JP3111528B2 - Asymmetric dioxazine compound and method for dyeing or printing fiber material using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the dyeing and printing of materials containing hydroxyl and / or amide groups, in particular cellulose fibers, natural or synthetic polyamide fibers, polyurethane fibers or leather, and their blended fibers. An improved asymmetric dioxazine compound which allows suitable, light-fast, wet-fast and chlorine-fast dyeing, and its application.

[0002]

2. Description of the Related Art Reactive dyes having a dioxazine skeleton in the molecular structure of the dyes are known, but they are inferior in dyeing performance, such as leveling, build-up, dyeing speed, or fastness, particularly chlorine fastness. It is sufficient, and further improvement is desired.

[0003]

SUMMARY OF THE INVENTION Hydroxyl groups and / or
Or the fastness of dyeing or printing of materials containing amide groups, especially the fastness of chlorine, especially in the case of hydroxyl group-containing fibers, is not at a satisfactory level, and the present inventors have enthusiastically worked to increase this level. At the same time, as a result of pursuing a compound having both excellent build-up property and dye reproducibility, an asymmetric dioxazine compound that can solve the above-mentioned problem has been found.

[0004]

The present invention provides a compound represented by the following general formula (I) in the form of a free acid:

[0005]

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Wherein R is a sulfo group, a halogen or alkoxy group, R ₁ and R ₂ are each independently hydrogen or an optionally substituted alkyl group, and R ₃ is hydrogen or an optionally substituted alkyl group. Or an acyl group, X ₁ and X ₂
Each independently represents hydrogen, halogen, an alkyl group, an alkoxy group, or a phenoxy group;

[0007]

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Wherein R ₄ is hydrogen or an optionally substituted alkyl group, R ₅ is hydrogen or an optionally substituted alkyl, phenyl or naphthyl group, and R ₆ is hydrogen or an optionally substituted Represents an alkyl group, B ₁ is a phenylene, alkylene or naphthylene group which may be substituted, Z ₁ is —SO ₂ CH ＝ CH ₂ or —SO ₂ CH ₂
CH ₂ Y ₁ (Y ₁ represents a group capable of leaving by the action of an alkali.) Q ₁ is a halogen, an optionally substituted pyridinio or alkoxy group, —N (R ₇ ) (R ₈ ) (R ₇ ,
R ₈ are each independently hydrogen or an optionally substituted alkyl, phenyl, Optionally substituted phenylene, alkylene or naphthylene group, R ₉ is hydrogen or an optionally substituted alkyl group, and Z ₂ is —SO ₂ CH ＝ CH ₂ or —SO ₂ CH ₂ C
H ₂ Y ₂ (Y ₂ represents a group capable of leaving by the action of an alkali).

[0009]

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Wherein Z ′ represents a fiber-reactive group. And a method for dyeing or printing a fiber material characterized by using the compound.

In the general formula (I), X ₁ and X ₂
Examples of the group represented by are chlorine, bromine, alkoxy and alkyl groups having 4 or less carbon atoms, and among them, chlorine and bromine are preferable.

The fiber reactive group represented by Z is represented by the following formula:

[0013]

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(Wherein Q ₁ , W, and Z ′ have the above-mentioned meanings), are preferred in terms of dyeing characteristics.

[0015] The fiber-reactive group represented by Z ', -OH textile dyeing conditions are those capable of forming a covalent bond by reacting with -NH- or -NH ₂ group.

Specific examples of the fiber reactive group represented by Z 'include the following.

5- or 6-membered aromatic-heterocyclic rings, for example monoazine, diazine or triazine rings, especially pyridine, pyrimidine, pyridazine, pyrazine, thiazine, oxazine or asymmetric or symmetric triazine Ring or one or more fused aromatic
Carbocyclic rings, such as those containing at least one reactive substituent attached to a quinoline, phthalazine, sinoline, quinazoline, quinoxaline, acridine, phenazine or phenanthridine ring system, an aliphatic reaction Or a group obtained by arbitrarily bonding these groups with an appropriate linking group.

[0018] On the double-containing ring and reactive substituents such on the carbon ring, halogen ammonium containing (Cl, Br or F) hydrazinium, sulfonium, sulfonyl, azide _(-N 3), thiocyanato, thio, thiolether Oxyether, sulfino and sulfo.

