JP2754659B2 - Asymmetric dioxazine compound and method for dyeing or printing fiber material using the same - Google Patents

Description

The present invention relates to a material containing a hydroxyl group and / or an amide group, in particular, cellulose fiber, natural or synthetic polyamide fiber, polyurethane fiber or leather, and a blend thereof. The present invention relates to a novel dioxazine compound which is suitable for dyeing and printing fibers and which enables light-fast, wet-fast and chlorine-fast dyeing, and its application.

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

<Problems to be Solved by the Invention> The fastness of dyeing or printing a material containing a hydroxyl group and / or an amide group, especially chlorine fastness, is not a satisfactory level, especially in the case of a hydroxyl group-containing fiber. The present inventors have worked diligently to improve this level,
A dioxazine compound that can solve the above problem has been found.

<Means for Solving the Problems> The present invention provides a compound represented by the following general formula (I) in the form of a free acid: (In the formula, R ₁ , R ₂ and R ₃ are each independently a hydrogen or an alkyl group which may have a substituent, and Y ₁ is an alkylene which may have a substituent, a phenylene or a naphthylene group. And Z ₁ represents —SO ₂ CH ＝ CH ₂ or —SO ₂ CH ₂ CH ₂ Z ′ (Z ′ represents a group capable of leaving under the action of an alkali), and X ₁ and X
₂ is hydrogen, halogen, a lower alkyl group, a lower alkoxy group or a phenoxy group, and Q ₁ is an amino group or a formula which may have a substituent. Wherein R ₄ is hydrogen or an alkyl group which may have a substituent, Y ₂ is an alkylene which may have a substituent, a phenylene or naphthylene group, and Z ₂ is -SO ₂ CH = CH ₂ or-
SO ₂ CH ₂ CH ₂ Z ″ (Z ″ represents a group capable of leaving under the action of an alkali.)｝, And Q ₂ and Q ₃ independently represent an amino group which may be substituted. And a method of dyeing or printing a fiber material characterized by using the compound.

Examples of the optionally substituted amino group represented by Q ₁ , Q ₂ and Q ₃ include alkylamino, N, N-dialkylamino, cycloalkylamino, aralkylamino,
Arylamino, mixed-substituted amino groups such as N-
Alkyl-N-cyclohexylamino and N-alkyl-N-arylamino, as well as amino groups containing heterocyclic groups (the cyclic groups can further have an addition-fused carbocyclic ring). And its amino nitrogen atom is N-
And an amino group which is a heterocyclic ring member (this N-heterocycle may optionally contain another hetero atom). The alkyl in the above may be straight-chain or branched, and may be low-molecular or high-molecular, but is preferably C ₁ -C ₄ alkyl. Particularly preferred as cycloalkyl, aralkyl and aryl are groups such as cyclohexyl, benzyl, phenethyl, phenyl and naphthyl. Examples of heterocyclic groups are furan, thiophene, pyrazole, pyridine,
Pyrimidine, quinoline, benzimidazole, benzothiazole and benzoxazole. Preferred as the amino group in which the amino nitrogen atom is a ring member of an N-heterocyclic ring is a 6-membered N-heterocyclic ring compound, which further contains nitrogen, oxygen and sulfur as heteroatoms. Is also good. The alkyl, cycloalkyl, aralkyl, aryl, heterocyclic ring and N-heterocyclic ring further include halogen, nitro, cyano, trifluoromethyl,
Sulfamoyl, carbamoyl, C ₁ -C ₄ - alkyl, C ₁
-C ₄ - alkoxy, acylamino, ureido, hydroxy, carboxy, optionally substituted by sulfomethyl and sulfo. Examples of the amino group which may have a substituent represented by Q ₁ , Q ₂ and Q ₃ include -NH ₂ , methylamino, hydroxymethylamino, ethylamino, propylamino, butylamino, hexylamino, β-methoxyethylamino, β-ethoxyethylamino, γ-
Methoxypropylamino, N, N-dimethylamino, N, N-
Dividroxymethylamino, N, N-diethylamino, β
-Chloroethylamino, β-cyanoethylamino, N, N
-Di-β-hydroxyethylamino, β-hydroxyethylamino, γ-hydroxypropylamino, benzylamino, phenethylamino, cyclohexylamino, N
-Methyl-N-phenylamino, N-ethyl-N-phenylamino, N-propyl-N-phenylamino, N-
Butyl-N-phenylamino, N-β-cyanoethyl-
N-phenylamino, N-ethyl-2-methylphenylamino, N-ethyl-4-methylphenylamino, N-
Ethyl-3-sulfophenylamino, N-ethyl-4-
Sulfophenylamino, phenylamino, toluidino,
Xylidino, chloranilino, anisidino, phenetidino, 2-, 3- and 4-sulfoanilino, 2,4- and
2,5-disulfoanilino, sulfomethylanilino, N-
Sulfomethylanilino, 3- and 4-carboxyphenylamino, 2-carboxy-5-sulfophenylamino, 2-carboxy-4-sulfophenylamino, 2-
Methoxy-5-sulfophenylamino, 2-methyl-5
-Sulfophenylamino, 4-sulfonaphthyl- (1)
-Amino, 3,6-disulfonaphthyl- (1) -amino,
3,6,8-trisulfonaphthyl- (1) -amino, 4,6,8-
Trisulfonaphthyl- (1) -amino, 6-sulfonaphthyl- (2) -amino, 4,8-disulfonaphthyl-
(2) -amino, 3,6,8-trisulfonaphthyl- (2)
-Amino, 4,6,8-trisulfonaphthyl- (2) -amino, pyridyl- (2) -amino, morpholino, piperidino, piperazino, N-β-hydroxyethyl-N-methylamino and N-ethyl-N -Hydroxymethylamino, β-carboxyethylamino, β-sulfoethylamino, N- (β-sulfoethyl) -N-methylamino and the like.

