JP2754660B2 - 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: [Wherein, R represents an alkyl or phenyl group which may be substituted, R ₁ , R ₂ and R ₃ independently represent a hydrogen or an alkyl group which may have a substituent, and W represents a carbonyl group. Or a sulfonyl group, Y is an alkylene, phenylene or naphthylene group which may have a substituent, and Z is -SO ₂ CH
CHCH 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 represent hydrogen, halogen, lower alkyl group, lower alkoxy group or phenoxy. Q represents an optionally substituted amino group or a group represented by the formula In the formula, R ₄ is hydrogen or an alkyl group which may have a substituent, Y ₁ is an alkylene which may have a relaxing group, a phenylene or naphthylene group, and Z ₁ is -SO ₂ CH = CH ₂ or-
SO ₂ CH ₂ CH ₂ Z ″ (Z ″ represents a group which is eliminated by the action of an alkali). Represents a group represented by｝. And a method of dyeing or printing a fiber material characterized by using the compound.

In the general formula (I), R—W— (R and W have the above-mentioned meanings) represents an acyl group, and examples of such an acyl group include alkyl such as acetyl, propionyl, and benzoyl. Examples thereof include an alkyl or arylsulfonyl group such as an arylcarbonyl group, a methanesulfonyl group, and a p-toluenesulfonyl group. The alkyl group and the aryl group in these acyl groups may be substituted by a carboxyl group or a sulfo group. Examples of such a substituted acyl group include a maleyl group, a succinyl group,
Examples are o-, m- and p-carboxyphenylcarbonyl groups, o-, m- and p-sulfophenylcarbonyl groups, o-, m- and p-sulfophenylsulfonyl groups.

Examples of the optionally substituted amino group represented by Q 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, which can have further addition-fused carbocyclic rings, and their amino nitrogens And an amino group in which the atom is an N-heterocyclic ring member (this N-heterocyclic ring 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. Amino nitrogen atom is N
Preferred as an amino group which is a ring member of a heterocyclic ring is a 6-membered N-heterocyclic ring compound, which may additionally contain nitrogen, oxygen and sulfur as heteroatoms.
The above alkyl, cycloalkyl, aralkyl, aryl, further heterocyclic ring and N- heterocyclic ring, halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C ₁ -C ₄ - alkyl, C ₁ ~ It may be substituted by C ₄ -alkoxy, acylamino, ureido, hydroxy, carboxy, sulfomethyl and sulfo. Examples of amino groups represented by Q, -NH _2,
Methylamino, hydroxymethylamino, ethylamino, propylamino, butylamino, hexylamino,
β-methoxyethylamino, β-ethoxyethylamino, γ-methoxypropylamino, N, N-dimethylamino, N, N-dihydroxymethylamino, 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 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 or Y ₁ 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 leads to ) 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.)
Is obtained by acylating a known dioxazine compound represented by the following general formula (III): (Wherein R, R ₁ , R ₃ , W, X ₁ and X ₂ have the above-mentioned meanings) and a dioxazine represented by the following general formula (I
V) (Wherein R ₂ , Y and Z have the above-mentioned meanings), and the following general formula (V) HQ (V) (wherein Q has the above-mentioned meanings). The indicated amines can be prepared by condensing each with 2,4,6-trihalogeno-s-triazine in any order.

Alternatively, a known dioxazine compound represented by the general formula (II) and an amine represented by the general formula (IV), and further, an amine represented by the general formula (V) are converted into 2,4,6-trihalogeno-
The following general formulas (VI) to (IX) obtained in the process of condensing each with s-triazine in any order (Wherein X represents halogen, X ₁ , X ₂ , R ₁ , R ₂ , R ₃ , Q, Y
And Z have the meaning given above. ) Is produced by acylating the dioxazine intermediate represented by the general formula (I) and then condensing the dioxazine intermediate represented by any of the general formulas (VI) to (VIII) with the remaining amine in any order. Can be.

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 a hydroxy group-containing or carboxyamino group-containing material. The material is preferably used in the form of a fibrous material or a mixture thereof.

The hydroxy-containing material is a natural or synthetic hydroxyl-containing material, such as a cellulosic fibrous 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.