The heterocyclic and carbocyclic ring system fiber-reactive groups include 2,4-difluorotriazin-6-yl, 2,4-dichlorotriazin-6-yl, monohalo-s-triazinyl, Monochlorotriazinyl and monofluorotriazinyl groups, especially substituted by alkyl, aryl, amino, monoalkylamino, dialkylamino, aralkylamino, arylamino, alkoxy, aryloxy, alkylthio or arylthio, such as 2-amino -4-fluorotriazin-6-yl, 2-methylamino-4-fluorotriazin-6-yl, 2-ethylamino-4-fluorotriazin-6-yl, 2-isopropylamino-4-fluorotriazin-6 Yl, 2-dimethylamino-4
-Fluorotriazin-6-yl, 2-diethylamino-4-fluorotriazin-6-yl, 2-β-methoxyethylamino-4-fluorotriazin-6-yl,
2-β-hydroxyethylamino-4-fluorotriazin-6-yl, 2-di- (β-hydroxyethylamino) -4-fluorotriazin-6-yl, 2-β-sulfoethylamino-4-fluorotriazine -6-yl, 2-β-sulfoethylmethylamino-4-fluorotriazin-6-yl, 2-carboxymethylamino-
4-fluorotriazin-6-yl, 2-di- (carboxymethylamino) -4-fluorotriazin-6-yl, 2-sulfomethyl-methylamino-4-fluorotriazin-6-yl, 2-β-cyanoethylamino -4
-Fluorotriazin-6-yl, 2-benzylamino-4-fluorotriazin-6-yl, 2-β-phenylethylamino-4-fluorotriazin-6-yl,
2-benzylmethylamino-4-fluorotriazine-
6-yl, 2- (4-sulfobenzyl) -amino-4-
Fluorotriazin-6-yl, 2-cyclohexylamino-4-fluorotriazin-6-yl, 2- (o
-, M-, p-methylphenyl) -amino-4-fluorotriazin-6-yl, 2- (o-, m-, p-sulfophenyl) -amino-4-fluorotriazine-6-
Yl, 2- (2 ′, 5′-disulfophenyl) -amino-4-fluorotriazin-6-yl, 2- (o-, m
-, P-chlorophenyl) -amino-4-fluorotriazin-6-yl, 2- (o-, m-, p-methoxyphenyl) -4-fluorotriazin-6-yl, 2-
(2′-methyl-4′-sulfophenyl) -amino-4
-Fluorotriazin-6-yl, 2- (2'-methyl-5'-sulfophenyl) -amino-4-fluorotriazin-6-yl, 2- (2'-chloro-4'-sulfophenyl) -amino -4-fluorotriazin-6-yl, 2- (2'-chloro-5'-sulfophenyl) -amino-4-fluorotriazin-6-yl, 2- (2 '
-Methoxy-4'-sulfophenyl) -amino-4-fluorotriazin-6-yl, 2- (o-, m-, p-
(Carboxyphenyl) -amino-4-fluorotriazin-6-yl, 2- (2 ′, 4′-disulfophenyl)
-Amino-4-fluorotriazin-6-yl, 2-
(3 ′, 5′-disulfophenyl) -amino-4-fluorotriazin-6-yl, 2- (2′-carboxy-
4'-sulfophenyl) -amino-4-fluorotriazin-6-yl, 2- (2'-carboxy-5'-sulfophenyl) -amino-4-fluorotriazine-6-
Yl, 2- (6′-sulfophenyl-2′-yl) -amino-4-fluorotriazin-6-yl, 2-
(4 ′, 8′-disulfonaphth-2′-yl) -amino-4-fluorotriazin-6-yl, 2- (6 ′,
8'-disulfonaphth-2'-yl) -amino-4-fluorotriazin-6-yl, 2- (N-methylphenyl) -amino-4-fluorotriazin-6-yl,
-(N-ethylphenyl) -amino-4-fluorotriazin-6-yl, 2- (N-β-hydroxyethylphenyl) -amino-4-fluorotriazin-6-yl, 2- (N-isopropylphenyl) -Amino-4-
Fluorotriazin-6-yl, 2-morpholino-4-
Fluorotriazin-6-yl, 2-piperidino-4-
Fluorotriazin-6-yl, 2- (4 ′, 6 ′,
8'-trisulfonaphth-2'-yl) -4-fluorotriazin-6-yl, 2- (3 ', 6', 8'-trisulfonaphth-2'-yl) -4-fluorotriazin-6-yl, 2 -(3 ', 6'-disulfonaphth-1'
-Yl) -4-fluorotriazin-6-yl, N-methyl-N- (2,4-dichlorotriazin-6-yl)
-Carbamyl, N-methyl-N- (2-methylamino-
4-chlorotriazin-6-yl) -carbamyl, N-
Methyl-N- (2-dimethylamino-4-chlorotriazin-6-yl) -carbamyl, N-methyl- or N-ethyl-N- (2,4-dichlorotriazine-6-
Yl) -aminoacetyl, 2-methoxy-4-fluorotriazin-6-yl, 2-ethoxy-4-fluorotriazin-6-yl, 2-phenoxy-4-fluorotriazin-6-yl, 2- (o- , M- or p-
Sulfophenoxy) -4-fluorotriazin-6-yl, 2- (o-, m-, or p-methyl or -methoxyphenyl) -4-fluorotriazin-6-yl, 2-β-hydroxyethylmercapto-4 -Fluorotriazin-6-yl, 2-phenylmercapto-4
-Fluorotriazin-6-yl, 2- (4'-methylphenyl) -mercapto-4-fluorotriazinyl,
2- (2 ', 4'-dinitrophenyl) -mercapto-
4-fluorotriazin-6-yl, 2-methyl-4-
Fluorotriazin-6-yl, 2-phenyl-4-fluorotriazin-6-yl, and the corresponding 4-chloro- or 4-bromo-triazinyl groups, and tertiary bases such as trimethylamine by halogen exchange;
Triethylamine, dimethyl-β-hydroxyethylamine, triethanolamine, N, N-dimethylhydrazine, pyridine or picoline, nicotinic or isonicotinic acid, the corresponding sulfinic acid salts, in particular benzene-sulfinic acid or hydrogensulfite Groups, mono-, di- or trihalopyrimidinyl groups, for example 2,4-dichloropyrimidin-6-yl,
2,3,5-trichloropyrimidin-6-yl, 2,4
-Dichloro-5-nitro- or -5-methyl- or -5-carboxymethyl- or -5-carboxy- or -5-cyano- or -5-vinyl- or -5
Sulfo- or -5-mono-, -di- or -trichloromethyl- or -5-carboalkoxy-pyrimidin-6-yl, 2,6-dichloropyrimidine-4-carbonyl, 2,4-dichloropyrimidine-5-carbonyl 2-chloro-4-methylpyrimidine-5-carbonyl, 2-methyl-4-chloropyrimidine-5-carbonyl, 2-methylthio-4-fluoropyrimidine-5-carbonyl, 6-methyl-2,4-dichloropyrimidine −
5-carbonyl, 2,4,6-trichloropyrimidine-
5-carbonyl, 2,4-dichloropyrimidine-5-sulfonyl, or 2-chloro-quinoxaline-3-carbonyl, 2- or 3-monochloroquinoxaline-6
Carbonyl, 2- or 3-monochloroquinoxaline-6-sulfonyl, 2,3-dichloroquinoxaline-6
-Carbonyl, 2,3-dichloroquinoxaline-6-sulfonyl, 1,4-dichlorophthalazine-6-sulfonyl or -6-carbonyl, 2,4-dichloroquinazoline-7- or -6-sulfonyl or -6-carbonyl , 2- or 3- or 4- (4 ', 5'-dichloropyridazo-6'-one-1'-yl) phenylsulfonyl or -carbonyl, β- (4', 5'-dichloropyridazo-6'-one- 1'-yl) ethylcarbonyl, N-methyl-N- (2,3-dichloroquinoxaline-6-sulfonyl) -aminoacetyl, N-methyl-