Examples of the alkylene group which may have a substituent represented by Y ₁ and Y ₂ include-(CH ₂ ) ₂ -,-(CH ₂ ) ₃ -,-
_{(CH 2) 2 O (CH} 2) 2 - , etc. are exemplified.

Further, the phenylene group or naphthylene group which may have a substituent is preferably substituted by one or two substituents selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chlorine, bromine and sulfo. Phenylene or naphthylene optionally substituted with one sulfo, for example, (In the formula, the bond indicated by an asterisk is Means a bond that is open. ) Etc. can be given.

Examples of the group capable of leaving by the action of an alkali represented by Z ′ and Z ″ include sulfate, thiosulfate, phosphate, acetate, and halogen.

As the optionally substituted alkyl of R ₁ , R ₂ , R ₃ and R ₄ , C _{1 to} C ₄ alkyl is preferable, and as the optionally substituted group, hydroxy, cyano, alkoxy , Halogen, carbamoyl, carboxy, alkoxycarbonyl, alkylcarbonyloxy, sulfo and sulfamoyl are preferred.

Particularly preferred R ₁ , R ₂ , R ₃ and R ₄ include, for example, hydrogen, 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-carbamoyl Ethyl, 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, 3-ethylcarbonyloxypropyl, 4-methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, sulfamoylmethyl, 2-sulfa Moylethyl, 3-sulfamoylpropyl, 4-sulfamoylbutyl can be mentioned.

As X ₁ and X ₂ , halogen is particularly preferable, and chlorine and bromine are preferable.

The compound of the present invention, its intermediate, and its raw material exist in the form of a free acid or a salt thereof, and particularly preferably an alkali metal salt and an alkaline earth metal salt, particularly preferably a soda salt, a potassium salt and a lithium salt.

The compound of the present invention can be produced, for example, as follows. The following intermediates and raw materials are shown in the form of a free acid. The following general formula (II) (Wherein R ₁ , R ₃ , X ₁ and X ₂ have the above-mentioned meanings) and a known dioxazine compound represented by the following general formula (II)
I) Wherein R ₂ , Y ₁ and Z ₁ have the above-mentioned meanings; and the following general formula (IV) H-Q ₁ (IV) (wherein Q ₁ has the above-mentioned meanings) Is condensed with 2,4,6-trihalogeno-s-triazine in any order to obtain an amine represented by the following general formula (V): (Wherein X ₁ , X ₂ , R ₁ , R ₂ , R ₃ , Q ₁ , Y ₁ and Z ₁ have the above-mentioned meanings).

Further, a dioxazine intermediate of the general formula (V):
An amine represented by the following general formulas (VI) and (VII) H-Q ₂ (VI) H-Q ₃ (VII) (wherein Q ₂ and Q ₃ have the above-mentioned meanings) The compounds of general formula (I) can be obtained by condensing each with 2,4,6-trihalogeno-s-triazine in any order.

