl or substituted C1-4alkyl,
n is 0 or 1,
T is
wherein
R16 has the meanings as defined above and Y has the meanings as defined in claim 1 and
R20 is H; unsubstituted C1-4alkyl or substituted C1-4alkyl;
formula (VI)
in which
R21 is H or —COOH,
each of R22 and R24 is independently H; —COOH; —SO3H; —NHCOCH3; —NHCOCHY2—CH2Y1; —NHCOCY2═CH2 or —NHCOCH2Y1,
R23—COOH,
Y1 is chlorine; bromine; —OSO3H or —SSO3H and
Y2 is H; chlorine or bromine;
formula (VII)
in which
Y has the same meanings as defined in claim 1,
R25 H or —SO3H,
R26 H or —SO3H;
and formula (VIII)
wherein
each Y has independently from each other the same meaning as defined in claim 1
R27 and R28 are independently from each other H; unsubstituted C1-4alkyl or substituted C1-4alkyl.

### Claim 9

Trichromatic coloring process for coloring a hydroxy-group-containing or nitrogen-containing organic substrate comprising the step of coloring the substrate with a dye mixture comprising at least one red-dyeing compound of the formula (I)
wherein
R1 is a C1-4-alkyl group or a substituted C2-4-alkyl group,
R2 and R3 are independently from each other H; —OH; —CN; C1-2-alkyl; —SO3H; —COOH; —OC1-2-alkyl or —NH2,
X is a halogen radical and
Y —CH═CH2 or —CH2CH2-Z, wherein Z is a radical which is eliminated by alkali;
at least one blue-dyeing compound is selected from the group consisting of: formula (V)
wherein
R16 is H or —SO3H,
R17 is
wherein
X and Y are defined above,
R18 and R19 are independently from one another H; unsubstituted C1-4alkyl or substituted C1-4alkyl,
n is 0 or 1,
T is
wherein
R16 has the meanings as defined above and Y is defined above and
R20 is H; unsubstituted C1-4alkyl or substituted C1-4alkyl;
formula (VI)
in which
R21 is H or —COOH,
each of R22 and R24 is independently H; —COOH; —SO3H; —NHCOCH3; —NHCOCHY2—CH2Y1; —NHCOCY2═CH2 or —NHCOCH2Y1,
R23—COOH,
Y1 is chlorine; bromine; —OSO3H or —SSO3H and
Y2 is H; chlorine or bromine;
formula (VII)
in which
Y is defined above,
R25 H or —SO3H,
R26 H or —SO3H;
and formula (VIII)
wherein
each Y is independently from each other defined above,
R27 and R28 are independently from each other H; unsubstituted C1-4alkyl or substituted C1-4alkyl;
and at least on yellow or orange -dyeing compound.

### Claim 10 (depends on 9)

Trichromatic coloring process according to claim 9, wherein the dye mixture comprises at least one yellow or orange -dyeing compound selected from the group consisting of: formula (IIa), (IIb), (IIc)
wherein A is
formula (IIIa), (IIIb),
wherein D is
and formula (IVa) and (IVb),
wherein RG is

### Claim 11 (depends on 1)

Trichromatic coloring process according to claim 1, wherein the coloring step further comprises the step of dyeing or printing the substrate.

### Claim 12

A dye mixture comprising:
at least one red-dyeing compound of the formula (I)
wherein
R1 is a C1-4-alkyl group or a substituted C2-4-alkyl group,
R2 and R3 are independently from each other H; —OH; —CN; C1-2-alkyl; —SO3H; —COOH; —OC1-2-alkyl or —NH2,
X is a halogen radical and
Y —CH═CH2 or —CH2CH2-Z, wherein Z is a radical which is eliminated by alkali,
at least one yellow or orange -dyeing compound,
and at least one blue-dyeing compound selected from the group consisting of: formula (V)
wherein
R16 is H or —SO3H,
R17 is
wherein
X and Y are defined above,
R18 and R19 are independently from one another H; unsubstituted C1-4alkyl or substituted C1-4alkyl,
n is 0 or 1,
T is
wherein
R16 has the meanings as defined above and Y is defined above, and
R20 is H; unsubstituted C1-4alkyl or substituted C1-4alkyl;
formula (VI)
wherein
R21 is H or —COOH,
each of R22 and R24 is independently H; —COOH; —SO3H; —NHCOCH3; —NHCOCHY2—CH2Y1; —NHCOCY2═CH2 or —NHCOCH2Y1,
R23—COOH,
Y1 is chlorine; bromine; —OSO3H or —SSO3H and
Y2 is H; chlorine or bromine;
formula (VII)
in which
Y is defined above,
R25 H or —SO3H,
R26 H or —SO3H;
and formula (VIII)
wherein
each Y has independently from each other the same meaning as defined above
R27 and R28 are independently from each other H; unsubstituted C1-4alkyl or substituted C1-4alkyl.