N- (2,3-dichloroquinoxaline-6-carbonyl) -aminoacetyl and the corresponding bromine and fluorine derivatives of the above-mentioned chlorine-substituted heterocyclic groups, for example 2-fluoro-4-pyrimidinyl, , 6-Difluoro-4-pyrimidinyl, 2,6-difluoro-5-chloro-4-pyrimidinyl, 2-fluoro-5,6-dichloro-4-pyrimidinyl, 2,6-difluoro-5-methyl-4-pyrimidinyl , 2-fluoro-5-methyl-6
-Chloro-4-pyrimidinyl, 2-fluoro-5-nitro-6-chloro-4-pyrimidinyl, 5-bromo-2-
Fluoro-4-pyrimidinyl, 2-fluoro-5-cyano-4-pyrimidinyl, 2-fluoro-5-methyl-4
-Pyrimidinyl, 2,5,6-trifluoro-4-pyrimidinyl, 5-chloro-6-chloromethyl-2-fluoro-4-pyrimidinyl, 5-chloro-6-dichloromethyl-2-fluoro-4-pyrimidinyl, 5-chloro-6
-Trichloromethyl-2-fluoro-4-pyrimidinyl, 5-chloro-2-chloromethyl-6-fluoro-4
-Pyrimidinyl, 5-chloro-2-dichloromethyl-6
-Fluoro-4-pyrimidinyl, 5-chloro-2-trichloromethyl-6-fluoro-4-pyrimidinyl, 5-
Chloro-2-fluorodichloromethyl-6-fluoro-
4-pyrimidinyl, 2,6-difluoro-5-bromo-
4-pyrimidinyl, 2-fluoro-5-bromo-6-methyl-4-pyrimidinyl, 2-fluoro-5-bromo-
6-chloromethyl-4-pyrimidinyl, 2,6-difluoro-5-chloromethyl-4-pyrimidinyl, 2,6-
Difluoro-5-nitro-4-pyrimidinyl, 2-fluoro-6-methyl-4-pyrimidinyl, 2-fluoro-
5-chloro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro-4-pyrimidinyl, 2-fluoro-
6-chloro-4-pyrimidinyl, 6-trifluoromethyl-5-chloro-2-fluoro-4-pyrimidinyl, 6
-Trifluoromethyl-2-fluoro-4-pyrimidinyl, 2-fluoro-5-nitro-4-pyrimidinyl, 2
-Fluoro-5-trifluoromethyl-4-pyrimidinyl, 2-fluoro-5-phenyl- or -5-methylsulfonylmethyl-4-pyrimidinyl, 2-fluoro-
5-carboxamido-4-pyrimidinyl, 2-fluoro-5-carbomethoxy-4-pyrimidinyl, 2-fluoro-5-bromo-6-trifluoromethyl-4-pyrimidinyl, 2-fluoro-6-carboxamido-4-pyrimidinyl , 2-fluoro-6-carbomethoxy-4-pyrimidinyl, 2-fluoro-6-phenyl-4-pyrimidinyl, 2-fluoro-6-cyano-4-pyrimidinyl, 2-fluoro-4-dichloromethyl-5-chloro Pyrimidin-6-yl, 2-fluoro-5-chloropyrimidin-4-yl, 2-methyl-4-fluoro-5-methylsulfonylpyrimidin-6-yl, 2,6-difluoro-5-methylsulfonyl-4- Pyrimidinyl, 2,6
-Dichloro-5-methylsulfonyl-4-pyrimidinyl, 2-fluoro-5-sulfonamido-4-pyrimidinyl, 2-fluoro-5-chloro-6-carbomethoxy-4-pyrimidinyl, 2,6-difluoro-5- Trifluoromethyl-4-pyrimidinyl, sulfonyl-containing triazine groups such as 2,4-bis- (phenylsulfonyl) -triazin-6-yl, 2- (3'-carboxyphenyl) -sulfonyl-4-chlorotriazine- 6
-Yl, 2- (3'-sulfophenyl) -sulfonyl-
4-chlorotriazin-6-yl, 2,4-bis-
(3'-carboxyphenylsulfonyl) -triazin-6-yl, sulfonyl-containing pyrimidine rings, such as 2-carboxymethylsulfonyl-pyrimidin-4-yl, 2-methylsulfonyl-6-methylpyrimidine-4
-Yl, 2-methylsulfonyl-6-ethylpyrimidin-4-yl, 2-phenylsulfonyl-5-chloro-6
-Methyl-pyrimidin-4-yl, 2,6-bis-methylsulfonyl-pyrimidin-4-yl, 2,6-bis-
Methylsulfonyl-5-chloro-pyrimidin-4-yl, 2,4-bis-methylsulfonyl-pyrimidin-5
-Sulfonyl, 2-methylsulfonyl-pyrimidine-4
-Yl, 2-phenylsulfonyl-pyrimidin-4-yl, 2-trichloromethylsulfonyl-6-methyl-pyrimidin-4-yl, 2-methylsulfonyl-5-chloro-6-methyl-pyrimidin-4-yl, 2 -Methylsulfonyl-5-bromo-6-methyl-pyrimidine-4-
Yl, 2-methylsulfonyl-5-chloro-6-ethyl-pyrimidin-4-yl, 2-methylsulfonyl-5-yl
Chloro-6-chloromethyl-pyrimidin-4-yl, 2
-Methylsulfonyl-4-chloro-6-methylpyrimidine-5-sulfonyl, 2-methylsulfonyl-5-nitro-6-methylpyrimidin-4-yl, 2,5,6-tris-methylsulfonyl-pyrimidine-4- Il, 2-
Methylsulfonyl-5,6-dimethyl-pyrimidine-4
-Yl, 2-ethylsulfonyl-5-chloro-6-methyl-pyrimidin-4-yl, 2-methylsulfonyl-6
-Chloropyrimidin-4-yl, 2,6-bis-methylsulfonyl-5-chloro-pyrimidin-4-yl, 2-
Methylsulfonyl-6-carboxypyrimidin-4-yl, 2-methylsulfonyl-5-sulfopyrimidine-4
-Yl, 2-methylsulfonyl-6-carbomethoxypyrimidin-4-yl, 2-methylsulfonyl-5-carboxypyrimidin-4-yl, 2-methylsulfonyl-
5-cyano-6-methoxypyrimidin-4-yl, 2-
Methylsulfonyl-5-chloropyrimidin-4-yl,
2-sulfoethylsulfonyl-6-methylpyrimidine-
4-yl, 2-methylsulfonyl-5-bromopyrimidin-4-yl, 2-phenylsulfonyl-5-chloropyrimidin-4-yl, 2-carboxymethylsulfonyl-5-chloro-6-methylpyrimidin-4-yl , 2-
Methylsulfonyl-6-chloropyrimidine-4- and -5-carbonyl, 2,6-bis- (methylsulfonyl) -pyrimidine-4- or -5-carbonyl,
-Ethylsulfonyl-6-chloropyrimidine-5-sulfonyl, 2,4-bis- (methylsulfonyl) -pyrimidine-5-sulfonyl, 2-methylsulfonyl-4-chloro-6-methylpyrimidine-5-sulfonyl or-
Carbonyl, 2-chlorobenzothiazole-5- or -6-carbonyl or -5- or -6-sulfonyl, 2-arylsulfonyl- or -alkylsulfonyl-benzothiazole-5- or -6-carbonyl or -carbonyl, -Phenylsulfonylbenzothiazole-5- or -6-carbonyl or-
5- or -6-sulfonyl, for example 2-methylsulfonyl- or 2-ethylsulfonyl-benzothiazole-5- or -6-sulfonyl or -5- or -6-carbonyl, as well as containing a sulfo group in the fused benzene ring Corresponding 2-sulfonylbenzothiazole-5- or -6-carbonyl or -sulfonyl derivatives, 2-chloro-benzoxazole-5- or -6-carbonyl or -sulfonyl, 2-chloro-benzimidazole- 5- or -6-carbonyl or -sulfonyl, 2-chloro-1-methylbenzimidazole-5- or -6-carbonyl or -sulfonyl, 2-chloro-4-methyl-1,3-thiazole-5-carbonyl or -4- or -5-sulfonyl, 4-chloro Or 4-nitro - quinolin-5
N-oxide of carbonyl and the like.