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, in one phase, for example by printing with a printing paste containing baking soda or other acid binders, then by steaming at 100-160 ° C., or in two phases, for example The printing can be carried out by printing with a neutral or weakly acidic printing paste and passing this through a hot electrolyte-containing alkaline bath, or overpadding 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 alkalis 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 weakly acidic dye bath under control of the pH value and then changing it 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 Dioxazines 59 represented by the above structural formula as a free acid
And 18 parts of cyanuric chloride were added to 1500 parts of water, and the mixture was stirred with sodium carbonate at pH 5-8 at 0-30 ° C. until the reaction was completed. To this, 17 parts of sulfanilic acid was added to adjust the pH to 5-8, 10
The mixture was stirred at 5050 ° C. until the reaction was completed. Further, 1-aminobenzene-3-β-sulfate ethyl sulfone 28
Then, the mixture was stirred at pH 3 to 6 and 30 to 80 ° C. until the reaction was completed to obtain an asymmetric dioxazine compound represented by the following structural formula as a free acid.

The dioxazines used here were synthesized as follows.

The following structural formula as a free acid Is dissolved in 500 parts of water, 10 parts of acetic anhydride is added, and the mixture is stirred at pH 2 to 7 and 10 to 50 ° C. until the reaction is completed to obtain dioxazines.

Example 2 In place of the dioxazines of Example 1, an asymmetric dioxazine compound represented by the following structural formula was obtained as a free acid by a method similar to that of Example 1 using dioxazines represented by the above structural formula as equimolar free acids. Obtained.

The dioxazines used here are represented by the following structural formula as an equimolar free acid instead of the dioxazine compound used in Example 1. Was obtained in the same manner as in Example 1 using the dioxazine compound represented by

Example 3 Each asymmetric dioxazine compound described in Examples 1 and 2
Each of 0.1, 0.3 and 0.6 parts was dissolved in 200 parts of water, 10 parts of Glauber's salt 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. 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.

Examples 4 to 115 Equimolar amounts of dioxazines (III) obtained by the same method as in Example 1 and 1-aminobenzene-
The corresponding asymmetric dioxazine compounds were obtained in the same manner as in Example 1 except that equimolar amine of the formula (IV) in the table was used instead of 3-β-sulfatoethylsulfone.

Example 116 (In the formula, x represents a degree of sulfonation of about 1.2.) In the same manner as in Example 1 except that the dioxazines represented by the above structural formula are used as equimolar free acids instead of the dioxazines of Example 1, As a free acid, an asymmetric dioxazine compound represented by the following structural formula was obtained.

(In the formula, x indicates a degree of sulfonation of about 1.2.) The dioxazines used here were synthesized as follows.

65 parts of the dioxazines used in Examples 36 to 51 were mixed with 5 to 30
% Fuming sulfuric acid and stirred at 20 to 70 ° C. until the reaction was completed. Thereafter, the reaction mass was charged into ice water and salted out to obtain dioxazines.

Examples 117 to 133 Equimolar amounts of dioxazines obtained in Example 116 (II
In the same manner as in Example 116, using the equimolar amine (IV) in place of 1-aminobenzene-3-β-sulfatoethylsulfone of Example 116 and 1-aminobenzene-3-β-sulfatoethylsulfone, the corresponding asymmetric A dioxazine compound was obtained.

Example 133 The corresponding asymmetric dioxazine compound was obtained in the same manner as in Example 1 except that the sulfanilic acid of Example 1 was replaced with the following amine in an equimolar amount.

(1) Orthanilic acid (2) Methanilic acid (3) 1-Aminonaphthalene-3,6-disulfonic acid (4) 1-Aminonaphthalene-4,6,8-trisulfonic acid (5) 2-Aminonaphthalene-4 , 8-Disulfonic acid (6) 2-aminonaphthalene-3,6,8-trisulfonic acid (7) aniline-2,5-disulfonic acid (8) aniline (9) m-toluidine (10) O-anisidine ( 11) Ammonia (12) Ethylamine (13) Ethanolamine (14) β-alanine (15) Taurine (16) N-methyltaurine Example 134 In Examples 4-132, used in Example 133 instead of sulfanilic acid. Similarly, the corresponding asymmetric dioxazine compounds were obtained using the amines of (1) to (16).

Example 135 0.1, 0.3 and 0.6 parts of each of the asymmetric dioxazine compounds described in Examples 4 to 132 were dissolved in 200 parts of water, respectively.
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 136 The same compound as in Example 1 was obtained also by changing the order of the reaction between 1-aminobenzene-3-β-sulfatoethylsulfone and sulfanilic acid in Example 1.