### Claim 13 (depends on 2)

Trichromatic coloring process according to claim 2, wherein the dye mixture comprises at least one yellow or orange -dyeing compound selected from the group consisting of formula (IIa), (IIb), (IIc)
wherein A is
formula (IIIa), (IIIb),
wherein D is
and formula (IVa) and (IVb),
wherein RG is

### Claim 14 (depends on 13)

Trichromatic coloring process according to claim 13, wherein the dye mixture comprises at Least one blue-dyeing compound selected from the group consisting of: formula (Va). (Vb), (Vc), (Vd), (Ve), (Vf)
wherein T is
formula (VIa), (VIb),
formula (VIIa), (VIIb),
and formula (VIIIa)

### Claim 15 (depends on 1)

A dye mixture comprising:
at least one red-dyeing compound of the formula (I)
wherein
R1 is a C1-4-alkyl group or a substituted C2-4-alkyl group,
R2 and R3 are independently from each other H; —OH; —CN; C1-2-alkyl; —SO3H; —COOH; —OC1-2-alkyl or —NH2,
X is a halogen radical and
Y —CH═CH2 or —CH2CH2-Z, wherein Z is a radical which is eliminated by alkali;
at least one blue-dyeing compound selected from the group consisting of: formula (V)
wherein
R16 is H or —SO3H,
R17 is
wherein
X and Y are defined above,
R18 and R19 are independently from one another H; unsubstituted C1-4alkyl or substituted C1-4alkyl,
n is 0 or 1,
T is
wherein
R16 has the meanings as defined above and Y is defined above, and
R20 is H; unsubstituted C1-4alkyl or substituted C1-4alkyl;
formula (VI)
in which
R21 is H or —COOH,
each of R22 and R24 is independently H; —COOH; —SO3H; —NHCOCH3; —NHCOCHY2—CH2Y1; —NHCOCY2═CH2 or —NHCOCH2Y1,
R23—COOH,
Y1 is chlorine; bromine; —OSO3H or —SSO3H and
Y2 is H; chlorine or bromine;
formula (VII)
in which
Y is defined above,
R25 H or —SO3H,
R26 H or —SO3H;
and formula (VIII)
wherein
each Y has independently from each other the same meaning as defined above
R27 and R28 are independently from each other H; unsubstituted C1-4alkyl or substituted C1-4alkyl;
and at least one yellow or orange-dyeing compound is selected from the group consisting of: formula (II)
wherein
R4 and R5 signify independently from each other H or —SO3H,
A is a group of formula (i) or (ia)
wherein
X and Y are defined above,
R6 and R7 signify independently from each other H; unsubstituted C1-4alkyl or substituted C1-4alkyl,
B is
wherein R8 C1-4alkyl; —NH2 or —NHC1-4alkyl,
and the asterisk marks the bond to the —N═N— group;
formula (III)
wherein
R9 —SO3H or —SO2Y, wherein Y has the same definition as defined in claim 1,
R10 H or —SO3H,
R11 H; unsubstituted C1-4alkyl or substituted C1-4alkyl,
D is
wherein
X and Y are defined above and
R12 is H; unsubstituted C1-4alkyl or substituted C1-4alkyl;
and formula (IV)
wherein
R13 is H; methyl; methoxy, ethoxy; —NHCONH2 or —NHCOCH3,
R14 is H; methyl; methoxy or ethoxy,
RG is
wherein
R15 is H or chlorine,
Y is defined above.