As the aliphatic fiber reactive group, acryloyl, mono-, di- or trichloroacryloyl, for example, -CO-CH = CH-Cl, -CO-CCl
ＣＨCH ₂ , —CO—CCl ＝ CH—CH ₃ , —CO—C
Cl = CH-COOH, -CO-CH = CCl-COO
H, β-chloropropionyl, 3-phenylsulfonylpropionyl, 3-methylsulfonylpropionyl, 2
-Fluoro-2-chloro-3,3-difluorocyclobutane-1-carbonyl, 2,2,3,3-tetrafluorocyclobutane-1-carbonyl or -1-sulfonyl, β- (2,2,3,3- Tetrafluorocyclobutyl) -aryloxy, α- or β-bromoacryloyl, α- or β-alkyl- or aryl-
Sulfoacryloyl groups, for example, α- or β-methylsulfonylacryloyl, chloroacetyl, vinylsulfonyl, —SO ₂ CH ₂ CH ₂ Z ₁ (Z ₁ represents a group eliminated by the action of an alkali) and the like.

The preferred fiber reactive group Z 'is represented by the following formula:

[0022]

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Wherein R ₁₀ is hydrogen or an optionally substituted alkyl group, R ₁₁ is hydrogen or an optionally substituted alkyl, phenyl or naphthyl group, and R ₁₂ is hydrogen or an optionally substituted An alkyl group; B ₃ represents an optionally substituted phenylene, alkylene or naphthylene group; Z ₃ represents —SO ₂ CH ＝ CH ₂ , or —SO ₂ C
H ₂ CH ₂ Y ₃ (Y ₃ represents a group which leaves under the action of an alkali.) Q ₂ is a halogen, an optionally substituted pyridinio or alkoxy group, —N (R ₁₃ ) (R ₁₄ )
(R ₁₃ and R ₁₄ are each independently hydrogen or optionally substituted alkylphenyl, A phenylene, alkylene or naphthylene group, R ₁₅ may be hydrogen or an optionally substituted alkyl group,
Z ₄ is -SO ₂ CH = CH _2, or -SO ₂ CH ₂ CH
₂ Y ₄ (Y ₄ represents a group which is eliminated by the action of an alkali.)]. ] The group shown by these is mentioned.

The optionally substituted alkylene group represented by B ₁ , B ₂ , B ₃ and B ₄ includes-(C
_{H 2) 2 -, - (} CH 2) 3 -, - (CH 2) 2 O (C
H _{2) 2} - and the like are exemplified. The optionally substituted phenylene group or naphthylene group is preferably phenylene optionally substituted by one or two substituents selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chlorine, bromine and sulfo. A naphthylene group which may be substituted with one group or one sulfo group, such as the following:

[0025]

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[0026]

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[0027] Represents a bond. )

Examples of the groups capable of leaving under the action of an alkali represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ include, for example, sulfates, thiosulfates, phosphates, acetates, halogens and the like. Of these, sulfates are preferred.

The optionally substituted alkyl groups represented by R ₁ , R ₂ , R ₃ , R ₆ , R ₉ , R ₁₂ and R ₁₅ include, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, 2-hydroxyethyl, 2-hydroxypropyl,
3-hydroxypropyl, 2-hydroxybutyl, 3-
Hydroxybutyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, cyanomethyl, 2-cyanoethyl, 3-cyanopropyl,
Methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-
Ethoxypropyl, 2-hydroxy-3-methoxypropyl, chloromethyl, bromomethyl, 2-chloroethyl, 2-bromoethyl, 3-chloropropyl, 3-bromopropyl, 4-chlorobutyl, 4-bromobutyl, carboxymethyl, 2-carboxyethyl , 3-carboxypropyl, 4-carboxybutyl, 1,2-dicarboxyethyl, carbamoylmethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 4-carbamoylbutyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, 2-methoxycarbonylethyl , 2-ethoxycarbonylethyl, 3-methoxycarbonylpropyl,
3-ethoxycarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, methylcarbonyloxymethyl, ethylcarbonyloxymethyl, 2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 3-methylcarbonyloxypropyl, -Ethylcarbonyloxypropyl, 4-methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, sulfamoylmethyl, 2-sulfamoylethyl, 3-sulfo Famoylpropyl and 4-sulfamoylbutyl can be mentioned, and particularly preferred are hydrogen, methyl and ethyl. R ₁ , R ₂ and R ₃ are more preferably hydrogen.

R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R
₁₃ and as the alkyl group which may be substituted represented by R _14, for example, alkoxy having 1 to 4 carbon atoms, sulfo, carboxy, hydroxy, chloro, 1 or 2 atoms selected from the group consisting of phenyl and sulfato And an alkyl group having 1 to 4 carbon atoms which may be substituted by the above substituent.

Among them, particularly preferred are methyl, ethyl,
n-propyl, iso-propyl, n-butyl, iso
-Butyl, sec-butyl, β-hydroxyethyl, β
-Sulfatoethyl, β-sulfoethyl, β-methoxyethyl, β-carboxyethyl and the like.

R ₅ , R ₇ , R ₈ , R ₁₁ , R ₁₃ , and R ₁₄
The optionally substituted phenyl group represented by
For example, alkyl having 1-4 carbon atoms, 1-4
A phenyl group which may be substituted with one or two substituents selected from the group consisting of alkoxy, sulfo, carboxy, chloro and bromo having two carbon atoms is preferred.

Among them, particularly preferred are phenyl, 2-,
3- or 4-sulfophenyl, 2,4- or 2,5-disulfophenyl, 2-, 3- or 4-carboxyphenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4- Examples include methylphenyl and 2-, 3- or 4-methoxyphenyl.

R ₅ , R ₇ , R ₈ , R ₁₁ , R ₁₃ , and R ₁₄
As the optionally substituted naphthyl group represented by
For example, substituted by 1, 2 or 3 substituents selected from the group of hydroxy, carboxy, sulfo, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms and chloro. An optionally present naphthyl group is preferred.

Among them, particularly preferred are 2-, 3- and 4
-, 5-, 6-, 7- or 8-sulfo-1-naphthyl,
1-, 5-, 6-, 7- or 8-sulfo-2-naphthyl, 1,5-, 5,7-, 6,8-, 4,8-, 4,7
-, 3,8-, 4,6-, 3,7- or 3,6-disulfo-2-naphthyl, 4,6,8-, 2,4,7- or 3,6,8-trisulfo-1 -Naphthyl, 1,5,7
-, 4,6,8- or 3,6,8-trisulfo-2-naphthyl and the like.

Examples of the optionally substituted benzyl group represented by R ₇ , R ₈ , R ₁₃ and R ₁₄ include, for example, 1-4
And a benzyl group which may be substituted with one or two substituents selected from the group consisting of alkyl having 1 carbon atom, alkoxy having 1 to 4 carbon atoms, sulfo and chloro.