Alternatively, a dioxazine compound represented by the general formula (II) and an amine represented by the general formula (VI) and the general formula (VII) are each converted into 2,4,6-trihalogeno-s-triazine in any order. By condensation, the following general formula (VIII) (Wherein X ₁ , X ₂ , R ₁ , R ₃ , Q ₂ and Q ₃ have the above-mentioned meanings), and a dioxazine intermediate represented by the general formula (VIII) And an amine represented by the general formula (III) and the general formula (IV) are condensed to 2,4,6-trihalogeno-s-triazine in any order to obtain a compound of the general formula (I) be able to.

Further, when Q ₁ and Q ₂ are the same, the general formula (II)
And an amine obtained by condensing the amine represented by the general formula (III) with 2,4,6-trihalogeno-s-triazine in an arbitrary order, is converted to a general formula (VI
The following general formula (IX) obtained by condensing the amine represented by I) with 2,4,6-trihalogeno-s-triazine in any order. (Wherein X ₃ and X ₄ each independently represent a halogen, X ₁ , X
_{2, R 1, R 2,} R 3, Y 1, Z 1 and Q ₃ are each as defined above. ) Is condensed with 2 mol of an amine represented by the general formula (IV).

The order of the condensation reaction with 2,4,6-trihalogeno-s-triazine is not particularly limited, and the reaction conditions are not particularly limited.
PH 2 to 9 at 40 ° C to 40 ° C, and secondarily at temperature 0 to 70 ° C.
H2 to 9 and, if tertiary, p
The dioxazine compound represented by the general formula (I) or a salt thereof can be obtained by condensation while adjusting to H2 to H7.

The compound of the present invention has fiber reactivity and can be used for dyeing or printing materials containing hydroxyl groups or carbonamide groups. The material is preferably used in the form of a fibrous material or a blend thereof.

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

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 hair, silk, leather, polyamide-6,
6, polyamide-6, polyamide-11 and polyamide-
4.

The compound of the present invention can be dyed or printed on the above-mentioned material, particularly on the above-mentioned fiber material, by a method depending on physical and chemical properties.

For example, in the case of exhaust dyeing on cellulose fibers, sodium carbonate, tertiary sodium phosphate, in the presence of an acid binder such as caustic soda, optionally a neutral salt, for example, sodium sulfate or sodium chloride,
If desired, dissolution aids, penetrants or leveling agents may be used in combination at relatively low temperatures. Neutral salts which promote the exhaustion of the dye can be added only after the original dyeing temperature has been reached or before, optionally in portions.

When dyeing cellulose fibers according to the padding method,
After padding and drying at room temperature or elevated temperature, it can be fixed by steaming or dry heat.

When printing on cellulose fibers, printing is carried out in one phase, for example with a printing paste containing baking soda or other acid binders, followed by steaming at 100-160 ° C., or in two phases, for example in medium The printing can be carried out by printing with an acidic or weakly acidic printing paste and passing it through a hot electrolyte-containing alkaline bath, or overpadging with an alkaline electrolyte-containing padding solution, steaming or dry heat treatment.

In the printing paste, a sizing or emulsifying agent such as sodium alginate or starch ether is optionally used,
For example, it is used in combination with a usual printing aid and / or dispersant such as urea.

Acid binders suitable for immobilizing the compounds of the invention on cellulose fibers are, for example, water-soluble basic salts of alkali metals or alkaline earth metals with inorganic or organic acids or compounds which liberate alkali under heating. 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. Examples of such an acid binder include 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.

The dyeing of synthetic and natural polyamide and polyurethane fibers is carried out by first exhausting the acid or reverse acid dyeing bath under controlled pH values and then changing to a neutral and possibly alkaline pH value for fixing. I can do it. Dyeing can usually be carried out at a temperature of 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 on fiber materials. Particularly suitable for dyeing cellulosic fiber materials, good light resistance and sweat-sunlight resistance, excellent wet resistance, for example, washing resistance, washing resistance to peroxide, sweat resistance, acid hydrolysis resistance and alkali resistance, Furthermore, it has good chlorine resistance, friction resistance and iron resistance.

In addition, it has excellent build-up properties, leveling properties and wash-off properties, and also has good solubility and exhaustion / fixing properties,
It is characterized by the fact that it is hardly affected by fluctuations in the dyeing temperature and the dyeing bath ratio and a dyed product of stable quality can be obtained.