Example 137 As a free acid, the following structural formula 55 parts of the dioxazine compound and 18 parts of cyanuric chloride are added to 1500 parts of water, and sodium carbonate is used to adjust the pH to 5 to 8 and 0 to 30 ° C.
And stirred until the reaction was completed. 17 parts of sulfanilic acid was added thereto, and the mixture was stirred at pH 5 to 8 and 10 to 50 ° C. until the reaction was completed. Next, 10 parts of acetic anhydride was added thereto, and the pH was adjusted to 2
The mixture was stirred at ７7, 10 to 50 ° C. until the reaction was completed. Further, an asymmetric dioxazine compound obtained by adding 28 parts of 1-aminobenzene-3-β-sulfatoethylsulfone and stirring the mixture at pH 3 to 6 at 30 to 80 ° C. until the reaction was completed was prepared in Example 1. It was identical to the resulting asymmetric dioxazine compound.

Example 138 In Example 137, 1-aminobenzene-3-β-
The same compound as in Example 137 was obtained also by changing the order of the reaction between sulfate ethyl sulfone and sulfanilic acid.

Example 139 As a free acid, the following structural formula 55 parts of the dioxazine compound and 18 parts of cyanuric chloride are added to 1500 parts of water, and sodium carbonate is used to adjust the pH to 5 to 8, 0 to 80 ° C.
And stirred until the reaction was completed. 17 parts of sulfanilic acid was added thereto, and the mixture was stirred at pH 5 to 8 and 10 to 50 ° C. until the reaction was completed. Next, in this, 1-aminobenzene-3
-Β-sulfate ethyl sulfone 28 parts, pH 3 ~
6. The mixture was stirred at 30 to 80 ° C. until the reaction was completed. further,
The asymmetric dioxazine compound obtained by adding 10 parts of acetic anhydride and stirring until the reaction was completed at pH 2 to 7 and 10 to 50 ° C. was the same as the asymmetric dioxazine compound obtained in Example 1. .

Example 140 In Example 139, 1-aminobenzene-3-β-
The same compound as in Example 139 was obtained by changing the order of sulfate ethyl sulfone and sulfanilic acid.

Example 141 25.3 parts of aniline-2,5-disulfonic acid were added and dissolved in 1500 parts of water while neutralizing with sodium carbonate. Where 5
At 30 ° C., 18 parts of cyanuric chloride were added, and the mixture was stirred until the reaction was completed. The dioxazines 59 obtained in Example 1 were added to the reaction mixture.
The reaction was terminated while neutralizing hydrochloric acid liberated with sodium carbonate. Further, 1-aminobenzene-3-β-
28 parts of sulfate ethyl sulfone was added, and while maintaining the pH at 2 to 5, the temperature was raised to 50 to 70 ° C. to terminate the reaction. The obtained asymmetric dioxazine compound was the same as the compound obtained in Example 133 (7).

Example 142 59 parts of the dioxazine obtained in Example 1 was dissolved in 1500 parts of water, and 18 parts of cyanuric chloride was added at a temperature of 5 to 30 ° C.
The mixture was stirred while maintaining the pH at 2 to 7 with sodium carbonate until the reaction was completed. Next, 28 parts of 1-aminobenzene-3-β-sulfatoethylsulfone was added, and while maintaining the pH at 2 to 6, 10 parts were added.
The mixture was stirred at 5050 ° C. until the reaction was completed. Next, 31 parts of 1-N-ethylaminobenzene-3-β-sulfatoethylsulfone was added thereto, and while maintaining the pH at 2 to 6, 4 parts were added.
By stirring at 0-90 ° C. until the reaction is completed,
As a free acid, an asymmetric dioxazine compound represented by the following structural formula was obtained.

Example 143 1-N-ethylaminobenzene-3-β of Example 142
-A corresponding asymmetric dioxazine compound was obtained in the same manner as in Example 142 using an equimolar amine having the following structure instead of sulfate ethyl sulfone.

_{(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 144 Example Instead of the dioxazines used in 142, using equimolar dioxazines used in Examples 9-132,
In the same manner as in Example 142, corresponding asymmetric dioxazine compounds were obtained.

Example 145 In the same manner as in Example 144, the amines (1) to (8) used in Example 143 were used instead of 1-N-ethylaminobenzene-3-β-sulfatoethylsulfone. The corresponding asymmetric dioxazine compound was obtained.

Example 146 0.1, 0.3 and 0.6 parts of each asymmetric dioxazine compound described in Examples 142, 143, 144 and 145 were 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 were added and dyed for 1 hour. Washing, soaping,
Wash with water and dry. A reddish blue dyeing having excellent fastnesses, particularly excellent chlorine fastness, and good build-up properties was obtained.

Example 147 A color paste having the following composition was prepared using each of the same asymmetric dioxazine compounds used in Examples 3, 135 and 146.