Among them, particularly preferred are benzyl, 2-,
3- or 4-sulfobenzyl and the like.

In the present invention, one of R ₇ and R ₈ is hydrogen, methyl or ethyl, and the other is C ₁ -C ₈ .
₄ alkyl, C ₁ ~ ₄ alkoxy, sulfo, phenyl optionally substituted by carboxy or halogeno, or C ₁ ~ ₄ alkoxy, sulfo, carboxy, hydroxy, chloro or sulfa, - optionally substituted with preparative C ₁ Or ₄ alkyl, or R ₇ and R ₈
Are particularly preferably hydrogen in terms of dye properties. R
The combination also corresponding to R ₇ and R ₈ given above for ₁₃ and R ₁₄ on dye properties preferred.

In the above formula, -N (R ₄ ) (R ₅ ) -N (R
_{7) (R 8) -N (} R 10) (R 11) and -N (R ₁₃₎
HNR ₄ R ₅ , HNR ₇ R ₈ , HNR ₁₀ R ₁₁ and H used to form a group represented by (R ₁₄ )
Examples of the compound represented by NR ₁₃ R ₁₄ include, for example, ammonia or 1-aminobenzene, 1-amino-2-,
-3- or -4-methyl-benzene, 1-amino-3,
4- or -3,5-dimethylbenzene, 1-amino-2
-, -3- or -4-ethylbenzene, 1-amino-2
-, -3- or -4-methoxybenzene, 1-amino-
2-, -3- or -4-ethoxybenzene, 1-amino-2-, -3- or -4-chlorobenzene, 3- or 4
-Amino-phenylmethanesulfonic acid, 2-, 3- or 4-aminobenzenesulfonic acid, 3-methylaminobenzenesulfonic acid, 3-ethylaminobenzenesulfonic acid, 4-methylaminobenzenesulfonic acid, 4-ethylaminobenzene Sulfonic acid, 5-aminobenzene-1,
3-disulfonic acid, 6-aminobenzene-1,3-disulfonic acid, 6-aminobenzene-1,4-disulfonic acid, 4-aminobenzene-1,2-disulfonic acid, 4-
Amino-5-methylbenzene-1,2-disulfonic acid,
2-, 3- or 4-aminobenzoic acid, 5-aminobenzene-1,3-dicarboxylic acid, 5-amino-2-hydroxybenzenesulfonic acid, 4-amino-2-hydroxybenzenesulfonic acid, 5-amino- 2-ethoxybenzenesulfonic acid, N-methylaminobenzene, N-ethylaminobenzene, 1-methylamino-3- or -4-methylbenzene, 1-ethylamino-4-chlorobenzene,
1-ethylamino-3- or -4-methylbenzene, 1
-(2-hydroxyethyl) -amino-3-methylbenzene, 3- or 4-methylaminobenzoic acid, 3- or 4
-Methylaminobenzenesulfonic acid, 2-aminonaphthalene-1-sulfonic acid, 4-aminonaphthalene-1-sulfonic acid, 5-aminonaphthalene-1-sulfonic acid, 6
-Aminonaphthalene-1-sulfonic acid, 7-aminonaphthalene-1-sulfonic acid, 8-aminonaphthalene-1-
Sulfonic acid, 1-aminonaphthalene-2-sulfonic acid,
4-aminonaphthalene-2-sulfonic acid, 5-aminonaphthalene-2-sulfonic acid, 6-aminonaphthalene-2
-Sulfonic acid, 7-aminonaphthalene-2-sulfonic acid, 7-methylaminonaphthalene-2-sulfonic acid, 7
-Ethylaminonaphthalene-2-sulfonic acid, 7-butylaminonaphthalene-2-sulfonic acid, 7-isobutylaminonaphthalene-2-sulfonic acid, 8-aminonaphthalene-2-sulfonic acid, 4-aminonaphthalene-1,3
-Disulfonic acid, 5-aminonaphthalene-1,3-disulfonic acid, 6-aminonaphthalene-1,3-disulfonic acid, 7-aminonaphthalene-1,3-disulfonic acid, 8
-Aminonaphthalene-1,3-disulfonic acid, 2-aminonaphthalene-1,5-disulfonic acid, 3-aminonaphthalene-1,5-disulfonic acid, 4-aminonaphthalene-1,5-disulfonic acid, 4-amino Naphthalene-1,
6-disulfonic acid, 8-aminonaphthalene-1,6-disulfonic acid, 4-aminonaphthalene-1,7-disulfonic acid, 3-aminonaphthalene-2,6-disulfonic acid,
4-aminonaphthalene-2,6-disulfonic acid, 3-aminonaphthalene-2,7-disulfonic acid, 4-aminonaphthalene-2,7-disulfonic acid, 6-aminonaphthalene-1,3,5-trisulfonic acid , 7-aminonaphthalene-1,3,5-trisulfonic acid, 4-aminonaphthalene-1,3,6-trisulfonic acid, 7-aminonaphthalene-1,3,6-trisulfonic acid, 8-aminonaphthalene Aromatic amines such as -1,3,6-trisulfonic acid and 4-aminonaphthalene-1,3,7-trisulfonic acid, or methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine; Isobutylamine, sec-butylamine, dimethylamine, diethylamine, methylethylamine, allylamine, 2-chloroethyl Min, 2-methoxyethylamine, 2-aminoethanol, 2-methylaminoethanol, bis- (2-hydroxyethyl) amine, 2-acetylaminoethylamine, 1-amino-2-propanol, 3-methoxypropylamine, 1- Amino-3-dimethylaminopropane, 2-aminoethanesulfonic acid,
Aminomethanesulfonic acid, 2-methylaminoethanesulfonic acid, 3-amino-1-propanesulfonic acid, 2-sulfatoethylamine, aminoacetic acid, methylaminoacetic acid, ε-aminocaproic acid, benzylamine, 2-3
-Or 4-chlorobenzylamine, 4-methylbenzylamine, N-methylbenzylamine, 2-, 3- or 4-sulfobenzylamine, 2-phenylethylamine, 1-phenylethylamine, 1-phenyl-2
Aliphatic amines such as -propylamine.

Particularly preferred compounds are, for example, ammonia, ethylamine, taurine, N-methyltaurine, methylamine, n-propylamine, monoethanolamine, β-alanine, 2-chloroethylamine, 2-sulfatoethylamine, aniline , Aniline-2-, -3- or -4-sulfonic acid, 2-, 3- or 4-carboxyaniline, N-methylaniline, N-
Ethylaniline, N-ethyl-2-, -3- or -4-
Chloroaniline, aniline-2,4- or -2,5-disulfonic acid, 2-, 3- or 4-chloroaniline, 2
-, 3- or 4-methylaniline, 3- or 4-methylaminobenzenesulfonic acid, and the like.

The halogen atom represented by Q ₁ and Q ₂ is preferably chlorine or fluorine.