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

Hereinafter, the present invention will be described in detail with reference to examples. In the example,
Parts and% represent parts by weight and% by weight, respectively.

Example 1 55 parts of the dioxazine compound represented by the above structural formula and 18 parts of cyanuric chloride were added as free acids to 1500 parts of water, and the mixture was stirred with sodium carbonate at pH 5 to 8, 0 to 30 ° C. until the reaction was completed. 13 parts of taurine is added thereto, and the pH is 4 to 7 and 10 to 50 ° C.
And stirred until the reaction was completed. Further, 13 parts of taurine was added, and the mixture was stirred at pH 4 to 7 and 30 to 80 ° C. until the reaction was completed to obtain a dioxazine intermediate represented by the following structural formula as a free acid.

87 parts of the obtained dioxazine intermediate and 18 parts of cyanuric chloride were added to 1500 parts of water, and sodium carbonate was used to adjust the pH to 5 to 8 and 0 to 30 ° C.
And stirred until the reaction was completed. 13 parts of taurine was added thereto, and the mixture was stirred at pH 4 to 7 and 10 to 50 ° C. until the reaction was completed. Further, 28 parts of 1-aminobenzene-3-β-sulfatoethylsulfone was added, and the mixture was stirred at pH 4 to 7 and 30 to 80 ° C. until the reaction was completed. A dioxazine compound was obtained.

Example 2 In place of the dioxazine compound used in Example 1, an asymmetrical compound represented by the following structural formula was obtained in the same manner as in Example 1 by using the dioxazine compound represented by the above structural formula as an equimolar free acid. A dioxazine compound was obtained.

Example 3 55 parts of the dioxazine compound represented by the above structural formula and 18 parts of cyanuric chloride were added as free acids to 1500 parts of water, and the mixture was stirred with sodium carbonate at pH 5 to 8, 0 to 30 ° C. until the reaction was completed. 17 parts of sulfanilic acid was added thereto and the pH was 4 to 7, 10
The mixture was stirred at 5050 ° C. until the reaction was completed. Further, 17 parts of metanilic acid was added, and the mixture was stirred at pH 4 to 7 and 30 to 80 ° C. until the reaction was completed to obtain a dioxazine intermediate.

Using this dioxazine intermediate, an asymmetric dioxazine compound represented by the following structural formula was obtained as a free acid in the same manner as in Example 1.

Example 4 0.1, 0.3 and 0.6 parts of each of the asymmetric dioxazine compounds described in Examples 1, 2 and 3 were dissolved in 200 parts of water, respectively.
10 parts of cotton and 10 parts of cotton were added, the temperature was raised to 60 ° C., 4 parts of sodium carbonate was added, and dyed for 1 hour. Perform water washing, soaping, water washing and drying, excellent in various fastnesses, especially chlorine fastness,
A reddish blue dyeing having good build-up properties was obtained.

Example 5 A corresponding asymmetric dioxazine compound was obtained in the same manner as in Example 1 except that 1-aminobenzene-3-β-sulfatoethylsulfone used in Example 1 was replaced with an equimolar amine shown below. Was.

_{(14) H 2 N- (CH} 2) 2 OC 2 H 4 SO 2 C 2 H 4 Cl (15) H 2 N- (CH 2) 2 OC 2 H 4 SO 2 CH = CH 2 (16) H 2 N- (CH _{2) 8} OC to _{2 H 4 SO 2 CH = CH} 2 instead of taurine used in example 6 example 1, in the same manner as in example 1 using equimolar following amines, the corresponding An asymmetric dioxazine compound was obtained.

(1) N-methyltaurine (2) β-alanine (3) Ethanolamine (4) Diethanolamine (5) Ethylamine (6) Ammonia (7) Sulfanilic acid (8) Metanylic acid (9) Ortanylic acid (10) Aniline ( 11) aniline-2,5-disulfonic acid (12) 2-aminonaphthalene-3,6,8-trisulfonic acid (13) 1-aminonaphthalene-3,6-disulfonic acid Example 7 Used in Example 6. Instead of 1-aminobenzene-3-β-sulfatoethylsulfone, equimolar Example 5
The corresponding asymmetric dioxazine compounds were similarly obtained by using the amines (1) to (16) used in the above.