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.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Naoki Harada 3-1-198 Kasuganaka, Konohana-ku, Osaka-shi, Sumitomo Chemical Industries, Ltd. (72) Inventor Takashi Omura Kasuga-hi, Konohana-ku, Osaka No. 3-98 No. 98 in Sumitomo Chemical Co., Ltd. (56) References JP-A-63-162763 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09B 62/503 D06P 1/38 CA (STN) REGISTRY (STN)

Claims (9)

(57) [Claims] 1. The following general formula in the form of a free acid: [In the formula, R is an alkyl group optionally substituted by a carboxyl group or a sulfo group, an alkenyl group optionally substituted by a carboxyl group, or may be substituted by a carboxyl group, a sulfo group or a methyl group. Represents a phenyl group, R ₁ , R ₂ and R ₃ are each independently selected from a hydrogen atom or a group consisting of hydroxy, cyano, alkoxy, halogen, carbamoyl, carboxy, alkoxycarbonyl, alkylcarbonyloxy, sulfo and sulfamoyl Y represents an alkyl group which may be substituted with a substituent, W represents a carbonyl group or a sulfonyl group, and Y represents a-(CH ₂ ) ₂ -group or-(CH ₂ ) _{3-.
Group, - (CH 2) 2 O} (CH 2) 2 - group and _{- (CH 2) 3 O (} CH 2)
An alkylene group selected from _2- groups, methyl, ethyl, methoxy, ethoxy, chlorine, bromine and a phenylene group optionally substituted by a substituent selected from the group of sulfo;
Or it represents an optionally naphthylene group optionally substituted by a sulfo, Z is, -SO ₂ CH = CH ₂ or _{-SO 2 CH 2 CH 2 Z '} (Z' of the sulfate groups, thiosulfate ester groups, phosphate ester X ₁ and X ₂ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a phenoxy group, and Q represents an alkyl, cycloalkyl, aralkyl, aryl And an amino group in which an amino nitrogen atom or an amino nitrogen atom which may be substituted by a substituent selected from the group consisting of a heterocyclic group and an amino group which is a ring member of an N-heterocyclic ring (wherein the above substituent and N- Heterocyclic rings further include halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, alkyl, alkoxy, acetylamino, ureido, hydroxy, carboxy. Sulfomethyl or may be substituted by sulfo. Also, if N- heterocyclic ring, represents a further another heteroatom may contain.), Or the formula -N (R ₄₎ -Y during ₁ -Z ₁ {wherein, R ₄ is hydrogen or, hydroxy, cyano, alkoxy, halogen, carbamoyl, carboxy, alkoxycarbonyl, alkylcarbonyloxy, optionally substituted with a substituent selected from the group consisting of sulfo and sulfamoyl Represents a good alkyl group, Y ₁ is — (CH ₂ ) ₂ —
An alkylene group selected from a group, a — (CH ₂ ) ₃ — group, a — (CH ₂ ) ₂ O (CH ₂ ) ₂ — group and a — (CH ₂ ) ₃ O (CH ₂ ) ₂ — group;
Methyl, ethyl, methoxy, ethoxy, chlorine, bromine and a phenylene group which may be substituted with a substituent selected from the group of sulfo, or a naphthylene group which may be substituted with a sulfo, Z ₁ represents -SO ₂ CH = CH ₂ or -SO ₂ C
H ₂ CH ₂ Z ″ (Z ″ represents a sulfate group, a thiosulfate group, a phosphate group, an acetate group or a halogen atom). Represents a group represented by｝. ] The asymmetric dioxazine compound represented by these. 2. The method according to claim _1, wherein X ₁ and X ₂ are chlorine or bromine.
The compound according to the above. 3. The compound according to claim 1, wherein R ₁ and R ₃ are hydrogen. 4. A compound represented by the following general formula in the form of a free acid: [Wherein, W, R, R ₁ , R ₃ , X ₁ and X ₂ have the same meaning as in claim 1. ] The dioxazine shown by these. (5) W is a carbonyl group, and R is an alkyl group optionally substituted by a carboxyl group or a sulfo group, or an alkenyl group optionally substituted by a carboxyl group. Item 10. Dioxidisans according to item 4. 6. The dioxazine according to claim 4, wherein W is a sulfonyl group, and R is a phenyl group optionally substituted with a carboxyl group, a sulfo group or a methyl group. 7. A compound of the following formula in the form of a free acid: Dioxazines represented by the formula: 8. The free acid form of the formula Dioxazines represented by the formula: 9. A method for dyeing or printing a fiber material, comprising using the asymmetric dioxazine compound according to claim 1.