The optionally substituted alkoxy represented by Q ₁ and Q ₂ includes phenyl, hydroxy, sulfo, carboxy, chloro, sulfate, methoxy,
Ethoxy or alkoxy having 4 or less carbon atoms, which may be substituted with allyloxy, may be mentioned. Among them, methoxy and ethoxy are preferred.

Examples of the optionally substituted pyridinio group represented by Q ₁ and Q ₂ include carboxy, carbamoyl, sulfo, halogeno and substituted or unsubstituted 1-4.
And a pyridinio group which may be substituted with an alkyl having two carbon atoms. Examples of the substituted alkyl include β-hydroxyethyl, β-sulfoethyl and the like. A carboxy or carbamoyl-substituted pyridinio group is preferred,
Among them, a carboxypyridinio group is preferred in terms of dye properties.

Examples of R include a sulfo group, chlorine, bromine, methoxy and ethoxy, with a sulfo group being particularly preferred. Examples of the acyl group represented by R ₃ include an alkyl, alkenyl, or arylcarbonyl group such as an acetyl group, a propionyl group, a maleyl group, and a benzoyl group, and an alkyl or arylsulfonyl group such as a methanesulfonyl group and a p-toluenesulfonyl group. Is done.

The compound of the present invention may exist in the form of a free acid, but is preferably an alkali metal salt or an alkaline earth metal salt, such as a sodium salt and a potassium salt.

The compound of the present invention can be produced, for example, as follows. The following general formula (II)

[0047]

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(Wherein R ₁ , R ₂ , R ₃ , R, X ₁ and X ₂ have the above-mentioned meanings) and an asymmetric dioxazine intermediate represented by the following general formula (III) XZ ( III)

(Wherein, X represents a halogen atom, and Z has the above-mentioned meaning). That is, an asymmetric dioxazine compound represented by the general formula (I) or a salt thereof can be obtained by condensing the compound of the formula (II) and the compound of the formula (III) by a known method in the presence of a deoxidizing agent.

The asymmetric dioxazine intermediate represented by the formula (II) is synthesized by a method known per se,
For example, they can be synthesized as follows.

The following general formula (IV) obtained by condensing the corresponding aniline compound with chloranil

[0052]

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(Wherein R ₁ , R ₂ , R ₃ and R have the above-mentioned meanings), and optionally cyclized in the presence of an oxidizing agent to obtain a compound of the general formula (II) An asymmetric dioxazine intermediate is obtained.

The compounds of the present invention have fiber reactivity and can be used for dyeing or printing materials containing hydroxy groups or carboxamide groups. The material is preferably used in the form of a fibrous material or a blend thereof.

The hydroxy group-containing material is a natural or synthetic hydroxy group-containing material such as a cellulose fiber material or a regenerated product thereof and polyvinyl alcohol. The cellulosic fiber material is preferably cotton and other vegetable fibers such as linen, hemp, jute and ramie fibers. Regenerated cellulose fibers are, for example, viscose staples and filament viscose.

The carbonamide-containing materials are, for example, synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hairs, silk, leather, polyamide-6,6, polyamide-6, polyamide-11 and polyamide-11. Polyamide-4.

The compounds of the present invention can be applied to the above-mentioned materials, in particular to the above-mentioned fibrous materials, by a method depending on physical and chemical properties,
It can be dyed or printed.

For example, when exhaustion dyeing is performed on cellulose fibers, an acid binder such as sodium carbonate, sodium tertiary phosphate, sodium hydroxide, sodium bicarbonate or the like is added in the presence of a neutral salt such as sodium sulfate or sodium chloride, and if desired, And a dissolution aid, a penetrating agent or a leveling agent, and is carried out at a temperature of 100 ° C. or less. The neutral salt which promotes the exhaustion of the dye can be added in portions depending on the case.

When dyeing cellulose fibers in accordance with the padding method, pad and dry at room temperature or at an elevated temperature,
Can be fixed by steaming or dry heat.

When printing on cellulose fibers,
Printing in one phase, for example with a printing paste containing baking soda or other acid binders and then steaming at 100-160 ° C. or in two phases, for example with a neutral or weakly acidic printing paste, This can be carried out by passing it through a hot electrolyte-containing alkaline bath, or by overpadging with an alkaline electrolyte-containing padding solution, steaming or dry heat treatment. Alternatively, a sizing or emulsifying agent such as starch ether is used, if desired, in combination as a usual printing aid and / or dispersant, for example, urea.

The acid binder suitable for immobilizing the compound of the present invention on cellulose fibers is, for example, a water-soluble basic salt of an alkali metal or an alkaline earth metal with an inorganic or organic acid or a compound capable of liberating alkali under heating. is there. In particular, mention may be made of hydroxides of alkali metals and alkali metal salts of inorganic or organic acids of weak to moderate strength, of which soda salts and potassium salts are particularly preferred. Such acid binders include, for example, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, sodium formate, potassium carbonate, primary, secondary or tertiary sodium phosphate, sodium silicate, sodium trichloroacetate and the like.

[0062] Dyeing of synthetic and natural polyamide and polyurethane fibers is carried out first by acid or weakly acidic dyeing.
This can be done by controlling the value to exhaust and then changing to a neutral and, if appropriate, alkaline pH value for fixation. Dyeing can usually be carried out at a temperature of from 60 to 120 ° C, but in order to achieve levelness, a conventional leveling agent, for example, a condensation product of cyanuric chloride with 3 times mol of aminobenzenesulfonic acid or aminonaphthalenesulfonic acid or For example, an addition product of stearylamine and ethylene oxide can be used.

The compound of the present invention is characterized in that it exhibits excellent performance in dyeing and printing fiber materials. Particularly suitable for dyeing cellulosic fibrous materials, good light fastness and sweat fastness, excellent wet fastness, such as wash fastness, peroxide wash fastness, sweat fastness, acid hydrolysis fastness and alkali It has fastness, better chlorine fastness, rub fastness and iron fastness.

In addition, it has excellent build-up properties, level dyeing properties and wash-off properties, good solubility, exhaustion / fixing properties, stable quality which is hardly affected by fluctuations in the dyeing temperature and dye bath ratio. It is characteristic in that a dyed product is obtained.

Further, the obtained dyed product is characterized by little discoloration during fix processing or resin processing, and little change due to contact with a basic substance during storage.

[0066]

The present invention will be described below in detail with reference to examples. In the examples, parts and% represent parts by weight by weight, respectively. Example 1

[0067]

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19.3 parts of the asymmetric dioxazine intermediate represented by the above structural formula in the form of the free acid are added to 200 parts of water, and 5.5 parts of cyanuric chloride are added thereto.
And the mixture was stirred until the reaction was completed. After completion of the reaction, salting out with potassium chloride gave an asymmetric dioxazine compound represented by the following structural formula in a free form.