Example 8 Each of the asymmetric dioxazine compounds 0.1, 0.3 and 0.6 described in Examples 5 to 7 was dissolved in 200 parts of water, 10 parts of sodium sulfate and 10 parts of cotton were added, and the temperature was raised to 60 ° C. and 4 parts of sodium carbonate was added. And stained for 1 hour. Washing, soaping, washing and drying were carried out to obtain a reddish blue dyeing material having excellent fastness properties, especially chlorine fastness property, and good build-up properties.

Example 9 The same compound as in Example 1 was obtained by changing the order of the reaction between 1-aminobenzene-3-β-sulfatoethylsulfone and taurine in Example 1.

Example 10 55 parts of the dioxazine compound represented by the above structural formula and 18 parts of cyanuric chloride were added as free acids to 1500 parts of water, and the mixture was stirred with sodium carbonate at pH 5 to 8, 0 to 30 ° C. until the reaction was completed. 13 parts of taurine is added thereto, and the pH is 4 to 7 and 10 to 50 ° C.
And stirred until the reaction was completed. Further, 28 parts of 1-aminobenzene-3-β-sulfatoethylsulfone was added, and the mixture was stirred at pH 4 to 7 and 30 to 80 ° C. until the reaction was completed. As a free acid, dioxazine represented by the following structural formula was obtained. An intermediate was obtained.

In the above, the same intermediate was obtained by changing the order of the reaction between 1-aminobenzene-3-β-sulfatoethylsulfone and taurine.

103 parts of the obtained dioxazine intermediate and cyanuric chloride 18
To 1500 parts of water, and pH 5-8, 0-30 with sodium carbonate.
Stirred at C until reaction was complete. Taurine 13 in this
The mixture was stirred at pH 4-7, 10-50 ° C until the reaction was completed. Furthermore, 13 parts of taurine was added, and pH 4-7, 30-8
The asymmetric dioxazine compound obtained by stirring at 0 ° C. until the reaction was completed was the same as the asymmetric dioxazine compound obtained in Example 1.

Example 11 55 parts of the dioxazine compound represented by the above structural formula and 18 parts of cyanuric chloride as free acids were added to 1500 parts of water, and the mixture was stirred with sodium carbonate at pH 5 to 8, at 0 to 30 ° C. until the reaction was completed. 13 parts of taurine is added thereto, and the pH is 4 to 7 and 10 to 50 ° C.
And stirred until the reaction was completed. Next, 18 parts of cyanuric chloride was added, and the mixture was stirred at pH 5 to 8, 0 to 30 ° C until the reaction was completed. Further, 1-aminobenzene-3-β
-28 parts of sulfate ethyl sulfone are added, pH 4-7, 1
By stirring at 0-50 ° C. until the reaction is completed,
A dioxazine intermediate represented by the following structural formula was obtained as a free acid.

In the above, the same intermediate was obtained by changing the order of the reaction between 1-aminobenzene-3-β-sulfatoethylsulfone and taurine.

118 parts of this dioxazine intermediate and 26 parts of taurine
In addition to 0 parts, the asymmetric dioxazine compound obtained by stirring at pH 4-7 at 30-80 ° C. until the reaction was completed was the same as the dioxazine compound obtained in Example 1.

Example 12 Instead of taurine used in Example 1, equimolar 1-
An asymmetric dioxazine compound represented by the following structural formula was obtained as a free acid in the same manner as in Example 1 using N-ethylaminobenzene-3-β-sulfatoethylsulfone.

Example 13 1-N-ethylaminobenzene-3 used in Example 12
The corresponding asymmetric dioxazine compounds were obtained in the same manner as in Example 1 except that equimolar amine having the following structure was used instead of -β-sulfatoethylsulfone.

_{(7) H 2 N- (CH} 2) 2 OC 2 H 4 SO 2 C 2 H 4 Cl (8) H 2 N- (CH 2) 2 OC 2 H 4 SO 2 CH = CH 2 Example 14 Example The corresponding asymmetric dioxazine compound was similarly obtained by using the amines (1) to (8) used in Example 13 in place of the taurine used in Example 5.

Example 15 Each of the asymmetric dioxazine compounds 0.1, 0.3 and 0.6 described in Examples 12, 13, and 14 was dissolved in 200 parts of water, and
Then, 10 parts of cotton and 10 parts of cotton were added, the temperature was raised to 60 ° C., and 4 parts of sodium carbonate was added, followed by dyeing for 1 hour. Washing, soaping, washing and drying were carried out to obtain a reddish blue dyeing material having excellent fastness properties, especially chlorine fastness property, and good build-up properties.