[0069]

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Example 2 In place of the dioxazine intermediate and cyanuric chloride used in Example 1, a compound was synthesized in the same manner as in Example 1 using the compounds in the second and third columns, respectively, of the following table. An asymmetric dioxazine compound was obtained. These compounds were dyed to give dyeings of the shades shown in column 4 of the table below.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

[Table 3]

[0074]

[Table 4]

Example 3 19.3 parts of the dioxazine intermediate used in Example 1 was added to 200 parts of water, and 5.5 parts of cyanuric chloride was added thereto.
After reacting at pH 5 to 6, 10 to 20 ° C, 3.7 parts of taurine was further added, and a condensation reaction was further performed at pH 5 to 8, 20 to 50 ° C. After completion of the reaction, salting out with potassium chloride gave an asymmetric dioxazine compound represented by the following structural formula in the form of a free acid.

[0076]

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Example 4 19.3 parts of the dioxazine intermediate used in Example 1 was
0 parts, and 5.5 parts of cyanuric chloride are added thereto, and the pH 5
After the reaction at ６，6,10-20 ° C., 8.4 parts of 1-aminobenzene-3-β-sulfateethylsulfone was further added, and a condensation reaction was further carried out at the same temperature and the same pH. After completion of the reaction, 3.7 parts of 3-carboxypyridine was added to the reaction solution, and a substitution reaction was carried out at 40 to 80 ° C to obtain an asymmetric dioxazine compound represented by the following structural formula in the form of a free acid.

[0078]

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Example 5 A compound was synthesized in the same manner as in Example 3 except that the dioxazine intermediate, cyanuric chloride and taurine used in Example 3 were replaced by the compounds shown in the second, third and fourth columns of the following table, respectively. Was performed to obtain a corresponding asymmetric dioxazine compound. These compounds were stained to give dyeings of the shades shown in column 5 of the table below.

[0080]

[Table 5]

[0081]

[Table 6]

[0082]

[Table 7]

[0083]

[Table 8]

[0084]

[Table 9]

[0085]

[Table 10]

Example 6 The dioxazine intermediate used in Example 4, 1-aminobenzene-3-β-sulfatoethylsulfone and 3-
Instead of carboxypyridine, column 2 in the table below,
Synthesis was carried out in the same manner as in Example 4 using the compounds in the third and fourth columns to obtain corresponding asymmetric dioxazine compounds. These compounds were dyed to give dyeings of the shades shown in column 5 of the table.

[0087]

[Table 11]

[0088]

[Table 12]

[0089]

[Table 13]

[0090]

[Table 14]

[0091]

[Table 15]

Example 7 The reaction of 3-carboxypyridine in Example 4 with 25 kinds of the asymmetric dioxazine compounds obtained in Examples 3 and 5 using the following pyridines and 6 kinds of derivatives thereof, respectively. The operation and conditions were similarly applied to obtain the corresponding asymmetric dioxazine compound.

[0093]

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Embodiment 8

[0095]

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In the form of the free acid, 17.9 parts of the asymmetric dioxazine intermediate represented by the above structural formula is added to 350 parts of water, 5.5 parts of cyanuric chloride is added thereto, and the pH is adjusted to 5 to 7, 10 to 20.
The mixture was stirred at ℃ until the reaction was completed. After the reaction is complete,
-Diaminobenzene-4-sulfonic acid (5.6 parts)
After the condensation, 1-aminobenzene-3-β-
Add 8.4 parts of sulfate ethyl sulfone and add pH 3 to 5,
The third condensation was performed at 60 to 80 ° C. By further adding 5.5 parts of cyanuric chloride to the reaction solution and performing a condensation reaction, an asymmetric dioxazine compound represented by the following structural formula in the form of a free acid was obtained.

[0097]

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Example 9 The dioxazine intermediate used in Example 8, cyanuric chloride, 1,3-diaminobenzene-4-sulfonic acid, 1-
In place of aminobenzene-3-β-sulfatoethylsulfone and cyanuric chloride (shown in the last condensation), columns 2, 3 and 4 in the table below, respectively.
Synthesis was performed in the same manner as in Example 8 using the compounds in the columns, columns 5 and 6, and corresponding asymmetric dioxazine compounds were obtained. These compounds were stained to give dyeings of the shades shown in column 7 of the table below.

[0099]

[Table 16]

[0100]

[Table 17]

[0101]

[Table 18]

[0102]

[Table 19]

Example 10 38.5 parts of the asymmetric dioxazine compound obtained in Example 8 was dissolved in 300 parts of water, and 1-aminobenzene-
8.4 parts of 3-β-sulfate ethyl sulfone was added, and p
The reaction is carried out at H4-6, 30-60 ° C. After the reaction,
By salting out with potassium chloride, an asymmetric dioxazine compound represented by the following structural formula in the form of a free acid was obtained.

[0104]

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Example 11 In place of the asymmetric dioxazine compound used in Example 10, 14 compounds obtained in Examples 9, Nos. 1, 6, and 7 to 18 were used. (1) 〜
The amine shown in (14) was reacted in the same manner as 1-aminobenzene-3-β-sulfateethylsulfone in Example 10 to obtain a corresponding asymmetric dioxazine compound.

[0106]

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Example 12 19.3 parts of the asymmetric dioxazine intermediate used in Example 1 was dissolved in 200 parts of water, and 5.5 parts of cyanuric chloride was added to this solution to carry out a reaction.
5.6 parts of 4-sulfonic acid was added to carry out a condensation reaction. 5.5 parts of cyanuric chloride are added to the reaction solution again,
The reaction was carried out at ３０30 ° C. and finally 1-aminobenzene-
8.4 parts of 4-β-sulfatoethylsulfone was added and reacted. Potassium chloride was added to the reaction solution, followed by salting out to obtain an asymmetric dioxazine compound represented by the following structural formula in the form of a free acid.

[0108]

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Example 13 Dioxazine intermediate used in Example 12, cyanuric chloride, 1,3-diaminobenzene-4-sulfonic acid, cyanuric chloride (the one used for the second time is shown), 1-aminobenzene In place of -3-β-sulfate ethyl sulfone, columns 2, 3, 4, 5
Synthesis was carried out in the same manner as in Example 12 using the compounds in the columns and the sixth column to obtain corresponding asymmetric dioxazine compounds. These compounds were stained to give dyeings of the shades shown in column 7 of the table below.

[0110]

[Table 20]

[0111]

[Table 21]

[0112]

[Table 22]

[0113]

[Table 23]

Example 14 40.0 parts of the asymmetric dioxazine compound obtained in Example 12 was dissolved in 300 parts of water.
8.0 parts were added, and the reaction was carried out at pH 3 to 6, 40 to 80 ° C. By salting out the reaction solution with potassium chloride,
An asymmetric dioxazine compound represented by the following structural formula was obtained in the form of a free acid.

[0115]

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Example 15 Instead of the asymmetric dioxazine compound used in Example 14, 16 kinds of compounds obtained in Example 13 were used, and each of them was represented by the following (1) to (10). The corresponding asymmetric dioxazine compound was obtained by reacting the amine with 3-carboxypyridine in the same manner as in Example 14.

[0117]

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Staining Example 1 0.1, 0.3, and 0.6 parts of each asymmetric dioxazine compound obtained in Examples 1 and 2 were dissolved in 200 parts of water, respectively.
10 parts of sodium sulfate and 10 parts of cotton were added, the temperature was raised to 50 ° C., and 4 parts of sodium carbonate was added, followed by dyeing for 1 hour. Washing, soaping,
After washing with water and drying, a blue dyeing material having excellent fastness properties, particularly excellent chlorine fastness property and good build-up properties was obtained.

Dyeing Example 2 Using 0.1, 0.3, and 0.6 parts of each asymmetric dioxazine compound obtained in Examples 3 and 5,
However, dyeing was performed at a dyeing temperature of 80 ° C., and a blue dyed product having excellent fastness properties and good build-up properties was obtained.

Dyeing Example 3 Using 0.1, 0.3 and 0.6 parts of each asymmetric dioxazine compound obtained in Examples 4 and 6 to 15, dyeing was carried out in the same manner as in Dyeing Example 1 except that the dyeing temperature was 60 ° C. Similarly, blue dyeings having excellent fastness properties and good build-up properties were obtained.

Dyeing Example 4 Using each of the asymmetric dioxazine compounds obtained in Examples 1 to 15, a color paste having the following composition was prepared. Asymmetrical dioxazine compound 5 parts Urine 5 parts Sodium alginate (5%) base paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 13 parts This color paste is printed on mercerized cotton broad, dried at 100 ° C after intermediate drying. Steamed for 5 minutes, rinsed, soaped, rinsed and dried. The resulting dyed product was excellent in various fastnesses, particularly fastness to chlorine, and had good build-up properties.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yutaka Kayane 3-1-1, Kasuganaka, Konohana-ku, Osaka-shi, Osaka Sumitomo Chemical Co., Ltd. (72) Inventor Shigeru Kawabata Kasuga, Konohana-ku, Osaka-shi, Osaka Sumitomo Chemical Co., Ltd. (1) 98, Sumitomo Chemical Co., Ltd. (72) Inventor: Naoki Harada, Inventor: 3-1-1, Kasuganaka, Konohana-ku, Osaka-shi, Osaka 61-14265 (JP, A) JP-A-64-22970 (JP, A) JP-A-3-770 (JP, A) JP-A-54-139931 (JP, A) JP-A-61-62566 (JP, A) A) JP-A-60-99169 (JP, A) JP-A-60-208367 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09B 62/503 C09B 62/04 D06P 1 / 38

Claims (9)

(57) [Claims] 1. Form of the free acidButAnd the following general formula (I):Wherein R is a sulfo group, a halogen or alkoxy group,
₁And R_TwoIs independently hydrogen or substituted
Good alkyl group, R_ThreeIs hydrogen, an optionally substituted
Alkyl group or acyl group, X₁And X_TwoAre independently
Hydrogen, halogen, alkyl group, alkoxy group, or
Represents a nonoxy group, and Z represents the following formula: [Wherein, R_FourIs hydrogen or an optionally substituted alkyl
Group, R_FiveIs hydrogen or an optionally substituted alkyl,
Phenyl or naphthyl, R₆Is hydrogen or substituted
An alkyl group which may be₁Is replaced
Good phenylene, alkylene or naphthylene group, Z₁Is
-SO_TwoCH = CH_TwoOr -SO_TwoCH_TwoCH_TwoY₁(Y₁Is
Represents a group that is eliminated by the action of an alkali. ) Group, Q₁Is
Logen, optionally substituted pyridinio or al
Coxy group, -N (R₇) (R₈) Group (where R₇, R₈Is
Hydrogen or alkyl which may be substituted independently of each other,
Phenyl, naphthylorRepresents a benzyl group. ) Or
The following formula -N(R ₉ )-B_Two-Z_Two [B_TwoIs an optionally substituted phenylene, alkylene
Or a naphthylene group, R₉Is hydrogen or may be substituted
Alkyl group, Z_TwoIs -SO_TwoCH = CH_TwoOr -SO_TwoC
H_TwoCH_TwoY_Two(Where Y_TwoDesorbs by the action of alkali
Represents a group. )The table You.A fiber-reactive group represented byW
Is Embedded imageAnd Z ′ represents a fiber-reactive group.
You. An asymmetric dioxazine compound represented by｝. 2. Z is the following formula: (Wherein R ₄ , R ₅ , R ₆ , B _1, and Z ₁ each represent the meaning described in claim 1). (3) Z is a compound represented by the following formula:中 where Q₁, W have the meaning of claim 1 and Z ′
Is the following formula: [Wherein, R_TenIs hydrogen or an optionally substituted alkyl
Group, R₁₁Is hydrogen or an optionally substituted alkyl,
Phenyl or naphthyl, R₁₂Is hydrogen or substituted
An alkyl group which may be_ThreeIs replaced
Good phenylene, alkylene or naphthylene group, Z_ThreeIs
-SO_TwoCH = CH_TwoOr -SO_TwoCH_TwoCH_TwoY_Three(Y_ThreeIs
Represents a group that is eliminated by the action of an alkali. ), Q_TwoIs haloge
, Optionally substituted pyridinio or alkoxy
Group, -N (R₁₃) (R₁₄) Group (where R₁₃And R₁₄
Are, independently of each other, hydrogen or an optionally substituted
Represents a kill, phenyl, naphthyl or benzyl group
You. ) Or group -N(R ₁₅ )-B_Four-Z_Four (B_FourIsExchangedPhenylene, alkylene or
Is a naphthylene group, R₁₅May be hydrogen or optionally substituted
Alkyl group, Z_FourIs -SO_TwoCH = CH_TwoOr -SO_TwoCH
_TwoCH_TwoY_Four(Where Y_FourIs a group that leaves under the action of an alkali
Represents )). Table shows the fiber-reactive groups
You. The fiber-reactive group represented by｝
Compound. 4. The compound according to claim _1, wherein X ₁ and X ₂ are chloro or bromo. 5. The compound according to claim 1, wherein R is a sulfo group. 6. The method of claim ₁ , wherein R ₁ , R ₂ and R ₃ are hydrogen.
A compound according to any one of claims 1 to 5. 7. A divalent crosslinking group represented by W is represented by the following formula: The compound according to any one of claims 1 to 6, wherein 8. The method according to claim ₁ , wherein B ₁ , B ₂ , B ₃ and B ₄ are substituted by one or two substituents selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chlorine, bromine and sulfo groups. The compound according to any one of claims 1 to 6, which is a good phenylene group or a naphthylene group optionally substituted with a sulfo group. 9. A method for dyeing or printing a fiber material, comprising using the compound according to any one of claims 1 to 8.