Example 16 A color paste having the following composition was made using each of the same asymmetric dioxazine compounds used in Examples 4, 8, and 15.

Asymmetric dioxazine compound 5 parts Urea 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, intermediate dried, and dried at 100 ° C for 5 minutes. Teamed, washed, soaped, washed and dried. The resulting dyed product was excellent in various fastnesses, particularly fastness to chlorine, and had good build-up properties.

Continued on the front page (72) Inventor: Naoki Harada 3-1-1, Kasuganaka, Konohana-ku, Osaka-shi Within Sumitomo Chemical Co., Ltd. (72) Inventor Takashi Omura 3-chome, Kasuganaka, Konohana-ku, Osaka-shi, Osaka No. 98 No. 98 Sumitomo Chemical Co., Ltd. (56) References JP-A-63-211378 (JP, A) JP-A-63-243387 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09B 62/503 D06P 1/38 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. The following general formula in the form of a free acid: [Wherein, R ₁ , R ₂ and R ₃ independently represent hydrogen or a group selected from the group consisting of hydroxy, cyano, alkoxy, halogen, carbamoyl, carboxy, alkoxycarbonyl, alkylcarbonyloxy, sulfo and sulfamoyl. Represents an alkyl group which may be substituted, and Y ₁ represents a-(CH ₂ ) ₂ -group, a-(CH ₂ ) ₃ -group,-(C
_{H 2) 3 O (CH 2} ) 2 - group and _{- (CH 2) 2 O (} CH 2) 2 - alkylene group selected from the group methyl, ethyl, methoxy,
Ethoxy, chlorine, bromine and a phenylene group which may be substituted with a group selected from the group of sulfo, or a naphthylene group which may be substituted with a sulfo, Z ₁ represents -SO ₂ C
H ＝ CH ₂ or —SO ₂ CH ₂ CH ₂ Z ′ (Z ′ represents a sulfate, thiosulfate, phosphate, acetate or halogen), and X ₁ and X ₂ represent hydrogen, halogen, Represents a lower alkyl group, a lower alkoxy group or a phenoxy group, and Q ₁ is an amino group or an amino nitrogen atom which may be substituted by a substituent selected from the group consisting of alkyl, cycloalkyl, aralkyl, aryl and heterocyclic groups. Represents an amino group that is a ring member of an N-heterocyclic ring (wherein the substituent and the N-heterocyclic ring further include halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, acetylamino, ureido, hydroxy, carboxy, optionally substituted by sulfomethyl or sulfo. Further, N The heterocyclic ring may further contain another hetero atom.), Or, where _{-N (R 4) -Y 2 -Z} 2 { wherein, R ₄ is hydrogen or, hydroxy, cyano , Alkoxy, halogen, carbamoyl, carboxy, alkoxycarbonyl, alkylcarbonyloxy, an alkyl group which may be substituted with a group selected from the group consisting of sulfo and sulfamoyl, Y ₂ represents a-(CH ₂ ) ₂ -group, −
A (CH ₂ ) ₃ — group, a — (CH ₂ ) ₃ O (CH ₂ ) ₂ — group and a — (C
_{H 2) 2 O (CH 2} ) 2 - alkylene group, methyl, ethyl, methoxy, ethoxy, chlorine, bromine and group optionally substituted phenylene group selected from the group consisting of sulfo selected from group, or sulfo Represents a naphthylene group which may be substituted, and Z ₂ represents —SO ₂ CH ＝ CH ₂ or —SO ₂ CH ₂ CH ₂ Z ″
(Z ″ represents a sulfate, thiosulfate, phosphate, acetate or halogen.)
Q ₂ and Q ₃ independently of one another, alkyl, cycloalkyl,
Represents an amino group optionally substituted by a substituent selected from the group consisting of aralkyl, aryl and heterocyclic groups, or an amino group in which an amino nitrogen atom is a ring member of an N-heterocyclic ring. (Here, the substituents and N- heterocyclic ring may further halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, acetylamino, Ureido,
It may be substituted by hydroxy, carboxy, sulfomethyl or sulfo. Further, the N-heterocyclic ring may further contain another hetero atom. )] An asymmetric dioxazine compound represented by the formula: 2. The compound according to claim _1, wherein X ₁ and X ₂ are chlorine or bromine. 3. The compound according to claim 1, wherein R ₁ and R ₃ are hydrogen. 4. A method for dyeing or printing a fiber material, comprising using the asymmetric dioxazine compound according to claim 1.